Sustainable Materials and Technologies 21 (2019) e00105

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Sustainable Materials and Technologies

journal homepage: www.elsevier.com/locate/susmat

Separable and recyclable meso-carbon@TiO2/carbon fiber composites for

visible-light photocatalysis and photoelectrocatalysis
Hua-Jun Chen a,b, Yan-Ling Yang a,⁎, Min Hong c, Jin-Geng Chen a, Guo-Quan Suo a, Xiao-Jiang Hou a,
Lei Feng a, Zhi-Gang Chen c,d,⁎
a
School of Material Science and Engineering, Shaanxi University of Science and Technology, Xi'an 710021, China
b
Department of Environment and Chemistry, Luoyang Institute of Science and Technology, Luoyang 471023, China
c
Centre for Future Materials, University of Southern Queensland, Springfield central, QLD, 4300, Australia
d
Materials Engineering, The University of Queensland, Brisbane, QLD 4072, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Recycle and reuse of the nanosized photocatalysts is a common challenge in the catalyst field. To address this
Received 23 January 2019 issue, we rationally load meso‑carbon@TiO2 core-shell microspheres on carbon fiber felt to synthesize macro-
Received in revised form 27 March 2019 sized meso‑carbon@TiO2/carbon fiber composites by an in-situ adsorption method. From the detailed microstruc-
Accepted 27 March 2019
tural and spectroscopic characterization, it has been found that the absorption edge of meso‑carbon@TiO2
core-shell microspheres is extended to the visible light region, and the recombination of photon-excited elec-
Keywords:
trons and holes can be significantly suppressed when compared with P25 TiO2 powder. The experiment results
TiO2 of meso‑carbon@TiO2/carbon fiber composites indicates that the photocatalytic degradation rate under UV–vis
Meso‑carbon light is much higher than that under visible light irradiation due to the higher charge carrier separation efficiency
Carbon fiber and the higher electron consumption of the direct Z-scheme. Moreover, the photocurrent density and the sepa-
Photocatalysis and photoelectrocatalysis ration of photon-excited electrons from holes can be effectively promoted in the photoelectrocatalysis of
meso‑carbon@TiO2/carbon fiber composites under visible light. The synergistic effect between electrocatalytic
and photocatalytic oxidation under visible light results in almost complete degradation of Rhodamine B. Our
study provides an avenue to recycle and reuse nanosized photocatalysts and open a possibility for practical indus-
trial application of photocatalysis and photoelectrocatalysis using separable and recyclable meso‑carbon@TiO2/
carbon fiber composites.
© 2019 Published by Elsevier B.V.

1. Introduction activity [37–41]. The incorporation of carbon to TiO2 can increase the
adsorption of adsorbates on the surface of the catalysts and further re-
TiO2-based photocatalysts have been widely employed to eliminate sult in the immigration of adsorbates to the surface of TiO2, where the
toxic chemicals from waste water [1–3]. TiO2-based photocatalysts have photocatalytic reaction occurs [42–46]. In addition, carbon has a large
a significant effect on the chemical oxidation of undesirable organic electron-storage performance and can accept electrons excited by TiO2
chemicals in the environment to CO2, H2O, and other inorganic constit- to suppress the recombination of the photo-excited electron-hole pair
uent. However, the wide bandgap for anatase TiO2 (about 3.2 eV) leads [47]. However, current preparation methods for carbon with TiO2 gen-
to lower adsorption efficiency in the visible light region of solar light erate bulky materials with low specific surface area and less separation
spectrum and in turn limit its wider application [4,5]. efficiency of the photo-excited electron-hole pairs and comparably low
Extensive efforts, such as cation (Cr [6], Fe [7], or Ni [8]) or anion photocatalytic activity. Moreover, three main issues, including the dis-
(C [9–11], N [12–15], B [16,17], I [18] or S [19–22]) substitution in tribution of single carbon particles, collection and recycle of catalysts
TiO2, defect engineering of TiO2 [23–26] and searching new after usage, highly limit the practical industry application [48–51]. To
photocatalysts (Bi2O3 [27,28], WO3 [29] and g-C3N4 [30–34]), have overcome these challenges, suitable supportive structures are highly
been devoted to increasing the photocatalytic activity under visible needed. A few attempts have been devoted to embed coating photo-
light region [35,36]. Very recently, heterojunction semiconductors, catalysts on various solid-state carriers such as titanium mesh [52,53],
such as carbon particles incorporated TiO2, presents high photocatalytic optical glass [54,55] and silicon [56,57] substrates by anodisation [58],
sol-gel process [59,60] and sputtering [61,62]. The modified photo-
⁎ Corresponding authors.
catalysts can be easily separated from wastewater for recycling usage.
E-mail addresses: [email protected] (Y.-L. Yang), [email protected], However, their photocatalytic activities is significat decreased due to
[email protected] (Z.-G. Chen). the low specific surface area of photocatalysts after coated on solid

https://doi.org/10.1016/j.susmat.2019.e00105
2214-9937/© 2019 Published by Elsevier B.V.
2 H.-J. Chen et al. / Sustainable Materials and Technologies 21 (2019) e00105

carriers [63]. Therefore, it is desirable to fabricate photocatalysts with for 24 h. After carbonized at 500 °C for 12 h under argon atmosphere,
high specific surface area immobilized on different solid-state sub- meso‑carbon microspheres were obtained.
strates and apply them in practical industry application.
In this work, we firstly use solvothermal method to fabricate 2.3. Synthesis of meso‑carbon@TiO2 core-shell microspheres
meso‑carbon@TiO2 core-shell microspheres with tunable thickness of
external shells and high specific surface area. After that, we use an The meso‑carbon@TiO2 core-shell microspheres were prepared by a
in-situ adsorption method to load meso‑carbon@TiO2 core-shell micro- solvothermal method. Meso‑carbon microspheres (10 mg) was first
spheres on carbon fiber felt to form macro-sized meso‑carbon@TiO2/car- dispersed in a solvent comprising of ethylene glycol (10 mL) and
bon fiber composites which can be easily separated and recycled after acetone (20 mL) by sonication for 30 min. Then, tetrabutyl titanate
usage. The morphologies, photocatalytic and photoelectrocatalytic (50–100 μL) was added and stirred at room temperature for 30 min.
(PEC) activities along with photocatalytic and PEC mechanism of The mixture was heated at 160 °C for 12 h at 100 mL reaction kettle
meso‑carbon@TiO2/carbon fiber composites are detailed investigated. (φ50 mm × 100 mm), and then the precipitate was collected and puri-
This comprehensive study could provide a new way to collect and recy- fied with distilled water by centrifugation and dried at 100 °C for 2 h.
cle nanosized photocatalysts and open the possibility for practical After calcined at 500 °C for 2 h under an argon atmosphere,
industrial application of separable and recyclable photocatalysis and meso‑carbon@TiO2 core-shell microspheres were obtained.
photoelectrocatalysis of meso‑carbon@TiO2/carbon fiber composites.
2.4. Preparation of meso‑carbon@TiO2/carbon fiber composites
2. Experimental
The meso‑carbon@TiO2/carbon fiber composites were prepared via
an in-situ adsorption method at room temperature under magnetic stir-
2.1. Materials
ring. Meso‑carbon@TiO2 core-shell microspheres (20 mg) was first dis-
persed in water by sonication for 10 min. Then, a carbon fiber felt with
3-Aminophenol (C6H7NO), ethylene glycol ((HOCH2) 2), acetone
an outline dimension of 10 mm × 20 mm was submerged in suspension
(CH3COCH3), tetrabutyl titanate (C16H36O4Ti), formaldehyde solution
and stirred for 10 min at room temperature. During magnetic stirring,
(37 wt% in H2O, HCHO) and ammonia solution (25 wt% in H2O) were
meso‑carbon@TiO2 core-shell microspheres were adsorbed and
purchased from Shanghai Macklin Biochemical Co., Ltd. Rhodamine B
immobilized on carbon fiber felt, then the meso‑carbon@TiO2/carbon
(RMB, C28H31ClN2O3) and Sodium sulfate (Na2SO4) were purchased
fiber composites were prepared.
from Sinopharm Chemical Reagent Co., Ltd. All reagents were used
without additional purification for synthesis of meso‑carbon@TiO2/
2.5. Morphology/microstructure characterizations
carbon fiber composites.
Quantachrome Nova Station A was utilized to determine N2 adsorp-
2.2. Synthesis of meso‑carbon microspheres tion and desorption isotherms of meso‑carbon microspheres. The
Barret-Joyner-Halenda (BJH) and Brunauer-Emmett-Teller (BET)
The 3-AF resin microspheres were first synthesized and then car- method were utilized to confirm the pore size distributions and specific
bonized to fabricate meso‑carbon microspheres using the outlined liter- surface areas of meso‑carbon microspheres, respectively.
ature [64]. In particular, 3-aminophenol (3-AP, 0.40 g, 3.628 mmol) was The meso‑carbon@TiO2 core-shell microspheres were characterized
dissolved in a solvent comprising of water (80 mL) and ethylalcohol using field-emission scanning electron microscope (FESEM, Zeiss Sigma
(40 mL) under magnetic stirring. After 3-aminophenol was fully dis- HD) with an energy-dispersive X-ray (EDX) analyzer, X-ray diffraction
solved, 37 wt% formaldehyde and 25 wt% aqueous ammonia as a cata- (XRD), transmission electron microscopy (TEM, Tecnai G2 F20, FEI),
lyst were mixed and reacted at different temperature for 30 min. UV–vis diffuse reflectance spectroscopy (DRS) and X-ray fluorescence
Afterwards, 3-AF resin microspheres were collected and purified with spectrometer (XRF). The morphologies of meso‑carbon@TiO2/carbon
distilled water by centrifugation, then the sample was dried at 100 °C fiber composites were characterized by FESEM.

