A photoelectrochemical cell for pollutant degradation and simultaneous H2 generation

Article abstract of DOI:10.1016/j.cclet.2017.08.031

A visible-light driven photoelectrochemical (PEC) cell comprised of nanostructured BiVO₄ photoanode and Pt cathode was established for organic compounds degradation with simultaneous H₂ generation. BiVO₄ electrode film fabricated by a simple drip-coating method showed a porous nanostructure and an intense absorption in visible light range. The PEC process possesses a rate of about 0.3207 h^?1 for MO degradation, which is 8 times and 64 times faster than electrocatalytic (EC) and photocatalytic (PC) process, respectively. A simultaneous H₂ generation via the PEC process was also observed and a rate of 34.44 μmol h^?1 cm^?2 for H₂ generation was measured, which is 3 folds more efficient than the EC process. The nanostructured BiVO₄ photoanode shows outstanding PEC photocurrent density and recycle performance. The proposed PEC system would be a promising strategy for wastewater treatment and energy recovery with an outstanding stability and recyclability performance.

Full text of DOI:10.1016/j.cclet.2017.08.031

G Model
CCLET 4180 No. of Pages 5
Chinese Chemical Letters xxx (2017) xxx–xxx
Contents lists available at ScienceDirect
Chinese Chemical Letters
journal homepage: www.elsevier.com/locate/cclet
Communication
A photoelectrochemical cell for pollutant degradation and
simultaneous H2 generation
Jin Hana, Yaru Bianb, Xiuzhen Zhenga, Xiaoming Sunb, Liwu Zhanga,
*
a
Department of Environmental Science and Engineering, Fudan University, Shanghai 200433, China
b
College of Science, Beijing University of Chemistry Technology, Beijing 100029, China
A R T I C L E I N F O
A B S T R A C T
Article history:
A visible-light driven photoelectrochemical (PEC) cell comprised of nanostructured BiVO4 photoanode
and Pt cathode was established for organic compounds degradation with simultaneous H2 generation.
BiVO4 electrode film fabricated by a simple drip-coating method showed a porous nanostructure and an
intense absorption in visible light range. The PEC process possesses a rate of about 0.3207 hꢀ1 for MO
degradation, which is 8 times and 64 times faster than electrocatalytic (EC) and photocatalytic (PC)
process, respectively. A simultaneous H2 generation via the PEC process was also observed and a rate of
Received 2 May 2017
Received in revised form 12 August 2017
Accepted 15 August 2017
Available online xxx
Keywords:
Solar energy
Hydrogen
Azo dye
PEC
34.44 m
mol hꢀ1 cmꢀ2 for H2 generation was measured, which is 3 folds more efficient than the EC
process. The nanostructured BiVO4 photoanode shows outstanding PEC photocurrent density and recycle
performance. The proposed PEC system would be a promising strategy for wastewater treatment and
energy recovery with an outstanding stability and recyclability performance.
© 2017 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Published by Elsevier B.V. All rights reserved.
BiVO4
The combustion of the fossil fuel not only leads to the growing
worldwide energy crisis, but also causes serious environmental
pollution problem, such as the acid deposition, haze and the
formation of PM2.5 [1–4]. Consequently, researches on alternative
and clean energy resources have become an urgent challenge for
scientists all over the world. There are many possible alternative
energy resources could be used as the new energy candidates, such
as the solar, wind, geothermal and hydrogen [5]. As a renewable,
green, safe and viable energy resource, hydrogen (H2), which owns
a high gravimetric energy density, has been widely investigated as
the next generation energy carrier during the past few decades [6–
11].
