Applied Surface Science 542 (2021) 148746

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Applied Surface Science

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Full Length Article

Coexposed TiO2’s (001) and (101) facets in TiO2/BiVO4 photoanodes for an

enhanced photocatalytic fuel cell
Munawar Khalil a, *, Fadlinatin Naumi a, Uji Pratomo b, Tribidasari A. Ivandini a, Grandprix T.
M. Kadja c, d, e, Jacob Y. Mulyana f
a
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, 16424 Depok, West Java, Indonesia
b
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Padjadjaran, 4533 Jatinagor, West Java, Indonesia
c
Division of Inorganic and Physical Chemistry, Institut Teknologi Bandung, Jalan Ganesha No. 10, Bandung 40132, Indonesia
d
Research Center for Nanosciences and Nanotechnology, Institut Teknologi Bandung, Jalan Ganesha No. 10, Bandung 40132, Indonesia
e
Center for Catalysis and Reaction Engineering, Institut Teknologi Bandung, Jalan Ganesha No. 10, Bandung 40132, Indonesia
f
Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, Tokyo 192-0397, Japan

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

Keywords: This paper reports an investigation on the role of coexposed TiO2’s (001) and (101) facets on the performance of
Crystal facet TiO2/BiVO4 photoanodes in the photocatalytic fuel cell. Here, the exposure of these facets was obtained by
TiO2 synthesizing TiO2 with different morphologies, i.e. nanospindles, nanocube, nanooctahedra and nano-truncated
BiVO4
octahedra. Based on the result, coexposed (001) and (101) facets were found to be responsible for the
Morphology
enhancement of photoelectrochemical response. The highest photocurrent density was achieved when the
Heterojunction
Photocatalytic fuel cell photoanode was fabricated using TiO2 nano-truncated octahedra/BiVO4 (29.8 μA/cm2 at 0.8 V vs. NHE), which
was primarily due to the improvement of charge separation as a result of the synergistic effect between the
formation of type-II heterojunction of TiO2/BiVO4 and internal surface heterojunction of (001) and (101) facet. A
similar trend was also observed in the PFC system when RhB was used as fuel. Under the illumination of 13 W
LED light, the highest electric power (0.00232 mW/cm2) was obtained with TiO2 nano-truncated octahedra/
BiVO4 photoanode. However, TiO2 nanospindles/BiVO4 was found to be more effective in removing RhB due to
its high surface area. Such variation was believed due to the fact that TiO2 nanospindles had less exposure of
(001) facet than TiO2 nano-truncated octahedra.

1. Introduction energy compared to several types of biodegradable organics [3–5]. In

general, photocatalysis using semiconducting materials is considered as
Water pollution has been regarded as one of the significant envi­ one of the most potential ways to facilitate both wastewater treatment
ronmental problems during the past several decades. The scarcity of and renewable energy generation [6,7]. Recently, the application of a
clean water is primarily associated with the fast advancement in solar-driven photocatalytic fuel cell (PFC) system for wastewater treat­
industrialization that produces a large amount of polluting materials, ment has drawn much attention due to its simplicity and cost-
which are often irresponsibly discharged into water bodies [1]. Besides, effectiveness [8]. Furthermore, the PFC system has also been reported
the energy crisis and air pollution due to the massive utilization of fossil to be able to facilitate fast and direct degradation of organic pollutants
fuels have also been considered as the most significant contributors to and efficient electricity generation [9,10]. In a typical single photo­
global warming [2]. Therefore, proper technological breakthroughs that electrode PFC system, semiconducting material is primarily used to
can be used not only to treat water pollutions but also to turn them into fabricate the photoanode, where it is connected via external load to a
useful energy forms such as electricity and renewable fuels such as dark cathode [11]. Upon light irradiation, the semiconductor-based
hydrogen are needed to solve these issues. This is because many organic photoanode can readily absorb the incident light energy to excite elec­
pollutants and some refractory organics can be used as the alternative trons to the conduction band (CB), leaving positively-charged holes at
carbon source that contains a more abundant amount of chemical the valence band (VB). Subsequently, the photogenerated holes may be

* Corresponding author.
E-mail address: [email protected] (M. Khalil).

https://doi.org/10.1016/j.apsusc.2020.148746
Received 23 September 2020; Received in revised form 9 December 2020; Accepted 10 December 2020
Available online 15 December 2020
0169-4332/© 2020 Elsevier B.V. All rights reserved.
M. Khalil et al. Applied Surface Science 542 (2021) 148746