Scheme 1. Schematic diagram of PEC system of meso‑carbon@TiO2/carbon fiber composites and the charge separation and transfer processes in meso‑carbon@TiO2/carbon fiber
composites.
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2.6. Adsorption capacity of meso‑carbon@TiO2 core-shell microspheres 2.7. PEC performance of meso‑carbon@TiO2/carbon fiber composites

To evaluate the adsorption capacity of RMB on meso‑carbon@TiO2 PEC system consists of a cuboidal quartz reactor with an effective
core-shell microspheres, static adsorption experiments were carried volume of 300 mL, visible light or UV–vis light and a two-electrode con-
out. Meso‑carbon@TiO2 core-shell microspheres were first dispersed figuration. The meso‑carbon@TiO2/carbon fiber composites (outline di-
in RMB solution of 10 mg/L, then the mixture was shaken at mension of 10 mm × 20 mm) as an anode and a stainless-steel mesh
200 r/min. During the adsorption process, the concentration of residual (outline dimension of 10 mm × 20 mm) as a cathode were positioned
RMB was analyzed by spectrophotometry at a regular time interval. in the reactor and linked by the potentiostat. Scheme 1 shows a brief
These data were used to calculate the absorption capacity of schematic diagram of PEC system using meso‑carbon@TiO2/carbon
meso‑carbon@TiO2 core-shell microspheres by Eq. (1). fiber composites.
In a typical PEC process, meso‑carbon@TiO2/carbon fiber composites
V ðc0 −ct Þ (outline dimension of 10 mm × 20 mm) and stainless-steel mesh cath-
qt ¼ ð1Þ
m ode were parallel placed in a cuboidal quartz reactor in which 200 mL
RMB solution comprising of 10 mg/L RMB and 1.0 g/L Na2SO4 acted as
where qt is the amount of RMB adsorbed on meso‑carbon@TiO2 core- the supporting electrolyte for the PEC oxidation process was added,
shell microspheres at time t, c0 (mg/L) and ct are the concentrations of then the potentiostat was connected. The incident visible light or UV–
RMB initially and at time t, respectively. V is the volume of RMB solution vis light was irradiated onto meso‑carbon@TiO2/carbon fiber compos-
and m is the mass of meso‑carbon@TiO2 core-shell microspheres. In the ites from the side through the cuboidal quartz reactor, the external
process of adsorption, three-parallel experiments were implemented bias voltage was employed in PEC oxidation process and meanwhile,
and average values were calculated. timer started.

Fig. 1. (a)–(c) SEM images of the products at the polymerization temperatures of 30, 20, and 10 °C, respectively. The corresponding particle sizes are 229 nm, 275 nm, and 306 nm,
respectively. (d) XRD patterns showing the formation of carbon phases. (e) N2 adsorption-desorption isotherms and (f) corresponding pore size distributions of as-prepared
meso‑carbon microspheres.
4 H.-J. Chen et al. / Sustainable Materials and Technologies 21 (2019) e00105

During the PEC process, the concentration of RMB was analyzed by where k is first-order kinetics rate constant for degradation process
spectrophotometry at a regular time interval. The degradation rate of of RMB.
RMB was calculated by Eq. (2).
3. Results and discussion
ce −ct
Degradation Rate ¼  100% ð2Þ 3.1. Morphology and microstructure of meso‑carbon microspheres
ce

The polymerization of 3-aminophenol and formaldehyde solution in

where ce (mg/L) and ct (mg/L) are RMB concentrations at adsorption ethanol/water (volume ratio 1:2) solution was initiated with the addi-
equilibrium and time t, respectively. The degradation process of RMB tion of ammonium hydroxide at a different temperature to generate
can be described by a first-order kinetics equation (Eq. (3)). phenolic resins and then the products were carbonized at 500 °C
for 12 h to obtain carbon microspheres. Fig. 1a–c are typical FESEM
ct images of the carbon microsphere samples and show the fabricated
ln ¼ −k  t ð3Þ
ce meso‑carbon microspheres has an average size of 229, 275, and

Fig. 2. FESEM and TEM images of meso‑carbon@TiO2 core-shell microspheres using different mass ratios of the carbon microspheres/TBT as the reaction substances: (a, c) 2:5, (b, d) 2:10.
(e) Element mapping images of the meso‑carbon@TiO2 core-shell microspheres and (f) a schematic diagram of synthesizing meso‑carbon@TiO2 core-shell microspheres.
 H.-J. Chen et al. / Sustainable Materials and Technologies 21 (2019) e00105 5

Fig. 3. UV–vis diffuse reflectance spectra and PL emission spectra of commercial TiO2 powder (P25) and meso‑carbon@TiO2 core-shell microspheres. (a) UV–vis diffuse reflectance spectra;
(b) PL emission spectra; Time-resolved PL spectra at the ns-level monitored at 343 nm under excitation by 223 nm light for commercial TiO2 powder (P25) (c) and meso‑carbon@TiO2 core-
shell microspheres (d).

Fig. 4. The effect of adsorption time on adsorption of RMB on meso‑carbon@TiO2 core-shell microspheres and adsorption kinetic. (a) The influence of adsorption time on qt and ct; (b) UV–
Vis spectra of RMB at different adsorption time; (c–d) The intraparticle diffusion and pseudo-second-order adsorption kinetic.
6 H.-J. Chen et al. / Sustainable Materials and Technologies 21 (2019) e00105