Till now, many technologies have been developed to produce H2
[5,12–17]. Water splitting by PEC process has been studied as an
environmental friendly and potential route for the transformation
from the inexhaustible solar energy to the directly used and green
H2 energy [5,12,18–24]. However, in a typical PEC water splitting
process, the half reaction on the photoanode is the O2 evolution
reaction, whose product O2 is not of significant value. It is more
energy efficient if we can replace the O2 evolution reaction with
some more useful oxidation reaction. We thus propose that the
wastewater treatment could be integrated to the PEC water
splitting, which may make the PEC water splitting economically
feasible [5,8,9,25–28]. The PEC wastewater treatment has been
reported by many researchers [8,29]. In this process, the organics
dye in wastewater is oxidized at the anode, while the H2 is
generated at the cathode. Thus, H2 generation can be well
integrated into the PEC of wastewater treatment simultaneously.
As an n-type semiconductor, bismuth vanadate (BiVO4), which
owns a narrow band gap (2.4 eV) and a broad response in visible
light range, has been considered as one of the most promising
photoanode candidates for water splitting [18,19,30–32]. Besides,
many references reported it has a high oxidation ability and
excellent stability for oxidation degradation [33,34]. Herein, we
use a nanostructured BiVO4 film as the photoanode for the
oxidation of azo dye with a simultaneously H2 production on the
cathode. As shown in Scheme 1, a two electrodes configuration was
employed with a Pt wire as the counter electrode, while BiVO4 as
the working electrode, and electrolyte is the solution of azo dye in
Na2SO4. During the PEC process, the oxidation of azo dye takes
place on the anode, while water is reduced on the cathode to
produce H2.
All chemical reagents are analytical grade and used without any
further purification. Deionized water was used throughout the
whole experiment. FTO glasses were sonicated by immersing in the
acetone, ethanol and DI water in sequence to remove the
impurities that existed in the surface of the FTO glasses.
* Corresponding author.
E-mail address: zhanglw@fudan.edu.cn (L. Zhang).
http://dx.doi.org/10.1016/j.cclet.2017.08.031
1001-8417/© 2017 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
Please cite this article in press as: J. Han, et al., A photoelectrochemical cell for pollutant degradation and simultaneous H2 generation, Chin.
Chem. Lett. (2017), http://dx.doi.org/10.1016/j.cclet.2017.08.031

G Model
CCLET 4180 No. of Pages 5
2
J. Han et al. / Chinese Chemical Letters xxx (2017) xxx–xxx
bubbled into the reactor cell. The size of the synthesized
mesoporous film electrode is 1 ꢃ1 cm2. 300 W Xe lamp was used
as the artificial solar light source and illuminate from the back side
of the film. The working electrode was illuminated from the light
source through a quartz window of the reactor cell. The bias
voltage applied to the film electrode was supplied by the
electrochemical a potentiostat. In this system, methyl orange
(MO, 10 ppm) was used as an azo dye during the PEC process. And
the Na2SO4 (0.5 mol/L) was used as the supporting electrolyte. The
adsorption spectra and contents of the MO in the solution were
measured by UV–vis spectrophotometer (SHIMADZU UV-2600).
The degradation ration of MO was defined in Eq. (2):
Scheme 1. Experimental device for methyl orange degradation with simultaneous
H2 generation via PEC route by nanostructured BiVO4.
Ct/C0 ꢃ100%
(2)
where C0 is the initial concentration of MO in the solution; Ct
denotes the concentration of MO at the different moment. HPLC
was performed by an Agilent 1100 Series. Samples were separated
The BiVO4/FTO was synthesized by a drop-coating method of
the BiVO4 precursor solution onto the conducting plane of the FTO.
In a typical procedure, 0.5 mmol of Bi(NO3)3 5H2O, 0.5 mmol
ꢁ
on a Zorbax SB C18 (4.6 mmꢃ 150 mm, 5
mm) reverse phase column
NH4VO3 were dissolved in the mixture of 5 mL nitric acid and 5 mL
DI water. After the solute was dissolved, 5 mL of ethanol was added
at 50 ꢂC. The mobile phase consisting of methanol/water = 50:50
(V/V) was set at a flow rate of 0.8 mL/min. The concentration of H2
was analyzed by gas chromatography (SHIMADZU, GC-2014) using
a thermal conductivity detector (TCD). The theoretical evolution
rate of H2 is calculated according to the following equation
(Eq. (3)):
to dilute the mixture. Then the BiVO4 precursor (40 mL) was
dripped to the surface of FTO. After dried at 60 ꢂC in an oven, the
catalysts were calcined at 500 ꢂC for 3 h with a ramping rate of 2 ꢂC/
min.
