e-ISSN 2150-5551

CN 31-2103/TB

REVIEW https://doi.org/10.1007/s40820-023-01047-z

Advances in Noble Metal‑Decorated Metal Oxide

Nanomaterials for Chemiresistive Gas Sensors:
Cite as
Nano-Micro Lett. Overview
(2023) 15:89

Received: 12 November 2022 Li‑Yuan Zhu1, Lang‑Xi Ou1, Li‑Wen Mao2, Xue‑Yan Wu1, Yi‑Ping Liu3,
Accepted: 25 February 2023 Hong‑Liang Lu1 *
Published online: 7 April 2023
© The Author(s) 2023

HIGHLIGHTS

• Recent progress in noble metal-decorated (NM-D) semiconducting metal oxides (SMOs) gas sensors are summarized.

• Gas sensing mechanisms related to noble metal decoration are carefully discussed.

• Crucial challenges facing the development of NM-D SMOs gas sensors are analyzed.

ABSTRACT Highly sensitive gas sensors with remarkably low detection limits
are attractive for diverse practical application fields including real-time environ-
mental monitoring, exhaled breath diagnosis, and food freshness analysis. Among
various chemiresistive sensing materials, noble metal-decorated semiconducting
metal oxides (SMOs) have currently aroused extensive attention by virtue of the
unique electronic and catalytic properties of noble metals. This review highlights
the research progress on the designs and applications of different noble metal-deco-
rated SMOs with diverse nanostructures (e.g., nanoparticles, nanowires, nanorods,
nanosheets, nanoflowers, and microspheres) for high-performance gas sensors with
higher response, faster response/recovery speed, lower operating temperature, and
ultra-low detection limits. The key topics include Pt, Pd, Au, other noble metals (e.g.,
Ag, Ru, and Rh.), and bimetals-decorated SMOs containing ZnO, ­SnO2, ­WO3, other
SMOs (e.g., ­In2O3, ­Fe2O3, and CuO), and heterostructured SMOs. In addition to
conventional devices, the innovative applications like photo-assisted room tempera-
ture gas sensors and mechanically flexible smart wearable devices are also discussed. Moreover, the relevant mechanisms for the sensing
performance improvement caused by noble metal decoration, including the electronic sensitization effect and the chemical sensitization
effect, have also been summarized in detail. Finally, major challenges and future perspectives towards noble metal-decorated SMOs-based
chemiresistive gas sensors are proposed.

KEYWORDS Noble metal; Bimetal; Semiconducting metal oxide; Chemiresistive gas sensor; Electronic sensitization; Chemical
sensitization

* Hong‑Liang Lu, [email protected]

1
State Key Laboratory of ASIC and System, Shanghai Institute of Intelligent Electronics and Systems, School of Microelectronics, Fudan University,
Shanghai 200433, People’s Republic of China
2
School of Opto‑Electronic Information and Computer Engineering, University of Shanghai for Science and Technology, Shanghai 200093,
People’s Republic of China
3
State Key Laboratory of Metal Matrix Composites, School of Material Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240,
People’s Republic of China

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89 Page 2 of 75 Nano-Micro Lett. (2023) 15:89

1 Introduction biomarkers for the non-invasive diagnosis of chronic kidney

diseases [12].
With the rapid development of Internet of Things (IoTs), Among various types of gas sensors including electro-
highly sensitive and selective gas sensors with remarkably chemical [13], optical [14], mass sensitive [15], thermo-
low limit of detection (LOD), fast response/recovery speed, electric [16], and magnetic [17] gas sensors, chemiresistive
and excellent long-term stability and reversibility are in sensors have attracted tremendous research enthusiasm for
ever increasing demand for smart cities, smart plants, and owning unique advantages of higher sensitivity, smaller size,
even smart healthcare [1–4]. On the one hand, ultra-sen- lower cost, easily manipulated, and even highly integrated
sitive gas sensors can monitor even trace level hazardous, for micro-electromechanical systems (MEMS)-based sensors
toxic, or explosive gases like volatile organic compounds [18, 19]. Generally, chemiresistive gas sensors are mainly
(VOCs), hydrogen sulfide ­(H2S), ammonia ­(NH3), formal- comprised of highly sensitive materials, a pair of sensing
dehyde (HCHO), nitrogen dioxide (­ NO2), methane ­(CH4), electrodes, and a pair of heating electrodes providing a high
and hydrogen (­ H2), protecting human health from environ- enough operating temperature to active the sensing materi-
mental pollutants or leakage accidents [5–7]. On the other als [20]. Since the sensitive material is regarded as the most
hand, highly selective and reliable gas sensors with precise crucial component of a chemeresistive gas sensor, many
accuracy have shown great application potential in vari- efforts have been devoted to develop satisfactory gas sensing
ous emerging fields closely related to our daily life, such as materials. Ever since Seiyama invented the first oxide-based
food freshness monitoring [8], drunk driving inspecting [9], gas sensor around the world in 1962 [21], nanostructured
and non-invasive disease diagnosis through human exhaled semiconducting metal oxides (SMOs) have been considered
breath analysis [10, 11], as shown in Fig. 1. For example, as prospective gas sensing materials by virtue of their high
with the advance of modern medicine, endogenous ammonia specific surface area, abundant active adsorption sites, supe-
in exhaled breath have been demonstrated to be important rior electrical properties, and low cost [22–24].

Fig. 1  Process of electronic olfactory sensing realization for important applications based on gas sensor arrays. The disease diagnosis figure is
reproduced with permission from Ref. [38]. Copyright 2017, Royal Society of Chemistry. The gas sensor array figure is reproduced with permis-
sion from Ref. [39]. Copyright 2016, American Chemical Society. The electronic olfactory sensing figure is reproduced with permission from
Ref. [40]. Copyright 2021, American Chemical Society

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Nano-Micro Lett. (2023) 15:89 Page 3 of 75 89

However, single SMO nanomaterial-based gas sensors innovative applications like photo-assisted room temperature
suffer from low response, poor selectivity, and too high oper- gas sensors and mechanically flexible smart wearable devices
ating temperature, which cannot satisfy the requirements of are discussed at the same time. Moreover, the relevant mecha-
practical applications. Therefore, diverse methods, mainly nisms for the sensing performance improvement caused by
consisted of constructing heterostructures [25, 26], decorat- noble metal decoration, including the electronic sensitization
ing catalysts [28], designing charge transfer hybrids [29], and chemical sensitization effect will also be summarized in
and introducing molecular probing and sieving effect [29, detail. Finally, crucial challenges facing the development of
30], have been widely explored for the improvement of gas noble metal-decorated SMOs-based gas sensors are identified
sensing performance [31]. Among all these strategies, the and feasible routes for effectively improving gas sensing per-
noble metal decoration, which involves hybrid nanocompos- formance like selectivity, power consumption, and long-term
ites with synergistic effects and introduces highly active cat- stability by constructing integrated sensor arrays, employing
alysts for gas chemisorption, exactly paves a new extraordi- neural network algorithms, as well as developing MEMS and
nary road for gas sensing performance enhancement and has field effect transistor (FET)-type devices are carefully con-
attracted widespread research attention [27, 32]. Recently, sidered and proposed. Constructing long-term stable noble
the widely used noble metals mainly include platinum (Pt),
palladium (Pd), gold (Au), silver (Ag), ruthenium (Ru),
rhodium (Rh), and their bimetal composites. The relevant
mechanisms for the gas sensing performance improvement
include the electronic sensitization effect of constructing a
metal–semiconductor contact [33] and the chemical sensi-
tization effect of the spillover effect [34]. As a result, the
synergistic effects not only promote fast interaction between
the noble metal decorated SMOs and target gases, but also
effectively decrease the operating temperatures by lowering
the gas sensing activation energy.
Actually, several reviews about noble metal-decorated
SMOs-based gas sensors are focused more on either cer-
tain type of noble metals, such as Ag-modified SMOs-based
gas sensors [35] and Pd-decorated nanostructures-based gas
sensors [36], or certain type of SMOs, such as noble metal-
decorated nanostructured ZnO-based H ­ 2 gas sensors [37].
However, few comprehensive reviews focusing on the recent
advances in diverse noble metal-decorated SMOs for high-
performance gas sensors have been reported. Herein, this
review will comprehensively reflect and summarize recent Fig. 2  Overview schematic representation of various noble metal
progress in SMOs-based chemiresistive gas sensors deco- decorated SMOs for gas sensors. The Pt NPs figure is reproduced
rated by not only common noble metals including Pt, Pd, and with permission from Ref. [32]. Copyright 2017, Wiley–VCH. The
Au NPs figure is reproduced with permission from Ref. [41]. Copy-
Au, but also other unusual noble metals like Ag, Ru, and Rh, right 2022, Elsevier. The Ag NPs figure is reproduced with permis-
and even well-structured bimetals containing alloy structures, sion from Ref. [42]. Copyright 2011, American Chemical Society.
The Ru NPs figure is reproduced with permission from Ref. [43].
core–shell structures, and heterostructures, as shown in Fig. 2. Copyright 2020, Elsevier. The Rh NPs figure is reproduced with per-
Meanwhile, the different effects of noble metal decoration on mission from Ref. [44]. Copyright 2019, American Chemical Society.
different SMOs containing common SMOs of ZnO, S ­ nO2, The core–shell NPs figure is reproduced with permission from Ref.
[45]. Copyright 2020, American Chemical Society. The heterostruc-
­WO3, other SMOs (e.g., ­In2O3, ­Fe2O3, ­TiO2, CuO, NiO, and ture NPs figure is reproduced with permission from Ref. [46]. Copy-
­Co3O4), and heterostructured SMOs will be comprehensively right 2013, Elsevier. The alloy NPs figure is reproduced with permis-
sion from Ref. [47]. Copyright 2021, Elsevier. The Pd NPs figure is
discussed and summarized as well. In addition to the detailed reproduced with permission from Ref. [48]. Copyright 2016, Ameri-
summarization on conventional gas sensing properties, the can Chemical Society

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89 Page 4 of 75 Nano-Micro Lett. (2023) 15:89

metals-decorated SMOs-based gas sensor arrays, combined resistance variation indicates the sensitivity of SMOs-based
with advanced neural computation, should allow real-life gas sensors.
electronic olfactory sensing in the future (Fig. 1). Overall, More specifically, for an n-SMO material, when a reduc-
the present topical review aims to provide a comprehensive ing gas is introduced, the width of the electron depletion
perspective on noble metal-decorated SMOs-based gas sen- layer will decrease, and thus the resistance of the n-SMO
sors, including the material structure, gas sensing mechanisms, material will be reduced correspondingly. When an oxidiz-
properties, applications, challenges, and prospects, hoping to ing gas is introduced, the width of the electron depletion
be served as an important reference for newcomers as well as layer and therefore the resistance of the n-SMO material
experienced researchers. will be both increased. For a p-SMO material, when fac-
ing a reducing gas, the width of the hole accumulation
layer will be reduced due to the recombination of the re-
2 Gas Sensing Mechanisms of Noble
injected electrons and holes, leading to an increase of the
Metal‑Decorated SMOs
resistance. Conversely, when introducing an oxidizing gas,
the width of the hole accumulation layer will be further
2.1 General Gas Sensing Mechanism of Chemiresistive
increased because of the further extraction of electrons,
SMOs
thus resulting in a decrease of the p-SMOs resistance.

2.1.1 Basic Gas Sensing Mechanism of Chemiresistive

SMOs
2.1.2 Mechanism of Heterojunction for Improved Gas
The basic sensing mechanism of chemiresistive SMOs-based Sensing Performance
gas sensors is based on the oxygen adsorption model [49].
Oxygen molecules in air will preferably accumulate on the The heterojunction is formed at the contact interface of
surface of SMOs and capture electrons from SMOs, lead- two different SMO materials, including anisotype hetero-
ing to the generation of chemisorbed oxygen species ­(O2−, junction (i.e., p–n or n–p) and isotype heterojunction (i.e.,
­O−, or ­O2−) [50] and an electron depletion layer (for n-type n–n or p–p) [51]. In order to balance the different Fermi
SMOs) or a hole accumulation layer (for p-type SMOs). levels at the interface, the charge transfer and depletion/
As a result, the resistance of n-SMOs/p-SMOs will then be barrier layers formation are introduced, which are positive
increased/reduced, respectively. The reaction processes are factors for improving gas sensing performance [51, 52].
listed as following: Actually, the additional depletion layers at the interface
could also participate in the gas sensing behaviors and
O2(gas) → O2(ads) (1) help increase the resistance variation of the sensing SMOs,
leading to the improvement of gas sensing properties.
O2(ads) + e− → O−2(ads) (2) First considering anisotype heterojunction, take the p–n
heterojunction as an example, depletion layers are created
O−2(ads) + e− → 2O−(ads) (3) by electron–hole recombination on the both p-side and
n-side. Thus, a potential conduction barrier is formed and
O−(ads) + e− → O2− (4) resistance is increased. Exposure of a reducing gas will
(ads)
help consume surface oxygen species and inject electrons
When SMOs are exposed to target gases, the adsorbed gas into the surface to shrink the depletion layer. It leads to a
molecules would react with the chemisorbed oxygen inter- significant reduction in electrical resistance and achieves
mediates, releasing the electrons back to SMOs (for reducing
a higher gas sensing response.
gas) or instead extracting more electrons from SMOs (for
As for isotype heterojunction, in the n–n heterojunction,
oxidizing gas), which depends on the redox characteristics
of the target gases. Thus, the width of the electron deple- for example, an additional electron depletion layer will be
tion layer/hole accumulation layer and further the resist- formed at the n–n interface causing an increase of the mate-
ance of SMOs will be changed accordingly. As a result, the rial resistance. After exposed to a reducing gas, the electron

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Nano-Micro Lett. (2023) 15:89 Page 5 of 75 89

depletion layer will be further decreased, resulting in a sharp a significant change of the resistance when exposure to
decrease of resistance and an enhancement of gas sensing target gases, resulting in a much higher response. Second,
response. during the chemical sensitization process, the noble met-
als could facilitate the dissociation of oxygen molecules
2.2 Mechanism of Noble Metal Decoration to produce more reactive chemisorbed oxygen ions which
for Improved Gas Sensing Performance then spill over the surface of SMO to react with more
target gas molecules [54–56]. Thus, the chemical sensiti-
2.2.1 Mechanism of Single Noble Metal Decoration zation is also known as the spillover effect. As exhibited
for Enhanced Response in Fig. 3b, oxygen molecules will preferentially adsorb on
the noble metal nanoparticles (NPs) and then be dissoci-
The remarkable improvement of gas sensing performance ­ − which then spill over to the surface of SMOs.
ated into O
Taking the reducing gas as an example, the large amount
after noble metal decoration could be attributed to two
of ­O− could react with more target reducing gas molecules
main mechanisms, the electronic sensitization and the
and cause the release of electrons, resulting in the rapid
chemical sensitization. First, during the electronic sensi-
resistance change and thus the significant improvement of
tization process, the majority carriers will transfer between
the gas sensing performance. Besides, the decoration of
noble metals and SMOs due to the mismatch of work func-
tions, leading to the generation of potential barriers. As noble metal NPs indeed increases the specific surface area
representatively shown in Fig. 3a, due to the higher work of the sensing materials, providing more catalytic active
function of noble metals, the electrons generated during sites for gas diffusion and adsorption [57].
the sensing process will be transferred from the conduc-
tion band of SMOs into noble metals until the Fermi level 2.2.2 Mechanism of Bimetal Decoration for Enhanced
is equal [33, 48, 53]. This behavior leads to the forma- Response
tion of a Schottky barrier and an increase in the thickness
of the electron depletion layer, which could inhibit the The mechanisms of bimetallic decoration on SMOs for the
recombination of separated electron–hole pairs and cause gas sensing performance enhancement are also discussed

Fig. 3  a Schematic energy band diagram of noble metal decorated n-SMO. b Schematic illustration of the chemical sensitization of noble metal
decorated n-SMO. c Schematic energy band diagram of bimetal decorated n-SMO. d Schematic illustration of the chemical sensitization of
bimetal decorated n-SMO

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89 Page 6 of 75 Nano-Micro Lett. (2023) 15:89

here. Figure 3c–d exhibit the representative electronic combing with dissociated H atoms, Pd can be converted
sensitization and the chemical sensitization processes of into ­PdHx according to the reaction of 2Pd + ­xH2 ↔ ­2PdHx
bimetal-decorated SMOs [58–60], respectively, which are [67]. Subsequently, due to the reduced work function of
similar to monometallic decoration discussed before. More ­PdHx compared with Pd, more electrons will be injected
specifically, Fig. 3c exhibits the established Schottky bar- into SMOs promoted by the lower Schottky barrier, lead-
rier and the additional depletion layer caused by the much ing to a further decrease of the material resistance [68].
higher work function of bimetals than SMOs. Accord- Therefore, Pd is considered as the best emerging noble
ingly, the additional depletion layer promotes the transfer metal for the decoration of SMOs-based ­H2 sensors.
of electrons during the gas sensing process, thus improv- Second, the strength of the coupling effects between spe-
ing the gas sensing properties of the bimetal-decorated cific noble metals and certain gas molecules will greatly
SMOs [57]. In addition, as shown in Fig. 3d, the bimetals influence the improvement of selective detection. The strong
could also catalyze the dissociation of oxygen molecules electronic effect of gas molecules will form a coupling effect
and lead to the spill-over of reactive chemisorbed oxy- with specific noble metals and therefore significantly affect
gen ions on the surface of SMO, facilitating the reaction the molecule adsorption behaviors on metals, which will
between target gases and reactive oxygen ions and there- even surpass the steric effect of certain molecules. More
fore enhancing the gas sensing performance [58]. Apart specifically, the coupling effect originates from the interac-
from the simple combination of two monometallic prop- tions between the adsorbate valence states and the s- and
erties, the synergistic effects further improve the physical d-states of a certain metal [69]. Since the influence of the
and chemical properties as well as promote the gas sensing coupling to the metal s-states is approximately the same for
performance [61]. Specifically, bimetal composites could different noble metals, the strength of the coupling effect
introduce tunable electronic structure, morphology, and largely depends on the coupling to the d electrons. Moreover,
stoichiometry, thus providing designable energy band since the d bands are recognized to be narrow, the coupling
structures and catalytic characteristics [62]. Moreover, of molecules to the d electrons will cause a splitting of the
bimetallic decoration could further lower the activation molecule resonance and generate both bonding state and
energy of the sensing reaction via synergistic catalysis, antibonding state above the d bands, leading to the strong
which contributes to a decrease of the operating tempera- interactions [69]. Therefore, the d-band model could effec-
ture and an acceleration of the response/recovery process tively reflect the trends in the molecule coupling strengths
[63, 64]. on noble metal surfaces, which will help to guide the selec-
tion of noble metals for highly selective target gases detec-
tion. Meanwhile, the band center (εd) could well describe the
2.2.3 Mechanism of Noble Metal Decoration characteristics of the d bands, which is commonly chosen
for Improved Selectivity as the representative parameter. For instance, as shown in
Fig. 4a, both the theoretical calculations and experimental
Based on various reported literatures, different noble metal results reveal that, as εd relative to the Fermi level becomes
decoration tends to promote the gas sensing performance more positive, the oxygen adsorption energy gets larger [69],
towards different certain gases due to the special catalytic which will greatly affect the gas sensing response. Similar
sensitization. Herein, some of the most important affect- theoretical calculation results were observed in the adsorp-
ing mechanisms related to the catalytic sensitization are tion energies of a series of 4d transition metals to CO and
discussed. First, the selective reaction occurred between a NO exhibited in Fig. 4b.
specific noble metal and a certain gas greatly attributes to Last but not least, since the adsorption of gas molecules
the enhanced selectivity. Most obviously, the Pd-decorated on the noble metal surface is the primary condition for any
SMOs have a specific enhancement for H ­ 2 gas molecules, possible catalytic reactions, the selective adsorption of gas
which could be ascribed to the reversible conversion of Pd molecules on a certain noble metal surface under different
to ­PdHx [65, 66]. Pd possesses the unique ability to adsorb temperature will also affect the selectivity of noble metal
and dissociate ­H2 molecules into H atoms. Particularly, by decorated SMOs-based sensors. For example, Kim et al.
[70] reported that Au decorated ­SnO2 NWs exhibited special

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Nano-Micro Lett. (2023) 15:89 Page 7 of 75 89

Fig. 4  a Calculated, model estimates, and experimental results of the variation in the oxygen adsorption energy of a series of 4d transition met-
als, which exhibited a good correlation with εd. b Calculated and model estimates of the variation in the adsorption energy of a series of 4d tran-
sition metals to CO and NO. Reproduced with permission from Ref. [69]. Copyright 2000, Elsevier

enhancement of selectivity to carbon monoxide (CO) rather system, and Esub/Egas denotes the energy of the substrate
than benzene (­ C6H6) and toluene (­ C7H8) at 300 °C, which and the isolated gas molecule, respectively. Accordingly,
can be attributed to the desorption of all ­C6H6 molecules and Eads < 0 implies that the adsorption process is exothermic
their dissociated biphenyl groups from Au surfaces above and spontaneous, leading to an energetically stable adsorp-
127 °C observed by the previous experimental result [71]. tion system [19]. Meanwhile, the more negative adsorption
energy indicates a much stronger adsorption reaction as
well as a higher sensing response. For example, Liu et al.
2.3 Recent Advanced Strategies for Further [75] constructed geometrically optimized P ­ d4 cluster-dec-
Understanding on the Gas Sensing Mechanism orated ­SnO2 and intrinsic ­SnO2 models for ­H2 and acety-
of Noble Metal‑Decorated SMOs lene ­(C2H2) adsorption and calculated the corresponding
adsorption energies via the DFT method. As a result, the
2.3.1 Density Functional Theory Calculations adsorption energies of H ­ 2 /SnO 2 , ­H 2 /Pd 4 -SnO 2 , ­C 2 H 2 /
SnO2, and ­C2H2/Pd4-SnO2 are − 0.205, − 0.574, − 0.974,
Recently, the first-principle calculations based on the den- and − 1.282 eV, respectively, indicating a better gas sens-
sity functional theory (DFT) have been widely employed ing performance of Pd decorated S ­ nO2 than intrinsic S ­ nO2.
for further exploration on the adsorption properties of Their follow-up experimental measurements further dem-
various noble metal-decorated SMOs-based gas sens- onstrate much higher responses of Pd decorated ­SnO2 than
ing materials [72–74]. Specifically, different parameters intrinsic ­SnO2 towards H­ 2 and C­ 2H2, which corresponds
including the adsorption energy, adsorption distance, and well with the theoretical calculation results.
charge transfer could all reflect the adsorption properties. Second, since the chemical adsorption takes place
First, the adsorption energy (E ads ) is defined as when the bonds between the target gas molecules and the
Eads = Esub-gas–(Esub + Egas), where Esub-gas represents the exposed atoms on the substrate materials are formed, the
total energy of the gas molecule–substrate adsorption

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89 Page 8 of 75 Nano-Micro Lett. (2023) 15:89

specific adsorption distance therefore can help reveal the ­ 2 sensors with excellent long-term stability. In detail, the
H
gas adsorption behaviors [76]. More specifically, the shorter morphological evolution of bimetal Pd–Ag nanoparticles on
the adsorption distance, the stronger the adsorption interac- the surface of ZnO nanowires at two characteristic operating
tion. For instance, for the comparison of the gas adsorption temperatures of 300 and 500 °C was observed in real time
performance between intrinsic ZnO and Pd decorated-ZnO, on the in-situ TEM characterization platform. Based on the
Liangruksa et al. [77] investigated the adsorption distances in-situ TEM analysis, two reasonable failure mechanisms
between the ­H2 molecule and the nearest atoms of the sub- of the bimetal Pd–Ag nanoparticles are proposed: particles
strates after adsorption. In detail, the adsorption distances coalescence at 300 °C and phase segregation at 500 °C.
for dO(ZnO)−H(gas) and dPd(Pd2 cluster)−H(gas) are calculated to be However, particles coalescence will lead to the formation
3.70 and 1.58 Å, respectively, implying the enhanced ­H2 of large nanoparticles with degraded catalytic activities, and
gas adsorption interaction after Pd decoration on the ZnO phase segregation of Ag migrating from the Pd–Ag alloy
surface. In addition, the H–H bond length of the H ­ 2 molecule nanoparticles will result in the decrease of the synergistic
stretches longer after the chemical adsorption, which ben- effect, both causing the degradation of gas sensing perfor-
efits the dissociation of the H–H bond and in turn promotes mance. In addition, Hui et al. [83] synthesized Au/WO2.7
the ­H2 adsorption reaction. nanocomposites and carefully investigated the changes in
Third, the charge transfer (∆Q) refers to the quantity of morphology and electronic structure under ­H2 atmosphere
electons transferred from gas molecules to substrate mate- by in-situ TEM, which helped to analyze the intrinsic inter-
rials. Consequently, the greater value of ∆Q means the action between Au/WO2.7 nanocomposites and H ­ 2. As a
more electrons transferred, further indicating the higher result, both swing and sintering processes of Au NPs were
gas sensing response [78]. For example, based on Barder observed at the heating environment, which could indicate
charge analysis, Chen et al. [79] discovered that the charge the inner mechanism for the change rule of sensing perfor-
transfer for the ­C6H6 molecule adsorbed on intrinsic, Pd- mance with increasing operating temperature. Meanwhile,
decorated, and Pt-decorated ZnO monolayers are calcu- no injection of H atoms was observed in the surface of Au/
lated to be approximately 0.01798e, 0.0231e, and 0.0243e, WO2.7 nanocomposites after the introduction of ­H2 into the
respectively. Accordingly, the noble metal (Pd, Pt) decora- vacuum environment, which suggested that the H ­ 2 sensing
tion could enhance the charge transfer as well as the gas mechanism for Au/WO2.7 nanocomposites under a vacuum
sensing performance. are dominated by mass transport pathways.

2.3.2 In‑situ Transmission Electron Microscopy Analysis 3 Single Noble Metal‑Decorated SMOs‑Based

Gas Sensors
With the rapid progress of modern science and technology,
increasingly advanced characterization techniques have been 3.1 Pt‑Decorated SMOs‑Based Gas Sensors
applied in the field of gas sensing to further reveal the mor-
phology and composition changes before and after the gas 3.1.1 Pt‑decorated ZnO Gas Sensors
sensing process. Significantly, the emerging in-situ trans-
mission electron microscopy (TEM) technique can help to Pt-decorated ZnO materials were synthesized with various
directly observe the solid–gas reaction process and record morphologies including zero-dimensional (0D) nanoparti-
the morphological and compositional evolution of the sens- cles [84], one-dimensional (1D) nanorods [85], nanotubes
ing materials during the real-time gas sensing process at the [86], two-dimensional (2D) nanosheets [87], and three-
desired temperature [80, 81], which is urgently deserved to dimensional (3D) hierarchical structures [88]. Benefiting
be used in gas sensing mechanism investigation. For exam- from high specific surface area and continuous electron
ple, Wang et al. [82] revealed the failure mechanisms of transfer pathways, Pt-decorated 1D ZnO nanostructures
bimetal Pd–Ag nanoparticles in ZnO-based H ­ 2 sensors under exhibit enhanced sensing behaviors such as reduced work-
operation conditions with the help of gas-cell in-situ TEM, ing temperature, remarkable sensitivity and selectivity,
which further guided the optimized design of satisfactory and fast response/recovery process. For instance, Yu et al.

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Nano-Micro Lett. (2023) 15:89 Page 9 of 75 89

[89] reported a Pt-decorated ZnO nanorods sensor through brief, the excellent ­H2S sensor can be achieved by combin-
a facile immersion-calcination method, which was highly ing the sensitization effect of Pt and the specific surface
sensitive to target ppb-level ­H2S gas. As shown in Fig. 5a, area of nanorods. Young et al. [85] prepared Pt NPs-dec-
the Pt-decorated ZnO-based sensor exhibited the highest orated ZnO nanorods via a hydrothermal strategy. Due to
response at each concentration (20–80 ppb) than that of the spillover effect of Pt, the response of Pt-decorated ZnO
other sensors. Owing to the excessive enhanced surface nanorods-based sensor to 1000 ppm methanol was signifi-
catalytic activity, when the concentration of the Pt NPs cantly improved from 1.34 to 121.03 at 270 °C (Table 1).
was increased, the response of the sensor was degraded. Pt-decorated 2D ZnO structures have attracted much
Moreover, the response of the Pt-decorated ZnO-based attention owing to their controllable morphology, exhibiting
sensor was 23.1 towards at 260 °C at a low ­H2S concen- diverse sensing properties [90]. Wang et al. [34] fabricated
tration of 100 ppb, which was 5.8-fold higher than the pure the Pt-decorated ZnO nanosheets with various Pt concen-
ZnO sensor (3.4). Besides, the lowest H ­ 2S detection of the tration through a simple wet-chemical method. The 0.50
Pt-ZnO-based sensor could obtain as low as 1.1 ppb. In at% Pt-decorated ZnO displayed the most excellent sensing

Fig. 5  a Response of the pristine and Pt-decorated ZnO sensors towards different concentrations varying from 20 to 80 ppb. Reproduced with
permission from Ref. [89]. Copyright 2021, Elsevier. b Response and recovery behavior of 0.50 at% Pt-decorated ZnO to 50 ppm CO at 180 °C.
Reproduced with permission from Ref. [34]. Copyright 2020, Elsevier. c Mechanism of Pt-decorated ZnO sensor toward ­NH3. Reproduced with
permission from Ref. [90]. Copyright 2020, Elsevier. d Responses of pure ZnO, Pt-commercial ZnO, and Pt-decorated ZnO microspheres-based
sensors to various gases. Reproduced with permission from Ref. [72]. Copyright 2021, Elsevier. e Fabrication process of Pt@ZnO polyhedrons.
f SEM image of Pt@ZnO polyhedrons. Reproduced with permission from Ref. [91]. Copyright 2021, Elsevier. g Responses of 3DIO ZnO and
3DIO Pt-decorated ZnO@ZIF-8 based sensors to simulated H ­ 2S abnormal/healthy breath samples. Reproduced with permission from Ref. [92].
Copyright 2022, Elsevier

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89 Page 10 of 75 Nano-Micro Lett. (2023) 15:89

Table 1  Summary of the reported Pt-decorated SMOs-based gas sensors

Materials Structure Synthesis method Target gas O. T. (°C) Conc. (ppm) Response tres/tre LOD Refs.

