See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/264575236

Ternary polyaniline–graphene–TiO2 hybrid with enhanced activity for

visible-light photo-electrocatalytic water oxidation

Article · December 2013

DOI: 10.1039/C3TA13751A

CITATIONS READS

38 178

7 authors, including:

Lin Jing Yufei Zhao

UNSW Sydney Beijing University of Chemical Technology
18 PUBLICATIONS   469 CITATIONS    98 PUBLICATIONS   3,983 CITATIONS   

SEE PROFILE SEE PROFILE

Yiming Yan
Beijing Institute of Technology
62 PUBLICATIONS   3,291 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

FT reaction View project

photocatalysis View project

All content following this page was uploaded by Lin Jing on 17 August 2015.

The user has requested enhancement of the downloaded file.

 Journal of
Materials Chemistry A
View Article Online
PAPER View Journal | View Issue
Published on 30 October 2013. Downloaded by BEIJING INSTITUTE OF TECHNOLOGY on 27/02/2014 03:41:39.

Ternary polyaniline–graphene–TiO2 hybrid with

Cite this: J. Mater. Chem. A, 2014, 2,
1068
enhanced activity for visible-light photo-
electrocatalytic water oxidation†
Lin Jing, Zhi-Yu Yang, Yu-Fei Zhao, Yu-Xia Zhang, Xin Guo, Yi-Ming Yan*
and Ke-Ning Sun*

A polyaniline–graphene–TiO2 (PANI–GR–TiO2) hybrid has been successfully synthesized by coating

Received 18th September 2013
Accepted 30th October 2013
DOI: 10.1039/c3ta13751a
www.rsc.org/MaterialsA
graphene nanosheets (GR) on the surface of TiO2 and the subsequent chemical polymerization of
aniline. The synthesized ternary PANI–GR–TiO2 was thoroughly studied by using scanning electron
microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD) and Fourier transform infrared
spectroscopy (FTIR). The PANI–GR–TiO2 hybrid displays promising oxygen evolution reaction (OER)
activity for photoelectrocatalytic water oxidation. Moreover, the durability of the ternary hybrid was
greatly improved due to the coating of PANI and GR on the surface of TiO2. Finally, a reasonable
mechanism was proposed to understand the enhanced activity of the PANI–GR–TiO2 hybrid using UV-
Vis absorption spectroscopy and photoluminescence (PL) emission spectroscopy. Our results clearly
demonstrate that integrating GR and PANI with TiO2 through a simple route results in an efficient ternary
photocatalyst with prominent OER performance for visible-light photoelectrocatalytic water oxidation.

nitrogen-doped CsCa2Ta3O10, layered double hydroxides

Introduction
Photocatalytic water splitting has attracted increasing attention
in recent years because it could convert solar energy to chemical
energy.1 Due to the fact that sunlight and water are abundant
and renewable, photocatalytic water splitting represents a
promising technology to solve the global energy and environ-
mental challenges.2–6 However, the semiconductor photo-
catalysts that possess suitable redox potentials and bandgaps
for simultaneous water reduction and oxidation are rare.
Therefore, many research activities have been devoted to only
half of the reaction, which is the water reduction or water
oxidation by using sacricial reagents as electron donors or
acceptors, respectively.7–10 Generally, hydrogen production
from water reduction requires two electrons, while water
oxidation for oxygen evolution is more challenging since it
requires four holes to generate two oxygen–oxygen bonds for
the production of one oxygen molecule.11–13 To date, the
reported active photocatalysts for oxygen evolution from water
oxidation are scarce. Only several photocatalysts, such as WO3
and BiVO4 have been investigated.14–16 Recently, some new
semiconductors, for instance, BiCu2VO6, BiZn2VO6, TiNxOyFv,
Beijing Key Laboratory for Chemical Power Source and Green Catalysis, School of
Chemical Engineering and Environment, Beijing Institute of Technology, Beijing,
100081, China. E-mail: yanym@bit.edu.cn; bitkeningsun@163.com; Fax: +86-10-
6891-8696
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c3ta13751a
(LDH) and Ag3PO4 crystals have been reported as OER photo-
catalysts for water oxidation.17–21 Nevertheless, a cheap, reli-
able and highly efficient photocatalyst for OER is still needed
to be exploited considering the critical role of OER in the
development of high performance energy conversion and
storage devices.
TiO2 is one of the most important materials in photocatalysis
due to its advantages such as high stability, low cost, relatively
low toxicity, and excellent photocatalytic performance.
However, in respect to its application as an OER photocatalyst
for water oxidation, TiO2 not only suffers of limited absorption
of solar light (wavelengths below
380 nm) due to its large
bandgap (3.20 eV), but also shows poor photocatalytic activity
because of the fast recombination of charge carriers. Moreover,
the substantial energy loss caused by the high OER over-
potential on the TiO2 electrode, especially in the visible light
regime, must be essentially reduced. To solve these problems,
several strategies have been adopted, such as doping elements
(nitrogen, sulfur, carbon, niobium, antimony, boron and
chromium),22–26 integration of different bandgap semi-
conductors, or combination with noble metals as co-catalysts.
For instance, combining TiO2 with other semiconductors such
as MoO3, WO3, SnO2 and Fe2O3 may substantially extend the
light absorption prole and enhance the photocatalytic
performance.27,28 In particular, coupling TiO2 with carbon
nanomaterials such as carbon nanotubes (CNTs), graphene
oxide (GO) and graphene (GR) to form a carbon–TiO2 photo-
catalyst has proven to effectively promote the charge-separation,