306 nm at different polymerization temperatures of 30, 20, and 10 °C, semiconducting behavior. Because meso‑carbon microspheres consists
respectively. As can be seen, the particle size of carbon microspheres primarily of carbon nanoclusters, the semiconductive properties are
is sensitive to the polymerization temperature. The higher polymeriza- possibly due to the mesoscopically aggregated carbon nanoclusters
tion temperature results in the higher nucleation rate in the solution within meso‑carbon microspheres [69].
and thus the smaller particle size.
Fig. 1d is the XRD patterns of the samples, confirming the formation
of carbon phases. Fig. 1e–f show the N2 adsorption-desorption isotherm 3.2. Morphology and performance of meso‑carbon@TiO2 core-shell
and corresponding pore size distribution of the carbon microspheres. microspheres
Isotherms and hysteresis loop belong to Langmuir type IV and type H2,
respectively. The adsorption isotherm is relatively far away from the de- Meso‑carbon@TiO2 core-shell microspheres are prepared from
sorption isotherm at high pressure, suggesting the formation of mesopo- meso‑carbon microspheres (with particle size of 306 nm) as a hard tem-
rous structure of carbon microspheres [65]. From the BET results of plate. Fig. 2a–b are typical FESEM images of meso‑carbon@TiO2 core-
Fig. 1e, the meso‑carbon microspheres with average sizes of 229, 275, shell microspheres, which show that the microspheres have rough sur-
and 306 nm exhibit specific surface areas of 1086, 1013, and 936 m2/g, face and regular spherical shapes. Fig. 2c–d are typical TEM images of
respectively. Fig. 1f shows the pore size distribution of meso‑carbon mi- meso‑carbon@TiO2 core-shell microspheres prepared from different
crospheres, which indicates that pore size slightly decreases with mass ratios of carbon microspheres/TBT. As can be seen, the micro-
increasing polymerization temperature. To confirm the semiconducting spheres are core-shell microstructures. Moreover, the thickness of the
nature of the meso‑carbon microspheres, the optical band gap (Eg) of shell can be tuned by varying the amount of TBT, as evidenced in TEM
meso‑carbon microspheres can be estimated from the Tauc plot [66], characterizations. Fig. 2c shows a shell thickness of 113 nm, achieved
the Eg value of meso‑carbon microspheres can be estimated to be from a TBT amount of 50 μL. The shell thickness of 166 nm can be pro-
2.10 eV, which is close to the reported value of carbon materials duced from a double amount of TBT as shown in Fig. 2d, which indicates
[67,68]. The Eg indicates that meso‑carbon microspheres exhibits the that the shell thickness increases with increasing the amount of TBT,

Fig. 5. Images of as-prepared meso‑carbon@TiO2/carbon fiber composites and unmodified carbon fiber felt. (a) Macrophotograph of carbon fiber felt; (b)general view and surface of
unmodified carbon fiber felt; (c–d) general view and surface of as-prepared meso‑carbon@TiO2/carbon fiber composites; (e–f) low-magnification and high magnification SEM image of
the surface for a single meso‑carbon@TiO2/carbon fiber composite.
 H.-J. Chen et al. / Sustainable Materials and Technologies 21 (2019) e00105 7

meso‑carbon microspheres have a large electron-storage capacity and

may accept photon-excited electrons, resulting in the reduction of re-
combination of photon-excited electrons and holes and the increase of
the photon efficiency.
Time-resolved fluorescence spectra of the commercial TiO2 powder
(P25) and meso‑carbon@TiO2 core-shell microspheres were recorded
to investigate the transfer of photon-excited electrons and holes
in meso‑carbon@TiO2 core-shell microspheres under irradiation as
shown in Fig. 3c–d. As can be seen, they exhibit distinct radiative life-
times (τ), and τ of TiO2 (P25) and meso‑carbon@TiO2 core-shell micro-
spheres is 11.22 and 4.67 ns, respectively. The results indicate that in
meso‑carbon@TiO2 core-shell microspheres, meso‑carbon microspheres
can promote the storing and shuttling of electrons due to its excellent
electrical conductivity, and thus enhance electron transfer between ex-
terior TiO2 and meso‑carbon microspheres.

3.3. Adsorption kinetic of RMB in meso‑carbon@TiO2 core-shell

Fig. 6. Current density with a reproducible response to the on-off cycles of visible light
irradiation in 0.1 M Na2SO4 electrolyte, recorded on carbon fiber felt and meso‑carbon@ microspheres
TiO2/carbon fiber composite working electrode with Pt wire counter electrode, 0.1 V
constant bias vs. SCE, surface area of working electrode = 1.0 cm × 1.0 cm. Fig. 4a shows the influence of contact time on the adsorption capac-
ity of RMB on the meso‑carbon@TiO2 core-shell microspheres. The con-
suggesting that our synthetic strategy provides a high flexibility in centration of RMB and quantity of meso‑carbon@TiO2 core-shell
tuning the particle size and the shell thickness. microspheres were 10 mg/L and 100 mg/L, respectively. Initial adsorp-
Fig. 2e is the elemental mappings of C, Ti, and O and the signals of tion was finished within 30 min, then leveled off at above 30 min, indi-
C, Ti, and O can be clearly observed, confirming the formation of cating the adsorption of RMB for meso‑carbon@TiO2 core-shell
meso‑carbon@TiO2 core-shell microspheres. For further illustrating the microspheres is quick and efficient. Fig. 4b shows UV–vis spectra of
structure and formation process, Fig. 2f shows a schematic diagram RMB before and after adsorption. It is obviously that the absorbance in-
for the formation of meso‑carbon@TiO2 core-shell microspheres, in tensity of RMB decreases with increasing the adsorption time.
which the size-tunable meso‑carbon microspheres act as hard template Fig. 4c–d show the intraparticle diffusion (qt = k × t0.5) and pseudo-
to fabricate meso‑carbon@TiO2 core-shell microspheres with controlled second-order adsorption kinetics ( qt ¼ k 1q2 þ q1  t ) of RMB for the
t 2 e e

shell thickness. meso‑carbon@TiO2 core-shell microspheres [72], where, k is the rate

For evaluation the optical absorption edge of meso‑carbon@TiO2 constant, k2 is the pseudo-second-order rate constant, qe and qt are the
core-shell microspheres, UV–vis diffuse reflectance spectrum of the mi- capacity of adsorbing RMB onto the meso‑carbon@TiO2 core-shell mi-
crospheres is shown in Fig. 3a. For comparasion, the UV–vis diffuse re- crospheres at equilibrium and at time t, and t is contact time. Fig. 4c
flectance spectrum of commercial TiO2 powder (P25) is also shown in shows the kinetic process for adsorption of RMB on meso‑carbon@TiO2
Fig. 3a. As can be seen, meso‑carbon@TiO2 core-shell microspheres core-shell microspheres is closely consistent with intraparticle diffusion
have higher absorption efficiency of UV–vis light than that of commer- equation. However, the linear equation does not pass through
cial TiO2 (P25), suggesting that meso‑carbon microspheres can effec- coordinates-origin, indicating that intraparticle diffusion is not the
tively extend the absorption edge of TiO2 to the visible light region by only adsorption-determining step. It is well known that the pseudo-
acting as a photosensitizer [70]. second-order kinetics model postulates that chemical adsorption con-
Fig. 3b shows the PL emission spectra of the meso‑carbon@TiO2 core- trols the adsorption rate [73]. Fig. 4d shows the adsorption kinetic of
shell microspheres and commercial TiO2 (P25) excited by 223 nm UV RMB on the meso‑carbon@TiO2 core-shell microspheres follows
light. As can be seen, commercial TiO2 (P25) exhibits a higher PL inten- pseudo-second-order equation, which indicates that the adsorption of
sity than that of meso‑carbon@TiO2 core-shell microspheres. The emis- RMB on the meso‑carbon@TiO2 core-shell microspheres involves elec-
sion intensity of meso‑carbon@TiO2 core-shell microspheres at tronic sharing or electron transfer between RMB and meso‑carbon@
300–700 nm is drastically quenched, suggestinng that meso‑carbon mi- TiO2 core-shell microspheres. Therefore, in conclusion, the adsorption
crospheres can assist to supress the recombination of photon-excited of RMB on the meso‑carbon@TiO2 core-shell microspheres involves in
electrons and holes excited by TiO2 under UV light [71]. In fact, the intraparticle diffusion and chemical adsorption process.

Fig. 7. RMB degradation efficiency (a) and pseudo-first order kinetics plots (b) by meso‑carbon@TiO2/carbon fiber composites and P25 in presence of 10 mg/L RMB under UV–vis light
irradiation.
8 H.-J. Chen et al. / Sustainable Materials and Technologies 21 (2019) e00105

Fig. 8. RMB degradation efficiency (a) and pseudo-first order kinetics plots (b) by meso‑carbon@TiO2/carbon fiber composites under UV–vis light and visible light irradiation.