used for the oxidation of organic pollutants, and the hot electrons may (IV) isopropoxide (TTIP), titanium(IV) butoxide (Ti(OBu)4), and tita­
flow toward the cathode via an external circuit to generate electricity. nium(IV) fluoride (TiF4) were purchased from Sigma-Aldrich and used
In literature, the utilization of TiO2 nanostructures-based photo­ in the solvothermal synthesis of TiO2 nanocrystals. Furthermore, hy­
anode and Pt dark cathode is by far the most common PFC system drofluoric acid (HF) (Sigma-Aldrich), diethylenetriamine (DETA)
arrangement for simultaneous wastewater treatment and electricity (Merck), hydrazine hydrate (N2H4⋅H2O) (Sigma-Aldrich), isopropyl
generation [12]. In most cases, the utilization of TiO2 as a photoanode is alcohol (IPA) (Merck), and ethanol (Sigma-Aldrich) were also used for
preferred due to its excellent long-term photostability, chemical inert­ the synthesis of TiO2 nanocrystals. Meanwhile, bismuth(III) nitrate
ness, considerably high photocatalytic efficiency, and low cost [13–17]. pentahydrate (Bi(NO)3⋅5H2O) (Wako Ltd.), ammonium vanadate
However, the application of such system for large scale solar-driven (NH4VO3) (Sigma-Aldrich), nitric acid (HNO3) (Sigma-Aldrich), poly­
wastewater treatment and electricity generation is still hindered by ethylene glycol (PEG) (MW: 20,000) (Sigma-Aldrich), Triton-X (TCI
two inherent drawbacks, i.e., (i) TiO2’s wide bandgap energy (Eg = Ltd.), and fluorine-doped tin oxide (FTO) glass (R: 100 Ω/cm2) (Sigma-
~3.2 eV) which makes them only active at ultraviolet (UV) region, and Aldrich) were used in the preparation of TiO2/BiVO4 nanocomposites
(ii) fast surface and bulk electron-hole recombination. In the past several and fabrication of the photoanodes. Finally, sodium sulfate (Na2SO4),
years, tremendous efforts have been made to solve these issues. One of and rhodamine B (RhB) were purchased from Sigma-Aldrich and used in
the most promising approaches is by combining TiO2 with other narrow the PFC experiment.
bandgap semiconductors, such as BiVO4 (Eg = ~2.4 eV), to broaden the
light absorption ability into the visible light region and achieve better 2.2. Synthesis of TiO2 nanospindles
charge separation [18–20]. It is believed that the enhanced photo­
activity of BiVO4/TiO2 is mainly caused by the formation of a hetero­ TiO2 nanospindles were prepared using a solvothermal method
junction system between the two semiconductors. where TTIP was used as the titanium precursor, according to our pre­
Recently, it has also been known that the photocatalytic activity of vious reports [14,22]. Here, 0.15 mL of DETA was firstly added into a
TiO2 could also be further enhanced by co-exposing its highly reactive mixture solution of 1 mL of DI water and 30 mL of IPA. Subsequently, 1
(001) facet and thermodynamically stable (101) facet [21,22]. For mL of TTIP was then added dropwise into the mixture while vigorously
example, Liu et al. demonstrated that a hollow TiO2 microsphere (HTS) stirred using a magnetic stirrer for 30 min. The mixture was then
with ~20% exposure of (001) showed an excellent photocatalytic transferred into a Teflon-lined autoclave reactor and placed in an oven
decomposition ability towards highly stable azo dyes [23]. Meanwhile, at 180 ◦ C for 24 h. After the reaction, the white precipitate was then
another study reported by Chen and co-workers also suggested that TiO2 collected via centrifugation and washed with DI water and ethanol,
nanosheet with almost 100% exposure of (001) facets was able to exhibit respectively. The obtained final product was then dried at a vacuum
not only good photocatalytic activity but also excellent capability in oven at 60 ◦ C for 24 h and calcined at 450 ◦ C for two hours.
electrochemical energy storage [24]. In most cases, such superiority of
(001) facet is believed to be originated from its high surface energy 2.3. Synthesis of TiO2 nanocubes
(0.90 J/m2) compared to other more thermodynamically stable crystal
facets, such as (1 0 0) facet (0.53 J/m2) and (101) facet (0.44 J/m2) [25]. For the synthesis of TiO2 nanocubes, a similar solvothermal method
Besides, co-exposure between (101) and (001) facets could also induce with TTIP as the titanium precursor was also used. However, HF was
the formation of internal surface heterojunction within TiO2 crystal, used as the crystal directing agent, as reported in previous reports
which is essential for further prevention of fast electron-hole recombi­ [22,29]. In this method, 1.776 mL of HF (40 wt%) was added dropwise
nation [26]. In general, controlled conditions are required to direct the into 5 mL of TTIP. The mixture was then transferred into a Teflon-lined
formation of TiO2 crystal with high exposure of (001) facets. In some autoclave reactor and reacted at 180 ◦ C for 24 h. Subsequently, the
cases, crystal directing agent such as hydrofluoric acid (HF) is also often resulting white precipitate was collected by centrifugation and washed
used to maximize the exposure of (001) facet [27,28]. In our previous using DI water and ethanol, respectively. Finally, the obtained white
work, controlled synthesis of TiO2 with certain types of morphologies, powder was then dried using a vacuum oven at 60 ◦ C for 24 h and
such as nanospindles, octahedra, truncated octahedra, or nanosheet, calcined at 450 ◦ C for 2 h.
could also be used as a promising strategy to expose highly reactive
(001) facet [13,14,22]. 2.4. Synthesis of TiO2 nanooctahedra
In this work, we report an investigation on the influence of coex­
posed TiO2’s (001) and (101) facets on the performance of TiO2/BiVO4 In this study, TiO2 nanooctahedra was synthesized according to a
photoanode in PFC system. To the best of our knowledge, no prior re­ method reported by Gai and co-workers where TiF4 was used as titanium
ports have been made concerning the influence of coexposed (001) and source [30]. In this method, 2 mmol of TiF4 was added into 5 mL of DI
(101) facets to the ability of TiO2/BiVO4 photoanode in simultaneously water and 35 mL of hydrazine hydrate while vigorously mixed using a
removing organic pollutant and generating of electricity. Here, the magnetic stirrer for 1 h. The mixture was then reacted at 200 ◦ C for 24 h
exposure of both (001) and (101) facets was achieved by fabricating in a Teflon-lined autoclave reactor. The resulting precipitate was then
TiO2 nanocrystals with four different morphological shapes, i.e., nano­ collected using centrifugation and washed using DI water and ethanol,
spindles, nanocubes, nanooctahedra, and nano-truncated octahedra, respectively. Finally, the resulting white powder was dried using a
using the one-pot solvothermal method. Meanwhile, the photoanode vacuum oven at 60 ◦ C for 24 h.
was prepared by depositing TiO2/BiVO4 nanocomposites on fluorine-
doped tin oxide (FTO) glass electrode using the doctor blade method. 2.5. Synthesis of TiO2 nano-truncated octahedra
Finally, the photocatalytic activity and performance of the as-prepared
photoanodes in electricity generation were evaluated using a three- To prepare TiO2 nano-truncated octahedra, a solvothermal method
electrode PFC system against Rhodamine B (RhB), where Pt was used reported by Han and co-workers was adopted in this study [27]. Typi­
as dark cathode under the irradiation of 13 W LED light. cally, 3 mL of HF was slowly mixed with 25 mL of Ti(OBu)4 while
vigorously stirred using a magnetic stirrer for 30 min. Subsequently, the
2. Experimental mixture was transferred in a Teflon-lined autoclave reactor and reacted
at 180 ◦ C for 24 h. After the reaction, the precipitate was then collected
2.1. Materials via centrifugation and washed with DI water and ethanol, respectively.
Finally, the obtained white powder was then dried using a vacuum oven
In this work, a different type of titanium precursors, such as titanium at 60 ◦ C for 24 h and calcined at 400 ◦ C for 3 h.

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M. Khalil et al. Applied Surface Science 542 (2021) 148746

2.6. Preparation of FTO/TiO2/BiVO4 photoanode

C0 − Ct
Decolorization (%) = × 100% (1)
C0
The fabrication of TiO2/BiVO4 heterojunction photoanode was car­
ried out by depositing TiO2/BiVO4 nanocomposite paste on the FTO where, C0 is the initial concentration of RhB (mg/L), and Ct represents
substrate via the doctor blade technique as reported in our previous the concentration of RhB (mg/L) at reaction time t (min). Furthermore,
work [31]. To prepare the paste, NH4VO3 (2 mmol) and Bi(NO)3⋅5H2O the kinetics of the photocatalytic degradation of the dyes was also
(2 mmol) were initially ground in an agate mortar in the presence of 2 estimated using Langmuir-Hinshelwood theory as reported elsewhere
mL of 13.1 M HNO3. Subsequently, each of the as-prepared TiO2 [22,32]. According to the theory, the rate of the photodegrading reac­
nanocrystals with different morphology (1 mmol) was slowly added into tion can be determined using the following equation:
the mixture, followed by 0.2 mmol of PEG and a drop of Triton-X. At the
same time, continuously ground until the mixture turned into a yellow- r= −
dCt
= kσ =
kKCt
(2)
brown paste. Finally, the paste was then coated on the conductive side of dt 1 + KCt
an FTO substrate (0.81 cm2 film area) and calcined at 450 ◦ C for 3 h. For
convenience, the photoanodes made from TiO2 nanospindles, nano­ where, r represents the rate of reaction (mg/L-1min− 1), t expresses the
cubes, nanooctahedra, and nano-truncated octahedra were denoted as reaction time (min), k is the rate constant (mgL-1min− 1), σ represents the
FTO/TiO2-A/BiVO4, FTO/TiO2-B/BiVO4, FTO/TiO2-C/BiVO4, and FTO/ fractional coverage of the catalyst surface, and K is the adsorption
TiO2-D/BiVO4, respectively. equilibrium constant (Lmg− 1). However, since the adsorption is
considered to be very weak due to the low concentration of the reactant
(KCt ≪ 1), Eq. (2) can thereby be simplified to a pseudo-first-order ki­
netic model as follows:
2.7. Characterizations
dCt
= − kKCt = − kapp Ct (3)
In this work, various characterization techniques were employed to dt
study both the physical and chemical properties of the as-prepared TiO2
nanocrystals and the corresponding photoanodes. Here, X-ray diffrac­ where, kapp represents the apparent rate constant (min− 1) and can be
tion (XRD) analysis was carried out using PANanalytical X’Pert Pro MPD further estimated by calculating the slope of a plot between ln (Ct/C0)
(PANanalytical B.V., Amelo, the Netherland) (X-ray source: Cu-Kα, de­ versus time (t), according to the following equation:
tector: X’Celerator). Meanwhile, the morphological shape and size of the ( )
Ct
nanocrystals were studied by collecting the micrographic images and ln = − kapp t (4)
C0
selected area electron diffraction (SAED) using TECNAI G2 Spirt Twin
High-Resolution Transmission Electron Microscope (HR-TEM). Addi­ Finally, voltage outputs obtained from the PFC system with different
tionally, the micrographic analysis was also carried out using JEOL JSM- FTO/TiO2/BiVO4 photoanodes were also collected to evaluate their
6100 scanning electron microscope (SEM). Furthermore, QUADRASOB performance in electricity generation from the removal of RhB. Here,
evo (Quantachrome Instruments) equipped with FloVac Degasser was both open-circuit voltage (VOC) and short circuit current density (JSC)
used to study the surface properties of the samples, such as the was recorded using the same potentiostat. Meanwhile, the fill factor (FF)
Brunauer-Emmett-Teller (BET) surface area, Barret-Joyner-Halenda was estimated using the following equation:
(BJH) pore volume, and BET N2 adsorption-desorption isotherm. Pmax
Finally, both the electronic and optical properties of the samples were FF = (5)
JSC ∙VOC
studied using Shimadzu UV-2450 spectrophotometer. Here, the optical
bandgap (Eg) was estimated according to Kubelka-Munk theory by where, Pmax indicates the real maximum power density, and JSC⋅VOC
measuring the dynamic reflectance spectroscopy (DRS) of each sample represents the theoretical maximum power density produced by the PFC
(see Supporting Information). Furthermore, analysis using Raman system [32,33].
spectroscopy was also carried out using LabRAM HR Evolution micro­
scope (Horiba France SAS) to evaluate the percentage exposure of TiO2 3. Result and discussions
(001) facet.
3.1. Preparation and characterization of TiO2 nanostructures