1068 | J. Mater. Chem. A, 2014, 2, 1068–1075 This journal is © The Royal Society of Chemistry 2014
 View Article Online

Paper Journal of Materials Chemistry A

therefore increasing the photocatalytic activity.29–32 For
example, GR–TiO2 may gain excellent electron withdrawing and
storing ability, thus effectively increasing the charge transfer
rate of electrons.33–39 In addition, Park et al. reported that gra-
phene-wrapped anatase TiO2 has a bandgap of 2.80 eV, thus
Published on 30 October 2013. Downloaded by BEIJING INSTITUTE OF TECHNOLOGY on 27/02/2014 03:41:39.
powder by the modied Hummers method. The details of the
typical processes can be found in a previous report.47
Preparation of binary GR–TiO2, ternary PANI–GR–TiO2 and
binary PANI–TiO2

improving the photocatalytic activity under visible light irradi-

Binary GR–TiO2 was prepared according to a previous work.40
ation.40 However, to the best of our knowledge, studies on the
The as-prepared TiO2 (0.2 g) was rst dispersed in 150 mL of
preparation of a ternary TiO2 hybrid as an OER photocatalyst for
ethanol by sonication for 10 min. Then, APTMS (1 mL) was
visible-light-driven water oxidation have been seldom reported.
added, heated, and reuxed for 4 h. The APTMS-treated TiO2
On the other hand, photoelectrocatalytic (PEC) oxidation of
was rinsed with ethanol enough to wash away any remaining
water by driving the photo-generated electrons to a counter
APTMS. A GO suspension (5 mL, 0.1 mg mL1) was added to the
electrode via an external bias potential has been proven to
TiO2 dispersion under vigorous stirring. Aer mixing for 30
efficiently improve the quantum efficiency.41,42 In this regard,
min, the mixture was centrifuged and washed with deionized
polyaniline (PANI), a promising candidate as a conducting
water. For the crystallization of TiO2 from the amorphous to the
polymer with a delocalized conjugated structure, and electro-
anatase phase, a hydrothermal process was used as follows.
chemical active units of benzenoid and quinonoid,43,44 has the
GO–TiO2 (0.2 g) was dispersed in a solution of ethanol (20 mL)
advantages of high conductivity, good environmental stability
and deionized water (10 mL) and then autoclaved in a Teon-
and ease of preparation, for its incorporation to various oxides,
lined stainless steel vessel at 180  C for 18 h. Aer the hydro-
such as WO3, SiO2, V2O5 and Fe2O3 for numerous photo-
thermal reaction, calcination at 400  C was carried out for 2 h
electrochemical applications.45 Moreover, PANI has a high
under argon atmosphere to remove the organic components
absorption efficiency in the visible-light and high mobility of
and obtain highly crystalline binary GR–TiO2.
the charge carriers, making them efficient electron donors and
40.0 mg of the as-prepared binary GR–TiO2 was rst
good hole transporters upon visible-light excitation.
dispersed in 60.0 mL of ethanol in an ultrasonic water bath for
In this work, we report for the rst time the preparation of
10 min. The ethanol phase remained clear aer dispersing the
PANI–GR–TiO2 as a ternary hybrid through a stepwise synthetic
binary GR–TiO2. Then, 0.1 mL of aniline was added to the
route. The GR nanosheets were successfully coated on well-
solution, followed by another 10 min of sonication to fully
dened TiO2 in a controllable manner, subsequently followed
disperse the monomers in ethanol. Aerwards, 3 mL of a HCl
by the in situ chemical polymerization of aniline. The as-
aqueous solution (1.21 M) which contained 0.3 g of ammonium
prepared ternary PANI–GR–TiO2 shows a remarkable photo-
peroxydisulfate was added to the above ethanol phase. The
catalytic activity and photostability for visible-light photo-
solid–solution mixture was ultrasonicated continuously for
electrocatalytic water oxidation. The enhanced performance
another 0.5 h in an ultrasonic water bath during which the PANI
was understood by the intrinsic insight into the mechanism of
shells were formed. The dark green product was washed with
electron–hole separation and electron transfer at the surface of
ethanol and deionized water several times and stored in
the hybrid photocatalyst. We demonstrate that such a rationally
ethanol.
designed ternary hybrid possesses unique advantages over
40.0 mg of the as-prepared TiO2 was rst dispersed in 60.0
traditional TiO2 photocatalysts towards water oxidation. It is
mL of ethanol in an ultrasonic water bath for 10 min. Then, 0.1
expected that this study could pave a new way for the prepara-
mL of aniline was added to the solution, followed by another 10
tion of multicomponent TiO2-based photocatalysts, therefore
min of sonication to fully disperse the monomers in ethanol.
nding a variety of applications in photo-induced water split-
Aerwards, 3 mL of a HCl aqueous solution (1.2 M) which
ting, as well as in heterogeneous photocatalysis and photo-
contained 0.3 g of ammonium peroxydisulfate was added to the
catalytic selective transformations.
above ethanol phase. The solid–solution mixture was sonicated
continuously for another 0.5 h in an ultrasonic water bath
during which the PANI shells were formed. The dark green
Experimental section product was washed with ethanol and deionized water several
Materials times.
Titanium(IV) isopropoxide (TIP, 98%), 1-hexadecylamine (HAD,
90%), absolute ethanol (>97%), potassium chloride (KCl), Structural and morphological characterization
ammonia solution (25%), (3-aminopropyl) trimethoxysilane The morphological features of the synthesized powders were
(APTMS, 97%), HCl solution, aniline (99.5%), absolute ethanol characterized by scanning electron microscopy (SEM, QUANTA
(>97%), and ammonium peroxydisulfate were purchase from FEG 250 with an energy dispersive spectrometer). Raman
Sigma Aldrich and used without further treatment. spectra were taken using a Micro-Raman spectrometer system
(Renishaw RM 2000). Powder X-ray diffraction (XRD) patterns
were obtained (D8 Focus, Bruker instrument, Germany) with Cu
Preparation of TiO2 and graphene oxide (GO) Ka radiation (l ¼ 1.5406 Å) in the 2q range from 15 to 60 with a
Amorphous TiO2 was typically synthesised according to a step size of 0.02 s1. FTIR measurements (Perkin Elmer FT-IR
previous work.46 GO was synthesized from natural graphite spectrophotometer) were carried out in the transmittance mode