ZnO Nanorods Hydrothermal H2S 260 0.3 65a 40/430 s 1.1 ppb [89]
ZnO Nanorods Hydrothermal Methanol 270 1000 121.03a – – [85]
ZnO Nanosheets Hydrothermal CO 180 50 3.57a 6/19 s 100 ppb [34]
ZnO Ordered porous thin PS template NH3 330 100 324a 102/5731 s – [90]
film
ZnO Microspheres Hydrothermal TEA 200 100 242a 15/70 s – [72]
ZnO Polyhedrons Pyrolysis of ZIF-8 CO 300 0.5 9%b 1.5/14 s 100 ppb [91]
ZnO 3DIO PMMA template H2S 310 5.5 118a 136/200 s 40 ppb [92]
SnO2 Microbelts Electrospinning Acetone 350 2 93.56a 9.2 s/– – [55]
SnO2 Fibers Electrospinning Acetone 300 3 3.47a 11/6 s 120 ppb [95]
SnO2 Porous nanotubes Electrospinning Acetone 350 5 192a – 10 ppb [96]
SnO2 Nanoneedles Hydrothermal CO 250 100 23.18a 15/14 s – [98]
SnO2 Nanorods Hydrothermal H2 RT 1000 87.35%b 0.33/29.6 s – [99]
SnO2 Mesoporous nanoflow- Double-template H2S 30 1 68a 11/75 s 100 ppb [101]
ers technique
SnO2 Sheets Solution combustion Isopropanol 220 100 190.5a – – [56]
SnO2 Ultrathin film ALD TEA 200 10 136.2a 3/6 s 7 ppb [104]
WO3 Nanorods GLAD H2 200 3000 2.2 × ­105a ~ 5.6/ ~ 15 min – [53]
WO3 Nanorods Evaporation H2 110 5000 68%b 0.64/6.29 s 10 ppm [110]
WO3 Nanorods Hydrothermal H2S 200 10 1638.2a 42/37 s 5 ppb [112]
WO3 Porous belts Electrospinning H2S 365 5 378.12a 6.1/288.2 s 400 ppb [113]
WO3 Microporous nanofib- Electrospinning H2S 350 5 834.2a – 100 ppb [114]
ers
WO3 Ordered mesoporous Evaporation induced CO 125 100 10.1a 16/1 s – [32]
co-assembly
WO3 Films GLAD NO2 150 1 11.24a 27/34 s 80 ppb [115]
WO3 Nanoflakes Hydrothermal Acetone 250 3.8 290%b – 237 ppb [54]
WO3 Square-like Hydrothermal NH3 270 1000 100.09a 8/11 s 1 ppm [116]
In2O3 Mesoporous nanofibers Electrospinning NO2 RT 1 23.9a –/358 s 10 ppb [117]
In2O3 Nanorods Vapor–liquid–solid NO2 300 200 11a 45/60 s – [119]
growth
In2O3 Mesoporous nanofibers Electrospinning Acetone 180 1 15.1a 6/9 s 10 ppb [120]
In2O3 Nanowires Electrospinning Acetone 320 1 6.23a 11/13 s 10 ppb [121]
NiO Nanotubes Electrospinning Ethanol 200 100 20.85a – – [122]
NiO Core–shell structure Sol–gel H2 RT 5000 4.25a 91/8 s – [123]
NiO Thin films RF sputtering NH3 300 1000 1278%b 15/76 s 10 ppb [124]
NiO Porous nanosheets Hydrothermal HCHO 300 100 7.16a – 10 ppm [125]
Fe2O3 Nanocubes Hydrothermal Acetone 139 100 25.7a 3/22 s – [126]
Fe2O3 Nanowires Electrospinning H2S 175 10 157a – – [127]
CuO Porous structure Calcination HCHO 225 1.5 5.46a – 100 ppb [128]
SnO2/ZnO Core–shell nanowires ALD Toluene 300 0.1 279a – – [130]
SnO2/ZnO Core–shell nanosheets ALD H2S 375 5 30.43a 67/116 s 1 ppm [131]
SnO2/α-Fe2O3 Hollow nanospheres In-situ reduction Styrene 206 10 10.56a 3/15 s 50 ppb [132]
In2O3/WO3 Nano powder Impregnation NO RT 0.5 330a 10.5/132 min 25 ppb [133]
ZnO/In2O3 Nanofibers Electrospinning Acetone 300 100 57.1a 1/44 s 500 ppb [134]

O. T. operating temperature; Conc. concentration; tres/trec response time/recovery time; LOD limit of detection
a
Response is defined as R
­ a/Rg or ­Rg/Ra, ­Ra: resistance of the sensor in air, ­Rg: resistance of the sensor exposed to target gas
b
Response is defined as ∆R/Ra × 100% or ∆R/Rg × 100%, ∆R: the change in resistance, which equals to |Ra–Rg|

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Nano-Micro Lett. (2023) 15:89 Page 11 of 75 89

properties among 0.25, 0.75, and 1.00 at% Pt/ZnO, dem- (MOF) structures have been introduced to improve the capa-
onstrating that a reasonable Pt concentration was crucial to bility of electron transference between the target gas and the
promote the gas sensing behavior. Specially, the working noble metal. For instance, Qin et al. [91] reported a Pt-deco-
temperature of Pt-decorated ZnO senor was decreased from rated ZnO polyhedrons via an in-situ reduction method using
210 to 180 °C because that the catalyst Pt could decrease with a template of zeolitic imidazolate framework-8 (ZIF-8).
the activation energy of gas chemisorption. As shown in The synthesis process and the scanning electron microscopy
Fig. 5b, the response/recovery speed of the as-prepared ZnO (SEM) image of Pt@ZnO polyhedrons were exhibited in
sensor was shortened from 108/285 to 6/19 s toward 50 ppm Fig. 5e–f, respectively. In contrast to the pure ZnO sensor,
CO, which benefited from the addition of Pt decreasing the the obtained Pt@ZnO polyhedrons could not only promote
activation energy of gas reaction as well as accelerating the the response value but also lower the temperature owing to
gas adsorption and desorption. Li et al. [90] prepared Pt/ZnO the catalytic effect of Pt. The 2% Pt@ZnO sensor displayed
ordered porous monolayer films by a polystyrene sphere (PS) good response of 10 to 50 ppm CO at 100 °C, high selectiv-
monolayer colloidal crystal template method. The Pt-dec- ity, and long-term stability. Notably, the 2% Pt@ZnO sen-
orated ZnO-based sensor showed an excellent response of sor showed an ultra-low detection limit (100 ppb), which
324 towards 100 ppm N ­ H3, which was 200 times of the pure was ascribed to the highly dispersed Pt NPs, enhancing the
ZnO-based sensor. The mechanism of Pt-decorated ZnO utilization rate of active sites. Overall, the introduction of
toward ­NH3 is exhibited in Fig. 5c. When the as-prepared the MOF structure effectively improved the dispersity of Pt
gas sensors were surrounded by air, the oxygen molecules NPs on the ZnO, thus enhancing the gas sensing behavior
were adsorbed on the material, extracting electrons, and thus especially for detecting ppb-level gas. Zhou et al. [92] syn-
forming the chemisorbed oxygen ions ­(O−, ­O2−). The spillo- thesized a 3D inverse opal (3DIO) microporous ZnO, further
ver effect of Pt catalyzed the adsorbed oxygen molecules coated a ZIF-8 molecular sieve membrane through in-situ
to produce more chemisorbed oxygen ions and reacts with growth from the ZnO skeleton, and then functionalized with
more ­NH3 molecules, resulting in larger response. Another small Pt NPs. The microporous ZnO structure and the ZIF-8
advantage of using Pt is the modulation of the electronic filter membrane provided more active adsorption sites and
character of ZnO. The work function of Pt was 5.65 eV, eliminated the VOC interference, facilitating the gas sens-
which was higher than the ZnO (3.30 eV) Therefore, the ing behaviors. Thus, this 3DIO Pt-decorated ZnO@ZIF-8
electron transferred from ZnO to Pt NPs and then widened sensor exhibited great sensing behaviors that the response
the depletion layers. Moreover, P ­ tOx and ZnO could con- of the sensor was 118 toward 5.5 ppm H ­ 2S and the lowest
struct a p-n heterojunction to enhance sensing performance, ­H2S detection of sensor was 40 ppb. Moreover, the 3DIO
which could enhance the oxygen adsorption and modulate Pt-decorated ZnO@ZIF-8 sensor was widely used in various
the conduction channel. The mechanism agrees well with fields, such as food quality evaluation, diagnosis of halito-
the experimental results. sis, and environment monitoring. For instance, as shown in
Compared to 1D or 2D structures, Pt-ZnO with 3D struc- Fig. 5g, the response of the 3DIO Pt-decorated ZnO@ZIF-8
tures demonstrate enhanced performance owing to their sensor towards halitosis breath was 4.0, which was 2.4-fold
large effective specific surface area. Liu et al. [72] prepared enhancement of healthy counterparts (1.7), demonstrating
a hierarchical Pt-decorated ZnO microspheres with porous that 3DIO Pt-decorated ZnO@ZIF-8 sensor could efficiently
nanosheets through a hydrothermal strategy, followed by a detect halitosis. Moreover, compared with untreated automo-
reduction method. The as-prepared sensor exhibited high bile exhaust gas, the response of 3DIO Pt-decorated ZnO@
response towards 100 ppm triethylamine (TEA) of 242 at ZIF-8 sensor towards 1 L automobile exhaust with 330 ppb
200 °C, which was 50-fold enhancement for the pristine ­H2S was 3 times higher, indicating that it could be utilized to
ZnO sensor. Notably, it had excellent selectivity to react detect microscale concentrations of H ­ 2S. In summary, com-
with TEA gas while repressing other VOC gases, shown in bining the MOF as outer filter membrane and Pt modifica-
Fig. 5d. Moreover, the DFT calculation indicated the adsorp- tion was an efficient strategy to develop an efficient sensor
tion energy of TEA on Pt-ZnO (−3.16 eV) was lower than for trace ­H2S detection.
ZnO (−1.21 eV), proving Pt-ZnO was of great advantages
to sense TEA gas. In recent years, metal organic framework

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89 Page 12 of 75 Nano-Micro Lett. (2023) 15:89

3.1.2 Pt‑decorated SnO2 Gas Sensors work, the hollow protein nanocage was used to synthesize
Pt NPs with different diameters distributing on S ­ nO2 nano-
As a typical n-type SMO, ­SnO2 is currently attracting tre- tubes. Thus, combining the porous nanotubes could lead to
mendous attention owing to its environmentally friendly enhanced sensing performance because of the large specific
synthesis and wide application in the detection of various surface area and high gas accessibility. The Pt decorated-
gases. In terms of various Pt decorated S­ nO2 nanostructures, SnO2 nanotubes sensor displayed high response of 192 to
1D nanostructures like nanotubes and nanowires are effi- 5 ppm acetone at 350 °C.To sum up, electrospinning is an
cient structures for ­SnO2 to detect gas owing to the specific efficient method to synthesize the porous 1D structure com-
surface area and high gas accessibility [93]. Electrospin- posited with uniformly distributed Pt NPs, which is useful
ning was utilized to synthesize 1D nanotubes, nanofibers, for developing excellent sensing behaviors.
nanowires, and core–shell structures, due to its easy control Hydrothermal is a facile process of synthesizing 1D ­SnO2
of morphological [94]. It is suggested that various porous nanostructures, which is widely used for fabricating gas sen-
structures are obtained by changing the solution components sors [97]. For example, Zhou et al. [98] fabricated Pt-modi-
and electrospinning conditions. For example, Bulemo et al. fied ­SnO2 nanoneedles through a hydrothermal method. For
[55] reported Pt-decorated ­SnO2 hollow microbelts by elec- 3.125 at% Pt- modified ­SnO2 nanoneedle composites, a high
trospinning and calcination. The S ­ nO2 hollow microbelts sensing response of 23.18 is recorded towards 100 ppm CO
structure exhibited large specific surface area, small mean gas at 250 °C with the response/recovery speed of 15/14 s,
crystal size, and high porosity, which were advantages for respectively. Chen et al. [99] synthesized ­SnO2 nanorods
promoting oxygen adsorption–desorption kinetics. The Pt via hydrothermal strategy, followed by the ultraviolet (UV)-
(0.12%)-SnO2 hollow microbelts sensor exhibited a high irradiated photochemical reduction method to functionalize
response of 93.7 towards a low acetone concentration of Pt NPs. With decoration of 3.63% Pt NPs, the response of
2 ppm, short response time (9.2 s), and long-term stabil- sensor toward 1000 ppm ­H2 was enhanced from 1.4 to 7.9 at
ity for over six-month. The better sensing behavior of Pt- room temperature (RT). Generally speaking, sensors work at
SnO2 was owing to the specific surface area of microbelts RT are attractive for reducing cost and improving stability,
and electrical and chemical sensitization of Pt. In addition, but they often need long response time and recovery time,
the Pt (0.12%)-SnO2 hollow microbelts-based sensor also limiting their practical application [100]. Functionalizing of
showed high stability with response of 93.70 ± 0.89 to 2 ppm Pt NPs on the S ­ nO2 could promote the oxygen adsorption,
acetone for 25 repeated tests in a humid environment of 90% which are spilled over on the ­SnO2 to react with more gas
relative humidity (RH). Shin et al. [95] reported the hier- molecules. Moreover, Pt NPs were beneficial to the elec-
archical ­SnO2 fibers with wrinkled thin tubes produced by trons transfer owing to the higher work function than the
electrospinning and then decorated by Pt NPs via polyol ­SnO2. The Pt-SnO2 nanorods-based sensor responded to
method. The structure of Pt-decorated ­SnO2 fibers composed 1000 ppm ­H2 with short response time (0.4 s), owing to the
of wrinkled thin tubes is shown in Fig. 6a. The hierarchi- sensitization effect of Pt. Therefore, functionalizing Pt NPs
cal ­SnO2 fibers with wrinkled thin tubes with high porosity was potential to enhance the response speed of RT sensors.
not only promoted the decoration of Pt NPs, but also made In addition, Sun et al. [101] reported a Pt-decorated ­SnO2
gas molecules transfer to the entire sensing layer, shorten- mesoporous nanoflowers H ­ 2S sensor working at RT through
ing the response/recovery time less than 11/6 s. In conclu- a mixed template method followed by selective calcination.
sion, synthesizing the structures with high porosity and large As exhibited in Fig. 6c, the response towards ppb-level H ­ 2S
specific surface area under various preparation conditions at RT was significantly improved by decorating Pt NPs. The
would facilitate the uniform distribution of Pt NPs, enhanc- 0.3 wt% Pt-decorated ­SnO2 nanoflowers sensor showed high
ing the sensing behaviors for the potential use of exhaled response of 68 towards 1 ppm ­H2S at 30 °C, which was
breath sensor. In addition, it is essential to uniformly deco- 11-time improvement of pristine ­SnO2 sensor. Meanwhile,
rate Pt NPs on S­ nO2 nanostructures to further maximize the as shown in Fig. 6d, the decoration of Pt NPs significantly
catalyzation of Pt NPs. Jang et al. [96] synthesized the Pt- improved the selectivity of Pt-SnO2 sensors compared with
decorated meso/macro ­SnO2 nanotubes through an advanced pristine ­SnO2 sensor. The catalytic Pt NPs could effectively
electrospinning method, which is shown in Fig. 6b. In this promote electron transfer, thus accelerating the reaction not

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 13 of 75 89

Fig. 6  a Back scattered electrons (BSE) images of 20 wt% Pt-modified thin-wall assembled ­SnO2 fibers. Reproduced with permission from Ref.
[95]. Copyright 2012, Wiley–VCH. b Synthesis of pore loaded ­SnO2 nanotubes decorated by Pt NPs. Reproduced with permission from Ref.
[96]. Copyright 2016, Wiley–VCH. c Response versus time curves of the S ­ nO2-PVP, 0.1% Pt-SnO2, 0.3% Pt-SnO2, and 0.5% Pt-SnO2 based-
sensors to 100 ppb ~ 5 ppm H ­ 2S. d Selectivity behaviors of S
­ nO2-PVP, 0.1% Pt-SnO2, 0.3% Pt-SnO2, and 0.5% Pt-SnO2 based-sensors [101].
Reproduced with permission from Ref. [101]. Copyright 2020, Elsevier. e Response of pure S ­ nO2, 0.5 wt% Pt-decorated S
­ nO2, 1 wt% Pt-deco-
rated ­SnO2, and 2 wt% Pt-decorated S ­ nO2 sensors towards various isopropanol concentrations at 220 °C. Reproduced with permission from Ref.
[56]. Copyright 2014, Royal Society of Chemistry. f AFM characterization of Pt-SnO2 thin films. g Response and recovery behaviors of S ­ nO2
and Pt-decorated S ­ nO2 films sensor to 10 ppm TEA at 200 °C. Reproduced with permission from Ref. [104]. Copyright 2020, Royal Society of
Chemistry. h Schematic of the well-designed filter-sensor system, exhibiting the adsorption of hydrophilic compounds on the activated alumina
filter with no retention of hydrophobic isoprene. i Dynamic response curves of a Pt-SnO2 NPs sensor to 500 ppb isoprene, acetone, ethanol,
methanol, and ammonia without and with an activated alumina filter at 90% RH. Reproduced with permission from Ref. [106]. Copyright 2018,
American Chemical Society

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89 Page 14 of 75 Nano-Micro Lett. (2023) 15:89

only between chemisorbed oxygen and H ­ 2S but also between as 7 ppb, illustrating the high potential development for
­S nO 2 and ­H 2S molecules ( SnO2 + H2 S → SnS2 + H2 O ). sensitive detection of VOCs at ppb-levels. Owing to the
Therefore, the selectivity of Pt-decorated S
­ nO2 sensors were appropriate thickness of S ­ nO2 film synthesized by ALD,
further enhanced. Besides, the sensor also displayed short oxygen vacancies in films, and catalyzation of single atom
response/recovery time of 11/75 s. The enhanced sensing Pt, the Pt-SnO 2 thin film sensor showed an outstanding
behavior was due to the porous structure with high specific sensing performance.
surface area and the catalyzation effects by Pt NPs. In sum- Moreover, since selectivity is considered as one of the
mary, the surface decoration of Pt is a promise method to most crucial aspects for gas sensors in practical applica-
promote the gas sensing behaviors at the field of RT H ­ 2S tions surrounded with diverse interfering gases, many efforts
gas sensors. on constructing an efficient filter have also been devoted
There are various techniques to fabricate 2D S ­ nO2 struc- to further improve the selectivity of Pt-decorated S ­ nO2 gas
tures. Solution combustion synthesis has been regarded sensors. The filters, including sorption, size-selective, and
as an efficient, rapid, and energy-effective method for catalytic filters, will help to change the composition and/or
producing large-scale nanostructures [102]. For instance, concentration of molecules in gas mixtures before reach-
Dong et al. [56] synthesized Pt-decorated S ­ nO2 porous ing the sensor as expected [105], thus contributing to the
sheets with different Pt concentration via solution combus- enhancement of selectivity. For example, Broek et al. [106]
tion method. The 2 wt% Pt-decorated S ­ nO2 sensor exhib- designed an effective filter consisted of a packed bed of acti-
ited the highest response to a wide range concentration vated alumina powder with high porosity upstream of the
(5 ~ 100 ppm) of isopropanol gas, as displayed in Fig. 6e. flame-made Pt-SnO2 NPs sensor (Fig. 6h), achieving highly
Specifically, the response of the 2 wt% Pt–decorated ­SnO2 selective and rapid breath isoprene detection at the ppb-level
sensor towards 100 ppm isopropanol was 190.50, which and high humidity. Specifically, as shown in Fig. 6h, the
was 9-time enhancement of the pure ­SnO2 based sensor. well-designed filter can adsorb hydrophilic breath analytes
The enhanced response was ascribed to the electronic like acetone, ethanol, methanol, and ammonia, as well as
sensitization as well as the catalytic oxidation of Pt NPs. water molecules, leaving hydrophobic isoprene unhindered
Atomic layer deposition (ALD) technique has a great and transported to the downstream sensor. Finally, the well-
advantage of precisely controlling the film thickness at the designed filter-sensor system exhibited remarkable selectiv-
atomic level [103], which is beneficial to prepare efficient ity (> 100) to ppb-level isoprene at 90% RH in Fig. 6i, which
gas sensors. Besides, Xu et al. [104] reported Pt decorated was significantly enhanced comparing to the pristine non-
­SnO2 films sensor by ALD with different thicknesses vary- specific Pt-SnO2 NPs sensor. In addition, Oliaee et al. [107]
ing from 4 to 18 nm. The morphologies of pristine ­SnO2 reported a catalytic filter comprised of Au NPs decorated
and Pt-decorated ­SnO2 film were analyzed by atomic force ­Fe2O3 for the Pt-SnO2 sensor and realized highly selective
microscopy (AFM). The Pt-SnO2 film exhibited in Fig. 6f detection to propane or methane in the presence of CO and
had a surface root mean square roughness of 420 pm, ethanol. Actually, CO will be completely converted to insen-
which was similar with ­SnO2 thin film (470 pm), indicat- sitive ­CO2 by the catalytic filter at room temperature, and
ing both have similar surface features. Thus, ALD tech- ethanol will be adsorbed/oxidized by the filter at room tem-
nique could synthesize thin film with uniform thickness, perature/temperatures higher than 200 °C. Similarly, a Au
which was advantageous to fabricate stable sensing layers. NPs-promoted ­Ce0.8Zr0.2O2 catalytic filter was designed for
The Pt-decorated ­SnO2 ultrathin film sensor could reduce the Pt-SnO2 sensor by Fateminia et al. [108], demonstrating
the working temperature from 260 to 200 °C. The Pt-dec- selective detection of ethanol and methane in the presence
orated 9 nm ­SnO2 film sensor exhibited high response of of interfering gases. From their observations, the operat-
136.2 to 10 ppm TEA, which was 9 times improvement ing temperatures of the filter and the sensor will both affect
to the pure ­SnO2 sensor, and ultrafast response/recovery the selectivity of the filter-sensor system, which require
speed (3/6 s), as shown in Fig. 6g. Moreover, the Pt-deco- meticulously selection and control for different applicaion
rated 9 nm S­ nO2 film sensor could detect the TEA as low scenarios.

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Nano-Micro Lett. (2023) 15:89 Page 15 of 75 89

3.1.3 Pt‑decorated WO3 Gas Sensors of the optimal Pt-loaded ­WO3 nanorods sensor was 2.2 × ­105
(Ra/Rg) towards 3000 ppm ­H2 at 200 °C, while pristine ­WO3
WO3 is an important n-type SMO with a wide band gap nanorods sensor was almost no response, indicating that Pt
(2.8 eV), which is a potential material for developing excel- decoration was an efficient method to promote the H­ 2 detec-
lent gas sensors toward various gases due to its excellent tion. Moreover, the optimal Pt-loaded ­WO3 sensor showed
physical and chemical properties and superior sensing char- high sensitivity to 150 ppm at 150 °C and high selectiv-
acteristics [109]. Functionalization of ­WO3 with Pt NPs ity toward H
­ 2 among various gases. The improved sensing
could enhance the sensing performance of the resultant behavior was ascribed to the chemical sensitization of Pt,
material due to the catalytic properties of Pt. which dissociated H ­ 2 molecules into H atoms and reacted
Pt-decorated ­WO3 is often used for detecting ­H2 due to with ­WO3 through spillover effect, decreasing the depletion
the ability of Pt to dissociate hydrogen atoms effectively at width and electrical resistance. Fan et al. [110] developed
RT [110]. Horprathum et al. [53] successfully developed Pt- a Pt-decorated W­ O3 nanorods sensor through evaporation
loaded ­WO3 nanorods through the glancing angle deposition method and sputtering process. The Pt-decorated W ­ O3 sen-
(GLAD) method. As exhibited in Fig. 7a, the high response sor exhibited very fast response of 80 ms toward pure H ­ 2 at

Fig. 7  a Response of different Pt decoration times decorated ­WO3 nanorods sensors toward 100–3000 ppm of ­H2 at 200 °C. Reproduced with
permission from Ref. [53]. Copyright 2014, American Chemical Society. b SEM image of meso- and macroporous Pt-decorated W ­ O3 micro-
belts. c PCA result of the sensor array. Reproduced with permission from Ref. [113]. Copyright 2018, American Chemical Society. d Synthe-
sis route of Pt-decorated macroporous ­WO3 nanofibers. e PCA result of the healthy bodies and halitosis patients through the human exhaled
breath. Reproduced with permission from Ref. [114]. Copyright 2016, American Chemical Society. f Fabrication process of Pt loaded ordered
mesoporous ­WO3 composites. Reproduced with permission from Ref. [32]. Copyright 2017, Wiley–VCH

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89 Page 16 of 75 Nano-Micro Lett. (2023) 15:89

110 °C due to the chemical sensitization of Pt. Nishijima and low ­H2S detection of 100 ppb. The PCA result indicated
et al. [111] deposited Pt-WO3 nano/micro powder films on a that the sensor arrays achieve distinguish pattern recogni-
silica glass substrate using nanosecond pulsed laser ablation. tion of various gases, demonstrating their high selectivity.
They reported that the low limit of ­H2 detection (10 ppm) Moreover, as shown in Fig. 7e, the healthy breath and the
and short response time of 20 s towards 40,000 ppm ­H2 was halitosis breath was obviously distinguished, indicating the
obtained. sensor arrays was a potential method for the breath diagno-
Pt-decorated ­WO3 sensors are also utilized for effectively sis. In this regard, the porous structure and catalytic char-
detecting ­H2S gas. Yao et al. [112] synthesized Pt-decorated acter of uniformly distributed Pt NPs are crucial to enhance
­WO3 nanorods hydrothermal and chemical reduction meth- the sensing performance to target gases.
ods. The response of the 0.2 at% Pt-decorated W ­ O3 sensor In addition, Pt-loaded W­ O3 sensors are reported to detect
was 1,638 towards 10 ppm H ­ 2S at 200 °C, with the short other gases including CO, N ­ O2, acetone, and ammonia.
response/recovery time of 42/37 s, respectively. In com- Ma et al. [32] synthesized Pt-decorated highly ordered
parison with pristine W ­ O3 sensor, Pt-WO3 sensor exhibited mesoporous ­WO 3 via a multicomponent co-assembly
enhanced gas sensing behavior because of the electronic method. The fabrication process of the Pt-decorated ­WO3
modulation and its catalysis reaction between ­H2S and nanocomposite was shown in Fig. 7f. Owing to the sensi-
oxygen ions. The porous microstructure has advantages of tizing effect of the Pt NPs, the Pt-WO3 sensor showed the
numerous reaction sites and gas diffusing channels, leading response of 10 to 100 ppm CO at 125 °C, short response/
to better response performance. In this regard, Kim et al. recovery speed (16/1 s), and remarkable selectivity. Besides,
[113] reported Pt-decorated ­WO3 microbelts with a large Liu et al. [115] reported a Pt decorated W
­ O3 thin film sensor
amount of porosity via the electrospinning combined with based on the MEMS devices through GLAD and conven-
sacrificial templates and subsequent calcination. Figure 7b tional planar deposition. The Pt-decorated ­WO3 film sensor
showed the structure of meso- as well as macroporous Pt- displayed high response of 1,308.26 toward 10 ppm N ­ O 2,
modified ­WO3 microbelts. Moreover, Pt NPs were fabri- low detection of limit (80 ppb), and excellent selectivity to
cated by using biological protein cages, such as apoferritin ­NO2 among ­NH3, CO, acetone, and ethanol. Alev et al. [54]
to prevent the agglomeration of particles after calcination, fabricated ­WO3 nanoflakes through a hydrothermal route
thus further improving the gas sensing properties. The 0.05 and further loaded Pt NPs via a sputtering method. The cata-
wt% Pt-decorated W ­ O3 microbelts sensor displayed excel- lytic effect of Pt could dramatically enhance the gas sens-
lent sensing performance including high response of 372 ing behaviors of Pt-WO3 sensor which could detect acetone
towards 5 ppm ­H2S in 95% humid condition and excellent even at a low concentration of 237 ppb at 250 °C. Chao
selectivity to H
­ 2S among other gases, which were owing to et al. [116] fabricated Pt loaded square-like ­WO3 via a facile
the bimodally porous nanostructure and catalysis effect of hydrothermal and reduction method. It was found that the
Pt NPs. Furthermore, as exhibited in Fig. 7c, the principal response of the 1 wt% Pt-decorated ­WO3 sensor was 100.09
component analysis (PCA) result showed that the sensor towards 1000 ppm ­NH3 with short response/recovery time
arrays could clearly classify ­H2S from the other gases with- (8 /11 s), low detection of limit (1 ppm), and long-term sta-
out overlapping, indicating the potential application of the bility (70 days). In summary, Pt functionalized W ­ O3 sensor
sensor arrays to detect H­ 2S to diagnose halitosis. In addition, exhibits improved sensing properties toward target gases due
Choi et al. [114] developed Pt decorated microporous W ­ O3 to the sensitizing effect of Pt.
nanofibers via electrospinning technique and calcination.
In addition, Pt infiltrated block copolymers microparticles
(Pt-BCP MPs) were made through an oil-in-water emulsion 3.1.4 Pt‑decorated Other SMOs‑Based Gas Sensors
technique, which could be evenly distributed on the ­WO3,
further enhancing the gas sensing behavior. The fabrica- Apart from ZnO, ­SnO2, and ­WO3, there are various other
tion process of Pt-modified macroporous ­WO3 nanofibers metal oxide semiconductors like ­In2O3, NiO, CuO, and
is shown in Fig. 7d. The 0.042 wt% Pt-WO3 nanofibers sen- ­Fe2O3 have been investigated to enhance the gas sensing
sor exhibited an excellent response of 834.2 ± 20.1 toward performance by decorating Pt NPs.
5 ppm ­H2S at 350 °C in a high humid condition (95% RH)

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Nano-Micro Lett. (2023) 15:89 Page 17 of 75 89

In2O3 with wide band gap (3.6 eV), is a potential gas at 600 °C displayed highest response towards N ­ O2, which
sensing material owing to its high electrical conductivity was 7 times improvement of the pure I­ n2O3 nanorods. Liu
and stability [117]. In particular, Pt functionalized 1D I­ n2O3 et al. [120] reported a Pt-loaded I­ n2O3 porous nanofibers
structures were widely used for detecting ­NO2 and acetone. sensor fabricated through electrospinning method and calci-
Liu et al. [118] fabricated Pt-loaded mesoporous nanofibers nation, as exhibited in Fig. 8a. Due to the spillover effect of
through electrospinning and subsequent reduction method. Pt NPs and the large specific surface area of the porous 1D
Because of the porous microstructure, specific surface area, structure, the Pt-In2O3 sensor displayed improved gas sens-
and catalytic effect of Pt, the Pt-In2O3 mesoporous nanofib- ing properties towards 1 ppm acetone with high response
ers sensor could detect N ­ O2 at as low as 10 ppb at 40 °C of 15.1 at 180 °C with fast response/recovery speed (6/9 s)
(Rg/Ra = 2.8). Lee et al. [119] synthesized Pt decorated I­ n2O3 and excellent long-term stability (50 days). In addition,
nanorods through vapor–liquid-solid growth and calcina- Liu et al. [121] fabricated Pt-In2O3 core–shell nanowires
tion treatment. The Pt-modified ­In2O3 nanorods calcined via co-electrospinning method, as displayed in Fig. 8b.

