Surfaces and Interfaces 45 (2024) 103838

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Surfaces and Interfaces

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Defect engineered N-doped black-V2O5 nanostructures for hydrogen

production via solar-catalytic water splitting in the presence of different
sacrificial agents
R. Vijayarangan a, Sakar Mohan b, Manickam Selvaraj c, *, Mohammed A. Assiri c, Samuel
Lalthazuala Rokhum d, R. Ilangovan a, *
a
National Centre for Nanoscience and Nanotechnology, University of Madras, Guindy Campus, Chennai 600025, Tamil Nadu, India
b
Centre for Nano and Material Sciences, Jain (Deemed-to-be University), Jain Global Campus, Kanakapura, Bangalore 562112, Karnataka, India
c
Department of Chemistry, Faculty of Science, King Khalid University, Abha 61413, Saudi Arabia
d
Department of Chemistry, National Institute of Technology Silchar, Assam 788010, India

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, vanadium pentoxide (V2O5) is synthesized via hydrothermal method and annealed in a normal and
Photocatalysis NH3 gas ambience, which led to the formation of pristine and defective-V2O5 systems, respectively. This
Defects defective-V2O5 contained both doped-nitrogen and oxygen-vacancies defects, confirmed through XRD and XPS
Doping
analysis. Interestingly, this process also led to the exfoliation of V2O5 into a 2D layered structure, confirmed by
Layered materials
Nanostructures
FESEM analysis. A band gap energy of ~2.11 and 2.26 eV is estimated for the defective and pristine-V2O5,
H2 production respectively from the Tauc’s plots. The solar-catalytic green H2 production efficiency (in mmol g− 1 h− 1) of the
pristine and defective-V2O5 in presence of different sacrificial is investigated and estimated, and it is found to the
order of glycerol (2.369) > methanol (1.969) > triethanolamine (1.441) > sodium sulphate/sodium sulfide
mixture (1.210) > ethylene glycol (0.967). While accounting the inherent properties of the various sacrificial
agents, the observed enhanced efficiency of defective-V2O5 is attributed to their surface-active sites, suitable
band structure along with the modulations in the charge carrier separation and transfer characteristics of the
system, confirmed through BET, PL, Mott–Schottky, electrochemical impedance, and photocurrent measure­
ments. Further, the cyclic photocatalytic efficiency of defective-V2O5 is found to be consistent in all the 3 cycles
in a total period of 9 h. The post-characterizations of the recycled defective-V2O5 system suggested that the
developed photocatalyst is stable in terms of its photo-chemical and physical properties, suitable for scale up
green H2 productions.

1. Introduction vanadium ions and flexible structural geometrics [4,5]. Vanadium ions
in oxide settings have different oxidation states ranging from V2+ to V5+
Photocatalysis is a multifunctional process that finds applications in and mixed states such as V5+/4+ and V4+/3+ as well [4,6,7]. These mixed
both, or rather, simultaneous environmental cleaning and energy pro­ oxidation states typically lead to the formation of two types of phases
duction [1–3]. To realize and implement the full potential of photo­ known as Magnéli [8] and Wadsley phase with general chemical formula
catalytic processes, it requires suitable photoactive semiconductors with of VnO2n− 1 and VnO2n+1, respectively [4,7]. The increasing ‘n’ in the
tunable band edge potentials and band gap structures to improve charge former phase can modify the electrical and magnetic properties of V-O
carrier separation and recombination resistance, thereby to achieve the system [8–10], while in the latter phase, it leads to the changes towards
required redox reactions for the specific photocatalytic process [3]. In making it suitable for physiochemical processes [11]. Notably, the
pursuit of such systems, vanadium pentoxide (V2O5) could be an inter­ changes in the structure of V–O systems often originate due to the
esting material due to its narrow bandgap energy, promising concentration of oxygen [12], which can eventually decrease the energy
photo-stability, structural tunability via multiple oxidation states of required for their formation. The Wadsley phases with chemical

* Corresponding authors.
E-mail addresses: [email protected] (M. Selvaraj), [email protected] (R. Ilangovan).