This journal is © The Royal Society of Chemistry 2014 J. Mater. Chem. A, 2014, 2, 1068–1075 | 1069
 View Article Online

Journal of Materials Chemistry A Paper

in the spectral range 400–2000 cm1 with a resolution better

than 0.1 cm1. UV-vis spectra were recorded using a Shimadzu
UV-2450 spectrometer. Photoluminescence spectra (PL) were
acquired at room temperature using a Hitachi FL4600 lumi-
nescence spectrophotometer in diffuse reection mode and
Published on 30 October 2013. Downloaded by BEIJING INSTITUTE OF TECHNOLOGY on 27/02/2014 03:41:39.

with an excitation wavelength of 310 nm.

Electrochemical and photoelectrochemical measurements

The working electrode was prepared as follows: 3 mg of the as-
prepared ternary PANI–GR–TiO2 was dispersed in 1 mL ethanol
by sonication for 10 min to obtain a homogeneous suspension.
Then, 20 mL of the suspension was loaded onto an ITO electrode
(1  1 cm squares) and dried in air at room temperature. A TiO2
electrode and a binary GR–TiO2 electrode were also prepared for
comparison. All photocurrent and electrochemical experiments
were performed with a CHI 660 electrochemical workstation
and conducted in a nitrogen-purged 0.5 M Na2SO4 electrolyte
solution at pH 7, using the three-electrode setup (particles-
coated ITO electrode as the photoanode, Hg/Hg2Cl2 as the
reference electrode, and a platinum wire as the counter elec-
trode). The photocurrent was measured with a bias voltage of
0.25 V. The relationship between the light wavelength and the
produced photocurrent on different modied electrodes was
studied in the light wavelength range of 300 to 600 nm. The
photocurrent was also measured for each switch-on/off event by
using a xenon lamp (450 W) with a 400 nm cut-off lter. Linear
sweep voltammetry (LSV) was recorded with a sweeping rate of
0.1 V s1 in the potential range of 0.4 to 0.8 V vs. Hg/Hg2Cl2
under 400 nm illumination or darkness. Electrochemical
impedance spectroscopy (EIS) was measured in 0.1 M KCl
containing 5 mM K3[Fe(CN)6] by applying an ac amplitude of 5
mV under an open circuit potential in a frequency range from
180 kHz to 0.05 Hz.
Results and discussion
Scheme 1 shows the synthetic procedure and illustrates the
composition of the as-prepared PANI–GR–TiO2 hybrid. Fig. 1
presents the SEM images of the prepared samples. The obtained
TiO2 through the sol–gel method has an average diameter of 900
 50 nm (Fig. 1A). Aer the successful coating of GR, which was
realized by a one-step reduction of GO on the TiO2 surface via
hydrothermal treatment, the obtained binary GR–TiO2 hybrid
exhibits a much rougher surface morphology (Fig. 1B), implying
that the bare TiO2 was fully wrapped by GR nanosheets. The
Fig. 1 SEM images of the as-prepared (A) bare TiO2, (B) binary GR–
TiO2, (C) ternary PANI–GR–TiO2 (0.5 h), and (D) ternary PANI–GR–
TiO2 (1 h). Scale bar: 200 nm.
observed rough surface is caused by the coating GR sheets,
which can be reasonably assumed by the morphology and size
of the prepared GR, as shown in Fig. S1.† As previously reported,
to achieve the best photocatalytic performance, the optimum
weight ratio of GR to TiO2 in the binary GR–TiO2 should be
0.02 : 1.40 Therefore, a sample of binary GR–TiO2 (0.02 : 1)
was used here to further fabricate the PANI–GR–TiO2 hybrid.
Polyaniline (PANI) was introduced on the surface of binary
GR–TiO2 by a chemical polymerization method. The content
of PANI in the hybrid material can be easily tuned by
controlling the polymerization time (0.5 h and 1 h). As shown
in Fig. 1C, uniform and smaller nanoparticles were clearly
overspread at the surface of the ternary PANI–GR–TiO2 (0.5 h)
in comparison with that of binary GR–TiO2, suggesting that
a thin layer of PANI was formed at the surface of binary
GR–TiO2. However, when a higher ratio of PANI was intro-
duced in the hybrid, e.g. the sample of ternary PANI–GR–TiO2
(1 h) as shown in Fig. 1D, severely aggregation at the surface
was observed, implying that a much thick layer of PANI was
coated on the surface. We noted that the photocatalytic
activity of the ternary PANI–GR–TiO2 (1 h) might be inhibited