The microstructure of as-prepared electrode was characterized
with scanning electron microscopy (SEM, Philips XL30FEG,
Netherlands). The crystal structure of the as-prepared electrode
was measured using X-ray diffraction (XRD) patterns by a Druker
v
= I ꢃ t/(Z ꢃ F ꢃA ꢃ 3600)
(3)
Where, v indicates the evolution rate of H2 (mol cmꢀ2 hꢀ1); I
indicates the average current (A); t indicates the time (s); Z
indicates the transferred electron number (1); F is the Faraday’s
constant (96500 C/mol); A is the area of the BiVO4 film (cm2).
The equation for the calculation of Faradaic efficiency is
described in Eq. (4):
with Cu K
a
radiation ranging from 10ꢂ to 70ꢂ. UV–vis spectrum of
UV–vis
the as-prepared electrode was performed using
a
spectrophotometer (SHIMADZU UV-2600) with an integrating
sphere attachment. The change in the total organic carbon (TOC) of
MO solution after degradation was tested using TOC analyzer (TOC
2500, Shimazu, Japan). X-ray photoelectron spectroscopy (XPS)
Faradaic efficiency (%) = m ꢃ n ꢃ F/(I ꢃ t)
(4)
was performed on
equipped with a dual X-ray source, using an Mg K
source and hemispherical energy analyzer. Linear Sweep
a
Perkin-Elmer PHI-5000C ESCA system
a
radiation
Where, m is the experimental value of H2 (mol); n is the reacted
electron number (1); F is the Faraday’s constant (96500 C/mol); I is
the average current (A); t is the time (s).
a
Voltammetry (LSV) measurements were carried out by an
electrochemical station (CHI 660E, Shanghai Chenhua Co., Ltd.
China).
The microstructure of the as-prepared BiVO4 film is investigat-
ed by SEM in Fig. 1a. The film of BiVO4 is composed of spherical
naoparticles with diameter of about 500 nm. And the sphere
consisted of nanoparticles, with diameter of about 9 nm (Fig. 1b). A
BiVO4 nanofilm can be successfully synthesized by this simple
drip-coating method, the nanofilm shows porous structure,
ultrathin thickness and high surface area, which are beneficial
for the photoelectrocatalytic oxidation reaction. The XRD experi-
ment is carried out to determine the chemical composition and
crystal structure of the photoelectrode, and the obtained XRD
spectra of BiVO4 and naked FTO are shown in Fig. 1c. It is clear that
the diffraction patterns of the synthesized BiVO4 is highly
consistent with the characteristic reflections of the monoclinic
scheelite structure (JCPDS NO. 14-0688), and the sharp peaks of
During the photoelectrochemical tests,
a standard three
electrodes configuration were employed, the synthesized BiVO4
film is used as the working electrode, Pt wire as the counter
electrode and Ag/AgCl as the reference electrode. The potential
conversion from vs. Ag/AgCl to vs. reversible hydrogen electrode
(RHE) was calculated using Eq. (1):
E(vs. RHE) = E(vs. Ag/AgCl) + 0.199 V + 0.0591 pH
(1)
The PEC degradation of organic contaminant and the amounts
of H2 were performed in a PEC reactor in a two-electrode system at
3.5 V under an air mass (AM) 1.5 G radiation in a 200 mL reactor
with 120 mL solution filled in. As the protective gas, Ar was
Fig. 1. (a) SEM images (b) HRTEM image of nanostructured BiVO4 film; (c) XRD patterns of BiVO4 and naked FTO; (d) UV–vis absorption spectrum and the Tauc plot of BiVO4
(insert).