Fig. 8  a Synthesis process of pristine I­n2O3 porous nanofibers and Pt-decorated I­n2O3 porous nanofibers. Reproduced with permission from
Ref. [120]. Copyright 2019, Elsevier. b Fabrication process for Pt-In2O3 nanowires. c Schematic diagram of a portable device including the Pt-
decorated ­In2O3 nanowire sensor. Reproduced with permission from Ref. [121]. Copyright 2018, Springer Nature. d TEM image of Pt-decorated
NiO nanotubes. e Response curves of the pristine NiO, 0.3% Pt-decorated NiO, and 0.7% Pt-decorated NiO nanotube gas sensors towards differ-
ent concentration of ethanol varying from 1 to 100 ppm at 200 °C; the inset image displayed linear relation of the response and the gas concen-
tration. Reproduced with permission from Ref. [122]. Copyright 2013, American Chemical Society. f Resistance changes of Pt-Fe2O3 to acetone
under different conditions. Reproduced with permission from Ref. [126]. Copyright 2019, Elsevier. g Responses of pristine CuO, Pt-CuO, Pd-
CuO, and Au-CuO-based sensors to 100 ppb HCHO at 225 °C. Reproduced with permission from Ref. [128]. Copyright 2019, Elsevier

13
89 Page 18 of 75 Nano-Micro Lett. (2023) 15:89

The Pt-In2O3 core–shell nanowires-based sensor exhibited decoration. In summary, Pt decoration is regarded as a useful
enhanced sensing performance with a high response up way to enhance the sensing behaviors of NiO gas sensors.
towards 27 to 10 ppm acetone which was six-fold enhance- Moreover, Pt functionalized ­Fe2O3 and CuO gas sensors
ment of pristine ­In2O3 nanofibers. Beyond that, a Santa Bar- are often used to detect VOCs. For instance, Zhang et al.
bara Amorphous-15 (SBA-15) molecular sieve containing [126] reported Pt-decorated F ­ e2O3 nanocubes via hydrother-
2D hexagonal channels was employed on top of the sensing mal and reduction method. Compared with pristine ­Fe2O3,
layer, effectively reducing the impact of humidity on the sen- the Pt-loaded ­Fe2O3 composites exhibited a higher response
sor. Thus, the as designed sensor could be potential to detect of 25.7 towards 100 ppm acetone at a 139 °C, with rapid
microscale acetone in exhaled breath. The Fig. 8c shows response/recovery speed of 3/22 s. The sensitizing effect of
a portable sensing device include the Pt-In2O3 nanowires Pt was crucial to the acetone detection. Besides, the sensor
sensor with the moisture filter layer. In summary, Pt deco- was investigated to detect acetone under various environment
rated ­In2O3 1D nanostructures is highly sensitive to ­NO2 and conditions. As displayed in Fig. 8f, the resistance changes of
acetone, which is an effective strategy to diagnose diseases the Pt-Fe2O3 sensor to 100 ppm acetone were very similar
through exhaled breath detection. under four conditions mimicking exhaled breath. Guo et al.
NiO has been extensively investigated because of its [127] synthesized Pt-decorated F ­ e2O3 nanowires with the Pt
important qualities such as wide energy bandgap (~ 3.8 eV), content varying from 0.5 to 3 mol% via homotaxial electro-
high chemical stability, and unique electrical properties spinning method. The 1 mol% Pt-decorated ­Fe2O3 nanowires
[122]. The sensors based on Pt functionalized 1D NiO struc- was demonstrated to have the best sensing behavior with
tures show improved sensing behaviors owing to their high high response of 157 to 10 ppm H ­ 2S at 175 °C due to the cat-
specific surface area and electrical and chemical sensitiza- alytic character of Pt and high specific surface area of ­Fe2O3
tion of Pt NPs. For instance, Fu et al. [122] synthesized nanowires. As for Pt decorated CuO-based sensor, Lee et al.
Pt-decorated NiO composite nanotubes via a facile elec- [128] produced porous CuO structure derived from MOFs of
trospinning method. The morphology of Pt-decorated NiO copper benzene-1,3,5-tricarboxylate (HKUST-1), and then
nanotubes is shown in Fig. 8d. The Pt-decorated NiO nano- decorated Pt NPs with 1 ~ 2 nm diameters via sonochemical
tubes sensor displayed the response to 100 ppm ethanol of synthetic process. The 0.06 wt% Pt-decorated CuO exhib-
20.85 at 200 °C, which was tenfold enhancement of pristine ited high response to HCHO (2.64 at 100 ppb) at 225 °C,
NiO based sensor (2.06), as shown in Fig. 8e. Wu et al. [123] and the linear relation between the concentration and the
prepared Pt@NiO NPs through sol–gel method and inves- response. Due to the porous structure derived from MOF and
tigated its sensing performance. The response of core–shell the sensitizing effect of Pt NPs, the Pt@CuO-based sensor
Pt@NiO (4.25) to 5000 ppm H ­ 2 was higher than that of NiO achieved better sensing performance. Moreover, Pd and Au
(1.02) with rapid response/recovery speed (91/8 s) at RT. NPs could be decorated on CuO using the same method.
In addition, Pt decorated 2D NiO structures sensors were Figure 8g shows that the response for Pd-CuO and Au-CuO
widely employed owing to their numerous active sites dur- to 100 ppb HCHO were 1.52 and 1.77, respectively, much
ing the adsorption and desorption of target gaseous species. lower than that of Pt-CuO, demonstrating that Pt is the best
For instance, Chen et al. [124] synthesized NiO thin film choice to functionalize CuO for HCHO detection.
via radio frequency (RF) sputtering and then deposited Pt
film via thermal evaporation followed by an annealing pro-
cess. The Pt/NiO thin film-based sensor exhibited improved 3.1.5 Pt‑decorated Heterostructured SMOs‑based Gas
sensing behavior including high response of 13.75 towards Sensors
1000 ppm ­NH3 at 300 °C with short response/recovery time
(15/76 s) and low limit of detection of 10 ppb. Liang et al. Designing hybrid structures with SMO is an efficient method
[125] synthesized Pt loaded NiO nanosheets through hydro- to promote gas sensing behaviors. In particular, core–shell
thermal and photo reduction method. The enhanced sens- structure has been extensively utilized to enhance sens-
ing behaviors of Pt-decorated NiO porous nanosheets could ing response because of the formation of a depletion layer
be attributed to the synergistic effect and facer-selective Pt [129]. Moreover, the attachment of Pt NPs to the core–shell
structure can modulate its resistance and further enhance

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 19 of 75 89

the sensing behavior. For instance, Kim et al. [130] fab- materials were fabricated on the MEMS devices which had
ricated ­SnO2-ZnO core–shell nanowires through ALD and many advantages including low power consumption, easy
attached Pt NPs via γ-ray radiolysis, as shown in Fig. 9a. The integration, and large-scale, as shown in Fig. 9c. The Pt-
Pt-decorated ­SnO2-ZnO core–shell nanowires based-sensor decorated ­SnO2-ZnO core–shell nanosheets-sensor exhibited
realized an extraordinarily high response of 279 to 100 ppb the response of 30.43 towards 5 ppm H ­ 2S at 375 °C with
toluene at 300 °C, which was higher than that of S ­ nO2-ZnO high selectivity among ­NO2, ­NH3, ethanol, and ­CH4. The
core–shell nanowires, pristine ­SnO2, and pristine ZnO sen- improved sensing behavior could be attributed to the hetero-
sor, as shown in Fig. 9b. The enhancement of the toluene junctions and the sensitization effect of Pt NPs. In summary,
sensitivity was depended on the formation of the electron- core–shell heterogenous nanostructures functionalized with
depleted region and the catalytic effect of Pt NPs. Wu Pt NPs demonstrate great potential for developing excellent
et al. [131] synthesized S­ nO2-ZnO core–shell nanosheets gas sensors towards various target gases.
through ALD and hydrothermal route, and then deposited In addition, many heterojunctions functionalized Pt
Pt NPs via magnetron sputtering. Moreover, the sensing NPs were also developed for remarkable gas sensors. For

Fig. 9  a Schematic illustrations of the fabrication process of the Pt-decorated ­SnO2/ZnO nanowires. b Responses of the Pt-decorated ­SnO2/
ZnO nanowires, ­SnO2/ZnO nanowires, pristine ­SnO2 nanowires, and pristine ZnO nanowires-based sensor to toluene. Reproduced with per-
mission from Ref. [130]. Copyright 2015, American Chemical Society. c Synthesis scheme of Pt-decorated S ­ nO2-ZnO core–shell nanosheets
in-situ on MEMS. Reproduced with permission from Ref. [131]. Copyright 2022, American Chemical Society. d Selectivity of pristine S ­ nO2,
­SnO2-α-Fe2O3, and Pt-decorated S ­ nO2-α-Fe2O3 sensors to various gases (10 ppm) at 206 °C. e Energy band diagram of Pt-SnO2-α-Fe2O3.
Reproduced with permission from Ref. [132]. Copyright 2018, Elsevier. f Response/recovery speed of Pt-decorated ZnO/In2O3 sensor towards
100 ppm acetone at 300 °C, the inset is the five periods of response and recovery curves. Reproduced with permission from Ref. [134]. Copy-
right 2018, Elsevier

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89 Page 20 of 75 Nano-Micro Lett. (2023) 15:89

example, Liu et al. [132] fabricated ­SnO2-α-Fe2O3 hollow response of 57.1 to 100 ppm at 300 °C, short response/recov-
nano-heterojunctions via hydrothermal and then loaded ery speed (1/44 s), and low limit of detection (500 ppb).
ultrafine Pt NPs through in-situ reduction and subse- The improved sensing properties was attributed to: (i) the
quent calcination treatment. The 6.45 wt% Pt embellished expanded electron depletion layer on the ­In2O3 caused by
­SnO2-α-Fe2O3-based sensor in Fig. 9d exhibited outstand- the n–n nano-heterojunctions, (ii) the sensitizing effect of
ing gas sensing behavior with a high response of 10.56 decorated ultra-small Pt NPs, and (iii) the increased sensor
to 10 ppm styrene with ultrafast response/recovery speed resistance induced by the p–n heterojunction. In summary,
(3/15 s), low limit of detection (50 ppb), and excellent selec- MOF could be utilized as an efficient platform to produce
tivity among other malodorous gases. Compared to pure ultra-small catalysts decorated on SMOs, promoting the
­SnO2 and ­SnO2-α-Fe2O3 sensors, the improvement in styrene development of highly sensitive gas sensors.
sensing behavior of the Pt embellished ­SnO2-α-Fe2O3 sensor
could be mainly attributed to the electronic sensitization. As
exhibited in Fig. 9e, the n–n heterojunction led to band bend- 3.2 Pd‑Decorated SMOs‑based Gas Sensors
ing at the interface of S­ nO2-α-Fe2O3 and the formation of
metal–semiconductor contact could induce band bending at 3.2.1 Pd‑Decorated ZnO Gas Sensors
the interface of Pt-α-Fe2O3. Thus, the electron would move
from ­SnO2 to α-Fe2O3 until the Fermi level was balanced, Various morphologies of nanostructures for ZnO including
leading to the 6electron accumulation layer in α-Fe2O3 nanorods, nanowires, nanofibers, nanosheets, agaric-like,
which could adsorb more oxygen molecules and modulate coral-like, and core–shell nanostructures have been fabri-
its resistance. Simultaneously, the metal–semiconductor cated and employed in Pd-decorated gas sensors to help
contact would migrate electron from Pt to α-Fe 2O3, fur- increasing the selectivity and response value, reducing
ther increasing the electron concentration of α-Fe2O3 side. operating temperature, and shortening the response and
Therefore, these two factors could facilitate the adsorption recovery time. Gao et al. [135] fabricated Pd-decorated
of oxygen molecules on the α-Fe2O3 side and significantly ZnO nanorods through the impregnation process and pro-
change the resistance of Pt-SnO2-α-Fe2O3. Besides, the posed that the Pd/PdOx covered on the ZnO surface has a
catalytic effect of Pt NPs was crucial to the styrene sensing significant enhancement on H ­ 2 sensing performance. The
0
owing to its selective catalytic oxidation of styrene. Overall, effect of ­Pd and ­PdOx content under different tempera-
it is promising to design n–n heterogenous nanostructures ture was further studied using in-situ Raman technique and
functionalized Pt NPs in the detection of specific gases. In found out that the appropriate variation of Pd/PdOx ratio
addition, Chang et al. [133] synthesized ­In2O3-WO3 nano can effectively improve the response value and shorten
powder via calcination method and then functionalized Pt the response/recovery time of pure ZnO sensor. Cao et al.
NPs through reduction process. The obtained Pt functional- [136] grew perpendicularly aligned ZnO nanorods by
ized ­In2O3-WO3 nano powder-based sensor could achieve chemical vapor deposition (CVD) method, followed by
ppb-level detection of nitric oxide (NO) at RT due to the n–n precise decoration of Pd NPs on their surface through
heterojunction of ­In2O3 and ­WO3 and the catalytic effect of magnetic sputtering and annealing process. The response
Pt NPs. In particular, the 0.25% Pt-decorated ­In2O3-WO3 of Pd-decorated ZnO nanorods sensor to ethanol was sig-
nano powder-based sensor exhibited high response of 330 nificantly enhanced owing to the catalytic effect of Pd
and 15.2 to 0.1 ppm and 25 ppb NO, respectively. In addi- NPs accelerating the dissociation and the chemisorption
tion, Guo et al. [134] prepared Pt functionalized ZnO-In2O3 of oxygen. In addition, the Pd-decorated ZnO nanorods
nanofibers through using ZIF-8 and electrospinning method. also respond well to trimethylamine. Meng et al. [137]
Owing to the noble metal NPs could be encapsulated in the reported Pd-decorated ZnO nanorod arrays which is in-situ
cavity of ZIF-8 resulting in ultra-small nanometers, it was synthesized on ceramic tubes by a simple wet-chemical
found that the average diameter of Pt NPs was only 3 nm method. Compared to pure ZnO nanorods, Pd-decorated
which could maximize their catalytic effect. As exhibited ZnO nanorods sensor exhibited better sensing properties
in Fig. 9f, the Pt-decorated ZnO-In2O3 sensor displayed in the lower operating temperature region with a large
an excellent gas sensing behavior toward acetone with the response of 5.5 to 5 ppm trimethylamine. What’s more,

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 21 of 75 89

photoactivation can also effectively improve metal oxide of 36.8% at 80 °C, while ZnO sensor showed no response
semiconductors gas sensing performance owing to the gen- and Pd/ZnO sensor showed a weak response of 2.3%. The
eration of photogenerated carrier favors the creation of temperature-programmed desorption of chemisorbed oxy-
reactive oxygen species at low temperature and promotes gen results revealed that the synergetic effect of various
chemisorption photocatalytic oxidation reactions. Chen surface chemisorbed oxygen species, Pd NPs, and visible
et al. [138] synthesized oxygen vacancy-enriched Pd-deco- light illumination played a decisive role in forming active
rated ZnO (OV Pd/ZnO) nanorods by heating the solution- chemisorbed oxygen species on the surface of ZnO, which
fabricated ZnO nanorods at 450 °C in H ­ 2 atmosphere for could be attributed to the improved sensing properties.
one hour. The sensors based on OV Pd/ZnO and Pd/ZnO Beyond that, Luo et al. [139] demonstrated a method to
both showed low responses of 5.4% and 1.1% to 0.1% C ­ H 4, further enhance the selectivity of the sensor. They fabri-
respectively. As presented in Fig. 10a, under visible-light cated a core–shell nanostructured ZnO/Pd@ZIF-8 through
illumination, OV Pd/ZnO exhibited an ultrahigh response self-templating process. Under visible light illumination,

Fig. 10  a Transient response of the sensors to 0.1% C

­ H4 based on the ZnO, OV ZnO, ZnO/Pd and OV ZnO/Pd composites under 590 nm light
illumination. Reproduced with permission from Ref. [138]. Copyright 2020, Elsevier. b Selectivity of the sensors based on pristine (@150 °C)
and Pd-ZnO nanowires (@100 °C) to different gases. Reproduced with permission from Ref. [140]. Copyright 2019, Elsevier. c Schematic dia-
gram of the Pd-ZnO nanowires-based nanosensor device. d Transient response of the sensors based on single Pd-ZnO nanowire with different
diameters. Reproduced with permission from Ref. [141]. Copyright 2018, Elsevier. e Measurement system for the detection of dissolved H ­ 2 in
transformer oil. Reproduced with permission from Ref. [144]. Copyright 2016, Elsevier. f Optical images of the flexible RT H
­ 2 sensor based on
Pd/ZnO nanorods under different bending angles. Reproduced with permission from Ref. [145]. Copyright 2013, Elsevier. g Selectivity of the
sensors based on ultrathin agaric-like Pd-decorated ZnO nanosheets with the background of Pd/ZnO SEM image. Reproduced with permission
from Ref. [148]. Copyright 2020, American Chemical Society. h SEM image of porous coral-like Pd-decorated ZnO nanosheets. Reproduced
with permission from Ref. [149]. Copyright 2021, Elsevier. i Selectivity performance and BET surface area of the Pd@ZnO core–shell NPs.
Reproduced with permission from Ref. [150]. Copyright 2021, Elsevier

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89 Page 22 of 75 Nano-Micro Lett. (2023) 15:89

the ternary compound showed a response of 16.9% to 0.1% Besides, Pd-decorated 2D ZnO nanomaterials have also
­CH4 at 80 °C and successfully excluded the interference attracted the interest of researchers due to their small thick-
of ­NO2, as the kinetic molecule (4.5 Å) of ­NO2 is larger ness and high specific surface area, which are ideal for the
than the aperture size (4.0–4.2 Å) of ZIF-8, while the dif- enhanced surface reactions and detections of target gas. Kim
fusion of ­CH4 (3.8 Å) is less influenced. Chen et al. [140] et al. [146] prepared 2D ZnO nanosheets with a thickness
presented Pd-decorated ZnO nanowires for N ­ O 2 sensor of approximately 1 nm via facile hydrothermal process and
via one-pot hydrothermal process. The Pd NPs were self- modified with Pd through UV radiation. The Pd-modified
assembled on the surface of ZnO nanowires, helping to nanosheet successfully detects ­H2 at the concentration down
lower the operating temperature, increase the response to 0.1 ppm with excellent selectivity. In addition, the Pd/
value, and enhance the selectivity towards ­NO2, as shown ZnO nanosheets were further prepared on PI substrates and
in Fig. 10b. Lupan et al. [141] displayed a RT H ­ 2 sen- tested by bending, tilting and stretching to demonstrate the
sor based on Pd/ZnO nanowires synthesized via one-step great mechanical flexibility. Xiao et al. [147] synthesized
electrochemical deposition, and the schematic illustra- high-performance acetone sensors based on the Pd-modified
tion of the nano-sensor is shown in Fig. 10c. The sensi- porous single-crystal ZnO nanosheets. The ZnO nanosheets
tivity of gas sensors increases as the grain size of metal was produced by solvothermal method, while Pd NPs were
oxide decreases [142, 143]. The authors also derived the self-assembled on their surface. The authors contributed the
response value of nanowires as a function of diameter, fabulous sensing properties to the Pd modification effect and
indicating that nanowires with smaller diameters typically the high percentage of the single-crystal ZnO nanosheets
have greater sensitivity. Their theory is also confirmed encased in (100) facets. Furthermore, they proposed that
by the experimental results in Fig. 10d. Furthermore, the different 2D and 3D ZnO nanocrystals encapsulated in high
sensor exhibited high-performance sensing properties index facets could greatly enhance the sensing performance
with response value of 13,100, response/recovery time of of chemical sensors. Beyond that, a variety of interesting
6.4/7.4 s to 100 ppm ­H2 at RT. The low current values morphologies based on ZnO nanosheet have also been pre-
(pA-nA), ultralow power consumption, and great long- pared for high-performance gas sensors. Zhang et al. [148]
term stability (> 30 days) also demonstrate the prospect prepared Pd-modified ultrathin agaric-like ZnO nanosheets
of handheld instruments. Uddin et al. [144] fabricated a aniline sensors by facile hydrothermal process. As shown in
­H2 sensor based on Pd-modified ZnO nanorods arrays for Fig. 10g, the sample exhibited superior selectivity and sen-
monitoring dissolved ­H2 in transformer oil, as shown in sitivity to aniline, which is approximately two orders larger
Fig. 10e. The Pd catalysts modified on ZnO nanorods not than pristine ZnO nanosheets. Beyond that, the aniline sen-
only enhance the sensing performance of H ­ 2 at RT, but also sor has a low detection limit of 0.5 ppm with a response/
protect the ZnO nanorods in liquid oil, which makes the recovery time of 29/23 s. Hung et al. [149] synthesized
prepared devices have long-term stability. The prepared porous coral-like ZnO nanosheets by hydrothermal method
sensor exhibited a large response in the transformer oil and modified them by direct reduction of Pd ions, as shown
working environment for low concentrations (5–100 ppm) in Fig. 10h. With Pd modification, the optimal operating
of dissolved ­H2 at oil temperatures of 40–80 °C, render- temperature was significantly reduced from 450 to 350 °C,
ing it a potential candidate for transformer oil applica- with a threefold improved response to acetone, about three-
tions. Rashid et al. [145] reported a flexible RT H ­ 2 sen- fold faster response/recovery time, and a very low theoreti-
sor based on Pd/ZnO nanorods on polyimide (PI) through cal detection limit of 17 ppt compared to the pristine ZnO
aqueous solution and magnetron sputtering process. The nanosheets sensor. In addition to the modification of Pd
gas sensor exhibited fabulous sensing properties with a NPs on the ZnO surface, a H ­ 2 sensor based on hydrother-
great response of 91% to 1000 ppm ­H2, response time of mally synthesized Pd@ZnO core–shell NPs was reported by
18.8 s, and LOD of 0.2 ppm. What’s more, as presented in Nguyen et al. [150] The high Barrett-Emmett-Teller (BET)
Fig. 10f the sensor showed no degradation even under 90° specific surface area of the core–shell material also provides
bend and maintained high performance after ­105 bending/ a large number of active sites for accelerating the sensing
relaxing cycles, showing excellent flexibility properties. reaction, which is beneficial for enhancing the sensing

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Nano-Micro Lett. (2023) 15:89 Page 23 of 75 89

performance, as illustrated in Fig. 10i. Secondly, they also that, compared with the pristine ­S nO 2 sensors, the Pd-
found that the sensing performance of the core–shell sam- decorated ­SnO2 sensors have a large resistivity of 4 orders
ples calcined in argon was superior to that in air, attributed of magnitude and exhibited an increased response to ­H2
to the high content of metal ­Pd0 species. and a decreased response to N ­ O2, which can effectively
improve the selectivity of the sensors.
In addition to electrospinning, GLAD, solvothermal, and
3.2.2 Pd‑Decorated SnO2 Gas Sensors vapor–liquid-solid process have also been reported for the
preparation of S ­ nO2 1D nanostructures with high specific
To date, a variety of synthetic methods have been reported surface area. Jung et al. [154] used GLAD method to pre-
for the preparation of Pd-decorated ­S nO 2 for gas sens- pare ­SnO2 nanorods with an average height and diameter
ing. Firstly, as we all know, electrospinning is a kind of of 200 and 30 nm, respectively. Subsequent loading with
one-step synthesis technique with great properties such 5 nm thin layers of metal catalysts such as Au, Pt, or Pd,
as simple process, versatility, low cost, large-scale prepa- all of them improving the sensing performance of the ­SnO2
ration, and the ability to produce micron to nanometer nanorods sensors. However, the Pd-modified S ­ nO2 sen-
fibers. Metal oxides prepared by electrostatic spinning sor showed the best detection performance for ­C2H2 with
not only have a 1D nanostructure induced by the prepa- an ultralow detection limit of 0.01 ppm. Lu et al. [155]
ration process, but also have a high surface-to-volume synthesized colloidal S ­ nO2 nanowires with an ultrasmall
ratio and porosity owing to the interconnection between diameter of ~ 2 nm through a simple solvothermal process.
NPs. Various morphologies consisting of different pores Furthermore, the Pd-modification of the S ­ nO2 nanowires
and discontinuous segments can be obtained by adjust- by employing the ­PdCl2 surface ligand replacement tech-
ing the key factors of the electrospinning method, such as nique effectively reduce the sensor operating temperature
flow rate and volatile solvent. Teng et al. [151] prepared from 250 to 150 °C and decrease the response/recovery
mesoporous PdO-decorated S ­ nO2 nanotubes by one-step time to 6/3 s. Cai et al. [156] prepared S ­ nO2 nanowires by
electrospinning technique. The fabricated sensors exhib- the vapor–liquid-solid process and modified Pd NPs on the
ited high response of 20.3 with a rapid response time surface of ­SnO2 by UV irradiation of P ­ dCl2 solution. With
of 1.33 s to 100 ppm of N ­ O 2 at RT and reached a low the variation of the quantity of Pd NPs, the Pd-modified
detection limit of 10 ppb. The fabulous sensing properties ­SnO2 nanowires exhibit different ­H2 sensing responses,
can be attributed to the ­SnO2 tubular nanostructure and which can be well controlled by adjusting the irradiation
well-dispersed mesopores that provide abundant chan- time. What’s more, S ­ nO2 nanowires decorated with optimal
nels for gas diffusion and adsorption, and oxygen defects amounts of Pd NPs showed a 12.7-fold higher response than
and chemisorbed oxygen act as active sites for increasing bare ­SnO2 nanowires when exposed to 100 ppm H ­ 2. Choi
rates of electron transport due to the accelerated electron et al. [157] similarly prepared ­SnO2 nanowires using a facile
capture and charge transfer. In addition, Xie et al. [152] vapor–liquid-solid process and then achieved Pd-embedded
fabricated ­SnO2 nanofibers by electrospinning and formed ­SnO2−x modification via flame CVD. The response of the
porous nanostructure by subsequent carbonization treat- Pd-embedded ­SnO2−x gas sensor at 200 °C was 21.87, 2.23,
ment by calcination in air, as presented in Fig. 11a. The 1.69 and 1.51 for ­NO2, ethanol, benzene, and ­H2 gases at
carbonization treatment improved the response of Pd/ 10 ppm, respectively, reflecting its excellent selectivity for
SnO2 nanofiber sensors to all gases without sacrificing the ­NO2 gas, especially excluding the effect of H ­ 2. Pineau et al.
selectivity, as shown in Fig. 11b, which could be ascribed [158] fabricated ­SnO2 particles with different Pd contents by
to the formation of the hollow nanostructure, enhance- flame spray pyrolysis and treated with nitric acid, leaching
ment in surface area, and increased induced chemisorbed the Pd particles that were exposed to the ­SnO2 surface to
oxygen. Yang et al. [153] synthesized Pd-modified ­SnO2 obtain Pd-embedded ­SnO2 particles, as shown in Fig. 11d. In
nanofiber mats by electrospinning, hot pressing, and cal- addition, the Pd-embedded S ­ nO2 sensors exhibited a higher
cination, as presented in Fig. 11c. The Pd loading sup- response to acetone than the Pd-decorated S ­ nO2 particles
press grain growth and densification, resulting in smaller without leaching and demonstrated excellent resistance to
­SnO 2 nanofiber grains and higher surface area. Beyond humidity, as presented in Fig. 11e. This points out that small