Scheme 1 Illustration of the stepwise synthetic procedure and the structure of ternary PANI–GR–TiO2.

1070 | J. Mater. Chem. A, 2014, 2, 1068–1075 This journal is © The Royal Society of Chemistry 2014

Paper
due to the much thicker layer of PANI on the surface that
blocks the absorption of light.
To further verify the composition of ternary PANI–GR–TiO2,
Fig. 2 presents the Raman, XRD and FTIR characterization. It
was found that the Raman spectrum of binary GR–TiO2 shows
Published on 30 October 2013. Downloaded by BEIJING INSTITUTE OF TECHNOLOGY on 27/02/2014 03:41:39.
the typical features of GR with the presence of a D band located
at 1316 cm1 and a G band at 1591 cm1, as shown in Fig. 2A. It
is known that the G band indicates the in-plane vibration of the
sp2 bonded carbon atoms, while the D band demonstrates the
presence of sp3 defects. Further, when PANI was introduced, the
Raman spectrum of the resulting ternary PANI–GR–TiO2
displays the typical peaks at 1169 cm1 and 1464 cm1, which
correspond to C–H vibrations in the quinoid/phenyl groups and
the semiquinone radical cation structure in molecular PANI,
respectively. As such, the Raman measurements clearly
demonstrate the successful step-wise synthesis of ternary PANI–
GR–TiO2.
XRD can provide useful information of the crystallographic
structure of the samples. As shown in Fig. 2B, no peaks were
observed in the XRD pattern of bare TiO2, suggesting that it has
Fig. 2 (A) Raman spectra of bare TiO2, binary GR–TiO2, and ternary
PANI–GR–TiO2. (B) XRD patterns of bare TiO2, binary GR–TiO2, and
ternary PANI–GR–TiO2. (C) FTIR spectra of bare TiO2, binary GR–TiO2,
and ternary PANI–GR–TiO2.
This journal is © The Royal Society of Chemistry 2014
View Article Online
Journal of Materials Chemistry A
an amorphous structure. However, the XRD pattern of the
binary GR–TiO2 sample displays characteristic peaks at 2q
values of 25.3, 37.8, 48.0, 53.9 and 55.1, which are assigned to
the (101), (004), (200), (105) and (211) crystal planes of anatase
TiO2. It apparently indicates that hydrothermal treatment of
TiO2 with a GO solution can convert amorphous TiO2 into
anatase TiO2. However, we also noticed that no typical diffrac-
tion peaks of GR or PANI are observed in the obtained binary or
ternary samples. This might be explained by the fact that only
small amounts of GR and PANI are contained in these tested
samples.
Fig. 2C shows the FTIR spectra of the synthesized bare TiO2,
binary GR–TiO2 and ternary PANI–GR–TiO2. A broad absorption
band below 1000 cm1 is observed for all samples, which is
assigned to the Ti–O–Ti stretching and bending vibration
modes. For comparison, an absorption band at 1622 cm1 was
clearly observed for the binary GR–TiO2 composites which can
be attributed to the skeletal vibration of the GR nanosheets.
Moreover, in the spectrum of the ternary PANI–GR–TiO2
sample, the absorption bands of PANI were found at 1588 cm1
and 1501 cm1, which are ascribed to the C]N and C]C
stretching vibrations for the quinoid and benzenoid rings. In
addition, the bands at about 1305 cm1 and 1245 cm1 are
assigned to the C–N stretching mode of the benzenoid ring,
while the peak at 1148 cm1 is attributed to the plane bending
vibration of C–H, which may be formed by protonation during
the polymerization process.
Fig. 3A displays the UV-Vis absorption spectra of TiO2, binary
GR–TiO2 and ternary PANI–GR–TiO2. It can be seen that the
introduction of GR or PANI signicantly leads to a red-shi in
the absorption proles of the resulted binary GR–TiO2 or
ternary PANI–GR–TiO2, respectively. According to the obtained
absorption spectra, we plotted the modied Kubelka–Munk
function, i.e., [F(RN)hn]1/2, versus the energy of the exciting light
Fig. 3 (A) The UV-Vis absorption spectra of bare TiO2, binary GR–
TiO2, and ternary PANI–GR–TiO2. (B–D) The derived plots of the
transformed Kubelka–Munk function for the three samples versus the
energy of light.
J. Mater. Chem. A, 2014, 2, 1068–1075 | 1071