2.8. Photoelectrochemical experiments Fig. 1 shows the result obtained from the micrographic analyses of
the as-prepared TiO2 nanostructures with various morphological shapes.
To study the influence of the coexposed TiO2’s (101) and (001) Based on the outcome, it is evident that all of the as-prepared TiO2 was
facets, photoelectrochemical response of the FTO/TiO2/BiVO4 photo­ well faceted. Besides, TEM images revealed that the utilization of
anode was determined in a single compartment reactor using three- different types of crystal directing agents was able to produce uniform
electrodes system potentiostat (eDAQ ED410). In this work, the per­ and well-dispersed TiO2 nanoparticles with the desired shapes, i.e.,
formance of the photoanode was first evaluated using chro­ nanospindles, nanocubes, nanooctahedra, and nano-truncated octa­
noamperometry, linear sweep voltammetry (LSV), and cyclic hedra, respectively (Fig. 1a-d). This result was also supported by the
voltammetry (CV) techniques, consisting 0.1 M Na2SO4 (pH 7) as the micrographic images obtained from SEM analyses (Fig. 1i-l). Further­
electrolyte and 13 W LED light as the light source (intensity: 15,000 lx). more, SAED analyses also revealed that the crystal phase of the resulting
Here, the as-prepared FTO/TiO2/BiVO4 was used as the working elec­ TiO2 nanostructures with different morphological shapes could be
trode. Meanwhile, Ag/AgCl and Pt were used as the reference and indexed anatase since the resulting ring patterns were in a good agree­
counter electrodes, respectively. Besides, similar photoelectrochemical ment with the literature [20,27,34]. Besides, the formation of this
experiments were also carried out in the presence of 10 mg/L of RhB as anatase phase was also supported by the result obtained from HR-TEM
the organic pollutant to evaluate the performance of the photoanode in analyses (Fig. 1e-h). Based on the outcome, it is clear that the as-
the PFC system. In this study, the PFC reaction was conducted for 180 prepared TiO2 nanostructures exhibited the characteristic lattice
min. while the concentration of RhB was monitored at various reaction fringes for anatase crystal phase, such as at 0.35 nm and 0.25 nm for
time intervals, i.e., 0, 30, 60, 90, 120, 150, and 180 min using UV–Vis (101) and (004) planes, respectively [14,22]. However, it is worth to
spectrophotometer. The decolorization efficiency was calculated using note that the exposure of highly reactive (001) facet was only obtained
the following equation:

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M. Khalil et al. Applied Surface Science 542 (2021) 148746

Fig. 1. (a-d) TEM images (inset: SAED); (e-h) HR-TEM images (inset: FFT analyses); and SEM images of the as-prepared TiO2 nanospindles, nanocubes, nano­
octahedra, and nano-truncated octahedra, respectively.

in TiO2 particles with nanospindles and nano-truncated octahedra feature (>50 nm). However, it is worth noting that the mesopore feature
morphology (Fig. 1e and 1 h). This is indicated by the appearance of was found to be more pronounced in TiO2 nanospindles (Fig. 2d).
lattice fringes at 0.48 nm, which can be indexed as the (001) planes of Consequently, TiO2 nanospindles is expected to exhibit a significantly
anatase [35,36]. Moreover, it is also noticed from the FFT analysis that larger surface area than TiO2 nanostructures with other morphological
(001) plane appeared at the angle of 68.3◦ from (101) plane, which is shapes. Table 1 summarizes both the obtained BET surface area and BJH
consistent with the result reported elsewhere [37,38]. pore volume of the as-prepared TiO2 nanostructures.
The result from XRD analyses also supported the formation of the
anatase crystal phase with a high degree of crystallinity. As shown in 3.2. Characterization of FTO/TiO2/BiVO4 photoanodes
Fig. 2a, the diffractogram can be unambiguously indexed as anatase
where all of the Bragg’s peaks were in good agreement with the litera­ In this study, both XRD and SEM analysis was also carried out to
ture without any additional peaks for other TiO2 phases, such as rutile or evaluate the fabrication of the photoanodes. XRD patterns and SEM
brookite, regardless the variation in their morphological shapes images of the as-prepared FTO/TiO2/BiVO4 photoanodes are demon­
[22,27,36]. Furthermore, results from spectroscopic analyses also strated in Fig. 3. Based on the result, it is evident that the observed peaks
revealed that the as-prepared TiO2 nanostructures could strongly absorb of the photoanodes can be assigned as a mixture of the characteristic
light energy in the UV region (<400 nm) (Fig. 2b). This is primarily due peaks of the rutile phase of SnO2 (JCPDS 41-1445), the monoclinic
to the wide energy gap between TiO2’s conduction band (CB) and scheelite phase of BiVO4 (JCPDS 14-0688), and anatase phase of TiO2.
valence band (VB). Based on the estimation using Kubelka-Munk theory, Besides, this pattern was also very similar to the results published
the calculated bandgap energy (Eg) for TiO2 nanospindles, nanocubes, elsewhere, confirming the formation of TiO2/BiVO4 nanocomposites on
nanooctahedra, and nano-truncated octahedra, were found to be 3.19, the surface of FTO [42–44]. Additionally, SEM images also revealed that
3.17, 3.17, and 3.18 eV, respectively (Fig. S1, Supporting Information). the doctor blade technique was able to form a uniformly distributed thin
Furthermore, surface area analyses were also carried out to evaluate film of TiO2/BiVO4 nanocomposites on the surface of FTO. As shown in
the influence of the as-prepared TiO2 morphological shapes on their Fig. 3b-e, the thickness for TiO2-A/BiVO4, TiO2-B/BiVO4, TiO2-C/
surface properties. Fig. 2c-d show the BET N2 adsorption-desorption BiVO4, and TiO2-D/BiVO4 nanocomposites films were found to be 2.6,
isotherm and BJH pore size distribution (PSD) of the samples. Based 2.9, 2.1, and 2.4 μm, respectively. Furthermore, energy disperse X-ray
on the result, it is clear that the morphological shapes did not substan­ spectroscopy (EDS) of the photoanodes also supported the result since
tially affect the surface properties of TiO2. As shown in Fig. 2c, all of the the composition and elemental distributions for O, Ti, Bi, and V were
as-prepared TiO2 nanostructures exhibited a very similar type-IV detected (Figure S2 and Table S1, Supporting Information).
isotherm with type-II like hysteresis loop observed at P/P0 range of Additionally, the spectroscopic analysis also demonstrated that the
0.6–0.9. This indicates the presence of multimode porosity features fabrication of TiO2/BiVO4 nanocomposites was able to improve the
[39–41]. PSD analyses revealed that such surface behavior was most optical properties of TiO2. As shown in Fig. 4a, it is evident that TiO2/
likely due to the co-existence of mesopore (2–50 nm) and macropores BiVO4 nanocomposites exhibited a superior absorption ability at the

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M. Khalil et al. Applied Surface Science 542 (2021) 148746

Fig. 2. (a) XRD pattern, (b) UV–Visible spectra, (c) BET N2 adsorption-desorption isotherm, and (d) BJH pore size distribution (PSD) of the as-prepared TiO2
nanospindles, nanocubes, nanooctahedra, and nano-truncated octahedra.