13
89 Page 24 of 75 Nano-Micro Lett. (2023) 15:89

Fig. 11  a Schematic illustration of the fabrication process for carbonized Pd-SnO2 nanofiber. b The response and selectivity of the sensors
based on pristine ­SnO2 nanofiber, pristine Pd-SnO2 nanofiber, carbonized Pd-SnO2 nanofiber. Reproduced with permission from Ref. [152].
Copyright 2018, Elsevier. c Schematic illustration of the fabrication process for Pd-loaded S
­ nO2 nanofiber mats. Reproduced with permission
from Ref. [153]. Copyright 2010, Wiley–VCH. d Schematic illustration of the fabrication process for Pd-embedded S­ nO2 NPs. e The response to
0–1000 ppb acetone under different humidity conditions from Pd-embedded ­SnO2 NPs sensors before and after leaching. Reproduced with per-
mission from Ref. [158]. Copyright 2020, Springer Nature. f Schematic diagram of gas sensing mechanism for pristine S ­ nO2 and Pd-decorated
­SnO2 in humid condition. Reproduced with permission from Ref. [162]. Copyright 2015, American Chemical Society. g Handheld device for
indoor benzene sensing and envisioned chemical mapping application. Reproduced with permission from Ref. [163]. Copyright 2021, Wiley–
VCH. h Images of the handheld methanol sensor comprised of a flame-made Pd-SnO2 NPs microsensor and an upstream separation column
filled with Tenax TA particles. i Single and mixed dynamic response curves of the Pd-SnO2 NPs sensor connected without (left) and with (right)
the separation column. Reproduced with permission from Ref. [164]. Copyright 2019, Springer Nature

amounts of precious metals embedded in metal oxides may method, etc. Porous nanospheres of S ­ nO2 have also been
be more effective than on the surfaces. proved to have high gas response and fast gas responding
Furthermore, there are many methods to synthesize kinetics due to the large specific surface area that provides
porous nanospheres, such as the simple hydrothermal more contact area for gas molecules and helps taking full
process, template-sacrificial method, facile precipitation advantage of the catalytic effect of Pd NPs. Duan et al. [159]

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 25 of 75 89

synthesized Pd-modified S ­ nO2 porous spherical composites interference of disturbing gases such as challenging toluene
by simple hydrothermal method. The sensors exhibited a and xylene, exhibiting an ultrahigh selectivity. Beyond that,
significant response of 18.1 to 200 ppm H ­ 2 at 330 °C under ultralow concentrations (13 ppb) of benzene can be detected
UV radiation. Under UV radiation, a certain amount of pho- at relative humidity of 10 ~ 80% with superior stability. Fur-
togenerated electron–hole pairs are excited on the surface thermore, as presented in Fig. 11g, the device was also suc-
of SMOs. The photogenerated electron–hole pairs are less cessfully used to quantify the amount of benzene in spiked
bound to atoms than those generated during the redox reac- indoor air and transmits the data wirelessly to a terminal for
tion between SMOs and the target gas, which facilitates a analysis. Actually, Broek et al. [164] have already reported a
faster response speed and a larger response value. In addi- similar inexpensive and handheld methanol gas sensor com-
tion, the hollow nanospheres provide a larger gas contact prised of a flame-made Pd-SnO2 NPs microsensor and an
area, which can also be effective in improving sensor char- upstream separation column filled with Tenax TA particles
acteristics such as sensitivity. Cai et al. [160] synthesized (Fig. 11h). The difference lies in the type of the selected
porous ­SnO2 hollow nanospheres with the sacrifice of car- filter. Since methanol and ethanol are chemically similar
bon nanospheres and decorated Pd NPs by UV irradiation molecules, choosing the separation column as the filter is
to enhance their sensing properties. The Pd-modified ­SnO2 expected to acquire much better separation results. More
hollow spheres sensor exhibited a ultrahigh response of 121 specifically, the separation column can effectively separate
to 100 ppm ­H2 at 200 °C, while the response of the bare methanol from ethanol and other interfering analytes like H­ 2
­SnO2 hollow spheres sensor was only 3.1. Beyond that, after and acetone, contributing to the expected selective detection
Pd modification, the selectivity for ­H2 was significantly of methanol visually displayed in Fig. 11i. Notably, based on
improved, compared to reducing gases including ethanol, such an attractive handheld sensor with remarkable selectiv-
acetone, p-xylene, toluene, and benzene. Suematsu et al. ity, further practical applications in the discrimination of
[161] formed clustered ­SnO2 NPs (~ 45 nm) by aggregat- methanol adulteration in alcoholic beverages [165] and the
ing monodispersed nanocrystals (~ 5 nm) prepared through noninvasive diagnosis for methanol poisoning [166] were
hydrothermal method. The clustered NPs have particularly thoroughly demonstrated in their follow-up works. In addi-
high porosity owing to the loose accumulation of large tion, Broek et al. [167] also fabricated a portable formalde-
particles, which improves the gas diffusivity of the sens- hyde sensor with a high selectivity for indoor air monitoring
ing membrane. In particular, the clusters of Pd-decorated with the same filter-sensor structure consisting with a Tenax
­SnO2 NPs not only showed fabulous response to 200 ppm TA powder-based separation column and a flame-made Pd-
­H2 (S = 2,020), 200 ppm CO (S > 520), and 50 ppm toluene SnO2 NPs microsensor.
(S = 1,720), but also exhibited ppb-level detection capability.
Moreover, Pd decoration have also been reported to play a
significant role in the enhancement of humidity resistance 3.2.3 Pd‑Decorated WO3 Gas Sensors
properties of the sensors. Ma et al. [162] prepared Pd-
decorated ­SnO2 NPs and illustrated the oxygen adsorption In recent years, Pd-decorated W ­ O 3 sensors have been
behavior and sensing performance for ­H2 and CO under dif- reported to detect a wide range of gases, including ­H2, CO,
ferent humidity conditions. As illustrated in Fig. 11f, they ­NH3, ­H2S, acetone, toluene, and so on.
proposed that in a humid atmosphere, the adsorbed oxygen Han et al. [168] successfully fabricated multilayer
species on the pure ­SnO2 surface was mainly ­O−, and the Pd porous Pd-WO3 nanocomposite films via layer-by-layer
loading provided initial adsorption sites for the adsorption of deposition based on sol–gel process. The prepared sen-
­O2−, which is not easily affected by water vapor, thus reduc- sor exhibited a fast response time of 7 s and an ultrahigh
ing the effect of water vapor on the conductivity and sensor sensitivity (S = 956.5) to 1000 ppm H ­ 2, which is 346.5
response, and greatly enhancing the sensitivity of the sen- times larger than that of the pristine ­WO3 film. In addi-
sor in the humid atmosphere. Weber et al. [163] fabricated tion, Esfandiar et al. [169] utilized a controlled hydro-
a handheld benzene sensing device based on Pd/SnO2 NPs thermal process to incorporate ribbon-like Pd-WO 3 onto
prepared by flame spray pyrolysis. Meanwhile, they designed partially reduced graphene oxide (PRGO) sheets to form
­WO3 nanoparticle catalytic filters to selectively removed the layered Pd-WO3/PRGO composite with high surface area.

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89 Page 26 of 75 Nano-Micro Lett. (2023) 15:89

Fig. 12  a Transient response of Pd-WO3/PRGO sensors to different concentrations of ­H2. Reproduced with permission from Ref. [169]. Copy-
right 2014, Elsevier. b The sensitivity of pure and modified ­WO3 under different annealing temperature and operating temperature. Reproduced
with permission from Ref. [171]. Copyright 2018, Elsevier. c Schematic diagram of the effect of CO molecular valve. Reproduced with permis-
sion from Ref. [172]. Copyright 2018, Elsevier. d Schematic diagram of sensor fabrication through femtosecond laser direct-writing technique
and the SEM images of the prepared programmable patterns. Reproduced with permission from Ref. [174]. Copyright 2020, Elsevier. e Tran-
sient response of P
­ dxW18O49 sensors to different concentrations of acetone. Reproduced with permission from Ref. [47]. Copyright 2021, Else-
vier. f Schematic diagram of the electrospinning process for mesoporous W ­ O3 nanofibers modified with apoferritin-encapsulated proteins cata-
lyzed noble metal NPs. g Transient response of Pd-modified W ­ O3 nanofibers sensors to different concentrations of toluene. h 3D feature space of
PCA using the fabricated ­WO3 sensors with Pd, Pt and Rh modifications for different concentrations of 10 exhaled biomarker gases. Reproduced
with permission from Ref. [176]. Copyright 2016, American Chemical Society

PRGO can not only significantly improve the conductiv- a 3D urchin-like hierarchical nanostructure of Pd-W18O49
ity of the composite, but also increase the porosity of the assembled from nanorods. The novel nanostructure with
composite for more active sites and faster adsorption/des- large surface area, the abundance of oxygen vacancies in
orption. As shown in Fig. 12a, the Pd-WO 3/PRGO sen- ­W18O49, and the catalytic activity of Pd NPs lead to the
sor can detect a wide range (20 ~ 10,000 ppm) of ­H 2 at excellent ­H2 sensing performance of the Pd-W18O49 sen-
low temperatures and showed large response values with sor, including high response values of 1,600 to 0.1 vol%
fast response/recovery time. Zhou et al. [170] developed ­H2 at 100 °C and fast response/recovery time of 60/4 s.

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 27 of 75 89

Pd-modified ­WO3 was also used for direct detection and deposition method can not only deposit various sensing
model inference of CO concentrations. Marikutsaa et al. metal oxide, such as ZnO, CuO, and ­MoO3, but also pattern
[171] prepared ­WO3 NPs with variable particle size and into various shapes such as snake-shape and other stretch-
surface area by aqueous deposition and thermal treatment, able geometries, which provided numerous possibilities for
and Pd decoration was further carried out by impregnation multifunctional sensors based on various sensing nanoma-
to improve the sensitivity to CO. As shown in Fig. 12b, with- terials, such as configuration of stretchable functions and
out the addition of Pd, the W­ O3 did not interact with CO at optoelectronic sensing.
RT. While after Pd decoration, the sensors exhibited bet- Pd-modified ­WO3 has also been reported for the detection
ter working performance at lower operating temperatures, of various VOCs. Kim et al. [175] synthesized porous Pd-
which could be attributed to the strong binding of CO to embedded ­WO3 nanofibers through one-step electrospinning
the Pd sites and the oxidation of CO with surface aqueous and further decorated Pd NPs on the surface by polyol pro-
species. In addition, the CO concentration can be inferred cess. The Pd-NPs/Pd-embedded W ­ O3 nanofibers with both
from the ­H2 sensing performance under CO interference. inner and outer layers modified by Pd catalysts showed a
This provides a novel method for CO detection based on large toluene response (S = 5.5 to 1 ppm) and selectivity for
tunable interfacial effects. Xiao et al. [172] displayed Pd- ­H2S (S = 1.36 to 1 ppm), while the pristine ­WO3 nanofibers
modified ­WO3 sensors that were sensitive to ­H2 but not to showed a high response to ­H2S (S = 11.1 to 1 ppm) and low
CO. Moreover, the presence of CO inhibited the absorption response to toluene (S = 1.27 to 1 ppm), completely changed
and desorption of ­H2 by Pd NPs. As shown in the Fig. 12c, the sensing properties of W ­ O3 nanofibers. Moreover, the
in the air atmosphere, hydrogen atoms can easily spill over combination of highly porous ­WO3 nanofibers with novel
from the Pd NPs to the surface of ­WO3 and react with the nanostructures featuring internally and externally modified
chemisorbed oxygen to release electrons. However, in the Pd NPs attributed to low detection limit of 20 ppb, which
presence of CO, the hydrogen spillover is blocked, resulting is feasible for lung cancer diagnosis. Moreover, Pd-deco-
in a reduction of the amount of released electrons, which rated ­W18O49 was also used to fabricated acetone sensors.
acts as a molecular valve effect. By modelling the theory Li et al. [47] prepared P ­ dxW18O49 nanowires by a simple
of the molecular valve, the CO concentration can be calcu- hydrothermal method and analyzed the effect of Pd con-
lated from the ­H2 sensing response in the presence of CO tent on oxygen vacancies. With the increase of Pd content,
interference, demonstrating the possibility of single sensor the oxygen vacancy concentration gradually increased and
to sensing multiple gases. then decreased. The oxygen vacancy concentration reached
Other reducing gases such as ­H2S, ­NH3, etc. have also maximum at the Pd content of 7.18%, and the ­Pd7.18%W18O49
been reported to be detected by Pd-modified W ­ O3. Wang nanowire also exhibited best sensing performance of excel-
et al. [173] synthesized ­WO3 microspheres by solvother- lent selectivity, fast response/recovery time of 5/10 s, and a
mal process, followed by Pd modification through simple wide detection from 100 ppb to 300 ppm with large sensitiv-
impregnation. The sensitivity, response speed, and selec- ity, as presented in Fig. 12e.
tivity were significantly enhanced after Pd loading. The In addition to preparing a single gas sensor for the detec-
response to 25 ppm ­H2S reached 1029, which was 270 times tion of target gas, sensor arrays are recently being combined
larger than that of the pure ­WO3, along with outstanding with machine learning techniques to detect multiple gases.
resistance to humidity and short response time of 1 s. Dai Kim et al. [176] proposed an efficient catalyst loading route
et al. [174] innovatively employed a high-precision femto- for detecting ppb-level target gases in exhaled breath. Noble
second laser direct-writing technique to print semiconduc- metal NPs are embedded in polar protein nanocages com-
tor metal oxide NPs into mask-free microscale program- posed of hollow apoferritin and the apoferritin-encapsulated
mable patterns, as shown in Fig. 12d. They first prepared proteins catalyzed NPs are further dispersed in electrospun
Pd-WO3∙xH2O NPs by simple hydrothermal method, and mesoporous ­WO3 nanofibers. After calcination, the noble
then fabricated single microwires made of assembled NPs by metal NPs were uniformly distributed in the nanofibers,
laser direct writing, which can detect as low as 1 ppm ­NH3 and the shell layer of the apoferritin proteins effectively
at RT with high response, fast response/recovery, and great prevented massive aggregation of the noble metal NPs, as
selectivity. This programmable femtosecond laser-induced shown in Fig. 12f. The Pd-modified ­WO3 sensor showed

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89 Page 28 of 75 Nano-Micro Lett. (2023) 15:89

superior sensing characteristics even in fully humid air and oxides. Cheng et al. [178] prepared long-range ordered noble
was able to detect toluene down to 0.1 ppm, as presented in metal-decorated mesoporous I­ n2O3 with high integrity by
Fig. 12g. Furthermore, they applied the fabricated W
­ O3 sen- impregnation and template-sacrificial methods to acceler-
sors with Pd, Pt, and Rh modifications for PCA and success- ate gas diffusion and expose active sites, as presented in
fully identified 10 exhaled biomarker gases accurately, as Fig. 13d. Among various noble metal (Au, Ag, Pt, and Pd)
shown in Fig. 12h. With the combination of machine learn- decorated ­In2O3 sensors, Pd/In2O3 sensors exhibited the best
ing algorithms, multiple gases can be detected with only sensing properties enhancement for detecting ethanol with
three sensors in this work, revealing that the innovation of the largest response (39.0 to 100 ppm ethanol), the shortest
sensing data processing method is of significant role in the response/recovery time (25/9 s), and the lowest operating
development of electronic nose. temperature (250 °C), as performed in Fig. 13e. Beyond that,
the Pd/In2O3 sensors exhibited excellent selectivity towards
different gases, as presented in Fig. 13f, which could be con-
3.2.4 Pd‑Decorated Other SMOs‑Based Gas Sensors tributed to the facilitation of ­Pd2+ converting ethanol mol-
ecules into smaller and more active species. What’s more, Pd
Besides, various other semiconductor metal oxides, includ- doping effectively limits crystal growth and has the highest
ing ­In2O3, ­TiO2, ­Fe2O3, CuO, ­Co3O4, ­CeO2, ­MoO3, NiO, content of ­Oads, resulting in a wide depletion region, which
and ­V2O5 have also been reported to improve the properties increases the initial resistance. Wang et al. [180] constructed
of gas sensors by Pd decoration and exhibit promising gas a 3D ordered microporous Pd-decorated ­In2O3 using a col-
sensing characteristics. loidal crystal templating process and reduction precipita-
In2O3 has been extensively explored as a wide bandgap tion method. The response of the sensor to 500 ppb ­NO2 at
transparent conductive oxide in gas sensors. Pd-modified RT was 980, which was more than 5 times larger than pure
­In2O3 has been reported to be extremely valuable for the ­In2O3. The combination of the enhanced number of surface
wide detection of various gases, including acetone [177], defects and the concentration of electron, the excellent cata-
ethanol [178], carbon disulfide (­ CS2) [179], ­NO2 [180], ­H2 lytic effect of Pd, and the great synergetic effect between Pd
[181], and TEA [182]. Liu et al. [179] synthesized Pd-deco- NPs and the ­In2O3 carrier led to the superior performance.
rated ­In2O3 nanocomposites with yolk-shell nanostructure by Pd-decorated ­TiO2 hybrids are also one of the most attrac-
introducing MOF-templated route and annealing treatment, tive chemiresistive gas sensing materials owing to their non-
and the novel process preparation diagram and the corre- toxicity, low cost, and great stability in harsh environments
sponding SEM and TEM images are shown in Fig. 13a. The [183, 184]. Wang et al. [185] proposed a 2D porous ­TiO2
synthesized Pd/In2O3 is capable of detecting trace-level ­CS2 nanosheet with Pd nanocrystal sensitization by graphene
gas molecules. Figure 13b displayed a significantly enhanced oxide template method and impregnation process, and
Pd/In2O3 response and superior selectivity towards ­CS2 found that T ­ iO2 nanosheets could almost exactly replicate
compared to the pristine ­In2O3 sensor. More significantly, the dimensions of the graphene oxide template, as shown in
to better investigate the role of the loaded Pd in the C
­ S2 sens- Fig. 13g. The Pd/TiO2 sensor exhibited a unique selectivity
ing process, quasi-in-situ X-ray photoelectric spectroscopy for ­H2, which could be ascribed to the Pd modification, as
(XPS) analysis and DFT calculations were performed. Fig- shown in Fig. 13h. In addition, as performed in Fig. 13i, the
ure 13c exhibits the energy distribution of Pd/In2O3 and pure sensor also has a transient and efficient detection perfor-
­In2O3 in the process of ­CS2 sensing and concludes that Pd mance, with rapid response/recovery time of 1.6/1.4 s, low
NPs can catalyze the desulfurization reaction and the gen- limit of detection (1 ppm) and excellent long-time stability
erated intermediate S is essential to obtain high sensitivity (> 100 days). The unique sensing properties is ascribed to
and fabulous selectivity. Mesoporous ­In2O3 has been applied the synergy of 2D ultra-thin porous nanosheets structural
to prepare different morphologies of mesoporous Pd/In2O3 properties, Pd sensitization, and the superior adsorption
such as nanospheres [177], nanofibers [178], and 3D ordered properties. Mao et al. [186] presented nanoporous Pd/TiO2
macroporous structures [180]. The special mesoporous composite membranes for ­H2 sensors. It was observed that
structure, with its abundant active sites, large surface area, the Pd decoration resulted in significant needle-like jumps
and light weight, facilitates the interaction of gases with in the resistance sensing curve, while this phenomenon did

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 29 of 75 89

Fig. 13  a Schematic illustration of the fabrication process for carbonized Pd-decorated I­ n2O3 nanocomposites with yolk-shell nanostructure and
the corresponding SEM and TEM images. b Sensitivity of pure and Pd-modified I­ n2O3 for different gases at 10 ppm. c Calculation of the energy
distribution of the reaction between the Pd/In2O3 composite and the pristine I­ n2O3 surface in the process of C
­ S2 sensing. Reproduced with per-
mission from Ref. [179]. Copyright 2019, American Chemical Society. d Schematic illustration of the fabrication process for long-range ordered
noble metal-doped mesoporous ­In2O3 with high integrity. e Transient response of various noble metal (Au, Ag, Pt, and Pd) doped I­ n2O3 sensors
to different concentrations of ethanol. f Radar diagram of various noble metal (Au, Ag, Pt, and Pd) doped I­n2O3 sensors to different 100 ppm
gases. Reproduced with permission from Ref. [178]. Copyright 2021, IOP Publishing. g Schematic illustration of the fabrication process for 2D
porous Pd/TiO2 nanosheet. h The sensitivity of pure and Pd-modified T ­ iO2 for different gases at 1000 ppm. i Transient response of Pd/TiO2 to
different concentrations of ­H2. Reproduced with permission from Ref. [185]. Copyright 2021, Elsevier. j Schematic illustration of the fabrica-
tion process for PdO-Co3O4 HNCs and the corresponding SEM and TEM images. k Dynamic response curves of ­Co3O4 powders, ­Co3O4 HNCs,
PdO-Co3O4 powders, and PdO-Co3O4 HNCs towards 0.4 ~ 5.0 ppm acetone. l 3D feature space of PCA based on ­Co3O4 powders ­Co3O4 HNCs
and PdO-Co3O4 HNCs for different concentrations of gases reproduced with permission from Ref. [194]. Copyright 2017, American Chemical
Society

not occur with pure T ­ iO2. They suggest that the phenom- the subsequent reaction of adsorbed oxygen injects electrons
enon is the consequence of competition between increased into the ­TiO2 layer, resulting in a decrease in resistance and
resistance of Pd and decreased resistance of T
­ iO2. Pd has the a needle-like jump in resistance sensing curve.
ability to reversibly adsorb and desorb large amounts of ­H2 Iron oxide is also a traditional cost-effective gas sensing
(about 900 times its own volume). When first exposed to ­H2, material and Pd-doped iron oxide can also further enhance
the resistance of the entire material increases rapidly. And the sensing performance of pristine iron oxide chemiresistive

13
89 Page 30 of 75 Nano-Micro Lett. (2023) 15:89

gas sensor. Yang et al. [187] prepared Pd nanoparticle- extends the lifetime of thermally generated charges, and the
encapsulated α-Fe2O3 nanofibers by a simple electrospinning transformed ­PdHx injects electrons into the n-CeO2 shell
and calcination treatment. The optimal content of Pd NPs during ­H2 detection, speeding up the response and recovery.
can not only absorb abundant oxygen molecules to dissoci- Furthermore, the unique core–shell nanostructure results in
ate into adsorbed oxygen ions by spill-over effect, but also a high BET specific surface area and greater the Barrett-
activated the reaction between acetone and adsorbed oxygen Joyner-Halenda (BJH) adsorption and desorption average
ions by reducing the activation energy. Chemical sensitiza- pore sizes, accelerating the adsorption, diffusion, and des-
tion of Pd NPs and the formation of p-n heterojunctions orption processes. As a result, the sensor showed excel-
of Pd@α-Fe2O3 nanofibers resulted in enhanced sensors lent sensing characteristics with great selectivity, a large
properties with higher response (16.6 to 100 ppm acetone), response of 19 to 100 ppm ­H2, and a linear response to ­H2
faster response/recovery speed (4/4 s), low detection of limit concentrations from 0.5 to 100 ppm.
(50 ppb), better selectivity, and long-term stability (42 days). CuO is the most commonly used p-type metal oxide semi-
Sharma et al. [188] successfully synthesized Pd-loaded conductor material for chemiresistive gas sensors. However,
­Fe3O4 halloysite nanotubes nanohybrids. The response of Pd-modified CuO is rarely reported and does not perform
the hybrids to H­ 2 exhibited a peculiar concentration-depend- as well compared to ZnO, S ­ nO2, and W
­ O3, which are typi-
ent n-p-n variation. An n-type response was observed at H ­ 2 cal n-type metal oxide semiconductors. Some great works
concentrations of 250 ppb, an immediate p-type response at with excellent gas sensing performance have been reported
concentrations of 500 ppb, and a return to an n-type response though. Mikami et al. [190] reported Pd-decorated ­Cu2O/
at 1–5 ppm. This unusual sensing property can be ascribed CuO ­H2S sensors and proposed that Pd modification could
to the formation of n-Fe3O4/p-Fe–O-Pd/n-Fe3O4 heterojunc- facilitate the reaction between adsorbed oxygen and ­H2S,
tion structures. However, this phenomenon was not noticed thus blocking the formation of C ­ u2S and improving the
in other F ­ e3O4 gas sensors and was probably attributed to the stability of the sensor response. However, the excessively
unique nanostructure. Although this phenomenon is rare, it long response time (20 min) and recovery time still need
contributes to a better understanding of the sensing mecha- to be further improved. Nha et al. [191] prepared CuO nan-
nism of Pd-decorated metal oxide semiconductors. oplates using a hydrothermal method and modified them
CeO2 is an n-type semiconductor material with excellent with Pd NPs by directed reducing pathway at RT, and the
oxygen storage/release capacity and a low redox potential sensors worked well even at 90% relative humidity. The Pd-
between ­Ce3+ and C ­ e4+, leading to it being considered as a decorated sensors have higher sensitivity, faster response/
promising material for gas sensing in recent years. In con- recovery speed compared to pure CuO sensors, although
trast, pristine ­CeO2 gas sensors have an unimpressive per- the performance is still not comparable to other reported
formance due to their high band gap, low intrinsic carrier Pd-modified n-type metal oxide semiconductors.
concentration, and high carrier recombination rate, which Co3O4 has received attention as a novel p-type gas sens-
can be modified by decorating. Hu et al. [189] proposed that ing material, showing good stability and excellent perfor-
Pd decoration can be used to modulate the ratio of ­Ce3+ and mance in the evaluation of analytes such as ­H2, CO, NO,
­Ce4+ to enhance the methanol response. The content of C ­ e3+ ­NH3, and VOCs [192]. Koga [193] successfully prepared
affects the number of oxygen vacancies, which can contrib- aggregates of ­Co3O4 NPs (~ 3 nm) with uniformly dispersed
ute to the absorption of surface oxygen, improving the sens- Pd additives through a novel preparation route of pulsed
ing performance. With proper Pd modulation to maximize laser ablation. And the morphology of Pd can be modified
the ­Ce3+ content, the response Pd-CeO2 sensor is nearly four from single atoms to oxide clusters (1–2 nm). The best ­H2
times higher than pristine C ­ eO2 sensor. What’s more, Dao sensing performance is achieved with the highest density of
et al. [68] prepared Pd@n-CeO2 core–shell nanoplatforms single Pd atoms at 5% Pd loading. Contributions of electrons
for ­H2 detection. Nitrogen doping helps to increase the num- ­ o3O4 valence band are provided by the decoration
to the C
ber of C­ e3+ active species and oxygen vacancies, narrowing of a single Pd atom in the ­Pd4+ state at the ­Co3+ sites on the
the energy bandgap and introducing more free electrons to surface of C­ o3O4 NPs and leads to the higher concentration
the conduction band, thus reducing its initial resistance. In of free electrons, increasing the chance of oxygen to adsorb
addition, Pd noble metal is an effective electron trap that free electrons and form high concentration of ion-adsorbed

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Nano-Micro Lett. (2023) 15:89 Page 31 of 75 89

oxygen. What’s more, the catalytic redox cycle between ­Pd4+ in the nanocomposites. With the assistance of Pd NPs, the
and ­Pd2+ facilitates the reaction between H­ 2 and adsorbed amount of reactive adsorbed oxygen ions increases signifi-
oxygen during ­H2 sensing. Consequently, this Pd single- cantly due to the easy adsorption of oxygen molecules and
atom catalysis effectively improve sensitivity and response the rapid conversion of oxygen molecules. Moreover, the
speed. Koo et al. [194] fabricated Pd NPs-loaded ­Co3O4 hol- activation of Pd NPs catalyzes and strengthens the oxidation
low nanocages (HNCs) with MOF templates. The porous of butane molecules on the ­SnO2 and ­In2O3 surfaces through
structure of zeolitic imidazolate framework-67 (ZIF-67) the spillover effect. Consequently, the as-prepared nanocom-
acted as a sieve to limit the size of Pd NPs (2–3 nm) and posites exhibited broad detection range (1–3000 ppm), rapid
enable homogeneous dispersion of Pd NPs. Subsequently, as response/recovery time (3.5/7.9 s), high response value (71.3
shown in Fig. 13j, after calcination, the PdO NPs (3–4 nm) to 3000 ppm butane), and great selectivity towards common
are dispersed uniformly on the walls of the C ­ o3O4 HNCs, flammable gases. Kundu et al. [196] prepared Pd-decorated
whose unique nanostructure can provide high specific sur- indium tin oxide powders for selective N ­ H3 detection. They
face area and high catalytic activity. Figure 13k displayed found that after calcined at 650 °C, Pd was converted to
dynamic response curves of C ­ o3O4 powders, ­Co3O4 HNCs, PdO, which exhibited faster oxygen chemisorption than ­Pd0,
PdO-Co 3O 4 powders, and PdO-Co 3O 4 HNCs towards favoring increased sensitivity. In addition, the Pd modifica-
0.4 ~ 5.0 ppm acetone. Obviously, the acetone sensing tion contributed to an enhancement in sensing performance,
performance was markedly improved after Pd decoration, with a significant reduction in the lower detection limit from
which could be attributed to the effect of nanoscale catalyst. 30 to 3 ppm, an increased sensitivity, excellent long-term
Furthermore, a sensor array consisting of ­Co3O4 powders, stability (90 days), and negligible cross response.
­Co3O4 HNCs, and PdO-Co3O4 HNCs was carried out. As Recently, SMOs derived from MOFs have exhibited
exhibited in Fig. 13l, with the help of PCA analysis, acetone promising prospects in gas sensing area due to their unique
with different concentrations (1–5 ppm) were apparently dis- characteristics such as extraordinarily high specific sur-
criminated from other interfering gases ­(H2S, ­NH3, ethanol, face area, ultrahigh porosity, and various nanostructures.
pentane, and toluene), demonstrating its potential prospects In particular, MOFs are capable to encapsulate noble metal
for exhaled acetone analyzers. NPs within their interlayers or cavities, which can be easily
converted into the corresponding noble metal decorated-
SMOs by facile calcination. This preparation process is
3.2.5 Pd‑decorated Heterostructured SMOs‑Based Gas also reported for the preparation of Pd-decorated hetero-
Sensors structured SMOs-based gas sensors. Jo et al. [197] presented
2D MOFs-derived PdO/Co3O4-In2O3 sensing film for high-
The formation of heterostructured nanomaterials is an effec- performance acetone sensor. Figure 14a illustrates the sche-
tive strategy to improve gas sensing performance more than matic diagram of its fabrication. I­ n2O3 hollow spheres were
that of single-component SMOs. The electron transport is first prepared by ultrasonic spray pyrolysis. Subsequently,
highly modulated by the heterojunction potential, result- an ultrathin cobalt zeolitic-imidazolate framework (Co-ZIF-
ing in a strong modulation of resistance when detecting L) nanolayer was coated onto the surface of the I­ n2O3 hol-
target gases. In addition, the decoration of Pd metal NPs low spheres by dip coating, followed by calcination to form
can further enhance the properties of multiple SMO het- ­Co3O4-In2O3 shell. Finally, ­Co3O4 nanoclusters encapsulat-
erojunction-based sensors through chemical sensitization ing PdO NPs were loaded in I­ n2O3 hollow spheres by reduc-
and electronic sensitization. Dong et al. [195] reported Pd- ing the ­Pd2+ at the intercalation layer of the ZIF-L interlayer.
decorated ­SnO2/In2O3 nanocomposites for butane sensing. The incorporation of Pd in Co-ZIF-L allows the mixture of
When the nanocomposites are exposed to air, electrons in two different catalytic components at the atomic scale, thus
the conductive bands of S ­ nO2 and I­ n2O3 are trapped by oxy- enhancing the synergistic catalytic promotion. Furthermore,
gen, forming adsorbed oxygen ions, such as O ­ −, and O
­ 2−, aggregation and coarsening of C ­ o3O4 and PdO NPs during
which leads to an increase in the electron depletion layer calcination is also avoided as the Co and Pd sources were
and in the height of the potential barrier, thus increasing restricted by the unique MOF nanostructure. As a result,
the initial resistance. In this case, they found no PdO phase the mixed-phase nanocatalysts can be uniformly dispersed