Journal of Materials Chemistry A
(hn), to estimate the bandgap of the samples (Fig. 3B–D).48,49 The
bandgaps were calculated to be 3.23 eV, 2.65 eV and 2.18 eV for
TiO2, binary GR–TiO2 and ternary PANI–GR–TiO2, respectively.
The observed bandgap value for TiO2 is similar to the reported
Eg value of TiO2. Meanwhile, the slight red-shi for ternary
Published on 30 October 2013. Downloaded by BEIJING INSTITUTE OF TECHNOLOGY on 27/02/2014 03:41:39.
PANI–GR–TiO2 compared to binary GR–TiO2 also suggests that
PANI essentially extends the absorption to the visible-light
region. This observed phenomenon is consistent with the
previously results reported for PANI–TiO2 materials. It is
accepted that the existence of the p–p* transition of the
benzenoid ring, polaron-p*, and p-polaron exaction transition
of the quinonoid rings in the PANI structure leads to a high
absorption both in the UV and the visible-light region. There-
fore, the incorporation of PANI on the surface may substantially
improve the utilization of solar energy. As a result, we expect
that ternary PANI–GR–TiO2 can reasonably produce more elec-
tron–hole pairs under visible-light illumination, and thus
increase the photo-catalytic activity.
To compare the photoelectrochemical performance, the
same amount of bare TiO2, binary GR–TiO2, and ternary PANI–
GR–TiO2 were deposited onto clean ITO electrodes. The
performance of the modied electrodes was investigated by
linear sweep voltammetry (LSV). The current of the modied
electrodes was recorded in the dark and under visible light
irradiation, respectively. As shown in Fig. 4A, the observed
oxidation current at all the modied electrodes under
Fig. 4 (A) LSVs of bare TiO2, binary GR–TiO2, and ternary PANI–GR–
TiO2 measured in a 0.5 M Na2SO4 solution electrolyte in the dark and
under visible light irradiation (400 nm). (B) The percentage of the
increased oxidization current of the ternary PANI–GR–TiO2 electrode
at different applied bias potentials. (C) The photocurrent–wavelength
curves obtained with bare the TiO2, binary GR–TiO2, binary PANI–TiO2
and ternary PANI–GR–TiO2 modified ITO electrodes in 0.5 M Na2SO4
with a bias voltage of 0.25 V. The photocurrent responses of bare TiO2,
binary GR–TiO2, binary PANI–TiO2 and ternary PANI–GR–TiO2 under
the whole wavelength light irradiation. (D) The photocurrent responses
of bare TiO2, binary GR–TiO2, binary PANI–TiO2 and ternary PANI–
GR–TiO2 for each switch-on/off event under visible light irradiation
(400 nm). The potential of the working electrode was set at 0.25 V vs.
the Pt counter electrode.
1072 | J. Mater. Chem. A, 2014, 2, 1068–1075
View Article Online
Paper
illumination was apparently higher than that observed in dark.
It suggests that the photoelectrocatalytic oxidation of water
essentially occurred at the modied electrode. The oxidation
peak of the ternary PANI–GR–TiO2 modied electrode is
assigned to the redox peak of PANI. However, under visible-light
irradiation, the photocurrent at the ternary PANI–GR–TiO2
modied electrode was much higher than that obtained in the
dark. In contrast, nearly no change of the photocurrent was
found at the TiO2 modied electrode, and only a slight increase
of the photocurrent was recorded at the binary GR–TiO2
modied electrode. As such, the LSV results strongly demon-
strate that ternary PANI–GR–TiO2 possesses a much better
activity towards photoelectrocatalytic water oxidation than TiO2
and binary GR–TiO2. We have also examined the effect of the
photoelectrocatalytic water oxidation at the ternary PANI–GR–
TiO2 electrode by comparing the percentage of the increased
oxidization current at different applied bias potentials. As
shown in Fig. 4B, a much higher photocurrent was achieved
when the potential was scanned towards more positive poten-
tials, indicating that the photo-generated electrons can be
effectively driven at more positive potentials, representing a
typical photoelectrochemical process.
Fig. 4C shows the relationship of light wavelength with the
produced photocurrent observed with the different modied
electrodes at a certain bias potential. For a clear understanding
of the roles of the components, binary PANI–TiO2 was also
prepared and investigated to compare its photoelectrocatalytic
activity. As expected, the photocurrent of the ternary PANI–GR–
TiO2 electrode was signicantly higher than that obtained with
the TiO2, binary PANI–TiO2, and binary GR–TiO2 electrodes at
all irradiation wavelengths. We also recorded the transient
photocurrent responses of all the modied electrodes under
certain irradiation light wavelengths and bias potentials in a
light switch “on–off” model. As shown in Fig. 4D, all the elec-
trodes show well-dened current responses to the light “on–off”
switches, implying a reasonable photoelectrocatalytic process at
the modied electrodes. Signicantly, the highest photocurrent
at the ternary PANI–GR–TiO2 electrode clearly conrms that it
possesses the highest photoelectrocatalytic OER efficiency
among all the electrodes.
As the durability of the photocatalyst plays an important role
in its commercial application, we then investigated the photo-
stability of the ternary PANI–GR–TiO2 photocatalyst towards
photoelectrocatalytic OER under continuous measurement. For
comparison, TiO2 and binary GR–TiO2 were also tested under
the same conditions. As shown in Fig. 5, almost 94% of the
initial photocurrent was maintained aer 10 000 s of contin-
uous illumination at the ternary PANI–GR–TiO2 modied elec-
trode, while these values were only 31% and 64% for the TiO2
and binary GR–TiO2 electrodes, respectively. We note that the
signicant durability of the ternary PANI–GR–TiO2 obtained
here is also comparable to the previously results reported with
other OER photocatalysts, such as cobalt phosphate–ZnO, WO3/
Co–Pi and BiVO4.14,15 Such a promising photostability of this
ternary hybrid may be either ascribed to the facilitated electron
transport at the surface, thus inhibiting the photo-corrosion, or
due to the modication of PANI as a chemical inert component
This journal is © The Royal Society of Chemistry 2014