https://doi.org/10.1016/j.surfin.2023.103838
Received 11 October 2023; Received in revised form 15 December 2023; Accepted 30 December 2023
Available online 31 December 2023
2468-0230/© 2023 Elsevier B.V. All rights reserved.
R. Vijayarangan et al. Surfaces and Interfaces 45 (2024) 103838

structure of VnO2n+1 form the layered structure of vanadium oxides with X-ray diffractometer (Rigaku Mini Flux XRD). The chemical oxidation
single- and double-layer configuration depending upon the formation of states of the samples were investigated using the X-ray photoelectron
V4+ and V4+/5+ states, respectively [13]. The presence such layers often spectrometer (XPS, ULVAC-PHI Inc, PHI5000-III). Field-emission scan­
facilitate the intercalation of different ions, which makes them potential ning electron microscope (FESEM, JEOL JSM-7100F) was used for
candidates for catalytic conversion and charge storage applications morphology analysis. Optical characterizations were performed using
[13–15]. Notably, these multi-oxidation states of V also create oxygen UV–visible absorption (PerkinElmer Lambda 650) and photo­
vacancies in the V–O system [4,9]. luminescence (PL) spectrometer (FluoroMax Plus, Horiba). The surface
In this direction, the stable layered vanadium oxide (V–O) phase is area analysis of the samples was performed using the Bru­
vanadium pentoxide (V2O5), where the spontaneous deformation in the nauer–Emmet–Teller (BET) N2 adsorption-desorption measurements
structure alters the V–O bonds in V2O5 that makes the energy of the (BET BELSORP Max).
system to be tunable and versatile [14,16,17]. The oxidization states of
V in V2O5 can be in the range of V2+ to V5+ depending upon the coor­ 2.4. Photocatalytic H2 evolution experiment
dination geometrics of V–O bonds [4,13,18]. These characteristics
variations in the V–O bonds, their coordination and multiple valence The photocatalytic H2 evolution efficiencies of the developed mate­
states along with defects can lead to the manifestation of strong aniso­ rials were investigated under solar irradiation. In this experiment, 47 mL
tropic properties such as 2D layered structures and different polymorphs of double distilled water and 3 mL of glycerol were taken in a quartz
such as α, β, and γ-V2O5 [19–21]. This layered structures and defects flask and stirred well for about 15 min. To this, 5 mg of the photocatalyst
enable the structural tunability in V2O5 and lead to the emergence of was added and dispersed via sonication. Then, the flask was closed using
interesting electrical and optical properties for the desired functional an airtight septum and sealed with Teflon tape to prevent leakage of
applications [22,23]. In this context, taking the advantages of their reaction mixture or gas and covered with aluminum foil to avoid the
structural flexibilities, V2O5 nanostructures have been synthesized via light exposure. The residual gases were evacuated by purging N2 gas for
hydrothermal method followed by thermal annealing in ammonia (NH3) about 30 min and the reaction mixture was stirred again under dark
gas environment, which resulted in the formation of oxygen defective condition. Then the wrapped aluminum foil was removed and the
nitrogen-doped V2O5 system. This synthesized defective-V2O5 is further reactor flask was kept under the direct sunlight. The intensity of incident
explored for its photocatalytic water-splitting properties in the presence light was estimated to be 93±6 mW/cm2 using a Newport power meter.
of different sacrificial agents for hydrogen generation under solar The evolved H2 gas was collected every one hour and injected into an
irradiation. offline gas chromatography having a thermal conductivity detector,
molecular sieve/5 Å column and N2 as a carrier gas at 70 ◦ C (Shimadzu
2. Experiment GC-2014). The readings were taken in triplicate in each time and the
average values were taken for the report.
2.1. Materials
2.5. Electrochemical characterizations
All chemicals and solvents used in the study were of analytical grade
and used as-received, which are procured from various commercial For the electrochemical impedance and photocurrent measurements,
sources. Chemicals were stored as per the standard instructions before a three-electrode setup was arranged by employing the platinum-wire
and after use. The ammonium metavanadate (NH4VO3) precursor was and Ag/AgCl as a counter and reference electrode, respectively. The
procured from Sigma-Aldrich. The chemicals and solvents such as working electrode was prepared by taking around 10 mg of material
glycerol (C3H8O3), triethanolamine (C6H15NO3), ethylene glycol dispersed in methanol and 3-aminopropyl triethoxysilane (binder)
((CH2OH)2), methanol (CH3OH), sodium sulphate (Na2SO4), and so­ mixture and drop-casted on a 1 × 1 cm FTO glass and dried at 60 ◦ C in a
dium sulfide (Na2S) were procured from SRL Chemicals, India. The vacuum oven. The impedance and photocurrent conductivity properties
ammonia (NH3) gas with a purity of 99.999 % (Bhuruka Gases Ltd., of the developed materials were analyzed using the electrochemical
India) was used for the reaction. The double distilled water was pre­ workstation (Autolab PGSTAT204). A bias of 0.8 V was applied during
pared using a double stage distillation setup in the laboratory. the photocurrent measurements, irradiated under a Xe lamp (150 W)
with 10 s ON-OFF cycles and 0.2 M Na2SO4 aqueous solution was used as
2.2. Synthesis of V2O5 nanostructures an electrolyte.

