Accepted Manuscript

Title: Design of Cu-Cu2 O/g-C3 N4 nanocomponent

photocatalysts for hydrogen evolution under visible light
irradiation using water-soluble Erythrosin B dye sensitization

Author: Piyong Zhang Tingting Wang Heping Zeng

PII: S0169-4332(16)31201-6
DOI: http://dx.doi.org/doi:10.1016/j.apsusc.2016.05.162
Reference: APSUSC 33355

To appear in: APSUSC

Received date: 13-4-2016

Revised date: 24-5-2016
Accepted date: 29-5-2016

Please cite this article as: Piyong Zhang, Tingting Wang, Heping Zeng, Design of Cu-
Cu2O/g-C3N4 nanocomponent photocatalysts for hydrogen evolution under visible
light irradiation using water-soluble Erythrosin B dye sensitization, Applied Surface
Science http://dx.doi.org/10.1016/j.apsusc.2016.05.162

This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
Design of Cu-Cu2O/g-C3N4 nanocomponent photocatalysts for

hydrogen evolution under visible light irradiation using water-soluble

Erythrosin B dye sensitization

Piyong Zhang, Tingting Wang, Heping Zeng*

State Key Laboratory of Luminescent Materials and Devices, Institute of Functional Molecules,

School of Chemistry and Chemical Engineering, South China University of Technology,

Guangzhou, 510641, P. R. China.

*Corresponding author. Tel.: +86-20-87112631; Fax: +86-20-87112631; E-mail:
hpzeng@scut.edu.cn

1
Graphical Abstract

2
Highlights

 A novel photocatalyst Cu-Cu2O/g-C3N4 was designed, synthesized and

characterized.

 Cu-Cu2O/g-C3N4 was sensitized by Erythrosin B and a significant enhancement

of H2 evolution rate was achieved.

 Electrochemical properties were measured and a possible mechanism of H2

evolution was proposed.

3
Abstract

Cu-Cu2O nanoparticles (NPs) decorated porous graphitic carbon nitride (g-C3N4)

(Cu-Cu2O/g-C3N4) photocatalysts were prepared. When investment of copper source
materials in the experiment increased to 7 wt%, the highest H2 evolution rate (400
μmol g-1 h-1) was obtained under visible light irradiation in triethanolamine solution.
This is about triple of pure g-C3N4 (140 μmol g-1 h-1). Moreover, various amount of
Erythrosin B dye was added into Cu-Cu2O/g-C3N4 photoreaction solution and a
significant enhancement of H2 production rate was achieved. The highest H2
production rate was 5000 μmol g-1 h-1 with 5 mg Erythrosin B in photoreaction system.
Erythrosin B dye sensitized Cu-Cu2O/g-C3N4 presented stable photocatalytic H2
evolution ability and no noticeable degradation or change of photocatalyst were
detected after six recycles. A possible photocatalytic mechanism of Erythrosin B dye
sensitized Cu-Cu2O/g-C3N4 for the enhancement of photocatalytic H2 evolution is
proposed.
Keywords: Cu-Cu2O/g-C3N4; hydrogen evolution; photocatalytic; sensitization