photoelectrochemical response of the photoanodes. Fig. 4b shows the J-

Table 1
E curve of the as-prepared FTO/TiO2/BiVO4 photoanodes measured in
Surface properties of TiO2 nanostructures with different morphological shapes.
0.1 M Na2SO4 aqueous solution at pH 7 and under 13 W LED light
Morphological shapes BET surface area (m2/ BJH pore volume (cm3/ irradiation. Based on the result, it is clear that all photoanodes exhibited
g) g)*
an instant generation of photocurrent response when the PEC system
TiO2 nanospindles 62.621 0.160 was illuminated. As expected, the current density increased slowly with
TiO2 nanocubes 12.653 0.018
the applied potential. Still, it exponentially increased when the applied
TiO2 nanooctahedra 16.133 0.026
TiO2 nano-truncated 29.803 0.043 potential was beyond 0.8 V vs. NHE due to the ability of the PEC system
octahedra to promote water oxidation [46]. Besides, the obtained current density
* of TiO2/BiVO4 nanocomposites was found to be higher than the current
Adsorption pore volume.
density of pristine BiVO4 (10.3 μA/cm2 at 0.8 V vs. NHE) (Fig. 4b). This
enhancement in photocurrent response is anticipated due to the for­
visible region with a distinct absorption edge positioned at 540 nm, as
mation of type-II heterojunction band alignment between TiO2 and
opposed to the pure TiO2’s absorption edge that observed at 380 nm
BiVO4 [42]. As a result, this heterojunction would enhance the pre­
(Fig. 2b). Similar enhancement in visible light absorption ability was
vention of the unfavorable recombination of charge carriers. A very
also reported elsewhere [43,45]. This redshift in the absorption edge
similar observation for the formation of heterojunction between TiO2
position was believed primarily due to the presence of a narrow bandgap
and BiVO4 was also reported Xu and co-workers where the charge
of BiVO4. According to the estimation using Kubelka-Munk theory, the
transfer efficiency was evaluated using electrochemical impedance
calculated optical bandgaps were found to be 2.23, 2.36, 2.33, 2.27, and
spectroscopy (EIS) under visible light illumination [47]. According to
2.10 eV for BiVO4, TiO2-A/BiVO4, TiO2-B/BiVO4, TiO2-C/BiVO4, and
their report, the charge-transfer resistance of TiO2/BiVO4 composite was
TiO2-D/BiVO4, respectively.
found to be significantly smaller than that of pristine BiVO4 and TiO2,
Furthermore, linear sweep voltammetry (LSV) analysis was also
which indicates that the formation of heterojunction was indeed
carried out to evaluate the influence of TiO2’s shapes on the
responsible for the promoting the charge separation efficiency.

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M. Khalil et al. Applied Surface Science 542 (2021) 148746

Fig. 3. (a) XRD pattern and (b)-(e) cross-section SEM images of FTO/TiO2/BiVO4 with different TiO2 morphological shapes.

Fig. 4. (a) UV–Visible spectra of BiVO4 and TiO2/BiVO4 nanocomposites with different TiO2 morphological shapes, and (b) J-E curve, (c) J-t curve (at 0.8 V vs. NHE)
of the corresponding photoanodes (measured in 0.1 M Na2SO4 aqueous solution at pH 7 and under 13 W LED light irradiation).

Interestingly, the increment of current density seems to be highly D) and nanospindles (TiO2-A), were used to fabricate the photoanodes.
dependent upon the morphological shapes of TiO2. As shown in Fig. 4b, Meanwhile, photoanodes that made from TiO2 without such features, i.
it is evident that the highest current density could be obtained when the e., TiO2 nanocubes (TiO2-B) and nanooctahedra (TiO2-C) showed a
photoanode was fabricated using TiO2 nano-truncated octahedra (FTO/ much lower current density. Such variation in current density is believed
TiO2-D/BiVO4). At water oxidation potential (0.8 V vs. NHE), such a to be originated from two major factors. First, it was due to the coex­
photoanode could generate up to 29.8 μA/cm2 (2.9 times higher than posed TiO2’s (101) and (001) facets. Such a feature is believed to be
pristine BiVO4) under the illumination of a considerably low-intensity responsible for the efficient charge separation due to the formation of
light source (13 W LED light). Meanwhile, the current density values internal surface heterojunction between (101) and (001) facets. This
of FTO/TiO2-A/BiVO4, FTO/TiO2-B/BiVO4, FTO/TiO2-C/BiVO4 were heterojunction was proven by DFT calculation, which showed that both
found to be 14.8, 19.7 and 19.5 μA/cm2, respectively. This result is conduction band minimum (CBM) and valence band maximum (VBM) of
significantly higher than the current density value of a similar photo­ (101) facet was found to be more negative than that of (001) facet [48].
anode system reported by Zhou and co-workers (6.9 μA/cm2), even Consequently, the photogenerated electrons were more likely to be
though the system was illuminated under high-intensity 500 W Xenon trapped at (101) facet, while the holes can selectively be accumulated at
light [45]. (001) facet [49]. Furthermore, in a recent study on charge-transfer ef­
A more detailed investigation in the photoelectrochemical response ficiency of porous (001)-faceted TiO2 in dye-sensitized solar cell (DSSC)
of the photoanodes was also carried out by using transient photocurrent by Shah et al., results from electrochemical impedance spectroscopy
decay analyses at water oxidation potential (0.8 V). As shown in Fig. 4c, (EIS) revealed that DSSC fabricated from TiO2 with higher exposure of
the J-t curve also demonstrated that the decay behavior of the current (001) facet showed significant reduction in charge-transfer resistance
density of the TiO2/BiVO4 photoanodes was also profoundly affected by (RCT) value than that of using TiO2 with low (001) exposure [50].
the morphological shapes of TiO2. During the first 50 s of the illumi­ Similar observation in the reduction of RCT due to the exposure of TiO2’s
nation, the highest current density was obtained when TiO2 with coex­ (001) facet was also reported elsewhere [51] This suggests that the
posed (101) and (001) facets, i.e., TiO2 nano-truncated octahedra (TiO2- coexposed TiO2’s (001) and (101) facets were indeed responsible for the

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M. Khalil et al. Applied Surface Science 542 (2021) 148746