Please cite this article in press as: J. Han, et al., A photoelectrochemical cell for pollutant degradation and simultaneous H2 generation, Chin.
Chem. Lett. (2017), http://dx.doi.org/10.1016/j.cclet.2017.08.031

G Model
CCLET 4180 No. of Pages 5
J. Han et al. / Chinese Chemical Letters xxx (2017) xxx–xxx
3
BiVO4 film sample indicate it has a good crystallinity. The thickness
of the as-prepared BiVO4 film is thin, as a result, the diffraction
peaks of FTO substrate are also observed.
UV-vis diffraction reflection spectroscopy (UV-vis DRS) is
conducted to investigate the optical property of the synthesized
BiVO4 film. As shown in Fig.1d, three broad absorption bands of the
synthesized BiVO4 film are observed at wavelengths of 200–
350 nm, 350–420 nm, and 420–500 nm, respectively. Besides,
diminishes gradually under the PEC and EC process. However, the
PC process test shows that MO is stable under visible light
irradiation, indicating that the photolysis of MO is negligible
during the whole catalytic period. Meanwhile, the color of the
suspension changed gradually during the PEC and EC process,
suggesting that the chromophoric structure of MO was decom-
posed. Additionally, new absorbance peaks that appeared ranging
from 210–250 nm indicated the formation of small molecular
intermediate products in Fig. 2a. Hence, the activity order of MO
degradation is follows the tendency of PEC > EC > PC. The relative
concentration (Ct/C0, Ct and C0 stand for the remnant and initial
concentrations of MO, respectively) as a function of time is shown
in Fig. 2b. As shown in Fig. 2b, the BiVO4 film exhibits the highest
catalytic activity via PEC process, which significantly outperformed
the same film under the EC and PC process. To further investigate
the degradation kinetics, the pseudo-first-order kinetic model (ln
(Ct/C0) = kt, k is the kinetic constant, t is the reaction time) is
applied to fit the degradation data and the fitting results are shown
in Table S1 in Supporting information. As seen in Fig. S2c and
Table S1, for the degradation rate of MO, the PEC process obtains
the highest rate constant of about 0.3207 hꢀ1, which is higher than
that of EC (about 0.0421 hꢀ1) or PC (about 0.005 hꢀ1). The results
indicate that the degradation efficiency of MO can be significantly
improved under the combination of the photocatalytic process and
the electrocatalytic process, which could effectively facilitate the
separation of photogenerated electron-hole pairs.
HPLC chromatograms of the MO solution at initial, and after
different catalytic route for 6 h are recorded in Fig. 2c. It is
remarkably to note that a much lower intensity of MO is presented
by PEC route than that of EC or PC route. Besides, the retention time
of MO moves forward, indicating the existence of obtained small
molecule intermediate from MO during the PEC process. The HPLC
results further confirm that the BiVO4 electrode film exhibits much
more excellent degradation performance of MO degradation by
PEC process as compared with EC or PC process. Despite its
effectiveness in MO decoloration, the catalytic degradation on the
BiVO4 film may not lead to the mineralization. The mineralization
depends on whether the refractory intermediate compounds are
more difficult to degrade relative to the original substrate.
Therefore, TOC measurements are conducted under different
catalytic degradation process. As shown in Fig. S2d, 66% of the TOC
is removed after discoloration of MO for 6 h with degradation by
PEC process. However, with PC process the mineralization of MO
took place at a much lower rate and TOC was reduced nearly 5%.
Obviously, the rate of the decolorization was much faster than that
of mineralization.
there is a strong absorption in the visible light region (l> 420 nm)
for the synthesized BiVO4 film. And, the band gap of the BiVO4 film
calculated from the Tauc plot is 2.5 eV (Fig. 1d inset), which is in
consistence with the reported band gap of BiVO4 [18]. The BiVO4
film with an intense absorption from the UV to visible light range
could be favor for the efficient utilization of the solar light.