4
Introduction

Hydrogen is considered to be one of the most potential fuels due to increasing anxiety
about the global energy crisis and environmental pollution. Wang et al. reported a
novel metal-free polymer n-type semiconductor, layered C3N4 with a graphitic
structure (g-C3N4), showing good visible light absorption property (Eg=2.7 eV) and
photocatalytic stability for hydrogen evolution [1-7]. However, photocatalytic
hydrogen evolution from water on unmodified g-C3N4 is limited, mainly due to the
rapid recombination rate of photogenerated electron-hole pairs. Up to now, two
methods have been considered effective to increase the separation efficiency of
photoinduced electron-hole pairs for g-C3N4. One is to load metal nanoparticles (NPs)
as co-catalysts, such as Au, Pt and Ag on the surface of catalysts [8-12]. Cu NPs have
attracted much attention due to enhancement of the photocatalytic activity [13]. It can
prevent the recombination of photoexcited electrons and holes as co-catalysts and
generate localized surface plasmon resonance (LSPR) effect which promotes the
separation of electron-holes [14]. The other way is to form semiconductor
heterojunctions with properly aligned band structure [15,16]. In the last decades,
several kinds of g-C3N4 based heterojunctions have been developed, such as
g-C3N4/TaON [15], g-C3N4/WS2 [17], g-C3N4/carbon fiber [18], g-C3N4/Ni(dmgH)2
[19] and g-C3N4/Cu2O [20-22].
In addition to above two methods, dye sensitization is also an effective method
for improving hydrogen evolution. Dye sensitization could convert long wavelength
of light to energy for photocatalyst in photocatalytic reaction [23-27]. Currently,
Erythrosin B (denoted as ErB and structure was shown in Fig. S1) sensitization has
attracted much attention in H2 evolution as dye-sensitizer. Xu et al. employed ErB to
sensitize graphitic carbon nitride (g-C3N4) for photocatalytic H2 evolution using
triethanolamine as a sacrificial agent and a significant enhancement of H2 evolution
was achieved [27]. Wang et al. reported that carbon nitride nanosheets for H2
evolution was enhanced by ErB sensitization and H2 evolution rate reached to 652.5

5
μmol h-1 [26]. Moreover, ErB sensitization has been applied in metal-organic
frameworks. Yuan et al. reported that photocatalytic hydrogen evolution of
metal-organic framework UiO-66 octahedrons enhanced by ErB dye-sensitization,
with the hydrogen evolution rate of 460 μmol g-1 h-1 [25]. So ErB dye sensitization
was proved to be appropriate for H2 evolution.
Based on our previous research [28-32], here three approaches mentioned above
were employed to enhance photocatalytic H2 evolution from water for the
photocatalysts. Cu-Cu2O NPs is loaded on the surface of catalysts, which could
greatly improve the visible light photocatalytic hydrogen evolution performance for
g-C3N4. Next, Cu-Cu2O/g-C3N4 composite was sensitized by low-cost ErB and they
exhibited higher H2 evolution rate using triethanolamine as an electron donor under
visible light irradiation. Moreover, we demonstrated that Cu-Cu2O/g-C3N4 and
dye-sensitized Cu-Cu2O/g-C3N4 have persistent photocatalytic activity after several
recycles. In addition, a possible photocatalytic mechanism was preliminarily
discussed.
1. Experimental

1.1. Synthesis process

All reagents were analytical grade and were used without further purification. g-C3N4
was prepared as follows: 5 g of urea were mixed with 1 mL of deionized water, the
resultant mixtures were grounded in a mortar for ~30 min until all of the water was
evaporated, and then heated at 500℃ for 2.5 h. Finally, a light yellow powder
consisting of porous g-C3N4 was obtained.
Cu-Cu2O NPs modified porous g-C3N4 photocatalysts were prepared by
chemical reduction method. In this process, Cu(NO3)2 was necessarily added as the
source of Cu-Cu2O NPs. Typically, 0.2 g of g-C3N4 was dispersed into deionized
water under vigorous stirring, and 1~10.0 mL of 50 mM Cu(NO3)2 solution was added
into the g-C3N4 suspension. The suspension was equilibrated for 60 min, and then