Paper
Published on 30 October 2013. Downloaded by BEIJING INSTITUTE OF TECHNOLOGY on 27/02/2014 03:41:39.
Fig. 5 The stability of the oxygen evolution reaction on bare TiO2,
binary GR–TiO2 and ternary PANI–GR–TiO2 electrode.
at the surface, therefore possibly blocking the chemical corro-
sion from solution during irradiation.
Photoluminescence (PL) spectra is a useful technique to
investigate the efficiency of charge carrier trapping, immigra-
tion and transfer at the surface of semiconductors, therefore
understanding the annihilation of electron–hole pairs in
semiconductors. The PL spectra of TiO2, binary GR–TiO2 and
ternary PANI–GR–TiO2 were measured and are presented in
Fig. 6. It is obvious that the bare TiO2 exhibits a strong PL signal
peak at 345 nm, while binary GR–TiO2 shows a weak peak at 356
nm, therefore suggesting that there is a lower recombination
rate of photo induced electrons and holes at the surface of
binary GR–TiO2 than that at the surface of TiO2. This could be
easily understood by the fact that the well-conducted GR could
effectively interact with TiO2, leading to enhanced electron
transport of the photo-induced electrons at the surface of TiO2.
In addition, we observed that the PL signal was further largely
depressed in ternary PANI–GR–TiO2, implying that the intro-
duction of PANI could essentially inhibit the recombination of
the photo-induced electrons and holes compared to binary GR–
TiO2 and bare TiO2. Moreover, the red-shi of the PL signal
peak for both binary GR–TiO2 and ternary PANI–GR–TiO2
are well in agreement with that observed in the UV-Vis
Fig. 6 PL spectra of bare TiO2, binary GR–TiO2 and ternary PANI–GR–
TiO2.
This journal is © The Royal Society of Chemistry 2014
View Article Online
Journal of Materials Chemistry A
absorption spectra. On the other hand, electrochemical imped-
ance spectroscopy (EIS) is a powerful technique to provide direct
evidence for interfacial electron transfer. As shown in Fig. S2,†
the Nyquist plots of the electrodes exhibit semicircles over the
high frequency, from which the charge-transfer resistance (Rct)
can be calculated. Compared to that of bare TiO2 and binary
GR–TiO2, the smaller semicircle and the corresponding lower Rct
of ternary PANI–GR–TiO2 clearly demonstrate the faster electron
transfer rate, which is attributed to the introduction of well-
conducted GR and PANI. As a conclusion, the PL and EIS results
strongly prove that the ternary PANI–GR–TiO2 hybrid can
substantially inhibit the electron–hole recombination and
improve the electron transfer rate, therefore efficiently enhancing
the photocatalytic performance.
Finally, we tried to understand the enhanced photo-electro-
catalytic performance for the as-prepared ternary hybrid by
illustrating the OER mechanism at the photocatalyst. We have
noted that wrapping GR apparently leads to a red-shi of the
absorption peak for the binary GR–TiO2 catalyst. Based on the
data calculated with the plots of the transformed Kubelka–
Munk function, the corresponding bandgap of binary GR–TiO2
was remarkably decreased to 2.65 eV, therefore largely extend-
ing the light absorption to the visible region. However, the
photocurrent at the binary GR–TiO2 hybrid was not signicantly
improved compared to the bare TiO2 electrode. On the other
hand, we also noted that a control experiment showed that
PANI–TiO2 gives a similar photocurrent as binary GR–TiO2,
which is much lower than that of the ternary hybrid. This could
be easily observed from the LSV results and the “on–off” tests
displayed in Fig. 4. Therefore, it seems that both GR and PANI
play important roles in determining the high performance of
ternary PANI–GR–TiO2. We suppose that the relative energy
levels of PANI (HOMO, p-orbital and LUMO, p*-orbital) and
TiO2 (conduction band, CB, and valence band, VB) may create a
synergistic effect (Scheme 2). In addition, it has been reported
that PANI can create a favorable p-conjunction structure
together with GR layers.50 By these virtues, the photo-induced
holes in the TiO2 VB can easily transfer to the HOMO of PANI.
Simultaneously, the photo-induced electrons can transfer to the
CB of TiO2, which results in an efficient charge separation,
therefore inhibiting the recombination process. As such, we
expect that, on one hand, many more electron–hole pairs can be
Scheme 2 Mechanism of ternary PANI–GR–TiO2 to enhance the
photocatalytic activity under visible light.
J. Mater. Chem. A, 2014, 2, 1068–1075 | 1073