3.4. Characterization of meso‑carbon@TiO2/carbon fiber composites This phenoma suggest that the meso‑carbon@TiO2 core-shell micro-
spheres immobilized on the surface of carbon fiber felt plays an impor-
Fig. 5a-b are typical SEM images of the unmodified carbon fiber tant role in generating photocurrent density.
felt and shows that the unmodified carbon fibers have a smooth
surface. Fig. 5c-d display typical SEM images of the as-prepared
meso‑carbon@TiO2/carbon fiber composites, in which meso‑carbon@ 3.5. PEC activity and mechanism of meso‑carbon@TiO2/carbon fiber
TiO2 core-shell microspheres are distributed on the surface of the car- composites
bon fiber felt. Fig. 5e-f display high-magnification SEM images of the
surface of meso‑carbon@TiO2/carbon fiber composites. As can be seen, The PEC activities of meso‑carbon@TiO2/carbon fiber composites
meso‑carbon@TiO2 core-shell microspheres tend to be preferentially along with kinetics were evaluated by the degradation of RMB
adsorbed on the surface of carbon fiber felt. In general, the surface of (200 mL, 10 mg/L) at different reaction conditions. Fig. 7 show the deg-
carbon fiber felt is negative-charged, owing to that zeta potential radation activity (Fig. 7a) of meso‑carbon@TiO2/carbon fiber composites
of the carbon fiber felt in water is −59.56 mV. On the contrary, the and pseudo-first order kinetics (Fig. 7b) of RMB for meso‑carbon@TiO2/
zeta potentials of the TiO2 nanoparticles calcined at different carbon fiber composites along with commercial TiO2 powder (P25) at
temperatures (500–800 °C) are positive around neutral Ph [74]. There- open circuit with and without light irradiation. The photocatalytic deg-
fore, the surface of negatively charged carbon fiber felt preferentially radation rates of meso‑carbon@TiO2/carbon fiber composites and com-
adsorbes positive meso‑carbon@TiO2 core-shell microspheres, forming mercial P25 TiO2 are 37.8% and 13.6% under UV–vis light irradiation,
meso‑carbon@TiO2/carbon fiber composites, which is characterized as respectively. Generally, the photocatalysis is a thermodynamically fa-
separable and recyclable material because of the introduction of carbon vorable reaction, which means surface molecular adsorption is the
fiber felt. rate-determining step [77,78]. Compared with commercial P25 TiO2,
It is well known that electrochemically assisted photocatalysis can meso‑carbon@TiO2/carbon fiber composites exhibit a higher adsorba-
effectively decrease the recombination of photon-excited electrons bility [79,80]. During photocatalytic degradation of RMB, the amount
and holes under the application of bias voltage. The photocatalytic and of adsorbed RMB on meso‑carbon@TiO2/carbon fiber composites is
photoelectrocatalytic activity of photocatalyst is largely related to higher than that of commercial P25 TiO2. The degradation rate of
the value of photocurrent [75,76]. Fig. 6 show the current density meso‑carbon@TiO2/carbon fiber composites is greatly higher than that
with a reproducible response to the on-off cycles of visible light irradia- of commercial P25 TiO2.
tion in 0.1 M Na2SO4 electrolyte, recorded on carbon fiber felt and As shown in Fig. 8, the photocatalytic degradation rates of
meso‑carbon@TiO2/carbon fiber composite working electrodes with meso‑carbon@TiO2/carbon fiber composites under UV–vis light and
Pt wire counter electrode. As can be seen, meso‑carbon@TiO2/carbon visible light are 37.8% and 26.2%, respectively. To reveal the underlying
fiber composite working electrode shows much higher photocurrent reason for the enhanced photocatalytic properties of meso‑carbon@
density than that from the carbon fiber felt working electrode. TiO2/carbon fiber composites under UV–vis light irradiation, the

Scheme 2. Schematic illustration of the proposed mechanism for the p hotocatalytic degradation of meso‑carbon@TiO2/carbon fiber composites: switching charge transfer from
conventional type II to direct Z-scheme by tuning light irradiation from visible light to UV–vis light.
 H.-J. Chen et al. / Sustainable Materials and Technologies 21 (2019) e00105 9

Fig. 9. RMB degradation efficiency and pseudo-first order kinetics plots by meso‑carbon@TiO2/carbon fiber composites in presence of 10 mg/L RMB at open circuit (OC) and a constant
potential of 3.0 V with and without visible light irradiation.

photocatalytic mechanism of RMB degradation for meso‑carbon@TiO2/ the CB of meso‑carbon microspheres and transfer electrons to the exter-
carbon fiber composites is proposed as illustrated in Scheme 2. The nal circuit due to the excellent electrical conductivity of carbon fiber,
analysis of UV–vis diffuse reflectance spectrum demonstrates the semi- leaving the holes in the VB of TiO2. Therefore, RMB adsorbed on the sur-
conducting nature of meso‑carbon microspheres. The optical band gap face of meso‑carbon@TiO2 core-shell microspheres should be redox-
of meso‑carbon microspheres was determined to be 2.10 eV from the active [85,86]. Fig. 10b shows the degradation kinetic of RMB for
UV–vis diffuse reflectance spectrum. The reported valence band energy meso‑carbon@TiO2/carbon fiber composites, which complies with
(Ev) of meso‑carbon microspheres is 0.60 eV [81]. The conduction band first-order kinetics [87].
energy (Ec) was thus estimated at −1.50 eV from Ev – Eg. Therefore,
meso‑carbon microspheres could be stimulated by visible light to gener- 4. Conclusion
ate photon-excited electrons and holes, whereas exterior TiO2 can not
be photoexcited under visible light irradiation. According to the conven- In this study, the size-tunable meso‑carbon@TiO2 core-shell mi-
tional type-II band alignment [82], for meso‑carbon@TiO2/carbon fiber crospheres are firstly prepared via solvothermal method and then
composites, the electrons in the conduction band (CB) of meso‑carbon the meso‑carbon@TiO2 core-shell microspheres were rationally
microspheres transfer to the CB of TiO2, while the holes in the valence loaded on the surface of carbon fiber felt to synthesize macro-sized
band (VB) of meso‑carbon microspheres transfer to the VB of TiO2. meso‑carbon@TiO2/carbon fiber composites which can be easily sep-
The RMB is then oxidized into CO2, H2O, and others.63 Therefore, the re- arated and recycled after usage. The microstructural and spectro-
combination of photon-excited electrons and holes can be decreased scopic characterization shows that the absorption edge is extended
due to the existence of meso‑carbon microspheres in meso‑carbon@ to the visible light region of meso‑carbon@TiO 2 core-shell micro-
TiO2/carbon fiber composites. spheres and the recombination of photon-excited electrons and
When meso‑carbon@TiO2/carbon fiber composites were irradiated holes can be significantly suppressed compared with P25 TiO2 pow-
by UV–vis light, both meso‑carbon microspheres and exterior TiO2 gen- der. The experiments results of meso‑carbon@TiO 2 /carbon fiber
erate photon-excited electrons and holes. The transfer pathway of composites show that the photocurrent density and the photocata-
photon-excited electrons and holes complies with Z-scheme [83], lytic degradation rate under UV–vis light is much better than that
namely, the electrons in the CB of TiO2 transfer to the VB of meso‑carbon under visible light irradiation owing to the higher charge carrier sep-
microspheres and then recombine with the holes in meso‑carbon micro- aration efficiency and the higher electron consumption of the direct
spheres [64]. Therefore, electrons in the CB of meso‑carbon micro- Z-scheme. In the process of PEC, the separation of photon-excited
spheres and holes in the VB of TiO2 are ideally separated. The spatially electrons from holes can be effectively promoted, and the synergistic
separated holes in the VB of TiO2 reacted with H2O to form active spe- effect between electrocatalytic and photocatalytic oxidation under
cies ·OH, and then ·OH degraded RMB into CO2, H2O and others. Simul- visible light results in almost complete degradation of RMB. Our
taneously, carbon fibers acting as cocatalysts [84] can trap electrons in study provides a possibility for practical industrial application of
the CB of meso‑carbon microspheres due to its excellent electrical con- photocatalysis and photoelectrocatalysis using separable and recy-
ductivity, which thus optimizes the oxidation ability of TiO2. Accord- clable meso‑carbon@TiO2/carbon fiber composites.
ingly, the transfer pathway of Z-scheme photon-excited electrons and
holes results in more effective charge-carrier separation capacity and Author contributions
more effective consumption of electrons than that of conventional
type-II. Therefore, the photocatalytic degradation rate under UV–vis The first two authors contributed equally to this work.
light is much better than that under visible light irradiation in our All authors have given approval to the final version of the
meso‑carbon@TiO2/carbon fiber composites. manuscript.
Fig. 9a shows the electrocatalytic degradation rate of meso‑carbon@
TiO2/carbon fiber composites in the dark is 19.5%. When visible light ir- Competing interests
radiation is applied, the PEC degradation rate is greatly enhanced to be
97.2% originating from the high-efficiency separation of photon- The authors declare no competing financial interests.
excited electrons and holes in meso‑carbon@TiO2/carbon fiber compos-
ites under the condition of visible light irradiation and the external volt- Acknowledgments
age of 3.0 V, revealing the presence of synergistic effect between
photocatalytic and electrocatalytic oxidation. The process of charge sep- The authors acknowledge financial support from the National
aration and transfer of meso‑carbon@TiO2/carbon fiber composites is Natural Science Foundation of China (Grant Nos.: 51464020,
proposed as illustrated in Scheme 1. As can be seen, under the condition 51101076, 51704188, 51802181, 61705125 and 51702199), Jiangxi
of visible light irradiation and the external voltage of 3.0 V, negatively Natural Science Foundation (Grant Nos.: 20161BAB206164 and
charged carbon fiber acting as cocatalysts [65] can trap electrons in 20161BBH80062), and Austrlian Research Council.
10 H.-J. Chen et al. / Sustainable Materials and Technologies 21 (2019) e00105