13
89 Page 32 of 75 Nano-Micro Lett. (2023) 15:89

Fig. 14  a Schematic illustration of the fabrication process for 2D MOF derived PdO/Co3O4-In2O3 materials and its TEM image. Reproduced
with permission from Ref. [197]. Copyright 2020, Elsevier. b Transient response of Pd@ZnO-WO3 sensors to different concentrations of tolu-
ene. c Schematic illustration of the H
­ 2 sensing mechanism of Pd@ZnO-WO3 sensors. Reproduced with permission from Ref. [48]. Copyright
2016, American Chemical Society. d Schematic illustration of Pd/Al2O3/TiO2 sensors. e Energy band schematic diagram of Pd/Al2O3/TiO2 sen-
sors with and without H
­ 2 exposure. Reproduced with permission from Ref. [198]. Copyright 2018, Wiley–VCH

on the surface of sensing film and effectively catalyze the MOF-derived noble metal-embedded semiconductor metal
sensing reaction. The formation of ­Co3O4/PdO p–n junc- oxide multi-phase catalysts enables significant heterogene-
tions and ­Co3O4/In2O3 n–n junctions lead to an ultrahigh ous sensitization, facilitating optimal performance and mul-
response (145.9 to 5 ppm acetone) and selectivity at rela- tifunctional integration for gas sensors.
tively low operating temperatures (225 °C) and high humid- ALD is a widely employed deposition method in micro-
ity (80%RH). Koo et al. [48] synthesized ZIF-8-derived electronics, capable of controlled atomic level deposition
Pd-loaded ZnO nanocubes nanocatalysts, loaded on as-elec- with superior conformality, allowing the precious decoration
trospun ­WO3 nanofibers by calcination and formed Pd/ZnO of noble metals on SMO-based sensing materials with com-
and ZnO/WO3 dual heterogeneous multijunction. The Pd@ plex nanostructures to further improve the performance of
ZnO-WO3 nanofibers with multiple heterojunctions exhib- pristine SMOs. Kim et al. [198] grew transparent, ultrathin
ited large needle-like jumps toluene response (Fig. 14b), ­Al2O3/TiO2 thin film heterostructures by ALD and formed
which could be contributed to the enhanced work function two-dimensional electron gas (2DEG) at their interface. Sub-
of Pd@ZnO, resulting in a larger initial resistance and rapid sequently, island-type Pd NPs were deposited by e-beam
changes of resistance when exposed to toluene. In addition, evaporation to form Pd/Al2O3/TiO2 sensors, as present in
as present in Fig. 14c, they found that after exposure to tolu- Fig. 14d, which just had a total thickness of less than 15 nm.
­ d2+ was partially reduced to P
ene, the oxidation state of P ­ d0 Furthermore, adjusting the ALD process temperature modu-
state and donates electrons to ZnO, resulting in an effec- lates the 2DEG electron density on the ­Al2O3/TiO2 hetero-
tive modulation of the surface depletion layer. This unique structure, thus optimizing the sensitivity and response speed.

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 33 of 75 89

Under the optimal process, the sensor exhibited high H ­ 2 nanowires loaded with different sizes of Au NPs were suc-
sensing performance at RT, with a wide detecting range from cessfully synthesized for ethanol detection. As is shown in
5 ppm to 1% and a fast response time (28 s). The sensing Fig. 15b, the experimental results indicated that with the
mechanism was also proposed, as shown in Fig. 14e. When increase of the size of Au NPs, the gas sensitivity became
exposed to ­H2 atmosphere, ­H2 dissociates on the surface worse at low temperature (≤ 125 °C). Most importantly,
of the Pd NPs to form ­PdHx, which reduces the work func- the Au-loaded ZnO nanowires sensor showed long-term
tion of Pd (5.4 eV) to ­PdHx (4.7 eV). Therefore, the energy stability and repeatability at a low concentration of etha-
band bending on the surface of the T ­ iO2 layer increases, nol. The difference of gas responses is interpreted to the
implicating that electrons are transferred from Pd through Au NPs loadings with different sizes, the spillover effect of
the very thin ­Al2O3 layer (3 nm) to the surface of the T ­ iO2 Au loads, and the formation of Schottky barrier in Fig. 15c.
layer and the resistance of 2DEG decreases. Unlike con- Furthermore, Miao et al. [216] used a Langmuir–Blodgett
ventional semiconductors which use the 3D distribution of (LB) assembly technique to prepare a nanostructured thin
electrons to detect the target gas, the 2D system resulted in film of ZnO nanowire arrays, which was then sensitized with
a high sensitivity. Beyond that, the authors further prepared Au NPs synthesized by sputtering and post-annealing on
Pd/Al2O3/TiO2 on flexible PI substrate. After bending 500 the substrate in Fig. 15d. The resulting Au@ZnO_LB sen-
times, the flexible sensor still maintains reliable H
­ 2 sensing sor demonstrated excellent sensitivity and ppb-level sensing
performance. Therefore, ultrathin nanostructures endow the (3 ppb) to C ­ 2H2. It can be applied to environmental and
ALD-grown Pd/Al2O3/TiO2 with fabulous flexibility proper- health monitoring, biosensors, and other metal nanodot-
ties, which are hopeful for the development of wearable gas based applications. Besides, the Au NPs were loaded on
sensing applications (Table 2). the ZnO nanorods surface through UV-assisted deposition
method by Vuong et al. [217]. As presented in Fig. 15e, the
ethanol sensing characteristics were tested under different
3.3 Au‑Decorated SMOs‑Based Gas Sensors
working temperatures and the optimal operating tempera-
ture was 220 °C. The Au/ZnO sensor exhibited apparent
Various SMO materials decorated by Au NPs, such as ZnO
enhancement towards ethanol vapor, whose response is 167
[203], ­SnO2 [204], ­WO3 [205], and corresponding hetero-
times higher than that of the pristine ZnO.
geneous structures, for gas sensors has been widely studied.
2D nanostructures have demonstrated significant poten-
Meanwhile, Au-decorated gas sensors based on different
tial for delivering superior gas sensing performance of Au-
nanostructures, e.g., nanoparticles [206], nanorods [207],
decorated ZnO gas sensors due to high surface-to-volume
nanowires [208], nanosheets [209], and nanoflowers [210],
ratio [218]. Guo et al. [209] synthesized an acetone sensor
have been utilized to deliver superior sensing performance
based on Au NPs doped ZnO nanosheets through a hydro-
with high sensitivity, great selectivity, and fast response
thermal method combined with a calcination process, which
time.
exhibited ultra-response to acetone of 1012.6 at 100 ppm
and low limit of detection of 0.2 ppm, as shown in Fig. 15f.
3.3.1 Au‑Decorated ZnO Gas Sensors The prepared Au NPs doped ZnO is a potential material for
fabricating trace determination acetone sensor used in prac-
1D nanostructures such as nanorods [211] and nanowires tical medical diagnosis. Nagarjuna et al. [219] prepared the
[212] are believed to be able to facilitate reaction between Au doped ZnO nanosheets using hydrothermal synthesis and
materials and target gas molecules and thus improve the deposited them on the MEMS device, as shown in Fig. 15g.
gas sensing performance of Au-decorated ZnO gas sensors The MEMS device microheater was prepared, which had
[213]. Guo et al. [214] successfully fabricated Au-func- low power consumption, small designs, and low fabrication
tionalized ZnO nanorods gas sensor for ethanol detecting. cost. In order to better test the gas at different temperatures,
Au NPs as the sensitizer were fixed on the surface of ZnO the thermal performance of MEMS microheater was stud-
nanorods, which enhanced the performance of the sensor ied. Compared with pure ZnO nanosheets, the gas sensing
with short response-recovery time and great selectivity, response of Au doped ZnO nanosheets is increased by 15%
as shown in Fig. 15a. According to Li et al. [215], ZnO towards 60 ppm ethanol at 300 °C. In addition, Bae et al.

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89 Page 34 of 75 Nano-Micro Lett. (2023) 15:89

Table 2  Summary of the reported Pd-decorated SMOs-based gas sensors

Materials Structure Synthesis method O. T. (°C) Target gas Conc. (ppm) Response tres/trec (s) LOD Refs.

ZnO Nanoparticles Hydrothermal 350 H2 100 22a 1.4/7.8 min 5 ppm [150]
ZnO Nanorods Self-templating 80 CH4 1000 16.9%b 3.5/4.8 min 100 ppm [139]
ZnO Nanosheets Hydrothermal 250 H2 50 2.514a 336/294 s 0.1 ppm [146]
ZnO Coral-like nanoplates Hydrothermal 350 Acetone 125 66.7a < 15/ ~ 100 s 17 ppt [149]
ZnO Nanoparticles Hydrothermal 360 H2 100 11.3a 2/5 s 5 ppm [135]
ZnO Nanosheets Hydrothermal 280 Aniline 100 182a 29/23 s 0.5 ppm [199]
ZnO Nanorods Precipitation 80 CH4 1000 36.8%b 4/4.5 min 100 ppm [138]
ZnO Nanorods Wet-chemical 300 TMA 5 5.5a ~ 7/7 s 1 ppm [137]
ZnO Nanowires Hydrothermal 100 NO2 1 13.5a 141/177 s 1 ppm [140]
ZnO Nanorods CVD 260 Ethanol 500 81%b 6/95 s 100 ppm [136]
ZnO Nanowires Electrochemical RT H2 100 13100a 6.4/7.4 s 100 ppb [141]
deposition
ZnO Nanorods Hydrothermal 40 H2 100 90%b – 5 ppm [144]
ZnO Nanorods Hydrothermal RT H2 1000 91%b ~ 18/184 s 0.2 ppm [145]
ZnO Nanosheets Solvothermal 340 Acetone 100 70%b 9/6 s 10 ppm [147]
SnO2 Nanoparticles Flame Spray Pyroly- RT Benzene 1 2.1a 36/47 s 13 ppb [163]
sis
SnO2 Nanowires Solvothermal 150 H2 40 8.5a 6/3 s 2 ppm [155]
SnO2 Hollow spheres Hydrothermal 330 H2 200 14.5a 2.2/22.4 s 1 ppm [159]
SnO2 Nanowires Vapor–Liquid–Solid 200 NO2 10 21.87a 320/ ~ 750 s 2 ppm [157]
SnO2 Nanospheres Hydrothermal 200 H2 100 121a 34/162 s 1 ppm [160]
SnO2 Nanoparticles Flame Spray Pyroly- 350 Acetone 1 7a < 1/ < 2.3 min 5 ppb [158]
sis
SnO2 Nanorods GLAD 200 C2H2 10 ~ 0.99a 120 s/– 10 ppb [154]
SnO2 Nanowires Vapor–Liquid–Solid 300 H2 100 56a 22/164 s 1 ppm [156]
SnO2 Nanotubes Electrospinning RT NO2 100 ~ 20.30a ~ 1.33/22.66 s 10 ppb [151]
SnO2 Nanofibers Electrospinning 250 Toluene 100 24.6a ~ 3/29 s 1.6 ppb [152]
SnO2 Nanoparticles Hydrothermal 300 Toluene 50 1720a – 2.5 ppb [161]
SnO2 Nanofibers Nanofibers 350 H2 1 ~ ­3a – 50 ppb [153]
WO3 Nanowires Hydrothermal 175 Acetone 300 500a 5/10 s 100 ppb [200]
WO3 Microspheres Hydrothermal 190 H2S 25 1029a 1 s/– 2.5 ppm [173]
WO3 Nanoparticles Sol–gel 250 H2 2000 ~ ­2000a 7/ ~ 299 s 50 ppm [168]
WO3 Microwires Femtosecond laser RT NH3 50 ~ 1.035a 1.4/3.3 s 1 ppm [174]
WO3 Urchin-like nano- Hydrothermal 100 H2 1000 1600a 60/4 s 250 ppm [170]
structures
WO3 Nanoparticles Hydrothermal RT H2 5000 31a 60 s/– 1 ppm [172]
WO3 Nanocrystalline Aqueous deposition RT CO 20 > 1.5a 4/30 min ~ 1 ppm [171]
WO3 Nanofibers Electrospinning 350 Toluene 1 11a < 8.56/ < 9.2 s < 1 ppb [176]
WO3 Nanofibers Electrospinning 350 Toluene 1 5.5a 10.9/16.1 s 20 ppb [175]
WO3 Nanoribbon Hydrothermal RT H2 100 38a 52/35 s 20 ppm [169]
In2O3 Yolk-shell nanostruc- Calcination 135 CS2 50 135.3a 132.3/112.1 s 1 ppm [179]
ture
In2O3 Ordered macropo- Precipitation RT NO2 0.5 980a 90/114 s 100 ppb [180]
rous
In2O3 Ordered mesoporous Impregnation 250 Ethanol 100 39a 25/9 s 5 ppm [178]
In2O3 Microspheres Hydrothermal 220 TEA 50 47.56a 4/17 s 1 ppm [182]
In2O3 Nanospheres Precipitation 220 Acetone 50 ~ ­82a 6/17 s 5 ppm [177]
In2O3 Nanoparticles Flame spray pyroly- 250 H2 150 94a 2/180 s 0.1 ppm [181]
sis

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Nano-Micro Lett. (2023) 15:89 Page 35 of 75 89

Table 2  (continued)
Materials Structure Synthesis method O. T. (°C) Target gas Conc. (ppm) Response tres/trec (s) LOD Refs.

CeO2 Nanofibers Electrospinning 200 Methanol 100 6.95a 1/5 s 5 ppm [189]
CeO2 Nanoflatforms Precipitation 350 H2 100 19a 1/6 min 0.5 ppm [68]
CeO2 Nanoparticles Hydrothermal 250 SO2F2 50 153%b 67/773 s 1 ppb [201]
Co3O4 Hollow nanocages Calcination 350 Acetone 5 2.51a – 100 ppb [194]
Co3O4 Nanoparticles Pulsed laser ablation 125 H2 1000 ~ ­85a ~ 25/ ~ 80 s 1 ppm [193]
Co3O4 Hollow polyhedral Pyrolysis 150 Ethanol 100 ~ 20.8a 12/25 s 10 ppm [192]
CuO Nanoplates Hydrothermal 200 SO2 1 3.58a < 53 s/– 0.5 ppm [191]
CuO Nanocrystals Hot-soap 250 H2S 8 7.9a 20 min/– 1 ppm [190]
FeO Nanofibers Electrospinning 220 Acetone 100 16.6a 4/4 s 50 ppb [187]
FeO Nanotubes Reduction-precipi- 400 H2 100 19.8a ~ 6/11 s 250 ppb [188]
tation
TiO2 Nanosheet Calcination 230 H2 1000 9a 1.6/1.4 s 1 ppm [185]
TiO2 Nanoparticles Flame stabilizing on 450 CO 800 5.25a < 15/ < 60 s 80 ppm [183]
a rotating surface
TiO2 Thin films Spray pyrolysis RT H2 8000 ~ 1.5%b 4/13 s 4000 ppm [186]
TiO2 Nanofiber mats Electrospinning 180 NO2 2.1 38a – 0.16 ppm [184]
In2O3/ZnO Core–shell nanopar- Hydrothermal 300 H2 100 42a 0.4/4.0 min 5 ppm [202]
ticles
In2O3/Co3O4 Hollow spheres Annealing 225 Acetone 5 145.9a 14 s/– 1 ppm [197]
ITO Nanocrystalline Sol–gel 300 NH3 30 ~ 82%b 17/36 s 3 ppm [196]
Al2O3/TiO2 Thin films ALD 100 H2 5 59%b 15/245 s 5 ppm [198]
SnO2/In2O3 Nanoparticles Solvent-thermal 320 Butane 3000 71.28a 3.51/7.86 s 1 ppm [195]
ZnO/WO3 Nanofibers Electrospinning 350 Toluene 1 22.22a < 20 s/– 100 ppb [48]

O. T. operating temperature; Conc. concentration; tres/trec response time/recovery time; LOD limit of detection
a
Response is defined as R
­ a/Rg or ­Rg/Ra, ­Ra: resistance of the sensor in air, ­Rg: resistance of the sensor exposed to target gas
b
Response is defined as ∆R/Ra × 100% or ∆R/Rg × 100%, ∆R: the change in resistance, which equals to |Ra–Rg|

[203] synthesized strategic nanometric lamination of ZnO calculations by DFT method revealed that the adsorption of
nanofilms decorated with Au NPs using ALD and thermal ethanol molecules on the Au-modified ZnO surface had the
evaporation techniques. The Au NPs-ZnO nanofilms were best mental concentration, which was consistent with the
optimized by the density and size control, whose response to experimental results. In addition, Wang et al. developed ZnO
methyl mercaptan ­(CH3SH) was 4.99% at the concentration nanoflowers decorated by Au NPs with different Au concen-
down to 50 ppb. The prepared low detection limit sensor can trations. Experimentally, ZnO nanoflowers with 10 wt% Au
selectively and accurately identify ppb-level ­CH3SH among NPs remarkably enhanced the acetone sensing performance of
volatile sulfur compounds, which could be applied in the high sensitivity, short response/recovery time, and favorable
early diagnosis of periodontitis. selectivity. Such behaviors were benefited from the increased
In addition to the 1D and 2D nanostructures mentioned surface area by surface coarsening and the hybrid formation of
above, other Au-decorated ZnO nanostructures have also Au/ZnO. In addition, the research confirmed that the loading
aroused great interest of researchers. The ethanol sensing per- concentration of the Au catalysts is significant to gas sensing
formance of ZnO NPs decorated with different contents of characteristics. At this optimum operating temperature, when
Au NPs (0.5, 2, 4, and 7 wt%) were investigated by Eyvaraghi the Au content was increased from 0 to 14 wt%, the sensor
et al. [220]. What’s more, theoretical calculations were car- displayed responses of 6.92, 28.78, 41.89, 74.41, and 35.57,
ried out using the DFT method, and the experimental results respectively. The response of the ZnO decorated with 10 wt%
were verified. The 4 wt% Au@ZnO sensor showed about 5 Au was 10.75 times higher than that of the pure ZnO, which
times higher response than that of pure ZnO sensor as well directly verified the promoting effect of Au NPs. The modu-
as a reduced response time from 36 to 3 s. The theoretical lation of surface defects by electrical and chemical effects

13
89 Page 36 of 75 Nano-Micro Lett. (2023) 15:89

Fig. 15  a Response histogram of Au/ZnO gas sensor to ethanol, methanol, and acetone with different concentrations. Reproduced with permis-
sion from Ref. [214]. Copyright 2014, Elsevier. b Response of Au-ZnO nanowires to 50 ppm ethanol at different operating temperatures. c Sche-
matic diagram of Au NP sizes on sensing performance. Reproduced with permission from Ref. [215]. Copyright 2021, Royal Society of Chem-
istry. d Schematic diagram and transient response curve of Au@ZnO_LB towards 10–100 ppb of C ­ 2H2. Reproduced with permission from Ref.
[216]. Copyright 2020, American Chemical Society. e Transient responses of Au/ZnO sensors towards 4769 ppm ethanol under different oper-
ating temperatures. Reproduced with permission from Ref. [217]. Copyright 2021, IOP Publishing. f Responses of Au doped ZnO nanosheets
towards xylene, ethanol, and acetone under different concentrations, and the insert displays the selectivity to 100 ppm gases. Reproduced with
permission from Ref. [209]. Copyright 2021, Elsevier. g SEM image of the Au–ZnO sample and the MEMS microheater. Reproduced with per-
mission from Ref. [219]. Copyright 2020, MDPI

of Au NPs is regard as an important reason to improve the suitable material for gas sensors [222, 223]. The Au-deco-
gas sensing performance. Meanwhile, the Schottky contacts rated ­SnO2 gas sensors with numerous morphologies have
between the Au NPs and the ZnO nanoflowers form an addi- attracted great interest of researchers [41, 224–226].
tional depletion layer at the interface by extracting electrons 3D hierarchical nanostructures are usually high-dimen-
from ZnO surface defects, resulting in a decrease in electron sional nanomaterials periodically assembled from low-
mobility and carrier concentration. And the subsequent reac- dimensional nanomaterials with high surface accessibility
tion of adsorbed oxygen with the target gases would produce and specific surface area, which are attracting attention
stronger resistance changes and greater sensor responses. At as highly sensitive gas sensors [224]. As is shown in
the same time, the catalytic activity of Au NPs also made for Fig. 16a, Guo et al. [225] immobilized Au NPs on the sur-
the faster response [221]. face of 3D ­SnO2 microstructures assembled by 2D porous
nanosheets via a solution reduction process. The Au/SnO2
sensor exhibited the better performance over pristine ­SnO2
3.3.2 Au‑Decorated SnO2 Gas Sensors
to ethanol due to unique sensitizer properties of Au NPs.
The response of Au/SnO2 towards 150 ppm ethanol is 29.3,
Au-decorated ­S nO 2 has excellent electrical conductiv-
which is 2 times higher than that of pure S ­ nO2 (13.7) at
ity, well chemical stability, and low cost, which makes it a

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 37 of 75 89

Fig. 16  a SEM image of Au/SnO2 microstructures. Reproduced with permission from Ref. [225]. Copyright 2016, Elsevier. b Schematic view
­ nO2 samples. Reproduced with permission from Ref. [224]. Copyright 2016, Elsevier. c Responses of the
of sensing mechanism to Au-loaded S
­SnO2 and 1.5-Au/SnO2 sensors towards different ­CH4 concentrations at 120 °C. Reproduced with permission from Ref. [226]. Copyright 2019,
Elsevier. d Optical photograph of wireless sensing module and dynamic concentration curve of the sensor when exposed to TEA (50 ppm).
Reproduced with permission from Ref. [41]. Copyright 2022, Elsevier. e Chemo-resistive and SERS multimodal sensing platform with
3D-CMA. Reproduced with permission from Ref. [227]. Copyright 2021, Wiley–VCH. f Photograph of transparent Au-SnO2 sensor. Repro-
duced with permission from Ref. [231]. Copyright 2021, Wiley–VCH

340 °C. Moreover, Bing et al. [224] successfully grew flow- Au-decorated ­SnO2 nanoflowers were prepared through a
erlike ­SnO2 nanosheets assembled from multilayered walls facile impregnation process by Xue et al. [226]. The 1.5 wt%
and hexagonal mesoporous. The Au loading S ­ nO2 hollow Au-decorated ­SnO2 sensor to 500 ppm C ­ H4 had approxi-
nanosheets exhibited more favorable performance to CO mately 6 times higher response than that of pristine S
­ nO2 at
compared with pure ­SnO2. The sensing mechanism of Au- 120 °C on account of Au NPs served as catalysts shown by
loaded ­SnO2 samples is shown as Fig. 16b. The improved Fig. 16c. The mechanism of Au-decorated ­SnO2 was also
CO sensing response can be ascribed to the unique hol- investigated in detail. Loading small size Au NPs on the
low configuration and the introduction of Au. Besides, the surface of S
­ nO2 not only ensured the nanostructure of S­ nO2

13
89 Page 38 of 75 Nano-Micro Lett. (2023) 15:89

nanofibers, but also increased the specific surface area of working temperature, shorter response/recovery time, and
­SnO2 nanofibers. Secondly, the chemical catalysis provided greater selectivity. The introduced Au NPs obviously increased
more active sites for the adsorption of oxygen molecules, the surface-adsorbed oxygen, which is consistent with the XPS
and promoted the dissociation of the adsorbed oxygen to results. From the point of view on detecting organophosphorus
accelerate capture and release of electrons. Thirdly, because compounds, preparing gas sensors that combine fast response/
of the different work functions of S ­ nO2 and Au, a Schottky recovery time with low detection limits remains challeng-
junction was formed between Au NPs and ­SnO2 nanofibers, ing. Recently, Yang et al. [229] fabricated a dimethyl methyl
resulting in electron transfer from ­SnO2 to Au. These above phosphonate (DMMP) sensor from the Au NPs deposited onto
three factors led to the remarkably enhanced sensing perfor- ­SnO2 based on ceramic tube. Further decoration of Au NPs as
mance of the Au-decorated ­SnO2. the sensitizer can achieve apparent sensing enhancement in
Cui et al. [210] used a new self-reductive hydrothermal terms of low detection limit of 4.8 ppb, fast response/recovery
method to synthesize hierarchical Au-loaded ­SnO2 nano- time (26/32 s), and good selectivity. The research can extend a
flowers for ethanol detection. The Au-loaded S ­ nO2 had BET- feasible way for quick detecting trace organic compounds. In
2 −1
specific surface area of 84 m­ ­g , which was at least 2 times addition, Lian et al. [230] developed a promising material of
higher than pure S ­ nO2 hierarchical structures. The improved Au-SnO2 NPs synthesized by a simple hydrothermal method
response showed a wider detection range of 1–500 ppm for for n-butanol gas monitoring. Experimentally, the response
ethanol, more excellent selectivity, and greater long-term of Au-SnO2 NPs (251.23) is over 21 times higher than that
stability. In the detection of organic matter, reported by of pristine S
­ nO2 (11.5) at 200 ppm n-butanol. The sensor
Feng et al., a novel mesoporous Au-SnO2 nanosphere struc- based on Au-decorated ­SnO2 NPs showed low detection limit
ture manifested high response (5.16) at a low temperature (1 ppm), good stability, and outstanding selectivity towards
(50 °C), quick response (~ 30 s), and low detection limit n-butanol.
(0.11 ppm) towards TEA [41]. The gas sensor integrated Except the development of VOC gas sensors, Lim et al.
a wireless module that can obtain gas information from a [231] reported a transparent nanopatterned sensor composed
smartphone for TEA environmental monitoring, as shown of 1D Au-SnO2 nanofibers on the indium tin oxide (ITO) trans-
in Fig. 16d. parent electrodes, which realized the unique room-temperature
Apart from the 3D structure, other dimensional Au-deco- ­NO2 detection under visible light irradiation, as is shown in
rated ­SnO2 nanostructures have also been developed for gas Fig. 16f. The nanopattern Au-SnO2 nanofibers were prepared
sensors, which have excellent performance in VOC detec- on a glass substrate with transparent electrodes by direct-write
tion. As shown in Fig. 16e, Han et al. [227] successfully pre- and near-field electrospinning methods, which contribute to
pared a systematically assembled 3D cross-point multifunc- low coverage (0.3%) and high transparency (93%). The as-
tional architecture (3D-CMA) based chemo-resistive/surface prepared sensor exhibited a superior sensitivity, selectivity,
enhanced Raman spectroscopy (SERS) multimodal sensor, and reproducibility to sub-ppm levels of ­NO2, whose detection
whose sensing elements were integrated with S ­ nO2 nanowires limit isas low as 6 ppb. The unique RT N ­ O2 sensor assisted
and Au metallic NPs. The 0D contacting points can enhance by the visible light is derived from the localized surface plas-
chemo-resistive sensing response and the high density cross- monic resonance effect of Au NPs, enabling the sensor to
points are used to massive SERS (optical) signal improvement. require no external heater or light source. This work provides
Not only detecting ppm-level VOCs, but also identification an application strategy in air quality assessment under indoor
of gas molecular structure was realized by 3D-CMA-based natural sunlight or light-emitting diode (LED) illumination,
multimodal sensor. The sensor with excellent performance, outdoor environmental monitoring, and respiratory analysis
low-cost, and good reusability will be applied in various for asthma diagnosis.
fields, including biomedical diagnosis, food safety and quality
monitoring, environmental detection, and explosive detection. 3.3.3 Au‑Decorated WO3 Gas Sensors
What’s more, Feng et al. [228] investigated the xylene gas
sensing properties of the Au-SnO2 nanorods. Compared with WO3 has served as a promising gas sensing material to
pure ­SnO2, the enhanced performance of 6 and 12 mol% Au- detect ­H2S [232], ­NO2 [233], and VOCs [234], and other
SnO2 nanorods was displayed, such as a higher response, lower