improvement of photogenerated charge separation due to the formation carried out using TiO2 nanospindles-containing photoanode, followed
of surface heterojunction between (101) and (001) facets. by photoanodes with TiO2 nano-truncated octahedra, nanooctahedra,
Second, the variation in current density can also be linked to the and nanocube, respectively. It is believed that such variation can be
surface properties of TiO2. As shown in Table 1, TiO2 nanospindles and associated with the exposure of highly active TiO2’s (001) facet. In a
nano-truncated octahedra had a significantly larger surface area than recent study by Dufour and co-workers, it is reported that the exposure
that of nanocubes and nanooctahedra, which most likely due to their of such crystal facet was found to be responsible for a higher absorption
small particle size (Fig. 1). This large surface area would provide an rate of catalytic substrate, in this case, RhB, during photocatalytic re­
efficient interfacial contact area between TiO2 and BiVO4, which actions [54]. Besides, ab-initio DFT calculation also found that this
essential for the construction of their heterojunction. However, it is enhanced absorption ability is believed to be originated from the pres­
worth noting that the current density of FTO/TiO2-A/BiVO4 was found ence of pentacoordinate Ti atoms at (001) facet as against to the hex­
to be rapidly decayed after the initial 50 s of illumination, which acoordinated Ti atoms at (101) facet [55,56]. Additionally, a study by
probably caused by the rapid charge recombination at the surface of Liu and co-workers using in-situ diffuse reflectance Fourier-transform
TiO2 nanospindles. It is believed that such a phenomenon was primarily infrared spectroscopy (DRIFTS) also suggested that the exposure of
because TiO2 nanospindles had less exposure of (001) facet than TiO2 (001) facet could also increase the number of surface’s Ti3+ sites, which
nano-truncated octahedra. In literature, the estimation for the percent­ essential for the absorption and activation of intermediates during the
age exposure of TiO2 (001) facet could be determined by Raman spec­ reaction [48]. Therefore, it is expected that more RhB molecules could
troscopy, by calculating the ratio of Raman peak intensity originated be absorbed and oxidatively degraded when the photoanode was made
from vibration modes of A1g (514 cm− 1) and Eg (144 cm− 1) [52,53]. of TiO2 nanoparticles with exposure of (001) facet, i.e., TiO2 nano­
Based on the estimation, the exposure of (001) facet for TiO2 nano­ spindles (TiO2-A) and nano-truncated octahedra (TiO2-D) (Fig. 5a).
spindles and nano-truncated octahedra was found to be about 4.8% and Besides, the presence of both (101) and (001) facets could also
6.3%, respectively (Fig. S3, Supporting Information). enhance the lifetime of photogenerated electrons and holes. As
mentioned earlier, coexposed (101) and (001) facets could induce the
3.3. Decolorization and electricity generation formation of internal surface heterojunction between the two facets,
which prevents charge recombination. Upon the light irradiation, it is
To study the effect of coexposed TiO2’s (101) and (001) facets, the believed that the photogenerated electrons from BiVO4 can further be
performance of PFC in both decolorization and electricity generation transferred from the CBM of (001) facet to (101) facet. In contrast, the
was evaluated in the presence of RhB as the fuel and hole scavenger. holes are expected to be moving in the opposite direction. Besides, a
Fig. 5 shows the result of the decolorization of RhB and electricity recent study has also suggested that the ability of the two facets to trap
generation of the PFC system using different types of as-prepared pho­ electron/hole is proportional to the percentage of (001) facet exposure
toanodes. Based on the outcome, it is clear that the formation of TiO2 [49]. As a result, more photogenerated holes are available and scav­
and BiVO4 heterojunction was able to significantly enhance the ability of enged for the oxidation reaction of RhB when TiO2 nanospindles (TiO2-
the nanocomposite to facilitate the degradation of RhB (Fig. 5a). This is A) or nano-truncated octahedra (TiO2-D) was used in the fabrication of
expected since the formation of type-II band alignment was able to not photoanodes. A similar phenomenon for the enhancement of the pho­
only broaden the light absorption ability of the photocatalyst to the tocatalytic activity of TiO2 due to the formation of surface hetero­
visible range but also reduce the fast recombination of charge carriers junction between (101) and (001) facets were also reported elsewhere
[42]. Here, BiVO4 can readily absorb visible light energy to generate [57,58].
electron-hole pairs due to its narrow optical bandgap. Afterward, the Nevertheless, it is worth noting that the decolorization ability of the
photogenerated electrons can then be transferred to the CB of TiO2, former photoanode was found to be more superior than later. It is
which is promoted by the establishment of a built-in field at the heter­ believed that the occurrence of such a phenomenon was primarily due to
ojunction of BiVO4 and TiO2, facilitating a more efficient charge sepa­ the large surface area of TiO2 nanospindles. As shown in Table 1, TiO2
ration. As a result, the population of photogenerated holes that can be nanospindles had the largest surface area among all of the as-prepared
used for oxidative degradation of RhB is more pronounced, which ulti­ TiO2 nanoparticle samples. Consequently, more RhB could be absor­
mately enhances the decolorization ability of the photoanode. bed in the surface of the catalysts, which ultimately amplify the ability of
Results also demonstrated that the ability of photoanodes to facili­ the photoanode to facilitate the removal of the dye. This is proven by the
tate the decolorization of RhB was also found to be profoundly affected value of the apparent rate constant (kapp). Based on the estimation, the
by the morphological shapes of TiO2 nanoparticles. As shown in Fig. 5a, calculated value of kapp was found to be 0.007, 0.025, 0.0012, 0.0012,
the most efficient removal of RhB could be obtained when the PFC was and 0.0016 min− 1 for FTO/BiVO4, FTO/TiO2-A/BiVO4, FTO/TiO2-B/

Fig. 5. (a) Performance of the PFC system in decolorization of RhB; (b) J-t curve (measured at 0.8 V vs. NHE), and (c) JSC-VOC curve of the PFC system in the presence
of 10 ppm of RhB and 0.1 M of Na2SO4 using different types of photoanodes under 13 W LED light irradiation.

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M. Khalil et al. Applied Surface Science 542 (2021) 148746

BiVO4, FTO/TiO2-C/BiVO4, and FTO/TiO2-D/BiVO4, respectively. rationalized by estimating the positions of both VB and CB potential
Further analysis using chronoamperometry during the PFC process using energies at the point of zero charge for the as-prepared BiVO4 and TiO2
RhB as fuel was also carried out to study the influence of TiO2’s using Butler and Ginley approach [59,60]:
morphological shape on the performance of the photoanodes to generate ( )
ECB = Ee − X + 0.5 Eg (6)
electricity. Fig. 5c presents the J-t curve of the PFC system using
different types of photoanodes with various TiO2 morphological shapes.
EVB = ECB + Eg (7)
Based on the result, it is clear that a similar trend in then decolorization
of RhB was also obtained for the photocurrent density. Here, the highest
where, ECB and Ee represent the value of CB potential energy and the
photocurrent density was achieved when FTO/TiO2-A/BiVO4 was used
energy of free electrons at hydrogen scale (4.5 eV), respectively.
as the photoanode. However, this value was slightly lower than the
Meanwhile, X is the value of absolute Sanderson electronegativity of the
photocurrent density obtained in the absence of RhB (Fig. 4c). It is
semiconductors and Eg is the bandgap energy of the semiconductors
possible that such a phenomenon was most likely to occur due to the
estimated using Kubelka-Munk. Table 3 presents the calculated values of
ability of RhB to absorb some portion of light energy. Consequently, this
VB and CB potentials for the as-prepared semiconductors.
would reduce the intensity of light that could reach the photoanode,
Based on the estimation, it is evident that the bottom of BiVO4’s CB
which ultimately decreases the population of photogenerated charge
energy was found to be 0.38 eV against the normal hydrogen electrode
carriers.
(NHE), while the top of its VB energy was around 2.83 eV. Since BiVO4 is
The performance of the as-prepared photoanodes in power genera­
considered as an intrinsic semiconductor, it is believed the Fermi level
tion was also evaluated by collecting open circuit potential output ob­
would lie in the middle of its CB and VB, which is approximately around
tained during the PFC process. As shown in Fig. 5c, it is clear that JSC-
1.6 eV [61,62]. On the other hand, the Fermi level of TiO2 was
VOC curves obtained during the PFC process using different types of
considered to be approximately equal to –0.1 eV since the conduction
photoanodes were also highly dependent on the morphological shape of
band potential (ECB) of n-type semiconductor such as TiO2 is typically
TiO2 nanoparticles. Moreover, several electric power generation ability
ca. 0.1–0.2 V more positive that its Fermi level [59]. When the two
parameters could also be determined (Table 2). Based on the result, it is
materials were in contact, BiVO4’s Fermi level was then expected to be
clear that a similar trend was also obtained. Here, the formation of TiO2/
in the thermodynamical equilibrium with TiO2’s Fermi level (–0.1 eV)
BiVO4 heterojunction was able to significantly improve the ability of
[59,61]. As a result, both ECB and EVB of BiVO4 are shifted towards more
BiVO4 to generate electric power in the PFC system. As shown in Table 2,
negative potential from 0.38 and 2.83 eV to –1.32 and 1.13 eV,
the utilization of TiO2/BiVO4 heterojunction as a photoanode was able
respectively. Upon the irradiation of visible light, this post thermody­
to significantly improve the value of both open circuit potential (VOC)
namic equilibrium shift of BiVO4’s ECB would then allow the photo­
and maximum power density (Pmax) of the PFC system. It is believed that
generated electron to be transferred from BiVO4’s to TiO2’s CB. Fig. 6
such improvement was due to the efficiency of the nanocomposites to
shows the energy band diagram of TiO2 and BiVO4 before and after
facilitate the removal of RhB as the fuel. Besides, results also demon­
thermodynamic equilibrium.
strated that photoanodes with coexposed TiO2’s (101) and (001) facets
Based on the energy diagram after the thermodynamic equilibrium,
resulted in higher electric power than that of without such a feature.
it is evident that the position of BiVO4’s CB was more negative than CB
Nevertheless, the highest electrical power was obtained when FTO/
of TiO2. As a result, this would promote the photogenerated electrons to
TiO2-D/BiVO4 was used as the photoanode (0.00232 mW/cm2), even
be transferred from the CB of BiVO4 to CB of TiO2, and subsequently
though FTO/TiO2-A/BiVO4 was found as the most efficient in removing
flowed into the circuit for electricity generation via FTO. In most cases,
RhB. It is believed that such a phenomenon was caused by the variation
the electrons would flow to the Pt dark cathode and used for the oxygen
in the exposure of TiO2’s (001) facet. According to the estimation using
reduction to form water [63]. At the same time, the photogenerated
Raman spectroscopy, it was evident that TiO2 nanospindles had less
holes at the VB of BiVO4 could be used for the removal of RhB. In
percentage exposure of (001) facet than TiO2 nano-truncated octahedra,
literature, the act of holes in removing RhB can proceed under two
which may lead to the lack of charge separation efficiency.
different reaction pathways, i.e., direct and indirect mechanism [64]. In
the former mechanism, RhB can be removed into various degraded
products by an immediate oxidation reaction with photogenerated holes
3.4. Photocatalytic mechanism of the PFC system
at the surface of the catalyst. Meanwhile, in the latter mechanism, RhB
could also be degraded by highly reactive hydroxyl radicals (•OH) spe­
In general, the possible photocatalytic mechanism for the removal of
cies, which formed from the reaction of photogenerated holes and water
RhB using this PFC system was initiated by the absorption of visible light
molecules. In general, the overall reaction mechanism for the removal of
energy by BiVO4 to generate electron-hole pairs due to its narrow optical
RhB at the photoanode can be expressed as follows:
bandgap. When the photoanode was made from TiO2/BiVO4 nano­
composites, a build-in field was established due to the formation of type- BiVO4 + hν → BiVO4* (h+ + e− ) (8)
II band alignment at the heterojunction between the two semi­
conductors. Here, the formation of such heterojunction can be RhB + hν → RhB* (9)