Appendix A. Supplementary data pathways, Appl. Catal. B Environ. 199 (2016) 1–10, https://doi.org/10.1016/j.
apcatb.2016.06.024.
[22] K.M. Kumar, S. Godavarthi, T.V.K. Karthik, M. Mahendhiran, A. Hernandez-Eligio, N.
The ‘Supporting Information’ include supplementary discussion Hernandez-Como, V. Agarwal, L.M. Gomez, Green synthesis of S-doped rod shaped
about the TG and XRD analysis of meso‑carbon@TiO2 core-shell micro- anatase TiO2 microstructures, Mater. Lett. 183 (2016) 211–214, https://doi.org/10.
1016/j.matlet.2016.07.100.
spheres, the influence of UV–vis light irradiation on photocurrent den- [23] G. Ou, Y. Xu, B. Wen, R. Lin, B. Ge, Y. Tang, Y. Liang, C. Yang, K. Huang, D. Zu, R. Yu, W.
sity of the composites, the UV–vis spectra of RMB, and the cycling Chen, J. Li, H. Wu, L.M. Liu, Y. Li, Tuning defects in oxides at room temperature by
stability of meso‑carbon@TiO2/carbon fiber composites during the PEC lithium reduction, Nat. Commun. 9 (2018) 1302, https://doi.org/10.1038/s41467-
018-03765-0.
degradation process. [24] L. Ye, J. Mao, J. Liu, Z. Jiang, T. Peng, L. Zan, Synthesis of anatase TiO2 nanocrystals
with {101}, {001} or {010} single facets of 90% level exposure and liquid-phase pho-
tocatalytic reduction and oxidation activity orders, J. Mater. Chem. A 1 (2013)
References 10532–10537, https://doi.org/10.1039/C3TA11791J.
[25] X. Wu, Z. Chen, Q.M.L. Gao, L. Wang, Nanosized Anatase TiO2 single crystals with
[1] S. Afzal, E.M. Samsudin, N.M. Julkapli, S.B. Abd Hamid, Controlled acid catalyzed sol Tunable exposed (001) facets for enhanced energy conversion efficiency of dye-
gel for the synthesis of highly active TiO2-chitosan nanocomposite and its corre- sensitized solar cells, Adv. Funct. Mater. 21 (2011) 4166, https://doi.org/10.1002/
sponding photocatalytic activity, Environ. Sci. Pollut. R 23 (2016) 23158–23168, adfm.201100828.
https://doi.org/10.1007/s11356-016-7507-2. [26] X.Y. Ma, Z.G. Chen, S.B. Hartono, H.B. Jiang, J. Zou, S.Z. Qiao, H.G. Yang, Fabrication of
[2] C.A. Aggelopoulos, M. Dimitropoulos, A. Govatsi, L. Sygellou, C.D. Tsakiroglou, S.N. uniform anatase TiO2 particles exposed by {001} facets, Chem. Commun. 46 (2010)
Yannopoulos, Influence of the surface-to-bulk defects ratio of ZnO and TiO2 on 6608–6610, https://doi.org/10.1039/C0CC01473G.
their UV-mediated photocatalytic activity, Appl. Catal. B Environ. 205 (2017) [27] X. Li, C. Guan, Y.T. Hu, J. Wang, Nanoflakes of Ni-co LDH and Bi2O3 assembled in 3D
292–301, https://doi.org/10.1016/j.apcatb.2016.12.023. carbon Fiber network for high-performance aqueous rechargeable Ni/bi battery, ACS
[3] S. Okunaka, H. Tokudome, Y. Hitomi, R. Abe, Facile preparation of stable aqueous ti- Appl. Mater. Interfaces 9 (2017) 26008–26015, https://doi.org/10.1021/acsami.
tania sols for fabrication of highly active TiO2 photocatalyst films, J. Mater. Chem. A 3 7b06696.
(2014) 1688–1695, https://doi.org/10.1039/c4ta04680c. [28] H.J. Chen, D. Li, D. Xue, G.B. Yang, Preparation of bi-doped TiO2 Photoeatalyst
[4] C. Song, D. Zhou, L. Yang, J. Zhou, C. Liu, Z.G. Chen, Recovery TiO2 and sodium tita- and their visible-light Photocatalytic activity to degradation of resorcinol,
nate nanowires as Cd(II) adsorbent from waste V2O5-WO3/TiO2 selective catalytic Chin. Ceramic Soc. 40 (2012) 1483–1488, https://doi.org/10.14062/j.issn.
reduction catalysts by Na2CO3-NaCl-KCl molten salt roasting method, J. Taiwan 0454-5648.2012.10.013.
Inst. Chem. E. 88 (2018) 226–233, https://doi.org/10.1016/j.jtice.2018.04.006. [29] S. Chen, L. Zeng, H. Tian, X.Y. Li, J.L. Gong, Enhanced lattice oxygen reactivity over Ni-
[5] X. Wu, J. Liu, Z. Chen, Q. Yang, C. Li, G. Lu, L. Wang, Amino acid assisted synthesis of modified WO3-based redox catalysts for chemical looping partial oxidation of meth-
mesoporous TiO2 nanocrystals for high performance dye-sensitized solar cells, J. ane, ACS Catal. 7 (2017) 3548–3559, https://doi.org/10.1021/acscatal.7b00436.
Mater. Chem. 22 (2012) 10438–10440, https://doi.org/10.1039/C2JM16762J. [30] J.Q. Wen, J. Xie, H.D. Zhang, A.P. Zhang, Y.J. Liu, X.B. Chen, X. Li, Constructing multi-
[6] C. Liu, Y.M. Song, X.H. Yu, J.X. Liu, J.S. Deng, Electronic structure and optical absorp- functional metallic Ni Interface layers in the g-C3N4 Nanosheets/amorphous NiS
tion spectra of C-Cr co-doped anatase TiO2 based on first principles, Phys. Status Heterojunctions for efficient Photocatalytic H2 generation, ACS Appl. Mater. Inter-
Solid B 255 (2018), 1700616. https://doi.org/10.1002/Pssb.201700616. faces 9 (2017) 14031–14042, https://doi.org/10.1021/acsami.7602701.
[7] Y.Y. Gao, Z.X. Li, Y.H. Hao, Effect of M-doped (M = Cr, Fe, co, and Nb) V2O5/TiO2 [31] B.T. Dong, M.Y. Li, S. Chen, D.W. Ding, W. Wei, G.X. Gao, S.J. Ding, Formation of g-
(001) on mercury oxidation: the insights from DFT calculation, J. Phys. Chem. C C3N4@Ni(OH)2 honeycomb nanostructure and asymmetric Supercapacitor with
121 (2017) 27963–27975, https://doi.org/10.1021/acs.jpcc.7b08151. high energy and power density, ACS Appl. Mater. Interfaces 9 (2017)
[8] W.J. Tseng, P.T. Lin, Effect of solids concentration on TiO2/Ni composite foams pre- 17890–17896, https://doi.org/10.1021/acsami.7b02693.
pared by aqueous gelcasting of particle-stabilized emulsions, J. Eur. Ceram. Soc. 37 [32] L.X. Wang, Y. Li, X.C. Yin, Y.Z. Wang, A.L. Song, X.J. Qin, G.J. Shao, Coral-like-struc-
(2017) 5265–5272, https://doi.org/10.1016/j.jeurceramsoc.2017.03.040. tured Ni/C3N4 composite coating: An active Electrocatalyst for hydrogen evolution
[9] J.R. Rangel-Mendez, J. Matos, L.F. Chazaro-Ruiz, A.C. Gonzalez-Castillo, G. Barrios- reaction in alkaline solution, ACS Sustain. Chem. Eng. 5 (2017) 7993–8003,
Yanez, Microwave-assisted synthesis of C-doped TiO2 and ZnO hybrid nanostruc- https://doi.org/10.1021/acssuschemeng.7b01576.
tured materials as quantum-dots sensitized solar cells, Appl. Surf. Sci. 434 (2018) [33] Q. Xu, B. Cheng, J. Yu, G. Liu, Making co-condensed amorphous carbon/g-C3N4 com-