6
2~20 mL fresh prepared 50 mM NaBH4 solution was added dropwise and stirred for
another 60 min in an ice bath. The obtained Cu-Cu2O/g-C3N4 composite was
harvested by centrifugation at 10,000 rpm for 20 min and washed with ethanol and
deionized water 3 times, respectively. The residues were dried in a vacuum drying
oven at 50℃ for 3 h, and subsequently ground into fine powders using an agate
mortar. The reduction mechanism was shown in equation 1 and 2. Cu2+ was reduced
into Cu which was shown in equation 1 and then fresh-obtained Cu was oxidized partly
to Cu2O (equation 2) in the air. g-C3N4 modified with different amounts of Cu-Cu2O is
denoted as A (no Cu2+, pure g-C3N4), B (the Cu2+ content which was invested in the
experiment is 1 wt%), C (the Cu2+ content which was invested in the experiment is 3
wt%), D (the Cu2+ content which was invested in the experiment is 5 wt%), E (the
Cu2+ content which was invested in the experiment is 7 wt%), F (the Cu2+ content
which was invested in the experiment is 9 wt%). The molar ratio between Cu and
Cu2O was determined by atomic absorption spectroscopy.
ice
Cu ( NO3 ) 2  2 NaBH 4  6 H 2O  Cu  2 NaNO3  2 B(OH )3  7 H 2  (1)
bath

air
4Cu  O2  2Cu 2O (2)

1.2. Material characterization

X-ray diffraction (XRD) patterns were recorded on a D8 X-ray diffractometer (Bruker

AXS, German). Fourier transform infrared (FT-IR) measurements were performed
using a FT-IR spectrometer (Nicolet 670) only in the mid infrared range of the
instrument (400-4000 cm-1) for samples dispersed in KBr pellets in 1:99 ratios. The
UV-vis diffuse reflection absorption spectra (UV-vis/DR spectra) were recorded by a
UV-vis spectrometer (U3010, Hitachi, Japan) equipped with an integrating sphere
accessory in the diffuse reflectance mode (R), and referenced by BaSO4. The analysis
of photo-luminescence spectra (PL) was carried out at room temperature on a Hitachi
F-4500 fluorescence spectrophotometer. The Brunauer-Emmett-Teller (BET) specific

7
surface area of samples was evaluated on the basis of nitrogen adsorption isotherms
measured at 77 K using a 3H-2000PS1 static volume method instrument.
Transmission electron microscope (TEM) images were obtained on a JEOL
JEM-2100 electron microscope with an accelerating voltage of 200 kV equipped with
energy dispersive X-ray (EDX) spectrometer. Scanning electron microscopy (SEM)
images was obtained with a Zeiss Merlin emission scanning electron microscope.
X-ray photoelectron spectroscopy (XPS) data were obtained on a Kratos Axis-Ultra
DLD (with AES) instrument with a monochromatized Al Kα line source (150 W).The
molar ratio between Cu and Cu2O was determined quantitatively by atomic absorption
spectroscopy (AAS) on a HITACHI Z-2300 instrument.

1.3. Photocatalytic hydrogen evolution

The photocatalytic experiments were performed in a 300 mL flask at ambient

temperature, using a 300 W Xe lamp equipped with a UV cut off filter (λ> 420 nm).
The intensity of the light source was estimated to be 0.15 W cm-2. 5 mg of catalyst
was added to a solution mixture of 60 mL water and 10 mL triethanolamine.
Hydrogen gas evolution was measured by gas chromatography (GC-7900, Tian mei,
nitrogen as a carrier gas) with a thermal conductivity detector (TCD). Then, dye
sensitization experiments was investigated on composite E. 5 mg composite E and
various amount (1, 3, 5, 7, 10 mg) of ErB were dispersed in 70 mL solution
containing 10 mL triethanolamine under stirring for 40 min to form a homogenous
solution. Hydrogen gas evolution was measured as above.

1.4. Photoelectrochemical measurements

Electrochemical measurements were conducted with electrochemical analyzer

(CHI660C Instruments, Shanghai, China) in a conventional three electrode cell, using
an Ag/AgCl electrode (3 M KCl) as the reference electrode and a Pt plate as the

8
counter electrode. The electrolyte was 0.1 M Na2SO4 aqueous solution without
additive. The working electrode was prepared as follows: 0.1 g catalyst was dispersed
in 1 mL of DMF solution to get slurry with sonication. The slurry was then spread
onto ITO glass which was cleaned by sonication in deionized water for 40 min and
dried at 323 K. After air-drying, these electrolytes were dried at 313 K for 2 h to
improve adhesion under vacuum.