In the typical synthesis process, an equivalent gram of 0.1 M 3. Results and discussion
ammonium metavanadate precursor in 30 mL of double distilled water
was taken along with around 2 mL of 70 % concentrated HNO3 and XRD patterns of the samples (as shown in Fig. 1(a, b)), corresponding
magnetically stirred to obtain a homogenous solution. Then, this solu­ to deep-orange and black colored powder (insert of Fig. 1(b)), confirm
tion was transferred to Teflon-coated stainless-steel autoclave and kept the formation of vanadium pentoxide (V2O5) phase of the respective
at 120 ◦ C for 12 h. After the reaction, the formed product was separated material. The observed peak shifting and broadening in the XRD pattern
using a vacuum system and dried at 60 ◦ C overnight. Then, this dried of black-V2O5 with respect to the other could be attributed to the pres­
powder was transferred to an alumina boat and kept it in a tubular ence of oxygen vacancies and doped-nitrogen atoms in the lattices of
furnace and annealed at 550 ◦ C for 3 h. The resultant product, which V2O5 [26]. Notably, the intensity of peaks corresponding to the
appeared deep-orange in color [24], was ground using a mortar and diffraction planes (101) and (110) is switched in the case of black-V2O5
pestle and then stored at room temperature for further use. This pro­ compared to deep-orange-V2O5 as well as the standard JCPDS data
cedure was repeated by annealing the obtained product in an ammonia corresponding to the bulk-V2O5 [27,28]. This observation could be
(NH3) gas ambience (100 SCCM, controlled using a mass-flow attributed to the distortion occurred in the crystal structure/lattice of
controller) instead of the normal atmosphere [25,26]. The resultant V2O5, which might have led to the facet-oriented growth of V2O5 crystals
product from this process appeared black in color [27] and was stored as during their formation as confirmed from their morphology analysis
mentioned above. discussed in the following section.
The origin of N-doping and defects creation in the system could be
2.3. Characterizations proposed as follows. It can be realized that during NH3-annealing, the
dissociation of NH3 generates H2 and N2 gases, where the H+ ions reduce
The crystal structure and phase of the materials were analyzed using the V2O5 and create the oxygen vacancies in system [29]. Meanwhile,

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R. Vijayarangan et al. Surfaces and Interfaces 45 (2024) 103838

Fig. 1. (a, b) XRD patterns of the synthesized pristine and defective-V2O5 systems.