744–755, https://doi.org/10.1016/j.apsusc.2017.10.236. posites with improved visible-light photocatalytic H2-production performance
[10] J.R. Chen, F.X. Qiu, Y. Zhang, J.Z. Liang, H.J. Zhu, S.S. Cao, Enhanced supercapacitor using Pt as cocatalyst, Carbon 118 (2017) 241–249, https://doi.org/10.1016/j.
performances using C-doped porous TiO2 electrodes, Appl. Surf. Sci. 356 (2015) carbon.2017.03.052.
553–560, https://doi.org/10.1016/j.apsusc.2015.08.114. [34] B. Jing, Z. Ao, Z. Teng, C. Wang, J. Yi, T. An, Density functional theory study on the ef-
[11] Y. Zhang, Z.Y. Zhao, J.R. Chen, L. Cheng, J. Chang, W.C. Sheng, C.Y. Hu, S.S. Cao, C- fects of oxygen groups on band gap tuning of graphitic carbon nitrides for possible
doped hollow TiO2 spheres: in situ synthesis, controlled shell thickness, and supe- photocatalytic applications, Sustain. Mater. Technol. 16 (2018) 12–22, https://doi.
rior visible-light photocatalytic activity, Appl. Catal. B Environ. 166 (2015)https:// org/10.1016/j.susmat.2018.04.001.
doi.org/10.1016/j.apcatb.2014.11.054 (644–644). [35] H. Chen, W. Tian, W. Ding, Preparation of meso-Ag/Al2O3 and synergistic water dis-
[12] H.C. Wan, W.T. Yao, W.K. Zhu, Y. Tang, H.L. Ge, X.Z. Shi, T. Duan, Fe-N co-doped infection of metallic silver and ROS under visible light, Sol. Energy 173 (2018)
SiO2@TiO2 yolk-shell hollow nanospheres with enhanced visible light photocata- 1065–1072, https://doi.org/10.1016/j.solener.2018.08.047.
lytic degradation, Appl. Surf. Sci. 444 (2018) 355–363, https://doi.org/10.1016/j. [36] Z.G. Chen, L. Cheng, H.Y. Xu, J.Z. Liu, J. Zou, T. Sekiguchi, G.Q.M. Lu, H.M. Cheng, ZnS
apsusc.2018.03.016. branched architectures as optoelectronic devices and field emitters, Adv. Mater. 22
[13] O. Sacco, V. Vaiano, C. Daniel, W. Navarra, V. Venditto, Removal of phenol in aqueous (2010) 2376–2380, https://doi.org/10.1002/adma.200903643.
media by N-doped TiO2 based photocatalytic aerogels, Mater. Sci. Semicond. Pro- [37] D.N. Li, Y. Chen, F. Yin, L.Z. Zhu, J.N. Li, X.J. Ma, Facile synthesis of Mn/N-doped TiO2
cess. 80 (2018) 104–110, https://doi.org/10.1016/j.mssp.2018.02.032. on wood-based activated carbon fiber as an efficient visible-light-driven
[14] O.A. Osin, T.Y. Yu, X.M. Cai, Y. Jiang, G.T. Peng, X.M. Cheng, R.B. Li, Y. Qin, S.J. Lin, Pho- photocatalyst, J. Mater. Sci. 53 (2018) 11671–11683, https://doi.org/10.1007/
tocatalytic degradation of 4-Nitrophenol by C, N-TiO2: degradation efficiency vs. s10853-018-2429-7.
embryonic toxicity of the resulting compounds, Front. Chem. 6 (2018)https://doi. [38] P.F. Xu, X.F. Shen, L. Luo, Z. Shi, Z.X. Liu, Z.G. Chen, M.F. Zhu, L.S. Zhang, Preparation of
org/10.3389/Fchem.2018.00192. TiO2/Bi2WO6 nanostructured heterojunctions on carbon fibers as a weaveable
[15] X. Zong, Z. Xing, H. Yu, Z. Chen, F. Tang, J. Zou, G.Q. Lu, L. Wang, Photocatalytic water visible-light photocatalyst/photoelectrode, Environ. Sci. Nano 5 (2018) 327–337,
oxidation on F, N co-doped TiO2 with dominant exposed {001} facets under visible https://doi.org/10.1039/c7en00822h.
light, Chem. Commun. 47 (2011) 11742–11744, https://doi.org/10.1039/ [39] S. Huang, X. Lu, Z.Y. Li, H. Ravishankar, J.F. Wang, X.G. Wang, A biomimetic approach
C1CC14453G. towards the synthesis of TiO2/carbon-clay as a highly recoverable photocatalyst, J.
[16] G. Liu, Y. Zhao, C. Sun, F. Li, G.Q. Lu, H.M. Cheng, Synergistic effects of B/N doping on Photoch. Photobio. A 351 (2018) 131–138, https://doi.org/10.1016/j.jphotochem.
the visible-light photocatalytic activity of mesoporous TiO2, Angew. Chem. Int. Ed. 2017.10.017.
Eng. 47 (2008) 4516–4520, https://doi.org/10.1002/anie.200705633. [40] X.F. Chen, Z.L. Xie, Y. Liang, J. Wei, Y.G. Zhu, Y.N. Huo, X.W. Zhang, H.T. Wang, Hy-
[17] J. Liao, B.A.D. Luna, A. Manthiram, TiO2-B nanowire arrays coated with layered MoS2 bridizing TiO2 with nitrogen-doped carbon: a new route to a highly visible light-
Nanosheets for Lithium and sodium storage, J. Mater. Chem. A 4 (2016) 801–806, active Photocatalyst, Chemistryselect 2 (2017) 1565–1572, https://doi.org/10.
https://doi.org/10.1039/C5TA07064C. 1002/slct.201700017.
[18] G. Liu, C. Sun, X. Yan, L. Cheng, Z. Chen, X. Wang, L. Wang, S.C. Smith, G.Q. Lu, H.M. [41] Y.H. Su, P. Chen, F.L. Wang, Q.X. Zhang, T.S. Chen, Y.F. Wang, K. Yao, W.Y. Lv, G.G. Liu,
Cheng, Iodine doped anatase TiO2 photocatalyst with ultra-long visible light re- Decoration of TiO2/g-C3N4 Z-scheme by carbon dots as a novel photocatalyst with
sponse: correlation between geometric/electronic structures and mechanisms, J. improved visible-light photocatalytic performance for the degradation of
Mater. Chem. 19 (2009) 2822–2829, https://doi.org/10.1039/B820816F. enrofloxacin, RSC Adv. 7 (2017) 34096–34103, https://doi.org/10.1039/c7ra05485h.
[19] M.S. Mahmoud, M.S. Akhtar, I.M.A. Mohamed, R. Hamdan, Y. Abu Dakka, N.A.M. [42] J.J. Araña, J.M. Doña-Rodrı́guez, E. Tello Rendón, C. Garriga i Cabo, O. González-
Barakat, Demonstrated photons to electron activity of S-doped TiO2 nanofibers as Dı́az, J.A. Herrera-Melián, J. Pérez-Peña, G. Colón, J.A. Navı́o, TiO2 activation by
photoanode in the DSSC, Mater. Lett. 225 (2018) 77–81, https://doi.org/10.1016/j. using activated carbon as a support: part II. Photoreactivity and FTIR study,
matlet.2018.04.108. Appl. Catal. B Environ. 44 (2003) 153–160, https://doi.org/10.1016/S0926-
[20] A.J. Xie, X.M. Zhou, W.T. Zhou, S.P. Luo, C. Yao, Preparation and enhanced photocat- 3373(03)00075-4.
alytic activity of S-doped TiO2/palygorskite composites, Mater. Technol. 32 (2017) [43] J. Matos, J. Laine, J.M. Herrmann, Synergy effect in the photocatalytic degradation of
265–271, https://doi.org/10.1080/10667857.2016.1204040. phenol on a suspended mixture of titania and activated carbon, Appl. Catal. B Envi-
[21] Y.H. Lin, H.T. Hsueh, C.W. Chang, H. Chu, The visible light-driven photodegradation ron. 18 (1998) 281–291, https://doi.org/10.1016/S0926-3373(98)00051-4.
of dimethyl sulfide on S-doped TiO2: characterization, kinetics, and reaction
 H.-J. Chen et al. / Sustainable Materials and Technologies 21 (2019) e00105 11