The PEC performances are evaluated both in dark and under AM
1.5 G simulated solar light illumination (100 mW/cm2) in the MO
solution. Fig. S1a in Supporting information displays the photo-
current density–bias (J-V) curves of BiVO4 electrode film in dark
and under irradiation by using a three-electrode configuration. It is
clearly that the current density is negligible in the dark condition.
The detected current increased remarkably when light is turned-
on. The nanostructured BiVO4 electrode film produced an anodic
photocurrent demonstrating the n-type nature of BiVO4 [35]. The
transient photocurrent performance is performed to preliminary
estimate the charge carrier recombination properties on the
interface of the semiconductor. As shown in Fig. S1b, the
photocurrent value presents fast and uniform results, alternatively
increasing to maximum value and decreased to zero corresponding
to the light switched on and off. Besides, the phenomenon of the
photoresponse is reversible. It is known that the generated
transient anodic photocurrent wave, when the light is turn-on,
represents the accumulation of holes at the electrode-electrolyte
interface. At the same time, the generated transient cathodic
photocurrent wave, when the chopped light is turn-off, represents
the recombination of electrons from the conduction band with the
accumulated holes. The obtained nanostructured BiVO4 displays
an outstanding photocurrent density compared with the published
researches [36,37].
The catalytic activities of the typical azo dye samples are
investigated using the degradation of MO at room temperature.
The PEC (at a bias potential of 3.5 V with irradiation), EC
(electrocatalytic process at a bias potential of 3.5 V, without
irradiation), and PC (photocatalytic, without a bias potential) in
neutral aqueous solutions are performed under the given
conditions. The UV–vis absorption spectra of MO solution are
conducted under wavelengths from 200–800 nm during the PEC,
EC and PC operations (Fig. 2a and Fig. S2a-b in Supporting
information). The MO solution was stirred for 30 min to reach the
adsorption equilibrium. The changes of MO concentration versus
the reaction time over BiVO4 film during the PEC, EC and PC process
were shown in Fig. 2a and Fig. S2a-b in Supporting information,
respectively. The major characteristic peak of MO (around 464 nm)
The H2 evolution is also studied at the same time with the MO
degradation during the PEC and EC process. Fig. 2d shows the H2
amount evolved theoretically (calculated from the photocurrent)
vs. evolved experimentally by PEC or EC process, and the current
density during these two processed are provided as well. In
addition, the current densities, theoretical evolution rates of H2,
Fig. 2. (a) The temporal evolution of UV-vis adsorption spectra and the corresponding optical images of MO solutions at different irradiation time by PEC degradation using
the as-prepared BiVO4 electrode film during visible light irradiation; (b) comparison of degradation performance by PEC, EC and PC process; (c) HPLC chromatograms of the
initial MO solution (I) and after 6 h degradation over PEC (II), EC (III) and PC (IV) routes; (d) Amount of hydrogen at an applied potential of 3.5 V in two-electrode system for 6 h.
Please cite this article in press as: J. Han, et al., A photoelectrochemical cell for pollutant degradation and simultaneous H2 generation, Chin.
Chem. Lett. (2017), http://dx.doi.org/10.1016/j.cclet.2017.08.031

G Model
CCLET 4180 No. of Pages 5
4
J. Han et al. / Chinese Chemical Letters xxx (2017) xxx–xxx
experimental evolution rates of H2 and the Faradaic efficiencies of
H2 during the PEC and EC process are summarized in Table S2 in
Supporting information. As shown in Fig. 2d and Table S2 in
Supporting information, the theoretical value and the measured
value during the PEC process is much higher than that of the EC
process. The H2 evolution rate by PEC process is 34.44
cmꢀ2, which is 3 times more efficient than the EC process
(11.37
mol hꢀ1 cmꢀ2). However, some of the generated electrons
m
mol hꢀ1
m
on the cathode can be consumed by the reduction of the small
intermediates formed by the degradation of MO, consequently, an
obvious difference between the theoretical H2 evolution rate and
measured H2 evolution rate during the PEC process is observed.