Journal of Materials Chemistry A
created by extending the absorption proles caused by the
introduction of GR and , on the other hand, a more effective
charge separation can be achieved by the favorable p-conjunc-
tion structure between PANI–GR, therefore resulting in an
improved photocurrent and enhanced photoelectrocatalytic
Published on 30 October 2013. Downloaded by BEIJING INSTITUTE OF TECHNOLOGY on 27/02/2014 03:41:39.
performance for the ternary PANI–GR–TiO2 hybrid. Such an
assumption was strongly supported by UV-Vis, PL and EIS
measurements. Meanwhile, it has to be noted that the
enhanced affinity of molecular water at the PANI layer should
not be neglected, as proved by previous studies of the binary
PANI–TiO2 system .
Conclusions
In summary, we have prepared a ternary PANI–GR–TiO2 hybrid
as a highly efficient photocatalyst by a simple method. The
ternary PANI–GR–TiO2 not only exhibits a remarkably higher
OER activity than binary GR–TiO2 and bare TiO2 for visible-light
photoelectrocatalytic water oxidation, but also possesses
promising photo-stability under continuous working condi-
tions. The improved photoelectrocatalytic OER performance is
attributed to the following crucial factors: (1) extended visible
light absorption with enhanced solar energy harvesting by
introducing the GR and PANI components; and (2) facilitated
charge separation at the surface and improvement of the elec-
tron transfer rate with the presence of PANI as an electro-
chemical active component. Although further work is needed to
optimize the ratio of PANI, GR and TiO2 to achieve a better
photoelectrocatalytic OER performance, our work essentially
paves the way to rationally design and synthesize novel TiO2-
based photocatalysts for a variety of applications, such as pho-
toelectrocatalytic water splitting, photocatalysis, articial
photosynthesis, and photoelectrical devices.
Acknowledgements
Financial support from the National Natural Science Founda-
tion of China (Grant no. 21175012, 21006015 and 21070623),
the Ministry of Science and Technology (2012DFR40240) and
the Chinese Ministry of Education (Project of New Century
Excellent Talents in University) is gratefully acknowledged.
Notes and references
1 A. Fujishima and K. Honda, Nature, 1972, 238, 37.
2 D. G. Nocera, Inorg. Chem., 2009, 48, 10001.
3 J. Barber, Chem. Soc. Rev., 2009, 38, 185.
4 R. Eisenberg and H. B. Gray, Inorg. Chem., 2008, 47, 1697.
5 T. A. Betley, Q. Wu, T. Van Voorhis and D. G. Nocera, Inorg.
Chem., 2008, 47, 1849.
6 D. K. Bediako, Y. Surendranath and D. G. Nocera, J. Am.
Chem. Soc., 2013, 135, 3662.
7 Q. Xiang, J. Yu and M. Jaroniec, J. Am. Chem. Soc., 2012, 134,
6575.
8 T. Noji, C. Kamidaki, K. Kawakami, J. R. Shen, T. Kajino,
Y. Fukushima, T. Sekitoh and S. Itoh, Langmuir, 2011, 27,
705.
1074 | J. Mater. Chem. A, 2014, 2, 1068–1075
View Article Online
Paper
9 R. Forgie, G. Bugosh, K. C. Neyerlin, Z. Liu and P. Strasser,
Electrochem. Solid-State Lett., 2010, 13, D36.
10 Q. Liu, J. Jin and J. Zhang, ACS Appl. Mater. Interfaces, 2013,
5, 5002.
11 R. Eisenberg and H. B. Gray, Inorg. Chem., 2008, 47, 1697.
12 T. A. Betley, Q. Wu, T. Van Voorhis and D. G. Nocera, Inorg.
Chem., 2008, 47, 1849.
13 D. K. Bediako, Y. Surendranath and D. G. Nocera, J. Am.
Chem. Soc., 2013, 135, 3662.
14 J. A. Seabold and K. S. Choi, Chem. Mater., 2011, 23, 1105.
15 J. A. Seabold and K. S. Choi, J. Am. Chem. Soc., 2012, 134,
2186.
16 J. Yang, D. Wang, X. Zhou and C. Li, Chem.–Eur. J., 2013, 19,
1320.
17 H. Liu, R. Nakamura and Y. Nakato, ChemPhysChem, 2005, 6,
2499.
18 H. Liu, R. Nakamura and Y. Nakato, Electrochem. Solid-State
Lett., 2006, 9, G187.
19 K. Maeda, B. Lee, D. Lu and K. Domen, Chem. Mater., 2009,
21, 2286.
20 X. Zong, C. Sun, Z. Chen, A. Mukherji, H. Wu, J. Zou,
S. C. Smith, G. Q. Lu and L. Wang, Chem. Commun., 2011,
47, 6293.
21 Z. Yi, J. Ye, N. Kikugawa, T. Kako, S. Ouyang, H. Stuart-
Williams, H. Yang, J. Cao, W. Luo, Z. Li, Y. Liu and
R. L. Withers, Nat. Mater., 2010, 9, 559.
22 R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki and Y. Taga,
Science, 2001, 293, 269.
23 T. Ohno, T. Mitsui and M. Matsumura, Chem. Lett., 2003, 32,
364.
24 H. Irie, Y. Watanabe and K. Hashimoto, Chem. Lett., 2003,
32, 772.
25 Y. F. Li, Z. P. Liu, L. Liu and W. Gao, J. Am. Chem. Soc., 2010,
132, 13008.
26 G. Liu, J. Pan, L. Yin, J. T. S. Irvine, F. Li, J. Tan,
P. Wormald and H. M. Cheng, Adv. Funct. Mater., 2012,
22, 3233.
27 S. H. Elder, F. M. Cot, Y. Su, S. M. Heald, A. M. Tyrysgkin,
M. K. Bowman, Y. Gao, A. G. Joly, M. L. Balmer,
A. C. Kolwaite, K. A. Magrini and D. M. Blake, J. Am. Chem.
Soc., 2000, 122, 5138.
28 T. Tatsuma, S. Saitoh, P. Ngaotrakanwiwat, Y. Ohko and
A. Fujishima, Langmuir, 2002, 18, 7777.
29 K. Woan, G. Pyrgiotakis and W. Sigmund, Adv. Mater., 2009,
21, 2233.
30 M. R. Hoffmann, S. T. Martin, W. Choi and
D. W. Bahnemann, Chem. Rev., 1995, 95, 69.
31 Y. J. Xu, Y. Zhuang and X. Fu, J. Phys. Chem. C, 2010, 114,
2669.
32 C. Chen, W. Cai, M. Long, B. Zhou, Y. Wu, D. Wu and
Y. Feng, ACS Nano, 2010, 4, 6425.
33 H. Kim, G. Moon, D. Satoca, Y. Park and W. Choi, J. Phys.
Chem. C, 2012, 116, 1535.
34 M. S. A. S. Shah, A. R. Park, K. Zhang, J. H. Park and P. J. Yoo,
ACS Appl. Mater. Interfaces, 2012, 4, 3893.
35 T. Kamegawa, D. Yamahana and H. Yamashita, J. Phys.
Chem. C, 2010, 114, 15049.
This journal is © The Royal Society of Chemistry 2014