[44] J. Matos, J. Laine, J.M. Herrmann, Association of activated carbons of different origins [66] J. Tauc, R. Grigorovici, A. Vancu, Optical properties and electronic structure of amor-
with titania in the photocatalytic purification of water, Carbon 37 (1999) phous germanium, Phys. Status Solidi 15 (1966) 627–637, https://doi.org/10.1002/
1870–1872, https://doi.org/10.1016/S0008-6223(99)00198-0. pssb.19660150224.
[45] J. Matos, J. Laine, J.M. Herrmann, Effect of the type of activated carbons on the pho- [67] M.M. Ackerman, X. Tang, P. Guyot-Sionnest, Fast and sensitive colloidal quantum
tocatalytic degradation of aqueous organic pollutants by UV-irradiated Titania, J. dot mid-wave infrared Photodetectors, ACS Nano 12 (2018) 7264–7271, https://
Catal. 200 (2001) 10–20, https://doi.org/10.1006/jcat.2001.3191. doi.org/10.1021/acsnano.8b03425.
[46] P.T. Benavides, D.C. Cronauer, F. Adom, Z. Wang, J.B. Dunn, The influence of catalysts [68] J.Z. Li, S.F. Zhang, H.X. Dong, Y.F. Ma, B. Xu, J. Wang, Z.P. Cai, Z.H. Chen, L. Zhang, Ul-
on biofuel life cycle analysis (LCA), Sustain. Mater. Technol. 11 (2017) 53–59, trafast Saturable absorption of Core/Shell colloidal quantum dots, Part. Part. Syst.
https://doi.org/10.1016/j.susmat.2017.01.002. Charact. 34 (2017) 1–7, https://doi.org/10.1002/ppsc.201600193.
[47] A. Kongkanand, P.V. Kamat, Electron storage in single wall carbon nanotubes. Fermi [69] C. Weon-Sik, A. Myoung-Jin, L. Sang-Wook, S. Min-Soo, Y. Kyung-Hwa, K. Yong-Rok,
level equilibration in semiconductor-SWCNT suspensions, ACS Nano 1 (2007) Templated carbon nanofiber with mesoporosity and semiconductivity, J. Phys.
13–21, https://doi.org/10.1021/nn700036f. Chem. B 110 (2006) 6447–6450, https://doi.org/10.1021/jp060295o.
[48] H. TAODA, Development of TiO2 photocatalysts suitable for practical use and their [70] W. Wang, P. Serp, P. Kalck, J.L. Faria, Visible light photodegradation of phenol on
applications in environmental cleanup, Res. Chem. Intermed. 34 (2008) 417–426, MWNT-TiO2 composite catalysts prepared by a modified sol–gel method, J. Mol.
https://doi.org/10.1163/156856708784040579. Catal. A Chem. 235 (2005) 194–199, https://doi.org/10.1016/j.molcata.2005.02.027.
[49] K. Anish Kumar, P. Senthil Kumar, S. Madhusudanan, V. Pasupathy, P.R. Vignesh, A.R. [71] Y. Yu, J.C. Yu, C.Y. Chan, Y.K. Che, J.C. Zhao, L. Ding, W.K. Ge, P.K. Wong, Enhancement
Sankaranarayanan, A simplified model for evaluating best biodiesel production of adsorption and photocatalytic activity of TiO2 by using carbon nanotubes for the
method: fuzzy analytic hierarchy process approach, Sustain. Mater. Technol. 12 treatment of azo dye, Appl. Catal. B Environ. 61 (2005) 1–11, https://doi.org/10.
(2017) 18–22, https://doi.org/10.1016/j.susmat.2017.03.002. 1016/j.apcatb.2005.03.008.
[50] A.A. Abdelmalik, Chemically modified palm kernel oil ester: a possible sustainable [72] H. Chen, D. Li, W. Ding, Template-less preparation of Meso-MnO2 Fibers by localized
alternative insulating fluid, Sustain. Mater. Technol. 1-2 (2014) 42–51, https://doi. Ostwald ripening and 2,4-Dinitrophenol adsorption mechanism, Sci. Adv. Mater. 10
org/10.1016/j.susmat.2014.06.001. (2018) 1241–1249, https://doi.org/10.1166/sam.2018.3285.
[51] X. Wang, G. Liu, L. Wang, Z.G. Chen, G.Q.M. Lu, H.M. Cheng, ZnO-CdS@cd [73] L. Guo, J. Li, T. Cao, H. Wang, N. Zhao, F. He, C. Shi, C. He, E. Liu, A chemical-adsorption
Heterostructure for effective Photocatalytic hydrogen generation, Adv. Energy strategy to enhance the reaction kinetics of Lithium rich layered cathodes via
Mater. 2 (2012) 42–46, https://doi.org/10.1002/aenm.201100528. double-Shell surface modification, ACS Appl. Mater. Interfaces 8 (2016), 24594.
[52] T. Ochiai, H. Nanba, T. Nakagawa, K. Masuko, K. Nakata, T. Murakami, R. Nakano, M. https://doi.org/10.1021/acsami.6b07254.
Hara, Y. Koide, T. Suzuki, Development of an O3-assisted photocatalytic water- [74] D.L. Liao, G.S. Wu, B.Q. Liao, Zeta potential of shape-controlled TiO2 nanoparticles
purification unit by using a TiO2 modified titanium mesh filter, Catal. Sci. Technol. with surfactants, Colloids Surf. A Physicochem. Eng. Asp. 348 (2009) 270–275,
2 (2011) 76–78, https://doi.org/10.1039/c1cy00315a. https://doi.org/10.1016/j.colsurfa.2009.07.036.
[53] H. Slimen, T. Ochiai, K. Nakata, T. Murakami, A. Houas, Y. Morito, A. Fujishima, Pho- [75] I. Mintsouli, N. Philippidis, I. Poulios, S. Sotiropoulos, Photoelectrochemical charac-
tocatalytic decomposition of cigarette smoke using a TiO2-impregnated titanium terisation of thermal and particulate titanium dioxide electrodes, J. Appl.
mesh filter, Ind. Eng. Chem. Res. 51 (2012) 587–590, https://doi.org/10.1021/ Electrochem. 36 (2006) 463–474, https://doi.org/10.1007/s10800-005-9100-0.
ie2016762. [76] J. Georgieva, S. Sotiropoulos, S. Armyanov, N. Philippidis, I. Poulios,
[54] S. Takeda, S. Suzuki, H. Odaka, H. Hosono, Photocatalytic TiO2 thin film deposited Photoelectrocatalytic activity of bi-layer TiO2/WO3 coatings for the degradation of
onto glass by DC magnetron sputtering, Thin Solid Films 392 (2001) 338–344, 4-chlorophenol: effect of morphology and catalyst loading, J. Appl. Electrochem.
https://doi.org/10.1016/S0040-6090(01)01054-9. 41 (2011) 173–181, https://doi.org/10.1007/s10800-010-0221-8.