The calculated Faradic efficiency of H2 during the PEC process (62%)
is thus lower than that of EC process (96%).
Besides, the stability of the H2 generation is confirmed by the
curves of photocurrent density vs. time, which is steady and shows
ignorable changes in 6 h H2 experiment with BiVO4 as the anode
material during the PEC and EC processes (Fig. S3 in Supporting
information). The stability is further confirmed by performing the
MO degradation for five runs by PEC route. These experiments are
carried out by applying the recycled BiVO4 film to fresh MO
solutions with the same concentration, and the results are shown
in Fig. S4 in Supporting information. Since there is no obvious
decrease in activity is observed after five runs, indicating that the
BiVO4 film owns outstanding stability and recyclability during the
PEC reaction and it would be a promising candidate for the
wastewater treatment and H2 production. Additionally, the
nanostructured BiVO4 photocatalyst shows more excellent recycle
performance than previous reports [33,38].
To investigate the origin of the enhanced PEC activity, the
electrochemical property of BiVO4 is performed by the electro-
chemical impedance spectroscopy (EIS). The EIS measurements are
conducted at the same electrolyte solution. (Fig. S5a in Supporting
information) shows the EIS Nyquist plots of BiVO4 film in the dark
and under the light illumination. Here, the EIS results are obtained
by using a three-electrode cell system, thus the arc radius in
Nyquist plot represents the charge transfer resistance on the
working electrode interface. The diameter of the arc radius on the
Nyquist plot in the presence of solar light (PEC process) is smaller
than that in the absence of solar light (EC process), indicating the
efficient charge separation and transport. Hence, the nanostruc-
tured BiVO4 electrode film exhibited outstanding catalytic perfor-
mance of degradation of azo dye and H2 generation during the PEC
process than that of EC process. Besides, the Bode phase plot of
nanostructured BiVO4 is shown in Fig. S5b. The result indicates that
there is no current passing through the external circuit. And the
nanostructured BiVO4 shows the highest Bode phase at 0.25 Hz.
In order to detect the micromorphology, structure and surface
of the catalysis after PEC degradation process, SEM image, XRD
pattern and XPS analysis of the photoanode were conducted after
PEC degradation process. As shown in Fig. S6a and b in Supporting
information, the micromorphology and structure keep unchanged
after PEC degradation process. Besides, after comparing the surface
elements of the photocatalyst before and after catalytic action with
XPS measurement (Fig. S6c), hardly any new elements could be
detected or any element disappeared. The above results indicate
that the physicochemical property of the nanostructured BiVO4
could not be destroyed during the PEC degradation process.
This PEC system involving a photocatalytic oxidation process on
the anode and a reduction process on the cathode is shown in
Scheme 2. The half reactions on the photoanode side are described
as follows: with the xenon light irradiation, the electrons of BiVO4
film are excited from the valence band (VB) to the conduction band
(CB), which producing positive holes (h+) in the VB and negative
electrons (eꢀ) in the CB (Eq. (5)). To avoid the recombination of
photogenerated h+ and eꢀ and provide enough energy potential for
Scheme 2. Schematic illustration of MO degradation with simultaneous H2
generation via PEC route.
H2 generation, an external bias is introduced. Then the photo-
generated eꢀ travels through the interface of BiVO4 electrode to the
cathode by external circuit, while h+ is involved in the oxidation
ꢄ
reaction of the MO (Eq. (8)), via OH radicals formed through the
reactionwith OHꢀ and H2O in the solution (Eqs. (6) and (7)). For the
ꢄ
MO degradation, the OH radicals attack the azo band in the MO
molecule and break down the N-N bond, and then the inter-
mediates are degraded to small molecules and finally oxidized to
CO2 and H2O [39]. On the cathode of the PEC system, H2O as
terminal electron acceptors is reduced to H2 and OHꢀ by accepting
the electrons from cathode with assistance of Pt wire (Eq. (9)). OHꢀ
is then generated on the cathode for the continuously consuming
on the photoanode side, forming the PEC process circle.