H2O + h+ → •OH + H+ (10)

Table 2
Electric power generation parameters for different types of photoanodes. RhB* + (•OH or h+) → degraded products → CO2 + H2O (11)
Photoanodes JSC VOC Jmax Vmax Pmax FF
(mA/ (V) (mA/ (V) (mW/
cm2) cm2) cm2) Table 3
FTO/BiVO4 0.013 0.285 0.0057 0.150 0.00085 0.25 The values of absolut Sanderson electronegativity, bandgap, calculated CB and
FTO/TiO2-A/ 0.011 0.390 0.0052 0.195 0.00102 0.24 VB of the semiconductors at the point of zero charge.
BiVO4
Semiconductors X (eV) Eg (eV) ECB (eV) EVB (eV)
FTO/TiO2-B/ 0.010 0.290 0.0048 0.135 0.00065 0.21
BiVO4 BiVO4 6.1 2.45 0.38 2.83
FTO/TiO2-C/ 0.004 0.295 0.0023 0.155 0.00035 0.27 TiO2 nanospindles 5.9 3.19 –0.20 2.99
BiVO4 TiO2 nanocubes 5.9 3.17 –0.19 2.98
FTO/TiO2-D/ 0.029 0.340 0.0145 0.160 0.00232 0.24 TiO2 nanooctahedra 5.9 3.17 –0.19 2.98
BiVO4 TiO2 nano-truncated octahedra 5.9 3.18 –0.19 2.99

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M. Khalil et al. Applied Surface Science 542 (2021) 148746

Fig. 6. Proposed energy band diagram for TiO2 nano truncated octahedral and BiVO4 before and after thermodynamic equilibrium.

In addition, coexposed of TiO2’s (001) and (101) facets were also reactive (001) facet was obtained only in TiO2 nanospindles and nano-
believed to be responsible for the enhancement of charge separation in truncated octahedra but absent in nanocube and nanooctahedra.
the nanocomposites. As mentioned in the previous section, the presence Further investigation revealed that the integration of TiO2 with BiVO4
of TiO2’s (001) facet could induce the formation of an additional in­ resulted in an increment photoelectrochemical response due to the
ternal surface heterojunction with (101) facet. As a result, this would formation of type-II heterojunction band alignment between the two
also contribute to the overall efficient distribution of chare carriers and semiconductors. However, it was also found that photoanodes with
prevent their fast recombination. Thereby, the overall proposed photo­ coexposed TiO2’s (001) and (101) facets feature showed a superior
catalytic mechanism of the PFC system for the removal of RhB and photoelectrochemical response. Here, the highest photocurrent density
electricity generation could be depicted as presented in Fig. 7. (29.8 μA/cm2) was achieved when the photoanode was fabricated with
TiO2 nano-truncated octahedra. It is believed that the formation of in­
4. Conclusion ternal surface heterojunction between (001) and (101) facet was
responsible for the enhancement of charge separation, which results in
The effect of coexposed TiO2’s (001) and (101) facets on the per­ better photoelectrochemical response. Similar trend was also obtained
formance of TiO2/BiVO4 photoanodes in the PFC system has been suc­ when the photoanodes were applied in PFC system where RhB was used
cessfully studied in this work. Here, the exposure of (001) and (101) as fuel. Under the illumination of low-intensity 13 W LED light, the
facets was achieved by synthesizing TiO2 with different morphological highest electric power (0.00232 mW/cm2) was obtained with TiO2
shapes, i.e., nanospindles, nanocubes, nanooctahedra, and nano- nano-truncated octahedra-based photoanode even though TiO2 nano­
truncated octahedra. Based on the result, it was found that the highly spindles was found to be more effective in removing RhB due to its high

Fig. 7. Schematic illustration of the proposed photocatalytic mechanism of RhB removal and electricity generation in the PFC system using FTO/TiO2/BiVO4
photoanode with coexposed TiO2’s (001) and (101) facets.