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Nano-Micro Lett. (2023) 15:89 Page 39 of 75 89

gases [235] due to its wide energy bandgap, great chemical In addition, many porous ­WO3 materials functioned by
and thermal stability, as well as higher diffusion coefficient Au NPs have also received a lot of attention for VOCs detec-
of the oxygen vacancy [205]. Au decoration can be consid- tion. For example, Wang et al. prepared mesoporous ­WO3
ered as an effective way to enhance the sensing performance modified by Au NPs with high specific surface area (17–20
of ­WO3 [76]. ­m2 ­g−1) to detect trimethylamine (TMA), which is usually
VOCs are ubiquitous, numerous and varied, and some of presented in seafood spoilage. Figure 17b shows the excel-
them can be harmful to human health or damage the natural lent selectivity for TMA of Au-loaded W ­ O3 sensors among
environment [236]. Au-modified W ­ O3 materials have been various gases including toluene, acetone, ethanol, xylene,
intensively studied for VOC detection. For example, Laser and methanol. Furthermore, the prepared sensor displayed
ablation in liquids (LAL) and annealing methods were used significant repeatability, stability, and quick response time
by Dai et al. to prepare Au NPs decorated ­WO3 nanoplate- (1 s). Besides, accurate detection of exhaled isoprene may
lets [205]. LAL-induced WOx clusters could in-situ reduce provide valuable application for monitoring human physical
­AuCl4− to Au NPs. With following aging treatment, Au- and physiological state or for early diagnosis of cardiovas-
loaded ­H2WO4·H2O nanoplatelets were formed by self- cular disease. However, since the concentration of isoprene
assembly of colloids. After annealing, Au-decorated ­WO3 in exhaled gas is extremely low, the development of a highly
nanoplatelets were finally prepared. Compared with pure selective and sensitive isoprene sensor still faces various
­WO3, the Au-WO3 nanoplatelets delivered superior response, challenges [240]. In a recent study, Park et al. [241] synthe-
excellent reproductivity, and lower operating temperature sized Au NPs modified macroporous ­WO3 microspheres,
to ethanol, which had potential application in heavy metal which displayed prominent response of 11.3 to 0.1 ppm iso-
ions detection and methanol electro-oxidation. Besides, prene and a relatively low detection limit (0.2 ppb). Mean-
Yang et al. [237] synthesized Au-decorated ­WO3 compos- while, as shown in Fig. 17c the authors systematically inves-
ite nanofibers for selective n-butanol sensing. TEM image tigated the effect of the Au loading concentration on the gas
of Au-WO3 composite nanofibers is shown in Fig. 17a, sensing performance of Au@WO3 sensors and found out
which can be observed that the obtained ­WO3 nanofiber is that in the entire operating temperature range, the Au@WO3
well- modified with Au NPs with an average particle size of sensor with a moderate Au loading concentration exhibited
∼7 nm. The sensing response of the Au-WO3 nanofibers was the best isoprene sensing performance. Furthermore, by
∼60 times higher than that of pure ­WO3 towards n-butanol, monitoring the concentration of isoprene exhaled by a nor-
which also showed significantly improved selectivity. The mal man during running (Fig. 17d), the response of the Au@
catalytic of Au NPs and the existence of depletion layers at WO3 sensor is linearly correlated with the concentration
the surface of the Au-WO3 nanofibers were considered as the measured by proton transfer reaction quadrupole mass spec-
reasons for improving sensing performance. In addition, a trometry (PTR-QMS). The present isoprene sensor has high
HCHO sensor fabricated from Au NPs loaded W ­ O3 thin film potential applications for personal healthcare monitoring.
was reported by Niu et al. [238]. The as-synthesized sen- Similarly, Lv et al. [242] prepared ­WO3 hollow microspheres
sor exhibited a low detection of 40 ppb and extremely high with different Au loading concentrations by a wet impregna-
response of 1303.5 under 20 ppm HCHO. For maintaining tion method and demonstrated the highest responses of the
the desired accuracy, gray algorithm GM (1, 1) and first- 1.5 wt% Au-WO3 to aromatic compounds, especially to tolu-
order differential approach was used in this study, which is ene and xylene.In addition, many researches have also been
beneficial to implement the HCHO sensor in IoT areas and focused on high-performance acetone sensors. For instance,
wireless transmission. Zhang et al. [239] presented the on- Zhang et al. [243] synthesized 3DIO W ­ O3 materials with
chip fabrication of bilayer Au NPs-loaded ­WO3 nanoporous Au-modification for highly sensitive and selective acetone
thin films (B-Au/WO3) using layer-by-layer stacking of the sensors. Figure 17e displayed the acceptable acetone selec-
template-assisted fabrication process with periodic physical tivity of 3DIO Au/WO3 sensors among common interferers
Au sputtering deposition. Under the low temperature condi- including CO, ­H2, ethanol, ­NH3, methanol, ­NO2, and ­H2S,
tion of 150 °C, the sensitivity of B-Au/WO3 film to 1 ppm which is one of important factors for practical applications.
­NO2 is 96, and the response/recovery time is 9/16 s, which Meanwhile, the reaction mechanism between acetone and
are obviously better than bare ­WO3. Au/WO3 is depicted in Fig. 17f. By modifying Au NPs, the

13
89 Page 40 of 75 Nano-Micro Lett. (2023) 15:89

Fig. 17  a TEM image of Au-WO3 composite nanofibers. Reproduced with permission from Ref. [237]. Copyright 2015, Elsevier. b Responses
of pristine ­WO3 and Au-WO3 sensors to various gases at 100 ppm. Reproduced with permission from Ref. [240]. Copyright 2021, Royal Society
of Chemistry. c Responses of Au@WO3 sensors with different Au loading concentrations to 0.1 ppm isoprene at 275 ~ 375 °C under ambient
humidity. d Schematic of the exhaled breath detection of a normal man during treadmill running based on the Au@WO3 sensor. Reproduced
with permission from Ref. [241]. Copyright 2022, American Chemical Society. e The selectivity behaviors of Au/WO3 sensors. f Gas sensing
schematic diagram of the Au/WO3 sensor. Reproduced with permission from Ref. [243]. Copyright 2020, Elsevier

catalytic action and spillover effect were generated to pro- The results revealed that when the optimum Au sputter-
mote the response of the 3DIO Au/WO3 gas sensor. ing time is set as 10 s, the ­H 2S sensing performance of
Furthermore, Punginsang et al. [244] applied different Au NPs functionalized W ­ O 3 nanowires is significantly
RF magnetron sputtering time with subsequent annealing improved in terms of the low detection limit (0.17 ppb)
to decorate ­WO3 nanowires with different size of Au NPs. and great sensitivity of 219 to 5 ppm H ­ 2S. The excellent

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 41 of 75 89

sensing performance was explained by spillover effects 3.3.4 Au‑Decorated Other SMOs‑Based Gas Sensors
and surface catalytic reactions of Au on heterogeneous
interfaces of Au-decorated ­WO3 nanowires. Apart from common SMOs of ZnO, S ­ nO2, and ­WO3, many
other SMO materials functionalized by Au NPs have also
been widely explored for gas sensors, such as CuO [245],
­Fe2O3 [246], and ­MoO3 [247].

Fig. 18  a Schematic of preparation of the Au/MoO3 sensor. Reproduced with permission from Ref. [248]. Copyright 2021, Elsevier. b
Responses of Au/ZnFe2O4 sensor towards 40 ppm of different gases. Reproduced with permission from Ref. [250]. Copyright 2021, Elsevier.
c Resistance curves of pure-Fe2O3 nanorods sensor and Au-Fe2O3 nanorods sensors to 50 ppm TEA at 40 °C. d Schematic gas mechanisms
of Au-Fe2O3 nanorods. Reproduced with permission from Ref. [251]. Copyright 2018, Elsevier. e Au/Co3O4-NPs on the MEMS substrate and
selectivity towards 10 ppm different gases. Reproduced with permission from Ref. [261]. Copyright 2021, Elsevier. f Schematic diagrams of the
fabrication process for Au NPs functionalized CuO nanowire. g Gas responses of various sizes of Au functionalized CuO nanowire sensors to
CO at 350 °C and N ­ O2 at 300 °C. Reproduced with permission from Ref. [262]. Copyright 2016, Elsevier

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89 Page 42 of 75 Nano-Micro Lett. (2023) 15:89

As a typical n-type SMO, 1D M ­ oO3 is considered as a nanorods was also discussed (Fig. 18d). The catalytic activ-
high-performance sensing material, which has low con- ity of Au DHs and the Schottky barrier in the surface of Au/
ductivity, high crystallinity, and effective gas diffusion and Fe2O3 were regarded as the reason for the improved sens-
charge transportation. Most importantly, different from tra- ing performance. The as-synthesized TEA sensor will have
ditional surface chemical adsorption mechanism of other widely application potential in chemical industry.
MOSs, the sensing mechanism of M ­ oO3 is lattice oxygen Besides, ­TiO2 has the characteristics of high electro-
reaction. The hydrothermal method and in-situ reduction chemical and catalytic activity, low cost, and high chemi-
were used by Fu et al. to fabricate the 4 wt% Au NPs deco- cal stability, which is widely studied as a gas sensing mate-
rated ­MoO3 nanobelts sensor (Fig. 18a), which showed rial [252]. However, RT T ­ iO2-based sensors with excellent
excellent selectivity to 1-butylamine [248]. The response of sensitivity and selectivity are still scarce and therefore are
the Au/MoO3 sensor is more than 3 times higher than that highly needed. Mintcheva et al. [253] prepared Au NPs-
of pristine M
­ oO3 nanobelts towards 100 ppm 1-butylamine decorated ­TiO2 NPs using the LAL method. LAL ablates a
at 240 °C. Furthermore, since 1-butylamine is a significant solid (usually metal) target immersed in a liquid medium to
marker compound in medical and food industries, another synthesize NPs with different sizes via a laser beam, which
type of 1-butylamine sensor is also investigated. is simple, environment friendly, and cost-efficient. The T ­ iO2
As an n-type SMO, ­V2O5 has also become a hot topic in with 1 and 5 wt% Au loading displayed a maximum response
the research of sensor materials in recent years due to its and selectivity towards acetaldehyde and benzene, respec-
advantages of high stability, low cost, and high corrosion tively. Experimentally, oxygen vacancies and ­Ti3+ ions were
resistance. Yang et al. [249] explored a high efficiency, low formed on the surface of T ­ iO2 after laser irradiation, while
cost, and easy operation method for preparing Au modified the defects of the latter disappeared after modification with
nanosheet-assembled ­V2O5 microflowers (Au/V2O5). The Au NPs, which enhanced the sensing response as well as
gas sensing response of the Au/V2O5 sensor to toxic 1-buty- selectivity.β-Ga2O3 has a wide bandgap of ~ 4.7 eV at RT
lamine were studied. In comparison with pristine ­V2O5, the and characteristics of high thermal, mechanical, and chemi-
Au/V2O5 sensor demonstrated lower operating temperature cal stability [254, 255]. Weng et al. [256] fabricated the sen-
(~ 240 °C), high sensitivity of 7.5 towards 100 ppm 1-buty- sor based on Au modified β-Ga2O3 nanowires via vapor–liq-
lamine, and excellent selectivity. This study provides a new uid-solid method for RT CO detection with great response/
insight for preparing noble metal functionalized V ­ 2O5 com- recovery time (5.85/10.13 s) and high sensitivity of 7.8% at
posites with high sensing properties. RT condition towards 100 ppm CO. Meanwhile, the point
In addition, the spinel type zinc ferrite (­ ZnFe2O4) nano- defect was oriented to form conductive channel because
structure is demonstrated to be beneficial to the detection of applying electric field. Thus, the Au modified β-Ga2O3
of VOCs. However, its poor sensing capabilities impede its device exhibited bipolar resistive switching behavior.
practical application. According to Nemufulwi et al. [250], Compared with n-type SMOs, p-type SMOs demonstrate
the sensing response towards acetone of ­ZnFe 2O 4 was several advantages such as lower humidity dependence and
improved by modifying it with Au, in terms of high response good selective oxidation ability towards various VOCs [257,
and selectivity in Fig. 18b. The XPS and photoluminescence 258]. Since the formation of the space charge layer of the
(PL) results demonstrated that Au decorated ­ZnFe2O4 nano- hole-accumulation space in p-type SMOs is not limited by
structures have a high defect concentration, which promote the free carrier concentration, p-type SMOs also have the
oxygen chemical absorption. The as-prepared Au-ZnFe2O4 excellent ability to chemisorb high concentration of oxy-
sensor have a good application prospect in the food industry. gen [259]. ­Co3O4 is a typical p-type SMO material with
What’s more, TEA is an explosive gas that can irritate skin, cubic spinel structure, whose surface could adsorb more
eyes, and respiratory system in concentrations higher than oxygen than other p-type SMOs [260]. Hsueh et al. [261]
10 ppm in air. Hence, Song et al. [251] prepared Au decahe- produced the MEMS-based Au NPs adsorbed ­Co3O4 NPs
drons (DHs)-modified porous F ­ e2O3 nanorods for TEA gas sensor through an ultrasonic wave grinding technology and
sensor, which exhibited low detection limit (~ 1 ppm) and a solution method for ­NO2 detection. The corresponding
high response at 40 °C towards 50 ppm TEA, as is shown MEMS device is shown in Fig. 18e. The prepared MEMS-
in Fig. 18c. The related sensing mechanism of Au-Fe2O3 based Au/Co3O4-NPs sensor has the highest response of

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 43 of 75 89

33% to 100 ppb ­NO2 and more excellent sensitivity towards diameter of 60 nm had the highest response to 1 ppm CO and
­NO2 than other gases (CO, ­NH3, ­SO2, ­CO2) at 136 °C (in ­NO2, which reveal more clearly that optimizing the size of
Fig. 18e). This study integrating Au/Co3O4-NPs materials Au NPs can obtain excellent sensing performance.
and MEMS technology into devices are suitable to wearable
applications and have promisingly used for sensing networks
in the IoT. 3.3.5 Au‑Decorated Heterostructured SMOs‑Based Gas
In addition, Lee et al. [262] investigated the influence of Sensors
the Au NP size on gas sensing properties of p-CuO nanow-
ires. The Au NPs functionalized CuO nanowires were real- Using different SMOs to construct heterogeneous structures
ized by heat treatment of the Au layer grown by sputtering, has become a favorable candidate for the preparation of
as shown in Fig. 18f. The responses to CO and ­NO2 of Au high-performance gas sensors [263, 264]. Besides, through
modified CuO nanowires with various Au-NP diameters is the decoration of Au NPs on heterostructures, the obtained
shown in Fig. 18g. The Au-CuO nanowires with an average sensing materials can achieve superior sensing performance.

Fig. 19  a Sensor device diagram of MOFs derived Au@Cr2O3-In2O3. Reproduced with permission from Ref. [265]. Copyright 2022, Elsevier.
b Schematic diagram of MEMS device and sensing mechanism. Reproduced with permission from Ref. [266]. Copyright 2019, Elsevier. c SEM
image of the Au-ZnO/In2O3 heterostructures. Reproduced with permission from Ref. [267]. Copyright 2017, Elsevier. d Comparative histograms
of five types of nanowires responses to CO at 300 °C. Reproduced with permission from Ref. [268]. Copyright 2017, Elsevier. e Response
curves of S­ nO2, ZnO/SnO2, and Au@ZnO/SnO2 sensors to different concentrations of TEA at 300 °C. Reproduced with permission from Ref.
[269]. Copyright 2018, Elsevier. f Spillover effect of Au NPs and the charge transfer process between Au and ­TiO2. Reproduced with permission
from Ref. [271]. Copyright 2021, Royal Society of Chemistry. g Schematic diagram of Au-decorated S ­ nO2-ZnO nanowires sensor with/without
self-heating. Reproduced with permission from Ref. [272]. Copyright 2018, Elsevier

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89 Page 44 of 75 Nano-Micro Lett. (2023) 15:89

In terms of research on Au-modified anisotype hetero- pulsed laser deposition (PLD) method were employed to
junction, in order to realize the trace detection of VOCs, synthesize uniform ZnO/SnO 2 nanosheets in-situ grew
Wu et al. fabricated a sensor based on MOFs derived Au@ on the ­A l 2O 3 tubes [269]. The Au NPs modification on
Cr 2O 3-In 2O 3 nanorods, as is depicted in Fig. 19a. The ZnO/SnO2 nanosheets was realized through a direct cur-
Au@Cr2O3-In2O3 sensor enabled ppb-level detection of rent (DC)-sputtering process. As shown in Fig. 19e, the
isoprene, ethanol, and HCHO with concentrations of 50, synthesized Au@ZnO/SnO 2 Nanosheets showed promi-
200, and 200 ppb, respectively. Meanwhile, the sensor dis- nent sensing response of 115 towards 100 ppm TEA at
played a superior response to other nonvolatile respiratory 300 °C, which was about 20 times stronger than that of
biomarkers of, CO, ­H2, ­NO2, and ­NH3. Remarkably, the the pure ­S nO 2 nanosheets. In addition, Xu et al. also
sensor had good long-term stability even at high humidity. fabricated TEA sensors from Au NPs functionalized
The results reveal that the heterojunction of C ­ r2O3-In2O3 ­S nO 2/α-Fe 2O 3 core–shell nanoneedles on ­A l 2O 3 tubes.
and electron sensitization of Au synthetically improve the According to Xu et al. [270], the Au@SnO 2 /α-Fe 2 O 3
gas sensing properties. The as-prepared Au@Cr2O3-In2O3 nanoneedles exhibited excellent gas sensing perfor-
nanorods can be a significant candidate for the breath dis- mance, such as superior selectivity to TEA and linearity
eases monitoring [265]. Besides, Wang et al. explored the (R = 0.9975) of sensing properties than of pristine ­S nO 2
potential of MEMS compatible heterostructure manufactur- and ­S nO 2/α-Fe 2O 3 sensors. The gas sensing mechanism
ing methods to produce wafer-level gas sensors. Specifi- of the above two TEA sensors with different Au NPs
cally, they prepared Au NPs functionalized ­SnO2-NiO thin modified heterostructures can be explained as Schottky
films using magnetron sputtering and self-assembly tech- contact between Au and shell layer, as well as the for-
nique for N ­ O2 gas detection. The MEMS device is shown mation of n–n heterojunction. Such TEA sensors can be
in Fig. 19b, with interdigitated Au electrodes fabricated on significant candidates to realize an accurate detection
Si/Si3N4 substrates by lithographic techniques. The sensor of TEA in food industries, chemical, biomedical, and
exhibited a low limit of detection (50 ppb), high sensing our daily life.
response of 185 towards 5 ppm ­NO2, low sensor-to-sensor UV photoactivation can perform to reduce the operat-
variation of < 15%, as well as good stability and selectivity. ing temperature of SMO-based gas sensors. For example,
The in-situ ­NO2 detection achieved by the Au NPs func- Kwon et al. [271] prepared Au NPs decorated ZnO/TiO2
tionalized ­SnO2-NiO thin films sensor can be used to assess core–shell nanorods for N ­ O2 gas detection. The fabricated
air quality [266]. ZnO/TiO2 nanorods decorated with Au NPs demonstrated
Among numerous Au-decorated isotype heterojunc- 9 times higher gas sensitivity and shorter response/recov-
tions, Wang et al. [267] synthesized belt-tooth shape Au ery time than ZnO nanorods based sensors. The enhanced
NPs functionalized ZnO/In 2 O 3 nano-heterostructures ­NO2 sensing performance is attributed to both the forma-
via a CVD process and sputtering method (Fig. 19c), tion of ZnO/TiO 2 heterojunction and the catalytic sen-
which displayed superior gas sensing performance for sitization effect of Au NPs. Under UV light irradiation,
­C 2H 2 at a low working temperature of 90 °C. Besides, the decorated Au NPs will absorb the light produced by
the ­C 2 H 2 sensor manifested faster response, greater UV-LED photo-activated ZnO and ­TiO2 defect layer, and
selectivity, and good long-term stability in 30 days. transfer the electrons remaining in the defect layer to the
The small size Au NPs as catalysts can be beneficial conduction band due to localized surface plasmon reso-
to promote the ­C 2 H 2 gas sensing response. In addi- nance (LSPR) effect, so as to increase the number of high-
tion, ultra-sensitive CO sensors based on Au NPs func- energy electrons (Fig. 19f). According to Kim et al. [272],
tionalized ­S nO 2 -ZnO core–shell nanowires have been a self-heating CO gas sensor composed of Au-decorated
achieved by Kim et al. [268]. Compared with other ­SnO2-ZnO core–shell nanowires was developed. As shown
nanowires sensors towards CO, the response of obtained in Fig. 19g, the temperature rise caused by Joule heating
sensor is extremely high at a low CO concentration of effect enhanced the sensor response at high applied volt-
100 ppb, which is shown in Fig. 19d. Another study age. The CO sensor not only demonstrated excellent selec-
on Au modification of ZnO and ­S nO 2 heterostructures tivity without the external heater, but also had extremely
by Zhai et al., a low-cost hydrothermal synthesis and low power consumption in the range of 0.81 nW-8.3 μW

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Nano-Micro Lett. (2023) 15:89 Page 45 of 75 89

Table 3  Summary of the reported Au-decorated SMOs-based gas sensors

Material Structure Synthesis Target gas O. T. (°C) Conc. (ppm) Response tres/trec LOD Refs.
method

ZnO Nanowires Hydrothermal Ethanol 380 100 33.6a 3/1 s 2 ppm [214]
ZnO Nanowires Hydrothermal Ethanol 200 50 151.86a 22/23 s 5 ppm [215]
ZnO Nanowires Hydrothermal H2 25 5000 470a 10/10 s 20 ppm [273]
ZnO Thick films Sputtering C2H2 325 25 5.8a 5 /320 s 3 ppb [216]
ZnO Hierarchical UV-assisted Ethanol 220 1000 323.69a – – [217]
nanostructure deposition
ZnO Nanosheets Hydrothermal Acetone 300 100 1012.6a – 0.2 ppm [209]
ZnO Nanosheets Hydrothermal Ethanol 300 60 35%b 15 s/– – [219]
ZnO Nanosheets Solvothermal Acetone 275 100 164a 3/5 s 5 ppm [274]
ZnO Nanofilms Thermal evapo- Methyl mercap- 250 0.05 4.99%b 134/368 s 50 ppb [203]
ration tan
ZnO Microspheres Impregnation CH4 250 100 4.16a – 1.83 ppm [275]
ZnO Nanoplates Hydrothermal Ethanol 300 200 45a 13 s/– 5 ppm [276]
ZnO Nanoflowers Hydrothermal Acetone 270 100 74.41a 5/3 s 5 ppm [221]
ZnO Nanoflowers Hydrothermal TEA 200 10 276a 20/216 s 0.17 ppb [277]
ZnO Nanoparticles Hydrothermal Ethanol 400 100 525a 3 s/– 1 ppm [220]
ZnO Nanoparticles Solvothermal Isoprene 350 1 1371a ~ 50/ ~ 5 s 6 ppb [278]
ZnO Nanospheres Photoreduction Ethanol 200 50 159a – 0.2 ppm [279]
SnO2 3D microstruc- Hydrothermal Ethanol 340 150 29.3a 5/10 s 5 ppm [225]
ture
SnO2 Nanosheets Hydrothermal CO 220 50 36.5a 1/4 s 1 ppm [224]
SnO2 Nanoflowers Hydrothermal CH4 120 500 8a – 5 ppm [226]
SnO2 Nanoflowers Self-reductive Ethanol 200 100 123a 3/6 s 1 ppm [210]
SnO2 Nanospheres Direct thermal TEA 50 5 5.16a ~ 30 s/– 0.11 ppm [41]
decomposition
SnO2 Nanowires Electron-beam Nitrobenzene 350 5 5a – 0.25 ppm [227]
evaporation Toluene 2.6a
Benzene 7.6a
SnO2 Nanorods Hydrothermal Xylene 279 50 7.9a 8/4 s 3 ppm [228]
SnO2 Nanoparticles In-situ reduction DMMP 320 0.034 1.22a – 34 ppb [229]
SnO2 Nanoparticles Hydrothermal N-butanol 240 50 251.23a 3/11 s 1 ppm [230]
SnO2 Nanofibers Hydrothermal NO2 22.4 5 42a – 6 ppb [231]
SnO2 Nanofibers Reduction N-butanol 340 300 667a 30/60 s – [280]
SnO2 Mesoporous Hydrothermal N-butyl alcohol 300 300 154a 50/35 s 10 ppm [281]
spheres
SnO2 Nanospheres Sol–gel process Ethanol 250 100 80a 16/53 s 1 ppm [223]
WO3 Nanofibers Hydrothermal N-butanol 250 10 63.6a 31/9 s 1 ppm [237]
WO3 Thin films Vacuum thermal HCHO 225 20 1303.5a 16/16 s 40 ppb [238]
evaporation
WO3 Thin films Sputtering NO2 150 1 96.0a 9/16 s 0.6 ppm [239]
WO3 Mesoporous Impregnation TMA 268 100 41.56a 1 s/- 5 ppm [240]
structure
WO3 Macroporous Spray pyrolysis Isoprene 275 0.1 11.3a 64/1204 s 0.2 ppb [241]
spheres
WO3 Hollow micro- Wet impregna- Toluene 340 10 6.7a 8/5 s 0.3 ppm [242]
spheres tion Xylene 8.5a 10/5 s
WO3 3D nanostruc- Sacrificial tem- Acetone 410 100 10.76a 7/8 s 100 ppb [243]
ture plate
WO3 Nanowires Sputtering H 2S 350 5 219a 2/20 min 0.17 ppb [244]

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89 Page 46 of 75 Nano-Micro Lett. (2023) 15:89

Table 3  (continued)
Material Structure Synthesis Target gas O. T. (°C) Conc. (ppm) Response tres/trec LOD Refs.
method

WO3 Nanoplates In-situ reduction H2S 50 10 220a > 200/ > 1000 s 0.5 ppm [232]
WO3 Thin films Spin-coating NO2 150 5 249a ~ 240/ ~ 50 s 28 ppt [233]
WO3 Nanowires Solvothermal N-butanol 250 100 147a 19/25 s 5 ppm [234]
Acetone 200 72a 17/24 s
WO3 Nanoplates Chemical reduc- NO 170 10 216a 24/26 s 0.5 ppm [235]
tion
WO3 Microspheres Hydrothermal NO2 50 5 15.6a ~ 50/ ~ 85 s 1 ppm [282]
WO3 Nanosheets Chemical reduc- NO2 175 5 212.3a 90/ ~ 110 s 50 ppb [283]
tion
MoO3 Nanobelts In-situ reduction 1-butylamine 240 100 ~ ­300a 23/388 s 1 ppm [248]
V2O5 Nanoflowers In-situ reduction 1-butylamine 250 100 7.3a 48/11 s 5 ppm [249]
α-Fe2O3 Nanorods One-pot polyol TEA 40 50 17a 12/8 s ~ 1 ppm [251]
reaction
ZnFe2O4 Nanostructures Microwave- Acetone 120 40 25a 3/13 s 2.5 ppm [250]
assisted hydro-
thermal
TiO2 Pecan-kernel- Precipitation Toluene 375 100 7.3a 4/5 s 10 ppm [252]
like nanostruc-
ture
TiO2 Nanoparticles Laser irradiation Ammonia 29 200 65a – – [253]
Acetaldehyde 115a
Benzene 55a
Co3O4 Nanoparticles Reduction NO2 136 0.1 35%b 84/68 s 10 ppb [261]
CuO Nanowires Sputtering CO 350 1 20%b – – [262]
NO2 300 61%b
Fe2O3 Nanorods Impregnation N-butanol 250 100 177a 126/49 s 5 ppm [284]
Cr2O3/In2O3 Nanorods Reduction Isoprene 180 1 6.4a 52/443 s 50 ppb [265]
Ethanol 10.6a 135/618 s 200 ppb
HCHO 4.3a – 200 ppb
SnO2/NiO Thin films Sputtering NO2 200 5 180a – 50 ppb [266]
ZnO/In2O3 Belt-tooth shape Sputtering C2H2 90 100 5a 8.5 s/– – [267]
SnO2/ZnO Nanowires Vapor–liquid– CO 300 0.1 26.6a – 100 ppb [268]
solid growth
ZnO/SnO2 Nanosheets Sputtering TEA 300 100 115a 7/30 s 2 ppm [269]
SnO2/α-Fe2O3 Nanoneedles Sputtering TEA 300 200 63a – 10 ppm [270]
ZnO/TiO2 Nanorods Hydrothermal NO2 RT 50 7.5a – 10 ppm [271]
WO3/SnO2 Nanofibers Hydrothermal Acetone 150 0.5 79.6a – 0.2 ppm [285]
ZnO/SnO2 Nanofibers Reduction H 2S 350 1 ~ ­75a 36/786 s 0.1 ppm [286]
SnO2/In2O3 Nanofibers Sputtering CO 200 50 29.2%b < 30/ < 30 s – [264]

O. T. operating temperature; Conc.: concentration; tres/trec response time/recovery time; LOD limit of detection
a
Response is defined as R
­ a/Rg or ­Rg/Ra, ­Ra: resistance of the sensor in air, ­Rg: resistance of the sensor exposed to target gas
b
Response is defined as ∆R/Ra × 100% or ∆R/Rg × 100%, ∆R: the change in resistance, which equals to |Ra–Rg|

at 1–20 V. This extremely low power sensor is a promis- idea for improving the gas sensing performance of hetero-
ing choice for integrated sensor arrays and wireless sensor structured gas sensors and promote the application in many
applications. In a word, Au NPs decoration provides an fields (Table 3).