the N-ions also get doped into the host V2O5 system by replacing the XPS wide-scan survey spectra of the pristine and defective-V2O5, as
oxygen atoms [30,31]. It can be corroborated from the matched JCPDS displayed in Fig. S1 in supporting file, indicated the presence of all the
card #41-1426 that the formed V2O5 possesses orthorhombic crystal respective elements (V, O, and N) in the respective system.
structure with α-V2O5 polymorph [32]. It is reported that the general The narrow scan spectra of V and O in the pristine and defective-
structure of α-V2O5 involves the V–O bonds connected via covalent V2O5 are displayed in Fig. 2(a) and the N 1s spectrum of defective-V2O5
bonds on XY-axis and weak V–O bonds Z-axis, which forms O–V–O (N-doping) is given in Fig. 2(b). The peaks corresponding to V 2p3/2 and
double layers bonded via van der Waals forces [33]. Therefore, it can be V 2p1/2 appeared at a characteristic binding energy of 517.5 and 525.1
proposed that during the formation of N-doped V2O5 under NH3 eV [34], while these peaks are found to be slightly shifted to lower
annealing, the N atoms intercalated into the double layers forming the binding energy values of 517.2 and 524.8 eV, respectively [35]. This
O–V–N by replacing the oxygen atoms in the network and the reduc­ suggests that the electrons in the defective-V2O5 are propagating more
tion via H-radicals (from NH3 gas) created the oxygen vacancies in the freely in the system, which delicately bound to the nucleus and require
system and led to the simultaneous N-doping and oxygen vacancy for­ less energy to remove the electrons from the orbital. This implies that
mation in V2O5 system. the electrons in the defective-V2O5 can be easily excited as they are
Furthermore, the average crystallite size of the material is estimated largely delocalized in the system compared to the pristine-V2O5 [16].
using Scherrer’s formula, D = 0.9λ/βcosθ and the micro-strain in the Further, the observed peak-broadening suggests that the vanadium
system is estimated using the formula, ε = βcosθ/4, where D represents ions possess dual oxidation states (V4+/5+) in defective-V2O5 compared
the average crystallite size in nm, 0.9 is the crystallite shape constant, λ to pristine system [35–37]. Accordingly, a clear hump-like peak is
is the wavelength of X-rays used (0.1513 nm), β is the full width at half observed in the O 1s spectrum of defective-V2O5 corresponding to ox­
maximum, and θ is the Bragg diffraction angle, and ε is micro-strain. ygen vacancy defects in the system [38,39]. In contrast, this hump-like
From the calculations, the average crystallite size of pristine and peak is relatively diminished in the case of pristine-V2O5 suggesting the
defective-V2O5 was estimated to be around 42 and 31 nm, respectively. meager existence of oxygen-defects in the system. The N 1s spectrum of
The micro-strain was found to be higher in defective-V2O5 (0.144 ε) defective-V2O5 (Fig. 2(b)) shows the successful and dominant incorpo­
compared to pristine (0.088 ε). These structural impacts in defective- ration of N-atoms in the lattices of V2O5 system. The peak appeared at
V2O5 could be assigned to N-doping, O-vacancies, and layered struc­ 399.6 eV shows the doping of N in O-site forming the O–V–N bonding
tures. While N-doping and O-vacancies create lattice distortions, leading [39]. The peak at 400.7 and 403.1 eV can be attributed to the surface
to lattice strain in the system, the surface reconstruction leads to adsorbed-N2 (during NH3 annealing) and nitrogen species bound to
controlled regrowth of anisotropic layered structures, thereby reducing various surface sites including O and C in the system [40]. These ob­
the average crystallite size of defective-V2O5. servations from XPS analysis confirm that both O and N play a crucial

Fig. 2. XPS narrow scan spectrum of V 2p, O 1s, and N 1s of pristine and defective-V2O5.

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R. Vijayarangan et al. Surfaces and Interfaces 45 (2024) 103838