9
M. Khalil et al. Applied Surface Science 542 (2021) 148746

surface area. This superiority was believed to be originated from the fact by Au–TiO2 on Au morphology and its plasmonic vibrational mode, Mater. Chem.
Phys. 123018 (2020).
that TiO2 nanospindles had less exposure of (001) facet than TiO2 nano-
[14] M. Khalil, T.H. Rangkuti, F. Naumi, J. Gunlazuardi, T.A. Ivandini, G.T. Kadja, J.
truncated octahedra. Y. Mulyana, A synergy of CdSe sensitization and exposure of TiO2 (001) facet in
CdSe-TiO2 nanostructures for photoreduction of bicarbonate, Inorg. Chem.
Commun. 107992 (2020).
CRediT authorship contribution statement
[15] K. Li, H. Zhang, T. Tang, Y. Xu, D. Ying, Y. Wang, J. Jia, Optimization and
application of TiO2/Ti–Pt photo fuel cell (PFC) to effectively generate electricity
Munawar Khalil: Conceptualization, Supervision, Funding acquisi­ and degrade organic pollutants simultaneously, Water Res. 62 (2014) 1–10.
[16] Y. Lu, Y. Chu, W. Zheng, M. Huo, H. Huo, J. Qu, H. Yu, Y. Zhao, Significant
tion, Writing - review & editing. Fadlinatin Naumi: Data curation,
tetracycline hydrochloride degradation and electricity generation in a visible-light-
Investigation, Software, Visualization. Uji Pratomo: Data curation, driven dual photoelectrode photocatalytic fuel cell using BiVO4/TiO2 NT
Investigation, Software, Visualization. Tribidasari A. Ivandini: Meth­ photoanode and Cu2O/TiO2 NT photocathode, Electrochim. Acta 320 (2019)
odology, Validation, Resources, Data curation. Grandprix T.M. Kadja: 134617.
[17] Y. Ye, H. Bruning, X. Li, D. Yntema, H.H. Rijnaarts, Significant enhancement of
Methodology, Validation, Resources, Data curation. Jacob Y. Mulyana: micropollutant photocatalytic degradation using a TiO2 nanotube array
Methodology, Validation, Resources, Data curation. photoanode based photocatalytic fuel cell, Chem. Eng. J. 354 (2018) 553–562.
[18] G. Odling, N. Robertson, BiVO4-TiO2 composite photocatalysts for dye
degradation formed using the SILAR method, ChemPhysChem 17 (2016)
Declaration of Competing Interest 2872–2880.
[19] X. Song, Y. Li, Z. Wei, S. Ye, D.D. Dionysiou, Synthesis of BiVO4/P25 composites
for the photocatalytic degradation of ethylene under visible light, Chem. Eng. J.
The authors declare that they have no known competing financial 314 (2017) 443–452.
interests or personal relationships that could have appeared to influence [20] M. Xie, X. Fu, L. Jing, P. Luan, Y. Feng, H. Fu, Long-lived, visible-light-excited
the work reported in this paper. charge carriers of TiO2/BiVO4 nanocomposites and their unexpected photoactivity
for water splitting, Adv. Energy Mater. 4 (2014) 1300995.
[21] B. Gao, J. Wan, D. Hu, Y. Chen, B. Lin, Enhanced visible-light-driven photocatalytic
Acknowledgment performance of In 2 O 3-loaded TiO 2 nanocubes with exposed (001) facet, Chem.
Res. Chin. Univ. 33 (2017) 934–938.
[22] M. Khalil, E.S. Anggraeni, T.A. Ivandini, E. Budianto, Exposing TiO2 (001) crystal
The authors are gratefully acknowledging the financial support facet in nano Au-TiO2 heterostructures for enhanced photodegradation of
provided by the Ministry of Research and Technology/National methylene blue, Appl. Surf. Sci. 487 (2019) 1376–1384.
Research and Innovation Agency of Republic Indonesia (RISTEK/BRIN) [23] S. Liu, J. Yu, M. Jaroniec, Tunable photocatalytic selectivity of hollow TiO2
microspheres composed of anatase polyhedra with exposed 001 facets, J. Am.
under Hibah Peneliatan Dasar Perguruan Tinggi (PDUPT) 2020 (Con­ Chem. Soc. 132 (2010) 11914–11916.
tract No. NKB-2818/UN2.RST/HKP.05.00/2020). [24] J.S. Chen, Y.L. Tan, C.M. Li, Y.L. Cheah, D. Luan, S. Madhavi, F.Y.C. Boey, L.
A. Archer, X.W. Lou, Constructing hierarchical spheres from large ultrathin anatase
TiO2 nanosheets with nearly 100% exposed (001) facets for fast reversible lithium
Appendix A. Supplementary data storage, J. Am. Chem. Soc. 132 (2010) 6124–6130.
[25] F. Tian, Y. Zhang, J. Zhang, C. Pan, Raman spectroscopy: a new approach to
Supplementary data to this article can be found online at https://doi. measure the percentage of anatase TiO2 exposed (001) facets, J. Phys. Chem. C 116
(2012) 7515–7519.
org/10.1016/j.apsusc.2020.148746. [26] J. Yu, J. Low, W. Xiao, P. Zhou, M. Jaroniec, Enhanced photocatalytic CO2-
reduction activity of anatase TiO2 by coexposed 001 and 101 facets, J. Am. Chem.
References Soc. 136 (2014) 8839–8842.
[27] X. Han, Q. Kuang, M. Jin, Z. Xie, L. Zheng, Synthesis of titania nanosheets with a
high percentage of exposed (001) facets and related photocatalytic properties,
[1] Y. Liu, J. Li, B. Zhou, X. Li, H. Chen, Q. Chen, Z. Wang, L. Li, J. Wang, W. Cai,
J. Am. Chem. Soc. 131 (2009) 3152–3153.
Efficient electricity production and simultaneously wastewater treatment via a
[28] Q. Xiang, K. Lv, J. Yu, Pivotal role of fluorine in enhanced photocatalytic activity of
high-performance photocatalytic fuel cell, Water Res. 45 (2011) 3991–3998.
anatase TiO2 nanosheets with dominant (0 0 1) facets for the photocatalytic
[2] B. Wang, H. Zhang, X.-Y. Lu, J. Xuan, M.K. Leung, Solar photocatalytic fuel cell
degradation of acetone in air, Appl. Catal. B 96 (2010) 557–564.
using CdS–TiO2 photoanode and air-breathing cathode for wastewater treatment
[29] E. Sever, H.I. Unal, Colloidal properties of surface functionalized nanocube-TiO2/
and simultaneous electricity production, Chem. Eng. J. 253 (2014) 174–182.
poly (3-octylthiophene) core/shell conducting nanocomposite, Appl. Surf. Sci. 355
[3] Y. Feng, H. Lee, X. Wang, Y. Liu, W. He, Continuous electricity generation by a
(2015) 1028–1036.
graphite granule baffled air–cathode microbial fuel cell, Bioresour. Technol. 101
[30] L. Gai, Q. Mei, X. Qin, W. Li, H. Jiang, X. Duan, Controlled synthesis of anatase
(2010) 632–638.
TiO2 octahedra with enhanced photocatalytic activity, Mater. Res. Bull. 48 (2013)
[4] V.R. Nimje, C.-Y. Chen, H.-R. Chen, C.-C. Chen, Y.M. Huang, M.-J. Tseng, K.-
4469–4475.
C. Cheng, Y.-F. Chang, Comparative bioelectricity production from various
[31] U. Pratomo, I. Purnama, J.Y. Mulyana, Photo-induced water oxidation via cascade
wastewaters in microbial fuel cells using mixed cultures and a pure strain of
charge transfer on nanostructured BiVO4/TiO2 modified with dye and co-catalyst
Shewanella oneidensis, Bioresour. Technol. 104 (2012) 315–323.
molecules, Inorg. Chim. Acta 500 (2020) 119223.
[5] X. Wang, Y. Feng, H. Wang, Y. Qu, Y. Yu, N. Ren, N. Li, E. Wang, H. Lee, B.E. Logan,
[32] S.-L. Lee, L.-N. Ho, S.-A. Ong, Y.-S. Wong, C.-H. Voon, W.F. Khalik, N.A. Yusoff,
Bioaugmentation for electricity generation from corn stover biomass using
N. Nordin, Exploring the relationship between molecular structure of dyes and
microbial fuel cells, Environ. Sci. Technol. 43 (2009) 6088–6093.
light sources for photodegradation and electricity generation in photocatalytic fuel
[6] Y. Liu, D. Huang, H. Liu, T. Li, J. Wang, ZnO Tetrakaidecahedrons with coexposed
cell, Chemosphere 209 (2018) 935–943.
001},{101}, and {100 facets: shape-selective synthesis and enhancing
[33] B. O’regan, M. Grätzel, A low-cost, high-efficiency solar cell based on dye-
photocatalytic performance, Cryst. Growth Des. 19 (2019) 2758–2764.
sensitized colloidal TiO2 films, Nature, 353 (1991) 737-740.
[7] Y. Liu, H. Liu, H. Zhou, T. Li, L. Zhang, A Z-scheme mechanism of N-ZnO/g-C3N4
[34] M. Khalil, G. Rahmaningsih, J. Gunlazuardi, A. Umar, The influence of plasmonic
for enhanced H2 evolution and photocatalytic degradation, Appl. Surf. Sci. 466
Au nanoparticle integration on the optical bandgap of anatase Tio2 nanoparticles,
(2019) 133–140.
Int. J. Technol. 10 (2019) 808–817.
[8] K. Zhao, J. Bai, Q. Zeng, Y. Zhang, J. Li, L. Li, L. Xia, B. Zhou, Efficient wastewater
[35] J. Jiang, F. Gu, X. Ren, Y. Wang, W. Shao, C. Li, G. Huang, Efficient light scattering
treatment and simultaneously electricity production using a photocatalytic fuel cell
from one-pot solvothermally derived TiO2 nanospindles, Ind. Eng. Chem. Res. 50
based on the radical chain reactions initiated by dual photoelectrodes, J. Hazard.
(2011) 9003–9008.
Mater. 337 (2017) 47–54.
[36] H. Wu, J. Fan, E. Liu, X. Hu, Y. Ma, X. Fan, Y. Li, C. Tang, Facile hydrothermal
[9] M. Li, Y. Liu, L. Dong, C. Shen, F. Li, M. Huang, C. Ma, B. Yang, X. An, W. Sand,
synthesis of TiO2 nanospindles-reduced graphene oxide composite with a
Recent advances on photocatalytic fuel cell for environmental applications—The
enhanced photocatalytic activity, J. Alloy. Compd. 623 (2015) 298–303.
marriage of photocatalysis and fuel cells, Sci. Total Environ. 668 (2019) 966–978.
[37] Y. Dai, C.M. Cobley, J. Zeng, Y. Sun, Y. Xia, Synthesis of anatase TiO2 nanocrystals
[10] P. Lianos, Production of electricity and hydrogen by photocatalytic degradation of
with exposed 001 facets, Nano Lett. 9 (2009) 2455–2459.
organic wastes in a photoelectrochemical cell: the concept of the photofuelcell: a
[38] M. Liu, L. Piao, L. Zhao, S. Ju, Z. Yan, T. He, C. Zhou, W. Wang, Anatase TiO 2
review of a re-emerging research field, J. Hazard. Mater. 185 (2011) 575–590.
single crystals with exposed 001 and 110 facets: facile synthesis and enhanced
[11] J. Bai, R. Wang, Y. Li, Y. Tang, Q. Zeng, L. Xia, X. Li, J. Li, C. Li, B. Zhou, A solar
photocatalysis, Chem. Commun. 46 (2010) 1664–1666.
light driven dual photoelectrode photocatalytic fuel cell (PFC) for simultaneous
[39] S. Bagwasi, Y. Niu, M. Nasir, B. Tian, J. Zhang, The study of visible light active
wastewater treatment and electricity generation, J. Hazard. Mater. 311 (2016)
bismuth modified nitrogen doped titanium dioxide photocatlysts: role of bismuth,
51–62.
Appl. Surf. Sci. 264 (2013) 139–147.
[12] J. Li, N. Wu, Semiconductor-based photocatalysts and photoelectrochemical cells
[40] S. Brunauer, L.S. Deming, W.E. Deming, E. Teller, On a theory of the van der Waals
for solar fuel generation: a review, Catal. Sci. Technol. 5 (2015) 1360–1384.
adsorption of gases, J. Am. Chem. Soc. 62 (1940) 1723–1732.
[13] M. Khalil, R.I. Pratama, M. Sujak, A. Garry, D. Djuhana, A. Umar, C.W. Lai, B.
M. Jan, Dependence of the photocatalytic reduction of bicarbonate to formic acid