1.5. Measurements of molar ratio between Cu and Cu2O

The molar ratio between Cu and Cu2O was determined by atomic absorption
spectroscopy. The calculation principle was shown in equation 3. Cu2+ was determined
by atomic absorption spectroscopy and content of Cu2O could be inferred by equation 3.
According to the Cu2+ content which was invested in the experiment, Cu content could
be gotten easily. Specific experimental steps are as follows: 5mg Cu-Cu2O/g-C3N4
composites were dissolved in 20mL dilute sulfuric acid (0.1 wt%) and stirred for 60
min at ambient temperature. The obtained suspension solution was centrifuged at
10,000 rpm for 30 min and supernatant was collected. Supernatant was measured by
atomic absorption spectroscopy.

Cu2O  H 2 SO4  Cu  CuSO4  H 2O (3)

2. Results and discussion

2.1. Formation and characterization

The XRD patterns of the prepared Cu-Cu2O/g-C3N4 composites and the pure g-C3N4
are shown in Fig. 1. The diffraction peaks of pure g-C3N4 (composite A) appearing at
27.4˚ and 13.1˚ correspond to the (002) and (100) planes, which are attributed to the
characteristic interplanar staking peaks of aromatic systems and the inter-layer

9
structural packing, respectively [1]. The other diffraction peaks match well with the
reference Cu2O (JCPDS 78-2076) and Cu (JCPDS 85-1326) [20]. The peak intensities
of Cu2O and Cu increase gradually with the Cu2+ content increasing. Composite B has
no peak for Cu or Cu2O due to low contents. For Cu-Cu2O/g-C3N4 composites, the
XRD patterns reveal a coexistence of g-C3N4, Cu2O and Cu. It can also be inferred
from Fig. 1 that the crystalline form of g-C3N4 has not been changed after the
modification with Cu-Cu2O NPs.
<Fig. 1.>
Fig. S2 presents the FT-IR spectrum of as-prepared Cu-Cu2O/g-C3N4. Three
characteristic absorption regions, >3000 cm-1, 1200-1700 cm-1 and <1000 cm-1, are
observed in sample of composite E. The former adsorption centered at 3364 cm-1,
which can be ascribed to the stretching mode of N-H bond [9,33]. Several typical
absorption peaks in the second region of 1200-1700 cm-1 are ascribed to the stretching
vibrations of CN heterocycles, such as 1267, 1332, 1419, 1630 cm-1 [9,34]. The band
at 808 cm-1 originates from an breathing mode of s-triazine ring system [9,35]. The
band at about 621 cm-1 corresponds to the stretching vibration of Cu(I)-O bond [36].
These characteristic absorptions of g-C3N4 and Cu2O all appear in the spectrum of
Cu2O/g-C3N4 heterojunctions, indicating the coexistence of these two semiconductors.
There is no peak for Cu NPs have been found, because it is not active for infrared
spectra.
The optical properties of the as-prepared Cu-Cu2O/g-C3N4 and g-C3N4 samples
were examined using UV-visible diffuse reflection spectroscopy. As shown in Fig. 2,
the pristine g-C3N4 (composite A), holds an absorption edge of 460 nm, which can be
assigned to a band gap of 2.70 eV [1]. Cu2O possesses a broad absorption in the
visible region from 400 to 600 nm, which is similar to those reported in literatures
[37,38]. After combining the two semiconductors of g-C3N4 and Cu2O, the
absorptions of composites heterojunctions within the visible light range obviously
increase and show a red shift in comparison with pure g-C3N4. The absorption
intensities of composites increase with increasing Cu2+ content due to principle of