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Nano-Micro Lett. (2023) 15:89 Page 47 of 75 89

3.4 Other Noble Metal‑Decorated SMOs‑Based Gas and abundant surface oxygen vacancies, the Ag-decorated
Sensors nanomaterials display strong catalytic activity compared
with pure nanomaterials and high photocatalytic efficiency
3.4.1 Ag‑Decorated SMOs‑Based Gas Sensors applied in light-assisted gas sensors. Wang et al. [299] fabri-
­ nO2-reduced graphene oxide gas sensor decorated
cated the S
Ag, as a relatively cheap metal compared with other noble with Ag NPs through a two-step wet-chemical method, and
metals, exhibits unique advantage in gas sensing perfor- the as-prepared material displayed good N ­ O2 detection abil-
mance because of its high solubility, larger size of ionic, ity operating at RT. This work also showed that decorating
and minimum orbital energy [287]. Ag NPs decoration Ag NPs was an efficient strategy to shorten the response and
could promote the sensitivity of the SMOs-based gas sen- recovery time. Dong et al. [300] proposed an Ag-decorated
sor, decrease the working temperature, and shorten the ­In2O3/ZnO gas sensor via a nonaqueous route. The results
response/ recovery time due to the unique catalytic activity exhibited that functionalizing Ag NPs with a reasonable Ag
of Ag NPs [288]. By decorating Ag NPs on SMOs, more NPs concentration of 3 wt% could enhance the response
active sites were provided for adsorbed oxygen ions contrib- about 842.9 towards 2000 ppm HCHO at 300 °C. The het-
uting to more efficient electron transfer in gas sensing appli- erostructure between ­In2O3 and ZnO and the influence of Ag
cations. The adsorption activation energies of gases were NPs decoration resulted in the excellent gas sensing prop-
reduced by decorating Ag NPs, and the active surface sites erties. At present, many novel Ag-decorated nanomaterials
generated by Ag NPs accelerated the adsorption of the gas have been synthesized to promote the gas sensing behavior
molecule, which promoted the gas sensing properties [289, due to their catalytic ability as well as the synergic interac-
290]. Moreover, the Ag NPs decorated on the SMOs could tion. However, the traditional Ag-SMOs-based sensors suffer
catalyze the dissociation of the gas molecules and promote from high operating temperature, which required the sensors
the surface reaction. On the basis of the chemical sensitiza- to work under a specific temperature. Fortunately, the light
tion effect, the Ag NPs served as potential sites for the oxy- wavelength makes many electrons accumulate at the sur-
gen molecules which adsorbed or desorbed on the materials face of the nanomaterials and further increase the surface
[291]. Particularly, the electronic sensitization was deter- adsorbed oxygen. Therefore, the light-assisted gas sensor
mined by the existence of a potential barrier between the was potential to detect the target gases at the RT. Typically,
SMOs and the Ag NPs. The different Fermi levels between some studies focused on the light-assisted Ag-decorated
the SMO material and Ag NPs lead to the accumulation or SMOs-based sensor for promoting the gas sensing behav-
depletion of charge carriers [292]. In conclusion, decorat- ior. Among them, ZnO-based gas sensors have accounted for
ing Ag NPs on SMOs is a potential strategy for enhancing much of this contribution. Zhang et al. [301] fabricated the
gas sensing behavior. The Ag-decorated gas sensors were Ag-loaded ZnO sensor through a modified polymer-network
demonstrated to have excellent sensing behavior towards gel method. The TEM image exhibited in Fig. 20a showed
many kinds of target gases in the current studies. According that an Ag NP was well decorated on the ZnO NP, which
to reported literatures, the Ag-decorated gas sensors were improved the sensing behavior due to its synergistic effect.
most extensively applied to detect ethanol, HCHO, and ­NO2. The as-prepared Ag-decorated ZnO sensor displayed strong
Some strategies were developed to enhance the perfor- and stable response signals even at a very low ­NO2 concen-
mance of the Ag-decorated SMOs-based gas sensors, such tration of 500 ppb. The response of the Ag-decorated ZnO
as designing special nanostructures, increasing surface sensor towards 500 ppb N ­ O2 was ~ 0.6. In this case, when
defects, constructing heterostructures, and introducing changing the LED light sources, the maximum response
light illumination. Different morphologies of Ag-decorated can be acquired. The results revealed that the Ag-decorated
SMOs materials such as nanoparticles [293], nanorods ZnO sensor showed the highest response, remarkable sta-
[294], nanofibers [295], nanowires [42], nanosheets [296], bility, and excellent selectivity with the blue-green LED
microspheres [297], and nanoflowers [298], were studied for (470 nm, 75 mW c­ m−2). Zhang et al. [302] also synthesized
the enhancement of gas sensing properties with high sensi- a light-activated Ag-decorated ZnO sensors for ­NO2 detec-
tivity, lower operation temperatures, lower detection limit, tion. In this case, Ag decoration could enhance the visible-
and remarkable selectivity. Owing to uniform distribution light-driven catalytic performances of ZnO nanocatalysts.

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89 Page 48 of 75 Nano-Micro Lett. (2023) 15:89

Fig. 20  a TEM image of a single Ag NP decorated on a ZnO NP. Reproduced with permission from Ref. [301]. Copyright 2018, Elsevier.
b Schematic of the gas-testing measurements of the Ag-decorated ZnO NPs gas sensor with UV and optimized red irradiation. Reproduced
with permission from Ref. [303]. Copyright 2020, Elsevier. c Preparation process of the Ag-decorated ­SnO2 nanowires network gas sensor.
Reproduced with permission from Ref. [42]. Copyright 2011, American Chemical Society. d TEM image of the Ag-ZnO/In2O3 heterojunction
nanofiber. e Selectivity of the Ag-ZnO/In2O3 heterojunction nanofibers gas sensor towards various target gases. Reproduced with permission
from Ref. [305]. Copyright 2021, Elsevier. f Photograph of the Ag-decorated ZnO flexible gas sensor. Reproduced with permission from Ref.
[306]. Copyright 2016, Elsevier. g Linearity of the response of the Ag-decorated ­SnO2 nanosheets sensor and the gas concentration. Reproduced
with permission from Ref. [307]. Copyright 2022, Elsevier. h Sensing mechanism of the 3D Ag-ZnO microspheres sensor with the help of the
Ag NPs decoration. Reproduced with permission from Ref. [309]. Copyright 2018, Elsevier

Moreover, the gas sensing performance degraded slightly Figure 20b exhibited the gas-testing equipment for the Ag-
under visible light irradiation. Dilova et al. [303] formed decorated ZnO NPs gas senor under light irradiation.
Ag-ZnO NPs gas sensor via the PLD method. The Ag NPs In addition to the 0D nanostructure materials mentioned
decoration on the ZnO nanostructure enhanced the response above, the 1D materials such as nanowires, nanofibers,
of sensors and shortened the response/recovery time. The nanorods, and nanotubes have drawn attention from many
outcomes revealed that UV and optimized red irradiation researches. Zhou et al. [304] synthesized Ag modified ZnO
promoted the sensing performance of the Ag-decorated ZnO nanorods-based ­C2H2 gas sensor through a solvothermal
NPs gas sensor towards CO, while inhibiting the response method. Ag NPs decoration could greatly promote the gas
towards the target gases like ­NH3, ethanol, and acetone. sensing behavior compared with the pristine ZnO nanorods.

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 49 of 75 89

The high response of the Ag-decorated ZnO nanorods sen- nanosheets gas sensor was declined by 8.8% while the pristine
sor towards 100 ppm ­C2H2 was 539 (Ra/Rg). In addition, the ­WO3 sensor was declined by 31.6%, which showed excellent
operating temperature of the Ag-decorated ZnO nanorods long-term stability. Zhang et al. [307] reported an Ag-decorated
sensors was decreased to 175 °C, and the response of the ­SnO2 nanosheets gas sensor based on a novel porous nano-
sensor was increased by 33 times, which exhibited the high- structure like fish-scale via a one-step method. Since a reason-
est value among most of sensors in detecting. Hwang et al. able noble metal concentration was crucial to promote the gas
[42] fabricated high-response Ag-decorated ­SnO2 nanowires sensing behavior, the concentration of the Ag NPs decorated
ethanol gas sensor. In this case, Ag NPs were decorated on on the ­SnO2 nanosheets was investigated varying from 1 to 3
the ­SnO2 nanowire via the e-beam evaporation. The prepara- at% in this case. As shown in Fig. 20g, the 2%-Ag-decorated
tion process of Ag-decorated S ­ nO2 nanowire gas sensors was ­SnO2 nanosheets sensor displayed the highest response value
illustrated in the Fig. 20c. The S ­ nO2 nanowire sensor modi- when exposed to the same concentration TEA compared with 1
fied by Ag NPs exhibited a 3.7-fold enhancement towards and 3%-Ag-decorated ­SnO2 nanosheets sensors. The outcomes
100 ppm ethanol compared to the pristine ­SnO2 nanowires revealed that the introduction of Ag NPs could greatly promote
sensor. Furthermore, the formation of heterojunction structure the adsorption of gas molecules, which could further promote
was extensively employed to adsorb more oxygen molecules the gas sensing behavior.
and target gases. Liu et al. [305] proposed a high-sensitivity Besides, Ag NPs could also be combined with the 3D
Ag-decorated ZnO/In2O3 nanofibers through an electrospin- hierarchical nanostructures, which promoted the gas sens-
ning method. In Fig. 20d, the morphological feature of the ing properties because that they helped to adsorb the gas
Ag-ZnO/In2O3 nanofibers was exhibited. With the existence molecule and promote the electron exchange between the
of multi-level heterojunctions, the high response of the as- Ag-decorated SMOs and the target gases. Zhang et al. [308]
prepared sensor was ~ 186 towards 100 ppm HCHO at 260 °C, reported the 3D Ag-ZnFe2O4 hollow sphere through a sim-
which headed the list in HCHO gas sensor research. Beyond ple hydrothermal method. The as-prepared Ag-decorated
that, the as-prepared gas sensor could also detect the HCHO ­ZnFe2O4 hollow sphere micromaterials with high specific
even at a low concentration of 9 ppb. The results shown in surface area provided a large number of adsorption sites.
Fig. 20e obviously displayed that the Ag NPs decoration Shen et al. [309] fabricated Ag-loaded ZnO microspheres
could vastly enhance the gas sensing behavior of the sensor gas sensor through a precipitation method for TEA detec-
towards various gases compared to the pristine ZnO nanofib- tion. The high response to 100 ppm TEA at 183.5 °C was
ers and the ZnO/In2O3 heterojunction nanofibers. Iftekhar 6043, which was 14.8-fold higher than the pristine ZnO sen-
Uddin et al. [306] proposed a novel flexible sensor based on sor. The mechanism of the 3D Ag-loaded porous ZnO micro-
Ag-decorated ZnO nanorods. The as-prepared flexible sensor spheres sensor was displayed in Fig. 20h. Ag NPs decoration
exhibited a high response of 27.2 towards 1000 ppm C ­ 2H2 at could promote the absorption of the oxygen species because
200 °C. As shown in Fig. 20f, the response of the Ag-loaded of the spillover effect for Ag NPs. Ag NPs providing many
nanorod flexible gas sensor degraded by a tiny amount ~ 2.1% active negative oxygen ions spill on to ZnO microspheres,
at a curvature angle of 90°. The successful immobilization of which trap electrons from conduction band of ZnO, widen
tiny sized Ag NPs and the remarkable flexibility of the Ag- the electron depletion layer thickness, and further increase
loaded vertical ZnO nanorods gas sensor maintained stable the resistance of the sensor.
­C2H2 sensing behavior even under the extreme bending stress.
Recently, the morphologies of the nanomaterials formed by
well-controlled synthesis processes demonstrated that both the 3.4.2 Ru‑Decorated SMOs‑Based Gas Sensors
2D nanostructure and Ag NPs decoration could greatly promote
the gas sensing behavior of SMO materials as well. Yu et al. Ru, as a catalyst metal, has been intentionally introduced for
[25] synthesized an Ag NPs-modified 2D W ­ O3 nanosheets gas certain gas sensing, which improves the sensing behaviors
sensor for HCHO detection. The outcomes revealed that the Ag especially the selectivity as well as time factors. Birajdar
NPs modification made the sensors shorten approximately 3 et al. [310] synthesized layer-structured ­V2O5 microparticles
times of the response time (5 s) and 2 times of the recovery time through a hydrothermal strategy, followed by a facile wet
(10 s). After two months, the response of the Ag-modified ­WO3 chemical route to modify Ru NPs. Figure 21a showed the

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89 Page 50 of 75 Nano-Micro Lett. (2023) 15:89

Fig. 21  a Image of a typical particle in which V

­ 2O5 microparticles surrounded by Ru NPs. Reproduced with permission from Ref. [310]. Copy-
right 2019, Royal Society of Chemistry. b Image of the nanostructure decorated with C­ o3O4 NPs and Ru NPs. Reproduced with permission from
Ref. [311]. Copyright 2018, Wiley–VCH. c Relationship between the response of Ru decorated W ­ O3 nanoparticle sensor and acetone gas con-
centrations. Reproduced with permission from Ref. [312]. Copyright 2018, Elsevier. d 3D diagram of pure and Ru-decorated ­WO3 nanowires.
Reproduced with permission from Ref. [313]. Copyright 2021, Royal Society of Chemistry. e Response of W ­ O3 NRs decorated with different
metals including Nb, Au, Ru and Ni. Reproduced with permission from Ref. [314]. Copyright 2015, Elsevier. f Mechanism of pristine ­WO3 and
Ru-decorated ­WO3 sensors. Reproduced with permission from Ref. [316]. Copyright 2018, Springer Nature. g-h SEM images of the MEMS-
based sensor with Ru-loaded-Al2O3/ZnO and unload sensing material. Reproduced with permission from Ref. [317]. Copyright 2018, Elsevier

morphology of a typical V
­ 2O5 particle decorated by Ru NPs. amount, which exhibited the highest response of 40 towards
The response of the as-prepared gas sensor was 4% towards 1000 ppm ethanol at 350 °C. The Ru NPs serve as the cat-
130 ppm ­NH3 at RT. Compared with other RT gas sensors, alyst to promote the oxidation rate of the ethanol around
the as-prepared sensor has short response/recovery time of Ru sites. Besides, the product of the reaction will spill over
0.52/9.39 s. The presence of the ­RuO2/Ru clusters makes to the surface of the adjacent ­Co3O4, which results to the
the water molecules dissociate less, and the greater sensi- improvement of the gas sensitivity. Li et al. [312] proposed
tivity is obtained. Kruefu et al. [311] proposed Ru-loaded ­WO3 NPs based on lamellar structure via an acidification
p-type ­Co3O4 NPs gas sensor through the precipitation and method, followed by a modified impregnation method to
impregnation methods. As shown in Fig. 21b, the Ru NPs decorate the Ru NPs. As shown in Fig. 21c, the Ru-dec-
were successfully loaded on the C ­ o3O4 NPs. Comparing orated ­WO3 NPs sensors still have relatively sensitive sig-
the ­Co3O4 NPs sensors decorated with different amount Ru nals even toward the low acetone concentration of 0.5 ppm.
NPs, the 0.25 wt%Ru decoration was regarded as the optimal For instance, the response of the 1 wt% Ru-decorated ­WO3

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 51 of 75 89

sensor towards 0.5 ppm acetone was 7.3, which was 5 times ­ uO2 and ­WO3 jointly determined the improvement of gas
R
higher than the pristine W­ O3 sensor. It was revealed that Ru sensitivity. Thus, Ru NPs decoration was a valid strategy to
NPs served as the catalyst to promote the activity of surface promote the sensing behavior of the SMOs-based sensor.
lattice oxygens due to the sensitization effect, which reacted Qiu et al. [316] synthesized ­WO3 nanosheets through an
with acetone and decrease the resistance of the sensor. acidification method, followed by a conventional impreg-
In addition to the nanoparticle structures and powder nation process to decorate the Ru catalyst. The response
compounds described above, the 1D nanostructure was of the Ru-decorated W ­ O3 nanosheets gas sensor was ~ 18
extensively applied for the enhancement of gas sensing towards 20 ppm N ­ H3 at 300 °C, which was approximately
properties. Li et al. [313] reported Ru-decorated 1D ­WO3 twice that of the pure W­ O3 nanosheets. The Ru NPs deco-
nanowires gas sensor via an electrospinning method. As ration could promote the surface reaction due to the cata-
shown in Fig. 21d, the Ru NPs were decorated onto ­WO3 lytic activity of Ru NPs. As shown in Fig. 21f, the catalytic
nanowires as expected. The ­WO3 nanowires decorated with effect of Ru NPs could make the ­NH3 more likely oxidize
4% Ru NPs exhibited the high response of ~ 120 towards into ­N2, which inhibited the adsorption of N ­ O2 molecule.
100 ppm ethanol, which was 47 times higher than the Moreover, ­RuO2 could interact with the surface of W ­ O 3,
pristine ­WO3 nanowires. Moreover, the as-prepared sen- and then form an additional depletion layer, which contrib-
sor could detect as low as 221 ppb ethanol. Beyond that, uted to the sensitization effect. Currently, the construction
the Ru-decorated W ­ O3 nanowires could also increase O ­ C, of heterojunctions has been widely applied to improve the
manifesting that more chemisorbed oxygen took part in the gas sensing properties because the interface states and the
surface reaction. The activation energy of the target gas was different energy band structures will change the carrier
reduced by the catalytic ability of ­RuO2, which could react concentration. Liu et al. [317] synthesized a Ru/Al2O3/
with the adsorbed oxygen. Kruefu et al. [314] synthesized ZnO sensor through the inkjet printing technology. In this
the Ru-functionalized ­WO3 nanorods via the hydrothermal case, the A­ l2O3 loaded with Ru NPs served as the catalyst,
and impregnation methods. The ultra-high response of the which was deposited onto the surface of ZnO nanosheets.
Ru-decorated ­WO3 nanorods gas sensor was ~ 192 towards The response of the Ru/Al2O3/ZnO nanosheets gas sensor
10 ppm ­H2S at 350 °C, with short response time of ~ 0.8 s. was ~ 65 towards 100 ppm S ­ O2 at 350 °C. The as-prepared
In addition, Ru-decorated W ­ O3 nanorods were more selec- Ru/Al2O3/ZnO nanosheets were loaded onto the MEMS
tive for ­H2S, compared with the pristine W­ O3 nanorods. As device, whose SEM image was exhibited in Fig. 21g–h.
shown in Fig. 21e, the Ru NPs decoration has higher catalyst With the MEMS device, the suspended structure could
selectivity towards H­ 2S than other metals such as Ni, Nb, improve the heat diffusion and maintain a consistent tem-
and Au. The Ru NPs could adsorb more oxygen species and perature with low power consumption.
­H2S molecules, which would spill over to react with oxygen
species on ­WO3 nanorods.
Moreover, 2D nanomaterials such as nanosheets deco- 3.4.3 Rh‑Decorated SMOs‑Based Gas Sensors
rated with Ru NPs were also currently employed to the
field of gas sensing. Wang et al. [315] fabricated the Ru- Rh, as a catalytically active transition metal, will form
decorated ­WO3 nanosheets gas sensor through a hydro- the metal–semiconductor contact between Rh NPs and
thermal method. In compared with the pristine W ­ O3 nanomaterials, which can change the carrier concentration
nanosheets sensor, the response of the 0.5 wt% Ru-deco- as well as oxygen vacancy and increase the chemisorbed
rated ­WO3 nanosheets sensor towards 100 ppm xylene was oxygen. Rh NPs could promote the gas sensing behavior
increased from 11 to 73, and the working temperature was because of its strong electron mobility and great catalytic
reduced from 375 to 280 °C. Moreover, the as-prepared property for gas interaction. Unlike other noble metals like
gas sensor was still sensitive towards the ultra-low con- Pt, Pd, Au, and Ag, Rh NPs is a catalytically active transi-
centration of 25 ppb. The outcome revealed that the sensor tion metal of V period [318]. In addition, the size of NPs
loaded with Ru NPs had better gas sensing performance will affect the gas sensing behavior. However, Rh displays
than that loaded with Au, Pt, and Pd NPs. The catalytic different gas sensing behavior compared to other noble
property of the Ru NPs and the heterojunction between metals. To be specific, the equilibration of the reaction

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89 Page 52 of 75 Nano-Micro Lett. (2023) 15:89

with oxygen was promoted through larger Pt NPs, while composite nanofibers exhibited in Fig. 22a demonstrated that
Rh was opposite [319]. To sum up, decorating Rh NPs the Rh NPs were decorated on the NiO nanofibers materials
was an efficient method to enhance the sensing behavior. successfully. The outcomes revealed that the response of the
Currently, the development of preparation technology lays Rh–decorated NiO nanofibers gas sensor working at 225 °C
a solid foundation for the development of metal modifica- towards 200 ppm acetone was 70.10, which was 37.9-fold
tion. The sensitization mechanism is not only related to the higher than the pristine NiO nanofibers sensor.
type of noble metal, but also related to the loading methods Besides, the GLAD technique has been extensively
[320]. How to decorate noble metals on the surface of nano- employed for the fabrication of Rh-decorated nanomaterials
materials efficiently and uniformly has become the focus of [322]. The morphology of Rh-decorated nanocolumnar struc-
many scholars in recent years. Over the years, the electro- tures was controlled through varying several deposition condi-
spinning technique has been proved to be an economic and tions [323]. Song et al. [44] fabricated a high sensing behav-
multifunctional method for mass production of 1D compos- ior acetone sensor based on the Ru-decorated ­WO3 nanorods
ite materials with high surface areas including nanofibers, gas sensor through the GLAD technique. When the glancing
nanotubes, and so on. Gao et al. [321] synthesized the Rh- angle was set to 80°, the vertical-ordered Rh-decorated W­ O3
decorated NiO nanofibers gas sensor through a facile elec- nanorods were synthesized successfully, as shown in Fig. 22b.
trospinning technique. The TEM image of 5 mol% Rh-NiO Decorating Rh NPs could enhance the sensing performance

Fig. 22  a TEM images of 5 mol% Rh-decorated NiO composite nanofibers. Reproduced with permission from Ref. [321]. Copyright 2021,
Springer Nature. b The structure diagram of Rh-modified ­WO3 nanorods synthesized by the GLAD method. c The selectivity of the Rh-modified
­WO3 nanorods gas sensor towards various target gases (5 ppm) at 300 °C. Reproduced with permission from Ref. [44]. Copyright 2019, Ameri-
can Chemical Society. d Schematic synthesis of Rh-decorated ZnO nanoflowers through ALD method. e The sensing mechanism of Rh-deco-
rated ZnO nanoflowers in air and in TMA. Reproduced with permission from Ref. [324]. Copyright 2022, Elsevier

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 53 of 75 89

through changing the morphological and producing the elec- the gas molecules, and increasing chemisorbed oxygen. In
tronic sensitization as well as the chemical sensitization. As comparison, bimetallic nanocrystals can not only combine
shown in Fig. 22c, the high response value of the as-prepared two monometallic properties but also promote the physical
Rh-decorated ­WO3 nanorods was ~ 80 and exhibited strong and chemical characteristics owing to the synergistic effect
selective detection towards acetone. between noble metals, which exhibits greater catalytic per-
Nevertheless, achieving precisely controlled growth still formance than the single metal decoration. Besides, the elec-
remains difficult, and Rh NPs with the nanostructure tend to tronic structure and geometric configuration on the surface
agglomerate, which affects their dispersity and utilization. For- of bimetal particles can be changed by controlling the com-
tunately, the presence of the ALD technique could overcome position of the alloy [342]. Therefore, decorating bimetals
the difficulty mentioned above. The ALD was a high control- was regarded as an effective strategy to further enhance the
lable technique, which generated Rh-decorated nanomaterials gas sensing performance.
at the atomic level with highly conformal and uniform. When The different nanostructure kinds of the bimetallic nano-
using ALD technique to prepare Rh-decorated nanomaterials, catalysts were crucial to enhance the gas sensing perfor-
the substrate was separately exposed to the precursor mate- mance. On the basis of the atomic ordering arrangement and
rial, and an insert gas was used to purge between the precursor construction of both two noble metals, diverse bimetallic
pulses. The unique property of depositing single monolayer nanostructures can be divided into three main types: alloy
makes it possible to control the deposition rate and form the structures, core–shell structures, and heterostructures.
film composition. Multi-layer nanocomposites could also be
deposited controllably through changing different precursor
materials. With these advantages, ALD became a powerful tool 4.1 Alloy Structure Bimetal Decoration
for depositing the Rh NPs onto the surface of the nanomateri-
als. Li et al. [324] reported a highly sensitive Rh-decorated ZnO Typically, the alloy structure which contains inter-metallic
flower-like nanostructures for TMA detection through the ALD and solid solution is most widely used in chemiresistive
technique. Figure 22d exhibited the synthesis of the Rh-deco- gas sensor. Zheng et al. [343] prepared AuPd/WO3 mate-
rated ZnO flower-like nanostructure. Specially, ALD technique rials with different content of bimetallic AuPd alloy NPs
has unique advantages to precisely control the Rh NPs depos- on the surface of three-dimensional ordered macroporous
ited on the ZnO materials through changing the ALD growth (3DOM) ­WO3 and systematically investigated the effect
cycles. The Rh/ZnO sensor with the 10 cycle Rh loaded by of Au/Pd molar ratio on gas sensing properties. As shown
ALD showed that the best response to 10 ppm TMA at 180 °C in Fig. 23a, on the one hand, bimetallic AuPd alloy NP-
was 11.3, which was threefold higher than that of pristine ZnO. decorated 3DOM ­WO3 exhibited higher acetone responses
The sensing mechanisms of ZnO and Rh/ZnO in air and in than monometallic-decorated one including AuW and PdW
TMA were exhibited in Fig. 22e. The Rh NPs decoration could sensors. Meanwhile, the highest acetone responses were
provide the oxygen molecules with more effective adsorption observed from the AuPdW sensor with the Au/Pd molar
site, which increased the oxygen adsorption. The electron ratio of 1:1, revealing the optimum alloy ratio. In result, the
depletion layer will become thicker, resulting the increase of the AuPdW sensor with best Au/Pd molar ratio presented high
resistance. In addition, the Rh NPs will decompose the TMA response to trace acetone with fast response/recovery behav-
molecules into the high-activity radicals, facilitating the reac- iors. Meanwhile, the AuPdW sensor had great selectivity
tion between the TMA and the oxygen adsorption (Table 4). and reproducibility. More importantly, the responses of the
sensor towards acetone exhibited no obvious decline over
4 Bimetal‑Decorated SMOs‑Based Gas 8 weeks, indicating a good long-term stability. Moreover,
Sensors Li et al. [344] realized the decoration of Pd, Au and PdAu
NPs on S ­ nO2 nanosheets by in-situ reduction. The as-syn-
As discussed previously, the single noble metal has great thesized PdAu/SnO2 sensor displayed excellent gas perfor-
enhancement to improve the gas sensitive performance like mance, which can effectively detect acetone and HCHO as
providing more active sites, promoting the dissociation of low as 45 and 30 ppb. The possible gas sensing mechanisms

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89 Page 54 of 75 Nano-Micro Lett. (2023) 15:89

Table 4  Summary of the reported other noble metal-decorated SMOs-based gas sensors
Materials Structure Synthesis method Target gas O. T. (°C) Conc. (ppm) Response tres/trec LOD Refs.