10
M. Khalil et al. Applied Surface Science 542 (2021) 148746

[41] M.D. Donohue, G. Aranovich, A new classification of isotherms for Gibbs [53] T.-Y. Lee, C.-Y. Lee, H.-T. Chiu, Enhanced photocatalysis from truncated octahedral
adsorption of gases on solids, Fluid Phase Equilib. 158 (1999) 557–563. bipyramids of anatase TiO2 with exposed 001}/{101 facets, ACS Omega 3 (2018)
[42] J. Resasco, H. Zhang, N. Kornienko, N. Becknell, H. Lee, J. Guo, A.L. Briseno, 10225–10232.
P. Yang, TiO2/BiVO4 nanowire heterostructure photoanodes based on type II band [54] F. Dufour, S. Pigeot-Remy, O. Durupthy, S. Cassaignon, V. Ruaux, S. Torelli,
alignment, ACS Cent. Sci. 2 (2016) 80–88. L. Mariey, F. Maugé, C. Chanéac, Morphological control of TiO2 anatase
[43] H. Zhang, C. Cheng, Three-dimensional FTO/TiO2/BiVO4 composite inverse opals nanoparticles: What is the good surface property to obtain efficient photocatalysts?
photoanode with excellent photoelectrochemical performance, ACS Energy Lett. 2 Appl. Catal. B 174 (2015) 350–360.
(2017) 813–821. [55] E. Araujo-Lopez, L.A. Varilla, N. Seriani, J.A. Montoya, TiO2 anatase’s bulk and
[44] L. Zhang, G. Tan, S. Wei, H. Ren, A. Xia, Y. Luo, Microwave hydrothermal synthesis (001) surface, structural and electronic properties: a DFT study on the importance
and photocatalytic properties of TiO2/BiVO4 composite photocatalysts, Ceram. of Hubbard and van der Waals contributions, Surf. Sci. 653 (2016) 187–196.
Int. 39 (2013) 8597–8604. [56] S. Köppen, W. Langel, Adsorption of small organic molecules on anatase and rutile
[45] W. Zhou, T. Jiang, Y. Zhao, C. Xu, C. Pei, H. Xue, Ultrathin TiO2/BiVO4 nanosheet surfaces: a theoretical study, PCCP 10 (2008) 1907–1915.
heterojunction arrays modified with NiFe-LDH nanoparticles for enhanced [57] X. Liu, G. Du, M. Li, True photoreactivity origin of Ti3+-doped anatase TiO2
photoelectrochemical oxidation of water, J. Colloid Interface Sci. 549 (2019) crystals with respectively dominated exposed 001},{101}, and {100 facets, ACS
42–49. Omega 4 (2019) 14902–14912.
[46] Y. Liu, J. Kong, J. Yuan, W. Zhao, X. Zhu, C. Sun, J. Xie, Enhanced photocatalytic [58] N.-Q. Ou, H.-J. Li, B.-W. Lyu, B.-J. Gui, X. Sun, D.-J. Qian, Y. Jia, X. Wang, J. Yang,
activity over flower-like sphere Ag/Ag2CO3/BiVO4 plasmonic heterojunction Facet-dependent interfacial charge transfer in TiO2/nitrogen-doped graphene
photocatalyst for tetracycline degradation, Chem. Eng. J. 331 (2018) 242–254. quantum dots heterojunctions for visible-light driven photocatalysis, Catalysts 9
[47] Y.-R. Lv, C.-J. Liu, R.-K. He, X. Li, Y.-H. Xu, BiVO4/TiO2 heterojunction with (2019) 345.
enhanced photocatalytic activities and photoelectochemistry performances under [59] S.R. Morrison, Electrochemistry at semiconductor and oxidized metal electrodes,
visible light illumination, Mater. Res. Bull. 117 (2019) 35–40. 1980.
[48] L. Liu, Y. Jiang, H. Zhao, J. Chen, J. Cheng, K. Yang, Y. Li, Engineering coexposed [60] Y.V. Pleskov, Y.Y. Gurevich, Semiconductor photoelectrochemistry, 1986.
001 and 101 facets in oxygen-deficient TiO2 nanocrystals for enhanced CO2 [61] Y. Hu, D. Li, Y. Zheng, W. Chen, Y. He, Y. Shao, X. Fu, G. Xiao, BiVO4/TiO2
photoreduction under visible light, ACS Catal. 6 (2016) 1097–1108. nanocrystalline heterostructure: a wide spectrum responsive photocatalyst towards
[49] M. D’Arienzo, M.V. Dozzi, M. Redaelli, B.D. Credico, F. Morazzoni, R. Scotti, the highly efficient decomposition of gaseous benzene, Appl. Catal. B 104 (2011)
S. Polizzi, Crystal surfaces and fate of photogenerated defects in shape-controlled 30–36.
anatase nanocrystals: drawing useful relations to improve the H2 yield in methanol [62] L. Shi, C. Xu, X. Sun, H. Zhang, Z. Liu, X. Qu, F. Du, Facile fabrication of
photosteam reforming, J. Phys. Chem. C 119 (2015) 12385–12393. hierarchical BiVO 4/TiO 2 heterostructures for enhanced photocatalytic activities
[50] A.A. Shah, A.A. Umar, M.M. Salleh, Porous (001)-faceted anatase TiO2 nanorice under visible-light irradiation, J. Mater. Sci. 53 (2018) 11329–11342.
thin film for efficient dye-sensitized solar cell, EPJ Photovoltaics 7 (2016) 70501. [63] M. Kaneko, H. Ueno, K. Ohnuki, M. Horikawa, R. Saito, J. Nemoto, Direct electrical
[51] L. Chu, Z. Qin, J. Yang, X.a. Li, Anatase TiO 2 nanoparticles with exposed {001} power generation from urine, wastes and biomass with simultaneous
facets for efficient dye-sensitized solar cells, Sci. Rep., 5 (2015) 12143. photodecomposition and cleaning, Biosens. Bioelectron. 23 (2007) 140–143.
[52] F. Søndergaard-Pedersen, N.L.N. Broge, J. Yu, M. Roelsgaard, B.B. Iversen, [64] A. Malathi, J. Madhavan, M. Ashokkumar, P. Arunachalam, A review on BiVO4
Maximizing the catalytically active 001 facets on anatase nanoparticles, Chem. photocatalyst: activity enhancement methods for solar photocatalytic applications,
Mater. (2020). Appl. Catal. A 555 (2018) 47–74.

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