BiVO4 ! h+ + eꢀ
(5)
(6)
(7)
h+ + H2O ! ꢄOH + H+
h+ + OHꢀ ! ꢄOH
C14H14N3NaO3S + 38ꢄOH ! 14 CO2 + 3 NO3
+ Na+ + SO42ꢀ + 52
(8)
ꢀ
H+
2 H2O + 2 eꢀ ! 2 OHꢀ + H2 (g)"
(9)
In summary, we prepared
a nanostructured BiVO4 film
electrode for the degradation of azo dye and simultaneously H2
production by PEC process. The BiVO4 electrode presented a strong
absorption from the UV to visible light range. The PEC process
shows excellent catalytic activity of MO degradation and also H2
production, which are both much higher than EC or PC process
alone. We show that the wastewater treatment can be well
integrated into the PEC water splitting, which may make the PEC
water splitting economically feasible. The proposed PEC system
shows the potential to be a sustainable and energy-saving way for
simultaneous wastewater treatment and energy recovery.
Acknowledgements
The authors gratefully acknowledge the financial support from
National Natural Science Foundation of China (Nos. 21507011,
21677037, 21607027), China Postdoctoral Science Foundation (No.
KLH1829017), and Ministry of Science and Technology of China
(Nos. 2016YFE0112200, 2016YFC0203700).
Please cite this article in press as: J. Han, et al., A photoelectrochemical cell for pollutant degradation and simultaneous H2 generation, Chin.
Chem. Lett. (2017), http://dx.doi.org/10.1016/j.cclet.2017.08.031

G Model
CCLET 4180 No. of Pages 5
J. Han et al. / Chinese Chemical Letters xxx (2017) xxx–xxx
5
References
[20] J. Seo, T. Takata, M. Nakabayashi, et al., J. Am. Chem. Soc. 137 (2015) 12780–
12783.
[21] T. Reier, Z. Pawolek, S. Cherevko, et al., J. Am. Chem. Soc. 137 (2015) 13031–
[1] S. Hameed, R.D. Cess, J.S. Hogan, J. Geophys. Res. Oceans 85 (1980) 7537–7545.
[2] J.J. Griffin, E.D. Goldberg, Geochimica. ET. Cosmochimica. Acta 45 (1981) 763–
769.
[3] H. Hevy, W.J. Moxim, Tellus. B 41 (1989) 256–271.
[4] S.S. Penner, Energy 16 (1991) 1417–1419.
[5] J.Y. Jiang, M. Chang, P. Pan, Environ. Sci. Technol. 42 (2008) 3059–3063.
[6] C.A. Reddy, M.P. Bryant, M.J. Wolin, J. Bacteriol. 110 (1972) 126–132.
[7] X. Zong, H.J. Yan, G.P. Wu, et al., J. Am. Chem. Soc. 130 (2008) 7176–7177.
[8] B. Cao, G.S. Li, H.X. Li, Appl. Catal. B: Environ. 194 (2016) 42–49.
[9] Z.W. Chen, X.Y. Jiang, C.B. Zhu, C.K. Shi, Appl. Catal. B: Environ. 199 (2016) 241–
251.
13040.
[22] F. Jiang, Gunawan T. Harada, et al., J. Am. Chem. Soc. 137 (2015) 13691–13697.
[23] L.L. Feng, G.T. Yu, Y.Y. Wu, et al., J. Am. Chem. Soc. 137 (2015) 14023–14026.
[24] C.A. Downes, S.C. Marinescu, J. Am. Chem. Soc. 137 (2015) 13740–13743.