role in determining the physiochemical and band structure of the formed modifications and (ii) layer structures-induced energy confinements in
defective-V2O5 system [16]. the system. It is known that the confinement in the system leads to the
The FESEM images the pristine and defective-V2O5 showed irregular band gap widening, while the doping and oxygen vacancies create mid
particulate- and 2D layered morphology of the respective system as gap structure, which narrows the band gap structure of the material.
displayed in Fig. 3(a–d) [36]. It is described that the initial synthesis of Accordingly, a synergistic modification is presumably occurred in
V2O5 was carried out via hydrothermal method followed by ambient and defective-V2O5 leading to new energy levels corresponding to the doped-
NH3 gas ambient annealing, formed the pristine and defective-V2O5 N atoms and oxygen vacancies created near the valence band (VB) and
system, respectively. It is evident that the conventional ambient conduction band (CB), respectively, which further dispersed the band
annealing largely leads to a typical growth of V2O5 phase, whereas, the structures due to the quantum confinement effect of 2D layered struc­
NH3 annealing leads to intercalation of N atoms into the V2O5 leading to tures [30]. Accordingly, a decreased band gap energy of ~2.11 eV was
their exfoliation into layer-structures [25]. It should be noted that these observed for defective-V2O5 system compared to pristine (2.26 eV),
layer structures largely populated on the surface of the particles and estimated using Tauc’s plots as shown in Fig. 4(c) [24,37].
propagated into the bulk. This indicates that the NH3 annealing leads to Further, the photoluminescence (PL) spectra of the samples show
the surface reconstruction in V2O5 creating the layered structures, and emission peaks at 490 nm due to the radiative recombination in the
thereby the intercalation of N atoms occurs via surface diffusion phe­ pristine and defective-V2O5 as displayed in Fig. 4(d). The reduced PL
nomenon. In such perspective, NH3 annealing essentially causes both intensity indicates that there is a delayed recombination in defective-
physical and chemical changes in V2O5 [14,25,26]. V2O5 compared to the pristine material. Such reduced PL intensity can
The surface characteristics of pristine and defective-V2O5 nano­ be typically correlated to the enhanced charge separation and increased
structures were analyzed using BET N2 sorption isotherms as shown in lifetime of the excited carriers in the system, which can ultimately favor
Fig. 4(a), exhibiting a surface area of 36.9 and 67.6 m2 g− 1, respectively for the improved photocatalytic redox activities in the material.
[41]. The obtained sorption curves of both the systems matched with Notably, there are some minor distorted peaks are observed in the PL
type II-H3 hysteresis characteristics, suggesting that the material surface spectrum of defective-V2O5, which can be associated with the secondary
could be conducive for the effective adsorption of adsorbates as well as emissions from the defective structures in the system [43,44].
their steady desorption during the reactions. Compare to pristine, an The photocatalytic H2 production efficiency of the pristine and
enhanced sorption isotherm is observed for defective-V2O5, suggests defective-V2O5 is studied via water-splitting in the presence of different
that there is a significant enhancement in the surface properties of V2O5. sacrificial agents[45] such as glycerol (Gly), triethanolamine (TEA),
This could be attributed to the defect-induced dangling bonds-rich ethylene glycol (EG), methanol (MeOH) and sodium sulphate/sodium
layer-structured morphology of defective-V2O5. Such surface can pro­ sulfide mixture (NS) under natural solar irradiation and the results are
vide a greater number of active sites for the effective catalytic reactions displayed in Fig. 5(a, b).
and it can be reversible, supporting for its quick regeneration for sus­ The results showed that the rate of H2 evolution (in mmol g− 1 h− 1)
tainable operation and reusability [42]. over the defective-V2O5 system in the presence of different sacrificial
UV–visible absorption spectrum of defective-V2O5 layers clearly agents is in the order of glycerol (2.369) > methanol (1.969) > trie­
show a broader absorption band from 350 to 700 nm stretching the thanolamine (1.441) > sodium sulphate/sodium sulfide mixture
entire UV–visible light region, while the pristine system showed ab­ (1.210) > ethylene glycol (0.967). The same trend is also observed for
sorption edge in the range of 450 nm as shown in Fig. 4(b). This sig­ pristine-V2O5, which is estimated to be around 1.888, 1.361, 0.892,
nificant improvement in defective-V2O5 could be attributed to a couple 0.671, and 0.521 mmol g− 1 h− 1 in the presence of the respective sacri­
of factors; (i) N-doped and oxygen vacancy-induced band gap structure ficial agents. The observed improved performance of the defective-V2O5

Fig. 3. FESEM images of (a, b) pristine and (c, d) defective V2O5 systems.

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R. Vijayarangan et al. Surfaces and Interfaces 45 (2024) 103838

Fig. 4. (a) BET N2 sorption isotherms, (b) UV–visible absorption spectra, (c) Tauc’s plots for bandgap estimation, and (d) PL spectra of the pristine and defective-
V2O5 systems.