Paper
36 N. Zhang, Y. Zhang, X. Pan, M. Q. Yang and Y. J. Xu, J. Phys.
Chem. C, 2012, 116, 18023.
37 J. Du, X. Lai, N. Yang, J. Zhai, D. Kisailus, F. Su, D. Wang and
L. Jiang, ACS Nano, 2011, 5, 590.
38 Y. H. Ng, I. V. Lightcap, K. Goodwin, M. Matsumura and
Published on 30 October 2013. Downloaded by BEIJING INSTITUTE OF TECHNOLOGY on 27/02/2014 03:41:39.
P. V. Kamat, J. Phys. Chem. Lett., 2010, 1, 2222.
39 R. Long, N. J. English and O. V. Prezhdo, J. Am. Chem. Soc.,
2012, 134, 14238.
40 J. S. Lee, K. H. You and C. B. Park, Adv. Mater., 2012, 24, 1084.
41 S. Chai, G. Zhao, Y. N. Zhang, Y. Wang, F. Nong, M. Li and
D. Li, Environ. Sci. Technol., 2012, 46, 10182.
42 Y. Wang, J. Xu, W. Zong and Y. Zhu, J. Solid State Chem.,
2011, 184, 1433.
This journal is © The Royal Society of Chemistry 2014
View publication stats
View Article Online
Journal of Materials Chemistry A
43 S. Xiong, S. L. Phua, B. S. Dunn, J. Ma and X. Lu, Chem.
Mater., 2010, 22, 255.
44 Q. Li, C. Zhang and J. Li, Appl. Surf. Sci., 2010, 257, 944.
45 X. Huang, G. Wang, M. Yang, W. Guo and H. Gao, Mater.
Lett., 2011, 65, 2887.
46 D. Chen, F. Huang, Y. B. Cheng and R. A. Caruso, Adv. Mater.,
2009, 21, 2206.
47 X. Pan, Y. Zhao, S. Liu, C. L. Korzeniewski, S. Wang and
Z. Fan, ACS Appl. Mater. Interfaces, 2012, 4, 3944.
48 P. Kubelka, J. Opt. Soc. Am., 1948, 38, 448.
49 L. Yang and B. Kruse, J. Opt. Soc. Am. A, 2004, 21, 1933.
50 Y. H. Tang, N. Wu, S. L. Luo, C. B. Liu, K. Wang and
L. Y. Chen, Macromol. Rapid Commun., 2012, 33, 1780.
J. Mater. Chem. A, 2014, 2, 1068–1075 | 1075