[25] P.A. Williams, C.P. Ireland, P.J. King, et al., J. Mater. Chem. 22 (2012) 20203–
20209.
[26] L. Wang, M.H. Cao, Z.H. Ai, L.Z. Zhang, Environ. Sci. Technol. 48 (2014) 3354–
3362.
[27] K.X. Li, Z.X. Zeng, L.S. Yan, et al., Appl. Catal. B: Environ. 187 (2016) 269–280.
[28] J. Ke, J. Liu, H.Q. Sun, et al., Appl. Catal. B: Environ. 200 (2017) 47–55.
[29] M. Panizza, P.A. Michaud, G. Cerisola, C. Comninellis, Electrochem. Commun. 3
(2001) 336–339.
[10] E. Gianotti, M. Taillades-Jacquin, Á. Reyes-Carmona, et al., Appl. Catal. B:
Environ. 185 (2016) 233–241.
[30] H. Tong, S.X. Ouyang, Y.P. Bi, et al., Adv. Mater. 24 (2012) 229–251.
[31] K.J. McDonald, K.S. Choi, Energy Environ. Sci. 5 (2012) 8553–8557.
[32] M. Zhou, J. Bao, Y. Xu, et al., ACS Nano 8 (2014) 7088–7098.
[33] J.L. Zhang, Y. Lu, L. Ge, et al., Appl. Catal. B: Environ. 204 (2017) 385–393.
[34] J. Bai, R. Wang, Y.P. Li, et al., J. Hazard. Mater. 311 (2016) 51–62.
[35] S.K. Pilli, T.E. Furtak, L.D. Brown, et al., Energy Environ. Sci. 4 (2011) 5028–5034.
[36] J.Q. Li, J. Zhou, H.J. Hao, L.W. Jie, Appl. Surf. Sci. 399 (2017) 1–9.
[37] N. Myung, W. Lee, C. Lee, S. Jeong, K. Rajeshwar, ChemPhysChem 15 (2014)
2052–2057.
[11] D.S. Hu, Y. Xie, L.J. Liu, et al., Appl. Catal. B: Environ. 188 (2016) 207–216.
[12] B.H. Wu, D.Y. Liu, S. Mubeen, et al., J. Am. Chem. Soc. 138 (2016) 1114–1117.
[13] H.H. Liu, D.L. Chen, Z.Q. Wang, H.J. Jing, R. Zhang, Appl. Catal. B: Environ. 203
(2017) 300–313.
[14] Y.F. Zhao, B. Zhao, J. Liu, et al., Angew. Chem. Int. Ed. 55 (2016) 4215–4219.
[15] Y.F. Zhao, X.D. Jia, G.I.N. Waterhouse, et al., Adv. Energy Mater. 6 (2016)
1501974.
[16] L. Shang, B. Tong, H.J. Yu, et al., Adv. Energy Mater. 6 (2016) 1501241.
[17] J.M. Liu, L. Han, H.Y. Ma, et al., Sci. Bull. 61 (2016) 1543–1550.
[18] L.W. Zhang, C.Y. Lin, V.K. Valev, et al., Small 10 (2014) 3970–3978.
[19] S.M. Sun, W.Z. Wang, D.Z. Li, L. Zhang, D. Jiang, ACS Catal. 4 (2014) 3498–3503.
[38] E. Aguilera-Ruiz, U. M.Garcia-Perez, M. Garza-Galvan, et al., Appl. Surf. Sci. 328
(2015) 361–367.
[39] S.B. Xu, Y.F. Zhu, L. Jiang, Y. Dan, Water Air Soil Pollut. 213 (2010) 151–159.
Please cite this article in press as: J. Han, et al., A photoelectrochemical cell for pollutant degradation and simultaneous H2 generation, Chin.
Chem. Lett. (2017), http://dx.doi.org/10.1016/j.cclet.2017.08.031