Fig. 5. (a) Photocatalytic H2 evolution as a function of time and (b) rate of H2 evolution over the pristine and defective-V2O5 in the presence of different sacrifi­
cial agents.

could be attributed to its improved physiochemical properties as real­ estimated for pristine and defective-V2O5, respectively and the VB po­
ized from various investigations [37,46,47]. tential is also estimated to be around 1.82 and 1.54 V, respectively [24,
The Mott–Schottky (MS) analysis was carried out to determine the 27,48]. The observed upshifted CB potential suggests that the excited
CB potential, and thereby the VB potential using the formula Eg = EVB − electrons in defective-V2O5 can effectively participate in the reduction
ECB, of the systems as shown in Fig. 6(a). From the plots, flat band po­ reactions compared to the pristine system as shown in the insert image
tential of pristine and defective-V2O5 is determined to be around − 0.54 of Fig. 6(a).
and − 0.67 V, respectively. The negative potential values on X-axis Based on the estimated band gap energy, VB, and CB edge positions,
suggested that the obtained systems are n-type semiconductors. The CB the observed H2 evolution efficiency of the defective-V2O5 compared to
position of a n-type material always lies at ~0.1 V lower than the flat- pristine system can be proposed as follows. Upon light irradiation, the
band potential. Accordingly, CB potential of − 0.44 and − 0.57 V is excitons get separated, where the electrons and holes move to the

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R. Vijayarangan et al. Surfaces and Interfaces 45 (2024) 103838

Fig. 6. (a) Mott–Schottky plots for the estimation of band edge potentials (insert) and (b) photocatalytic H2 evolution mechanism of the defective-V2O5
photocatalyst.

conduction band (CB) and valence band (VB), respectively. It can be electrons in the semiconductor photocatalyst. Among the various
fetched that the energy levels corresponding to the oxygen vacancies sacrificial agents used, glycerol solely tends to produce H2 during its
and doped-N can disperse the CB and VB energy levels, respectively in a oxidation by holes, whereas other agents do so to certain extent.
defective system. Under such circumstances, a greater number of elec­ Therefore, the observed higher yield of H2 in the presence of glycerol can
trons get excited to the CB and get effectively delocalized to reduce the be attributed to its reforming process, which results in the formation of
protons (H+) into molecular hydrogen (H2). Further, it is evident from greater number H2 molecules during the reactions.
the PL spectra that the recombination of electron-hole pairs is signifi­ The improved performance of defective-V2O5 was further assessed
cantly restricted in the defective-V2O5. This restriction arises from (i) the using the electrochemical and photocurrent conductivity analysis. The
dispersion of CB and VB, which limits carrier recombination, and (ii) the electrochemical impedance (Nyquist plots) of the materials, as shown in
limited availability of holes as they react with the sacrificial agents. Fig. 7(a), indicate that the interfacial charge transfer efficiency of
Therefore, the combination of oxygen defects and the energy levels of defective-V2O5 is superior than the pristine system. As discussed, the
the doped-N effectively dispersed the CB and VB of the system. This origin of such improved charge transfer process in defective-V2O5 could
enhancement facilitated charge separation through improved electron be attributed to the presence of doped-N and oxygen vacancies in the
delocalization and restricted electron-hole recombination. Conse­ system [49]. Notably, compared to bulk, the physical (morphology) and
quently, it augmented the H2 production, as depicted in Fig. 6(b) [49]. chemical (defects) modifications in layered materials create dangling
Notably, these layered structures also significantly contribute to the bonds on their surfaces, which establish functional interface with sur­
overall enhancement of the photocatalytic properties of the defecti­ rounding environments, thereby it improves the overall response to
ve-V2O5 system. The presence of these anisotropic structures creates external stimuli such as electrical bias or incident photons, and mani­
additional hotspots, as realized by the increased surface area determined festing the improved functionalities in the system [26,30,37,50].
through BET analysis. Thus, in turn, promotes enhanced adsorption of Similarly, the photocurrent measurements (Fig. 7(b)) showed an
surrounding molecules, facilitating effective redox reactions during the enhanced photo-conductivity for defective-V2O5 compared to pristine.
photocatalytic process. This observation signifies that the electrons are rapidly excited and
Notably, a maximum H2 evolution was observed in presence of delocalized in the CB of defective-V2O5, which eventually get promoted
glycerol in both cases (pristine and defective-V2O5), which can be pro­ to the surroundings, leading to an improved photo-conductivity in the
posed as follows. It is known that the sacrificial agents react with the system. As observed, the PL spectra suggested that the recombination
holes and further break down into sacrificial-intermediates during the rate of charge carriers is considerably decreased in defective-V2O5. This
water splitting reactions. This process potentially minimizes the avail­ can be correlated with the obtained photocurrent and EIS measure­
ability of photoinduced holes to recombine with the photoinduced ments, where the former confirms that there is improved charge

Fig. 7. (a) Electrochemical impedance and (b) photocurrent measurements of the pristine and defective-V2O5 photocatalysts.