[55] S. Gelover, P. Mondragón, A. Jiménez, Titanium dioxide sol–gel deposited over glass [77] C.M. Huang, G.T. Pan, P.Y. Peng, T.C.K. Yang, In situ DRIFT study of photocatalytic
and its application as a photocatalyst for water decontamination, J. Photochem. degradation of gaseous isopropanol over BiVO4 under indoor illumination, J. Mol.
Photobiol. A Chem. 165 (2004) 241–246, https://doi.org/10.1016/j.jphotochem. Catal. A Chem. 327 (2010) 38–44, https://doi.org/10.1016/j.molcata.2010.05.009.
2004.03.023. [78] P. Niu, L. Zhang, G. Liu, H.M. Cheng, Graphene-like carbon nitride Nanosheets for im-
[56] F. Alexander, M. AlMheiri, P. Dahal, J. Abed, N.S. Rajput, C. Aubry, J. Viegas, M. Jouiad, proved Photocatalytic activities, Adv. Funct. Mater. 22 (2012) 4763–4770, https://
Water splitting TiO2 composite material based on black silicon as an efficient doi.org/10.1002/adfm.201200922.
photocatalyst, Sol. Energy Mater. Sol. Cells 180 (2018) 236–242, https://doi.org/10. [79] I. Grčić, G. Li Puma, Photocatalytic degradation of water contaminants in multiple
1016/j.solmat.2017.05.024. Photoreactors and evaluation of reaction kinetic constants independent of photon
[57] T.J. Kuo, C.N. Lin, C.L. Kuo, M.H. Huang, Growth of Ultralong ZnO nanowires on sili- absorption, irradiance, reactor geometry, and hydrodynamics, Environ. Sci. Technol.
con substrates by vapor transport and their use as recyclable Photocatalysts, Chem. 47 (2013) 13702–13711, https://doi.org/10.1021/es403472e.
Mater. 19 (2007) 5143–5147, https://doi.org/10.1021/ie201676210.1021/ [80] H.J. Chen, W. Tian, W. Ding, Effect of preparation methods on morphology of active
cm071568a. manganese dioxide and 2,4-dinitrophenol adsorption performance, Adsorpt. Sci.
[58] X.Z. Li, F.B. Li, C.M. Fan, Y.P. Sun, Photoelectrocatalytic degradation of humic acid in Technol. 36 (2018) 1100–1111, https://doi.org/10.1177/0263617417752578.
aqueous solution using a Ti/TiO2 mesh photoelectrode, Water Res. 36 (2002) [81] D.S. Francis, S.K. Das, M.E. Zandler, A.S.D. Sandanayaka, I. Osamu, Bionano donor-
2215–2224, https://doi.org/10.1016/S0043-1354(01)00440-7. acceptor hybrids of porphyrin, ssDNA, and semiconductive single-wall carbon nano-
[59] T. Watanabe, S. Fukayama, M. Miyauchi, A. Fujishima, K. Hashimoto, Photocatalytic tubes for electron transfer via porphyrin excitation, J. Am. Chem. Soc. 133 (2011)
activity and photo-induced wettability conversion of TiO2 thin film prepared by 19922–19930, https://doi.org/10.1021/ja208380b.
sol-gel process on a soda-lime glass, J. Sol-Gel Sci. Technol. 19 (2000) 71–76, [82] Y.S. Xie, L. Yuan, N. Zhang, Y.J. Xu, Light-tuned switching of charge transfer channel
https://doi.org/10.1023/A:100876212. for simultaneously boosted photoactivity and stability, Appl. Catal. B Environ. 238
[60] C.S. Ryu, M.S. Kim, B.W. Kim, Photodegradation of alachlor with the TiO2 film (2018) 19–26, https://doi.org/10.1016/j.apcatb.2018.07.006.
immobilised on the glass tube in aqueous solution, Chemosphere 53 (2003) [83] B.C. Kezhen Qi, Jiaguo Yu, Wingkei Ho, A review on TiO2-based Z-scheme
765–771, https://doi.org/10.1016/S0045-6535(03)00506-X. photocatalysts, Chin. J. Catal. 38 (2017) 1936–1955, https://doi.org/10.1016/
[61] P. Zeman, S. Takabayashi, Effect of total and oxygen partial pressures on structure of S1872-2067(17)62962-0.
photocatalytic TiO2 films sputtered on unheated substrate, Surf. Coat. Technol. 153 [84] A. Iwase, H. Kato, A. Kudo, Nanosized au particles as an efficient Cocatalyst for Pho-
(2002) 93–99, https://doi.org/10.1016/S0257-8972(01)01553-5. tocatalytic overall water splitting, Catal. Lett. 108 (2006) 7–10, https://doi.org/10.
[62] M. Matsuoka, M. Kitano, M. Takeuchi, M. Anpo, J.M. Thomas, Photocatalytic water 1007/s10562-006-0030-1.
splitting on visible light-responsive TiO2 thin films prepared by a RF magnetron [85] X.F. Cheng, W.H. Leng, D.P. Liu, J.Q. Zhang, C.N. Cao, Enhanced photoelectrocatalytic
sputtering deposition method, Top. Catal. 35 (2005) 305–310, https://doi.org/10. performance of Zn-doped WO3 photocatalysts for nitrite ions degradation under
1007/s11244-005-3838-9. visible light, Chemosphere 68 (2007) 1976–1984, https://doi.org/10.1016/j.
[63] M.S. Akple, J. Low, S. Wageh, A.A. Al-Ghamdi, J. Yu, J. Zhang, Enhanced visible light chemosphere.2007.02.010.
photocatalytic H2-production of g-C3N4/WS2 composite heterostructures, Appl. [86] S.S. Shinde, C.H. Bhosale, K.Y. Rajpure, Kinetic analysis of heterogeneous
Surf. Sci. 358 (2015) 196–203, https://doi.org/10.1016/j.apsusc.2015.08.250. Photocatalysis: role of hydroxyl radicals, Catal. Rev. 55 (2013) 79–133, https://doi.
[64] D.S. Bin, Z.X. Chi, Y. Li, K. Zhang, X. Yang, Y.G. Sun, J.Y. Piao, A.M. Cao, L.J. Wan, Con- org/10.1080/01614940.2012.734202.
trolling the compositional chemistry in single nanoparticles for functional hollow [87] A. Houas, H. Lachheb, M. Ksibi, E. Elaloui, C. Guillard, J.-M. Herrmann, Photocatalytic
carbon Nanospheres, J. Am. Chem. Soc. 139 (2017) 13492–13498, https://doi.org/ degradation pathway of methylene blue in water, Appl. Catal. B Environ. 31 (2001)
10.1021/jacs.7b07027. 145–157, https://doi.org/10.1016/S0926-3373(00)00276-9.
[65] K. Kuratani, T. Kiyobayashi, N. Kuriyama, Influence of the mesoporous structure on
capacitance of the RuO2 electrode, J. Power Sources 189 (2009) 1284–1291,
https://doi.org/10.1016/j.jpowsour.2008.12.087.