Ag/ZnO Nanorods Photochemical Ethanol 280 50 34.8a – 1 ppm [325]

Ag/ZnO Nanoparticles Polymer-network gel NO2 25 5 ~ 4.2a ~ 150/180 s 0.5 ppm [301]
Ag/ZnO Microspheres Photochemical Ethanol 350 100 66.9a < 7 s/– 500 ppb [297]
Ag/ZnO Nanosheets Solvent reduction Ethanol 300 0.1 ~ 48%b 20 /25 s 1 ppb [296]
Ag/ZnO Microspheres Precipitation TEA 183.5 100 6043a 1 /60 s 1 ppm [309]
Ag/ZnO Nanocages Calcination of MOFs Ethanol 250 100 84.6a 510 s 23.1 ppb [326]
Ag/ZnO Nanoflowers Hydrothermal Ethanol 300 200 268a 2 /3 s 0.0178 ppm [298]
Ag/ZnO Nanocomposite PLD CO 25 40 ~ 150%b – 1 ppm [303]
Ag/ZnO Nanocomposite Polymer-network gel NO2 25 5 ~ 3.4a ~ 75/160 s 1 ppm [327]
Ag/ZnO Nanoparticles Polymer-network gel NO2 25 5 ~ 1.5a ~ 180/125 s 1 ppm [302]
Ag/ZnO Nanorods Solvothermal C2H2 250 100 255a 6/200 s 1 ppm [304]
Ag/ZnO Microspheres Solvothermal CO 130 100 ~ ­27a 2/25 s 44 ppb [288]
Ag/ZnO Nanoparticles Gas-phase physical Ethanol 250 100 ~ ­145a – 10 ppb [328]
vapor deposition
Ag/SnO2 Nanowires Electron-beam evapo- Ethanol 450 25 228.1a ~ 0.4/80 s 5 ppm [42]
ration
Ag/SnO2 Nanocomposite Wet-chemical NO2 25 5 2.17a 49/339 s 1 ppm [299]
Ag/SnO2 Nanosheets Hydrothermal TEA 170 100 1700a 6/15 s 10 ppm [307]
Ag/SnO2 Nanowires Sputtering H2S 25 0.5 21.2a 18/980 s 0.25 ppm [329]
Ag/WO3 Mesoporous Impregnating NO2 80 1 45a 303/147 s 100 ppb [330]
Ag/WO3 Nanocomposite Solution NO 250 40 38.3a – – [331]
Ag/WO3 Nanoplates Photo-induced reducing NO 170 5 ~ ­190a ~ 5/100 s 0.5 ppm [332]
Ag/WO3 Nanosheets Magnetic stirring HCHO 300 100 20.83a 5/5 s 10 ppm [333]
Ag/Fe2O3 Nanoparticles Chemical coprecipita- H2S 160 100 220a 42/26 s 50 ppm [293]
tion
Ag/In2O3 Nanoflowers Chemical reduction HCHO 200 20 ~ ­11a 0.9/14 s 5 ppm [334]
Ag/ZnFe2O4 Microspheres Hydrothermal Acetone 175 100 33.4a 17/148 s 0.8 ppm [308]
Ag/Bi2O3 Nanocomposite Precipitation Toluene 25 50 89.21a ~ 80/320 s 10 ppm [335]
Ag/ZnCo2O4 Microspheres Solution Acetone 220 20 12a 4/20 s 0.25 ppm [336]
Ag/CuO Nanocomposite Hydrothermal NO2 ~ 22 20 67.2%b 35/900 s 1 ppm [289]
Ag/VO2 Nanorods Stirring and ultrasonic NO2 25 5 2.54a 104/306 s 2.54 ppm [294]
dispersion
Ag/ZnO/SnO2 Nanotubes Electrospinning HCHO 210 50 ~ ­100a 21/64 s 9 ppb [337]
Ag/In2O3/ZnO Nanocomposite Nonaqueous HCHO 300 1000 ~ ­300a 4/20 s 1 ppm [300]
Ag/ZnO/In2O3 Nanofibers Electrospinning and HCHO 260 100 186a 10/67 s 9 ppb [305]
calcination
Ru/WO3 Nanowires Electrospinning Ethanol 200 100 ~ ­120a 23/58 s 221 ppb [313]
Ru/Co3O4 Nanoparticles Precipitation/impregna- Ethanol 350 100 ~ ­30a 0.08 s/– 10 ppm [311]
tion/spin coating
Ru/WO3 Nanosheets Hydrothermal Xylene 375 100 73a – 25 ppb [315]
Ru/WO3 Nanosheets Impregnation H2 350 500 ~ ­100a – 100 ppm [338]
Ru/WO3 Nanoparticles Acidification/impreg- Acetone 300 0.5 6.4a – 0.5 ppm [312]
nation
Ru/WO3 Nanosheets Acidification/impreg- NH3 300 5 ~ ­8a – 3 ppm [316]
nation
Ru/WS2 Nanoflakes Lithium intercalation CO2 25 500 ~ ­17a 52/138 s 19 ppm [339]
Ru/V2O5 Microparticles Wet chemical NH3 30 10 4a 1.5/9.3 s 10 ppm [310]
Ru/WO3 Nanorods Hydrothermal/impreg- H2S 350 10 ∼192a ~ 0.8 s/11 min 0.2 ppm [314]
nation
Rh/ZnO Nanosheets ALD TMA 180 10 11.3a 63/106 s 55 ppb [334]

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Nano-Micro Lett. (2023) 15:89 Page 55 of 75 89

Table 4  (continued)
Materials Structure Synthesis method Target gas O. T. (°C) Conc. (ppm) Response tres/trec LOD Refs.

Rh/NiO Nanofibers Electrospinning Acetone 225 200 70.10a 134/222 s 0.25 ppm [321]
Rh/MWCNTs Nanotubes Spray method C6H6 25 0.5 ~ ­2a – 50 ppb [340]
Rh/WO3 Nanorods GLAD Acetone 300 5 ~ ­70a 11 s/– 0.2 ppm [44]
Rh/MWCNTs Nanotubes CVD Toluene 25 6 ~ ­7a 17/11 min 0.4 ppm [341]
Rh/SnO2 Thin films Spray pyrolysis Ozone 250 ~1 ~ ­20a – – [318]

O. T. operating temperature; Conc. concentration; tres/trec response time/recovery time; LOD limit of detection
a
Response is defined as R
­ a/Rg or ­Rg/Ra, ­Ra: resistance of the sensor in air, ­Rg: resistance of the sensor exposed to target gas
b
Response is defined as ∆R/Ra × 100% or ∆R/Rg × 100%, ∆R: the change in resistance, which equals to |Ra–Rg|

Fig. 23  a Dynamic response curves of AuyPdzW, AuW, PdW, and 3DOM W ­ O3 sensors to 2 ~ 100 ppm acetone at 300 °C. Reproduced with
permission from Ref. [343]. Copyright 2021, American Chemical Society. b Sensing mechanism diagram of Pd, Au, PdAu NPs decorated
­SnO2 NSs in acetone or formaldehyde ambience. Reproduced with permission from Ref. [344]. Copyright 2019, Elsevier. c Sensing response of
ZnO, ­Pd20Au80@ZnO, ­Pd35Au65@ZnO, and ­Pd50Au50@ZnO in the range of 5–100 ppm ­H2. Reproduced with permission from Ref. [62]. Copy-
right 2020, Royal Society of Chemistry. d HRTEM image of the AuPt-decorated ZnO nanowires. e The fabrication of the AuPt-decorated ZnO
nanowires. f Gas-sensing properties of the AuPt-decorated ZnO nanowires sensor. Reproduced with permission from Ref. [64]. Copyright 2022,
Elsevier. g Selectivity comparison for pure S
­ nO2, Au/SnO2, Pd/SnO2, and AuPd/SnO2 sensors toward 10 different interfering gases under a con-
centration of 10 ppm at 135 °C. Reproduced with permission from Ref. [47]. Copyright 2021, Elsevier. h Two reproductive cycles of Au/Pd@
ZNWs were exposed to N ­ O2 at 100 °C. Reproduced with permission from Ref. [59]. Copyright 2019, Elsevier

13
89 Page 56 of 75 Nano-Micro Lett. (2023) 15:89

of ­SnO2 nanosheets decorated with PdAu bimetallic NPs 4.2 Core–Shell Structure Bimetal Decoration
were studied in detail, whose schematic diagram is shown in
Fig. 23b. Compared with decorated with single Pd or Au, the In addition to the alloy structure, the core–shell nanostruc-
improved response of PdAu NPs decorated ­SnO2 nanosheets ture of bimetallic nanocrystals has recently attracted the
may be attributed to the synergistic effect of PdAu bimetallic attention of many researchers due to a potential barrier
NPs. The PdAu/SnO2 sensor can detect low concentration generated at the interface, promoting the chemisorbed oxy-
of acetone and has good anti-interference to biomarkers and gen. The core–shell nanostructure is regarded as an ordered
humidity in human breathing gas. Therefore, the prepared assembly structure, which is made up of a metal shell coated
sensor has an appealing application in HCHO and breath onto the other metal core through chemical bonds or other
acetone detection. Beyond that, the ZnO-based bimetal forces. Zhang et al. [345] employed the bimetallic Pd@Au
decorated SMO materials has made great contribution to core–shell nanoparticles (BNPs) to decorate W ­ 18O49 nanow-
the field of gas sensing The PdAu@ZnO core–shell nano- ires. The ­W18O49 nanowires/BNPs sensor had dual selec-
particles (CSNPs) were successfully synthesized by Le et al. tivity at different temperatures, which showed the response
[62]. In the preparation process of hydrothermal method, the of 7.8 to 1000 ppm C ­ H4 at 320 °C and response of 55.5 to
chemical composition of bimetallic PdAu nucleus was opti- 50 ppm ­H2S at 100 °C, respectively. This study is significant
mized by changing the reaction time to achieve the sensing for detecting coal mine gases and appealingly applied to
purpose. The sensing response of pristine ZnO and PdAual- ensure coal mine safety production. Moreover, Hassan et al.
loy@ZnO CSNPs in the range of 5–100 ppm H ­ 2 was shown [346] synthesized Pt/Pd bimetallic core–shell NP-decorated
in Fig. 23c. The P­ d35Au65@ZnO sensor exhibited superior ZnO nanorod clusters (Pt/Pd-ZnO NRs) through hydrother-
response of 80 to 100 ppm ­H2 at 300 °C. Furthermore, the mal method and PLD process. The Pt/Pd-ZnO NRs clusters
obtained sensor had outstanding selectivity towards H ­ 2 and displayed excellent selectivity among various gases. At the
faster response/recovery time, which can be ascribed to the same time, the as-prepared sensor displayed a response of
synergistic effects between Pd, Au, and ZnO. This work pro- 58% and quick response of 5 s to 10,000 ppm ­H2 at 100 °C.
vides a promising design for sensitive and quick sensors to In addition, Hassan et al. [347] also synthesized Pt/Pd
detect ­H2 leakage. Currently, the MEMS device was exten- bimetal decorated-vertical ZnO nanorods on the polyimide/
sively employed to provide gas sensors with stable tempera- polyethylene terephthalate (PI/PET) substrate for a flexible
ture condition and low power consumption. Liu et al. [64] ­H2 sensor. The dynamic resistance changes of Pt/Pd-ZnO
fabricated the AuPt-decorated ZnO nanowires gas sensor NRs with different bending angles was tested. It was found
based on MEMS devices for the H ­ 2S detection. As shown in that the deviation of the response values was less than 4%
Fig. 23d, the fringe spacing of the AuPt NPs were observed not obvious after the bending to 90 degrees. The Pt/Pd-ZnO
from the high-resolution TEM (HRTEM) images, which NRs with light weight and stable mechanical properties are
indicated that the Au and Pt NPs dissolved into each other expected to become an important component of flexible H ­ 2
and the metal atoms randomly mixed thoroughly. The fabri- sensors with fast response and great stability. Moreover, Liu
cation of the MEMS-based AuPt-decorated ZnO nanowires et al. [47] demonstrated the modulation of both reaction
gas sensor was exhibited in Fig. 23e. The AuPt-decorated kinetic process and electronic structure of the sensing sur-
ZnO nanowires were dropped onto the MEMS devices which faces through introducing bimetal alloy catalysts. The sensor
could provide the heating condition for the gas sensor with of AuPd alloys modified ­SnO2 showed great gas response of
low power consumption. As shown in Fig. 23f, the MEMS- 36.6 and significant selectivity towards dimethyl disulfide
based AuPt-decorated ZnO nanowires sensor exhibits the (DMDS) in Fig. 23g. The DFT calculations were used to
response value of 17.7 towards 20 ppm ­H2S at 300 °C, which confirm the surface adsorption enhancement of DMDS and
is 4.0 times higher than the pristine ZnO sensor. Therefore, charge transfer from AuPd alloy surface to S ­ nO2, which
decorating AuPt NPs could enhance the sensitivity and may be the main reason for DMDS gas sensing response
selectivity of the sensors due to the electronic and chemical enhancement. Li et al. [60] used self-assemblies to obtain
sensitization and the synergistic effect of the AuPt bimetal. the PdPt NPs-decorated ­SnO2 nanosheets sensor, which
showed temperature-dependent dual selectivity towards CO
and ­CH4. The sensor also had great long-term stability and

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 57 of 75 89

anti-humidity property. The sensing mechanism based on ­ O 2.

sensitivity of 80 and great selectivity towards 0.1 ppm N
the diffusion depth of the measured gas in the PdPt/SnO2 Comparing with Pt-ZnO and Pd-ZnO nanowires, the bime-
nanosheets sensing layer was discussed. The enhancement tallic Pd/Pt NPs functionalized ­SnO2 nanowires sensor real-
of sensing response can be attributed to the electron sensi- ized shorter response/recovery (13/9 s) times, which is ben-
tization of PdO, the catalytic activity of PdPt bimetal, and eficial from the synergic effect of Pd and Pt NPs. According
the Schottky barrier between ­SnO2 and PdPt NPs. The pre- to Chen et al. [59], the ZnO nanowires with Au/Pd bimetallic
pared sensor shows great application potential in coal mine NPs decoration (Au/Pd@ZNWs) were synthesized for ­NO2
gas monitoring. Specially, the bimetal hollow nanoframe detecting. As shown in Fig. 23h, two reproductive cycles of
was proposed to further enhance the gas sensing properties, Au/Pd@ZNWs were exposed to ­NO2 at 100 °C. Due to Au/
which could increase the specific surface area, provide more Pd NPs decoration, the optimal working temperature of Au/
active sites, and form the heterojunction between both two Pd@ZNWs was reduced from 150 to 100 °C. At the same
metals. Luo et al. [45] reported a Pd-Rh-decorated ZnO hol- time, the Au/Pd@ZNWs exhibited higher gas response of
low nanocube (HC) with Rh-rich hollow frame and Pd-rich 94.2 and shorter response/recovery time to N ­ O2 than the
core frame using chemical method to etch the Pd-Rh bimetal Au@ZNWs and Pd@ZNWs. This study provided a feasible
solid nanocube (SC) in ­HNO3 aqueous solution. The unique way for preparing bimetallic NPs modified 1D metal-oxide
Pd-Rh-decorated ZnO HC nanostructure could promote the nanostructures for low-consumption and high-performance
electron transport during the sensing process. The enhanced gas sensor application. Furthermore, Liu et al. [349] applied
­H2S sensing properties could be ascribed to the excellent hydrothermal and in-situ reduction to fabricate the Ag/Pd@
conductivity of Rh-rich frame increasing the specific surface In2O3-based sensor. The decoration of Ag/Pd NPs improved
area and gas diffusion, the remarkable catalytic ability of the gas sensing performance with excellent sensitivity, quick
Pd-Rh bimetal, and the formation of Schottky barrier-type response/recovery speed, and low detection limit of 20 ppb
junctions and defect. Specially, PdRh-decorated ZnO HC to toluene. Additionally, excellent selectivity and reproduc-
sensor exhibited better response value of 185 towards 1 ppm ibility were acquired. The sensor develops a low-cost, and
­H2S at 260 °C, which was 1.7-fold higher than the PdRh- more competitive approach to the detection of toluene gas,
decorated ZnO SC sensor. with significant benefits for healthcare and public safety
monitoring (Table 5).

4.3 Heterostructure Bimetal Decoration

5 Challenges and Future Perspectives
In addition to several structures described above, hetero-
Although significant progress has been achieved in the
structure is also a widely used structure. Two kinds of met-
development of noble metal-decorated SMOs-based gas sen-
als were deposited on the surface of the material, which
sors, there still remain many challenges in the exploration of
formed the heterojunction at the interface of two metals and
crucial performance enhancement and thorough mechanism
enhanced the gas sensing properties. Feng et al. [348] syn-
investigation. Herein, the related challenges and future pros-
thesized the Ag-Pt-decorated W ­ O3 NPs through the hydrol-
pects of noble metal-decorated SMOs-based gas sensors are
ysis and hydrothermal strategies. The as-prepared sensors
summarized below:
exhibited the response of 250 (Ra/Rg) towards 100 ppm ace-
tone at 140 °C, which was 6.1-fold compared to the pristine (1) The gas sensing performance varies greatly depending
­WO3 NPs under the same test condition. The enhanced gas on the kinds of noble metals decorating on the SMOs,
sensing properties were owing to the chemical and electronic and bimetals-decorated SMOs have been demonstrated
sensitization of Ag and Pt NPs to W
­ O3 NPs, which increased to exhibit much better performance than that of sin-
the adsorption of oxygen, accelerated the reaction speed, and gle noble metal decoration. However, previous stud-
further promoted the gas sensing response. According to ies were mostly focused on monometallic decorations,
and fewer reports on bimetallic or even polymetallic
Choi et al. [46], the networked ­SnO2 nanowires were modi-
decorations have been published. Due to optimized
fied by bimetallic Pd/Pt NPs via the sequential γ-ray radi- electronic structures and geometric configurations as
olysis method. The as-prepared sensor exhibited significant

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89 Page 58 of 75 Nano-Micro Lett. (2023) 15:89

Table 5  Summary of the reported bimetal-decorated SMOs-based gas sensors

Materials Structure Synthesis method Target gas O. T. (°C) Conc. (ppm) Response tres/trec LOD Refs.

PtAu/ZnO Nanorods Hydrothermal H2 130 250 157.4a – – [58]

AuAg/MWCNTs/ Composite films Hydrothermal NO2 25 1 ~ 1700%b 267 s/– 45 ppb [350]
WO3
AgPt/WO3 Nanoparticles Hydrolysis and Acetone 140 100 250a 41/13 s – [348]
hydrothermal
AuPt/ZnO Nanowires Hydrothermal H2S 300 20 17.7a 17/151 s – [64]
AgPt/TiO2/CuO/ Thin films Sputtering and N-butanol 300 100 ~ 200%b 12.4/4.2 s – [351]
Cu2O hydrothermal
PdRh/ZnO Nanochips Hydrothermal and H2S 260 1 185a 28 s/– 15 ppb [45]
stirring
AuPd/SnO2 Nanosheets In-situ reduction Acetone 250 2 6.5a 5/4 s 45 ppb [344]
HCHO 110 100 125a 68/32 s 30 ppb
AuPd/SnO2 Hollow spheres In-situ reduction DMDS 135 10 36.6a 23.5/26.5 s 5 ppm [47]
AuPd/WO3 Nanorods In-situ reduction Acetone 1000 200 4.53a 98/112 s – [352]
and UV irradia-
tion
AuPd/WO3 Macroporous Solution reduction Acetone 300 10 12a 8/5 s 0.1 ppm [343]
structure
AuPd/ZnO Nanowires Dipping & heating NO2 100 1 94.2a 35/30 s 1 ppm [59]
evaporation
PdAu/ZnO Nanoparticles Hydrothermal H2 300 100 80a 0.6/12 min 5 ppm [62]
PdAu/W18O49 Nanowires Solvothermal H2S 100 50 55.5a 10.2/8.5 s – [345]
CH4 320 1000 7.8a 24.8/14.5 s
PtPd/ZnO Nanorod clusters PLD H2 100 10,000 58%b 5 s/– 0.2 ppm [346]
PtPd/ZnO Nanorods PLD H2 100 10,000 69.8a 5 s/– 0.2 ppm [347]
PdPt/SnO2 Nanosheets Hydrothermal CO 100 50 30a 30/78 s – [60]
CH4 320 50 5.2a 5 s/–
PdPt/SnO2 Nanowires γ-ray radiolysis NO2 300 0.1 880a 13/9 s 0.1 ppm [46]
AgPd/In2O3 Microsphere In-situ reduction Toluene 180 1 15.9a 7/13 s 20 ppb [349]

O. T. operating temperature; Conc. concentration; tres/trec response time/recovery time; LOD limit of detection
a
Response is defined as R
­ a/Rg or ­Rg/Ra, ­Ra: resistance of the sensor in air, ­Rg: resistance of the sensor exposed to target gas
b
Response is defined as ∆R/Ra × 100% or ∆R/Rg × 100%, ∆R: the change in resistance, which equals to |Ra–Rg|

well as special synergistic effects, the bimetallic and with the help of light irradiation, highly photocatalytic
polymetallic decorations are expected to be a promising noble metal-decorated SMOs have achieved great gas
research direction for further enhancing the gas sensing sensing performance at RT. Therefore, configuration
performance in the future. with low-power micro-LEDs for photosensitization
(2) With the development of IoTs, chemiresistive gas sen- of sensing materials is also a feasible sensitization
sors with small size, high integration, and low power method.
consumption are urgently required for the increasing (3) The long-term stability is one of the crucial indicators
demands in smart cities, healthcare, and especially for reliable applications of all the gas sensors, espe-
smart phones. For example, power consumptions of cially for noble metal-decorated SMOs-based sensors.
lower than 10 mW are universal demands for bat- However, noble metal nanoparticles suffer from short-
tery-powered smart phone applications. Accordingly, comings like easily being oxidized in air and agglom-
MEMS-type and FET-type gas sensors provide prom- eration at relatively high operating temperature, which
ising and feasible avenues. Furthermore, since noble are major issues for the long-term stability. Moreover,
metals exhibit high catalytic activities, exploring noble as for practical applications, the anti-humidity of the
metal-decorated SMOs-based gas sensors operating at gas sensors also needs close attention since the humid-
RT is another promising development trend. Besides, ity varies greatly in different environments like dry

© The authors https://doi.org/10.1007/s40820-023-01047-z

Nano-Micro Lett. (2023) 15:89 Page 59 of 75 89

desert region, coastal region, and even human exhaled tists have tried to conduct diverse in-situ characteriza-
breath. Therefore, more efforts are expected to effec- tions including in-situ TEM and synchrotron radiation
tively improve the long-term stability and anti-humid- to explore the deeper sensing mechanisms of noble
ity of noble metal-decorated SMOs-based sensors. metal decorations. Nevertheless, more comprehensive
For example, developing high performance RT gas and in-depth investigation is still needed in favor of
sensors is considered as a feasible strategy. Besides, explaining some special sensing behaviors and phe-
establishing the accurate relationship between environ- nomena.
ment humidity and gas sensing performance by sys- (6) The repeatability on the mass production is one of the
tematically recording different sensing behaviors under crucial issues between laboratory research and industry
different environment humidity and then introducing production, which will affect the stability of the sensors
applicable neural network algorithms to realize effec- as well. Among various fabrication processes, screen
tive humidity compensation is a promising approach to printing, inkjet printing, and in-situ fabrication meth-
minimize the humidity interference. ods are promising for mass production with satisfac-
(4) As is well known, related interfering gases existing in tory repeatability. However, screen printing and inkjet
the actual environment will definitely affect the sensing printing are typical physical coating processes at first,
performance of single gas sensors with poor selectiv- which may cause worse stability of the sensors owing
ity. Thus, satisfactory selectivity is of vital importance to the intrinsic limitation of poor contact. Meanwhile,
for the practical application of noble metal-decorated the consistency between devices is also limited by the
SMOs-based gas sensos. Fortunately, the well-designed uniformity of slurries and inks, which remains a dif-
noble metal-decorated SMOs-based gas sensor arrays ficult technical issue due to agglomeration. Therefore,
combined with machine learning algorithms for data various in-situ fabrication processes like ALD, hard-
processing have been broadly proposed, which dem- template methods, and in-situ solution reaction meth-
onstrate excellent abilities to recognize complex gas ods, have been widely applied to synthesize advanced
mixtures and even identify the concentrations of dif- noble metal-decorated SMOs in-situ on MEMS or other
ferent gas components. Accordingly, it is possible to gas sensor substrates, attracting extensive attention
substantially improve the selectivity of noble metal- with increasing demand. The satisfactory consistency
decorated SMOs-based gas sensors in combination and great contact contribute to the excellent repeatabil-
with excellent neural network algorithms, which is ity of mass production and great long-term stability of
unimaginable for traditional single sensors. However, sensors. Therefore, the in-situ fabrication processes are
at present, the mostly used algorithms for gas sensors prospective strategies for future industry mass produc-
adopt simple models, such as PCA and support vec- tion of gas sensor chips or devices.
tor machines, limiting the more effective utilization of
sensing data. Therefore, more sophisticated algorithms
like convolutional neural networks are extensively stud- 6 Conclusions
ied recently for further utilization of sensing data and
substantial enhancement of sensing performance of gas
In this review, the recent progress of various noble metal-
sensor arrays. The integrated configuration of gas sen-
decorated SMOs-based chemiresistive gas sensors have
sor arrays is a promising future trend for constructing
functional electronic noses with satisfactory selectivity. been systematically summarized. Our attention has con-
(5) This review summarizes the related sensing mecha- centrated on the comparative review of different kinds
nisms that have been proposed for noble metal-dec- of noble metals involving Au, Pt, Pd, Ag, Rh, Ru, and
orated SMOs-based gas sensors. However, different bimetals. Specifically, the preparation processes, gas
noble metals have their unique sensing mechanisms sensing properties, and practical applications of various
due to their specific chemical-physical properties. For SMO materials, including n-type SMOs (ZnO, ­S nO 2,
instance, Pd will react with O ­ 2 to uniquely produce
­WO3, ­In2O3, ­Fe2O3, ­TiO2, ­MoO3, CdO, C­ eO2, ­V2O5, etc.),
weakly bonded PdO, which could be easily dissociated
p-type SMOs (CuO, NiO, C ­ o3O4, ­Ga2O3, etc.), and their
and reproduce ­O2, thus improving sensing responses
and accelerating response/recovery speed. In addition, heterostructures, with noble metal decoration are compre-
the specific mechanisms of bimetallic and polymetallic hensively covered in this review. Meanwhile, the general
decorations like special synergistic effects also remain sensing mechanisms for the performance improvement
unclear and need further exploration Recently, scien- caused by noble metal decoration, including the electronic

13
89 Page 60 of 75 Nano-Micro Lett. (2023) 15:89

sensitization effect and the chemical sensitization effect, composition proportion of the bimetals to achieve the
are also paid specific attention and discussed in detail. best sensing performance.
Furthermore, challenges and perspectives toward highly (4) Different noble metals are specific for detecting dif-
sensitive and selective gas sensors with low power con- ferent certain gases. For instance, Pd-decorated SMOs
have a particularly high selectivity to H ­ 2 due to its
sumption and excellent long-term stability have been com-
unique reversible product of ­PdHx, while Ag-deco-
prehensively analyzed and discussed. This review is of rated SMOs are more sensitive to ethanol and HCHO
considerable reference value for the design, fabrication, as reported. Furthermore, the introduction of well-
and development of noble metal-decorated SMOs-based designed sorption, size-selective, or catalytic filters
gas sensors. upstream of the noble metal-decorated SMOs-based
In general, noble metal-decorated SMOs have the gas sensors has been demonstrated to significantly
advantages of facile synthesis, improved response values, improve the selectivity, which greatly benefits vari-
fast response/recovery, fabulous selectivity, and excellent ous practical applications especially in exhaled breath
analysis with high humidity.
stability. The key conclusions are summarized as follows:
(5) Diverse effective methods like light irradiation and
morphological innovations have been developed to
(1) Noble metal decoration could effectively enhance the
improve the catalytic activation of noble metals, further
gas sensing performance of SMOs-based gas sensors
enhancing the gas sensing performance of noble metal-
through changing the surface nanostructure and mor-
decorated SMOs-based gas sensors, such as reducing
phology of SMO materials, enhancing the surface lat-
the operating temperature even down to RT, acceler-
tice oxygen activity, generating more oxygen vacan-
ating the response/recovery speed, and lowering the
cies, and increasing the gas molecules adsorption
detection limit even down to ppb-level.
capacity. On the one hand, noble metals with excel-
lent catalytic properties help to reduce the activation
energy of the reaction between the gas molecules and Thanks to the introduction of emerging functional mate-
adsorbed oxygens, thus accelerating the dynamic equi- rials, novel nanostructures, as well as advanced fabrication
librium between oxygen adsorption and desorption. On process, high-performance noble metal-decorated nanoma-
the other hand, Schottky barriers are expected to be terials-based gas sensors have been more easily achieved.
formed when some noble metals with high work func- For the further step, the development of materials and
tions are in close contact with SMOs, which will cause devices with excellent consistency and long-term stabil-
the change of electron distributions and energy band ity become even more crucial for future practical appli-
structures in SMOs, and then lead to the increase in
cations. Furthermore, the realization of long-term stable
the thickness of electron depletion layer. More broadly,
the decoration of noble metals on SMOs is not limited noble metals-decorated SMOs-based gas sensor arrays,
to gas sensors. It could also be extended to other func- together with the arrival of the artificial-intelligence (AI)
tional applications including catalysis, C
­ O2 reduction, era, should allow real-life electronic olfactory sensing in
and so on. the future.
(2) The design and control of the morphology of noble
metal-decorated SMOs is well established. The devel- Acknowledgements This work was supported by the
opment of preparation techniques has provided the National Key R&D Program of China (No. 2020YFB2008604,
2021YFB3202500), the National Natural Science Foundation of
basis for the advancement of noble metal decoration.
China (No. 61874034), and the International Science and Technol-
Hydrothermal, UV reduction, ALD, electrochemical ogy Cooperation Program of Shanghai Science and Technology
deposition, electrospinning, precipitation, magnetic Innovation Action Plan (No. 21520713300).
sputtering, flame spray pyrolysis, and other preparation
methods with unique characteristics have been widely Funding Open access funding provided by Shanghai Jiao Tong
applied to synthesize various noble metal decorated University.
SMOs.
(3) Bimetallic decoration has exhibited much better gas Open Access This article is licensed under a Creative Commons
sensing performance than single noble metal decora- Attribution 4.0 International License, which permits use, sharing,
tion due to the synergetic benefits. Besides, the elec- adaptation, distribution and reproduction in any medium or format,
as long as you give appropriate credit to the original author(s) and
tronic structure and geometric configuration of bimetal-
the source, provide a link to the Creative Commons licence, and
lic nanoparticles can be modulated by controlling the

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Nano-Micro Lett. (2023) 15:89 Page 61 of 75 89

indicate if changes were made. The images or other third party B: Chem. 367, 132182 (2022). https://​doi.​org/​10.​1016/j.​snb.​
material in this article are included in the article’s Creative Com- 2022.​132182
mons licence, unless indicated otherwise in a credit line to the 11. W. Hu, W. Wu, Y. Jian, H. Haick, G. Zhang et al., Volato-
material. If material is not included in the article’s Creative Com- lomics in healthcare and its advanced detection technology.
mons licence and your intended use is not permitted by statutory Nano Res. 15(9), 8185–8213 (2022). https://d​ oi.o​ rg/1​ 0.1​ 007/​
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this licence, visit http://​creat​iveco​mmons.​org/​licen​ses/​by/4.​0/. et al., Correlation between breath ammonia and blood urea
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