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R. Vijayarangan et al. Surfaces and Interfaces 45 (2024) 103838

separation in the system, while the latter confirms that there is effective annealing it at 550 ◦ C for 3 h. While the ambient annealing led to have a
charge promotion to the surroundings [51,52]. As a result of this col­ pristine-V2O5 system, the NH3 annealing induced defects in V2O5
lective process, there is a significant delay in recombination of charge involving the simultaneous N-occupancy and oxygen vacancies in the
carriers in the system. The prolonged existence of holes and electrons in system as confirmed by XRD and XPS techniques. In addition, the NH3
VB and CB, respectively facilitates the effective redox reactions gener­ annealing also facilitated the exfoliation of defective-V2O5 into a 2D
ating a greater number of protons (H+) and their subsequent reduction layered structure, whilst the pristine was found to be irregular in
to hydrogen (H2) molecules [14,53,54]. morphology, as confirmed via FESEM images. The observed improved
The recyclable use of the developed defective-V2O5 was tested up to visible light absorption and recombination resistance in the system were
3 cycles and in each cycle the hydrogen evolution was monitored for attributed to both the physical and chemical modifications occurred in
every one hour for a total period of 3 h. The obtained results are pro­ the defective-V2O5. The results of solar water splitting reactions
vided in Fig. 8(a). The plots show that the hydrogen production is demonstrated that the N-doping, O-vacancy defects and layered struc­
consistent in all three cycles, suggesting the excellent chemical and tures were conducive toward enhancing the photocatalytic efficiency of
photostability of the system. The origin of observed chemical stability V2O5. The origin of such defect-mediated enhancements was attributed
could be attributed to the layered structure of V2O5, which facilitated to the formation of N and O energy levels near the valence band
the networking of defective sites and their stabilization through the maximum (VBM) and conduction band minimum (CBM) of V2O5,
doped-N atoms in the system [55]. Similarly, the observed photo­ respectively. This offered a suitable positioning of CB and VB edges for
stability of this defective-V2O5 could be attributed to its excellent uti­ effective redox reactions, while the layered structures paved the way for
lization of photogenerated charge carriers for the subsequent redox the effective charge carrier separation and transportation to the surface
reactions with surrounding molecules rather than accumulating in the of the photocatalyst for efficient H2 generation. These observations were
defective sites that leads to deteriorating photostability of the system further corroborated and validated using Mott–Schottky, electro­
[56]. The stability of defective-V2O5 is further validated by obtaining its chemical impedance and photocurrent measurements. In addition, the
XRD, UV–visible absorption spectrum, and FESEM image after the cyclic cyclic H2 production efficiency of the defective-V2O5 system was
studies as shown in Fig. 8(b–d), respectively. The photographic images promising, made possible owing to its excellent structural, optical and
of the fresh and used defective-V2O5 photocatalyst are provided in the morphological properties confirmed through the respective character­
inset of Fig. 8(c), confirming its surface regeneration for sustainable use izations of the recycled defective-V2O5 photocatalyst. The findings of the
for photocatalytic reactions. study revealed that defective-V2O5 nanostructures could be a promising
photocatalyst for scaled-up green hydrogen production via photo­
4. Conclusions catalytic water splitting reactions under solar irradiation.

This study explored the development of pristine and defective-V2O5

photocatalysts via normal and NH3 gas ambience, respectively, by

Fig. 8. (a) Cyclic H2 production over the defective-V2O5 photocatalyst, (b) XRD, (c) UV–visible absorption spectrum [insert: photographic image of fresh and used
photocatalyst], and (d) FESEM image of the recycled defective-V2O5 photocatalyst.

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CRediT authorship contribution statement spur ion kinetics in V2O5 structures for superior aqueous zinc-ion batteries, Adv.
Funct. Mater. (2023) 2305659, https://doi.org/10.1002/adfm.202305659.
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