10
superposition about Cu2O NPs. In addition, the absorption intensity also increases
when wavelength longer than 600 nm because of localized surface plasmon resonance
(LSPR) effect of Cu NPs [13].
<Fig. 2.>
Photo-luminescence (PL) spectroscopy has been widely used to examine the
charge transfer, migration and separation in photocatalysts [39]. Fig. 3 shows the PL
spectra of photocatalysts. All the photocatalysts exhibited a broad emission peak
centered at around 460 nm, corresponding to the band gap of g-C3N4 [2], and a tail
extending to 650 nm. The PL emission intensity exhibits the highest value for the pure
g-C3N4 and decreases with increasing Cu2+ content. Although PL emission intensity
decreases with presence of Cu-Cu2O NPs, composite E is the optimal deposition
amount to suppress recombination. As Cu2+ content increases to a certain degree,
Cu-Cu2O NPs aggregate on the surface of g-C3N4 and become recombination centers
to decrease suppression [40].
<Fig. 3.>
Fig. 4 shows SEM images of composites. The pure g-C3N4 (Fig. 4a) appears as
porous and planar materials and its surface is glossy. Fig. 4b and Fig. 4a are similar
due to the fact that few Cu-Cu2O NPs are loading on the surface of g-C3N4. As the
content of Cu2+ increase gradually, morphologies of composites have some change.
Surfaces of composites become more and more rough and finally a bulk is obtained.
Fig. 4c, 4d and 4e show rough surfaces of composites because of modification with
Cu-Cu2O NPs. Cu-Cu2O NPs were dispersed on the surface of the g-C3N4 and result
in formation of heterojunctions structure which could enhance separation of
electron-holes. However, as the content of Cu2+ increases to 9%, the aggregation of
Cu-Cu2O NPs would occur on the surface and massive particles are observed
apparently (Fig. 4f). The obtained agglomeration structures have a negative effect on
photocatalytic reaction and could result in lower quantum efficiency [40].
<Fig. 4.>
Morphology and microstructure of the composite E were further examined by

11
TEM and HRTEM. Fig. 5a appears as obvious porous materials and it also illustrates
by Fig. 5e. Fig. 5b shows HRTEM image and it clearly reveals the close interfacial
connections between g-C3N4 and Cu-Cu2O NPs. The lattice spacing of 0.21 nm
corresponds to the (111) plane of Cu and 0.25 nm corresponds to the (111) plane of
Cu2O. Fig. 5c is EDX spectrum and it reveals the existence of C, N, O and Cu.
Elemental mapping patterns (Fig. 5d) show the same conclusion with EDX. The
dark-field of TEM image (Fig. 5e) shows that the Cu-Cu2O NPs are well dispersed on
the surface of g-C3N4 with a mean particle size of 7.3 nm and size distribution of
Cu-Cu2O NPs is shown in Fig. 5f. Particle size of Cu-Cu2O NPs is found to be 1-11
nm, showing that the preparation of composites used in our work is effective with
homogeneous particle size distribution. These observations suggest the formation of
composites between Cu-Cu2O NPs and g-C3N4 which would be an ideal system to
achieve electron-hole separation. In addition, TEM image of composite F which
contains more Cu-Cu2O NPs than composite E was also investigated and it was
shown in Fig. S3. The dark-field of TEM image indicates aggregation of Cu-Cu2O
NPs and the particle size was about 20~40 nm. Moreover, porous of material was
disappeared due to cover of aggregated Cu-Cu2O NPs.
<Fig. 5.>
The XPS was carried out to determine the chemical composition of composite E
and the binding energies obtained in the XPS analysis were corrected by referencing
C 1s to 284.6 eV with specimen charging. Fig. 6a indicates the presence of C, N, O
and Cu in the composite. Fig. 6b shows the high-resolution XPS spectra of C 1s. Two
peaks can be distinguished to be centered at 284.7 and 288.1 eV. The former peak is
typically ascribed to sp2 C-C bonds, and the latter is identified as sp-bonded carbon in
N- containing aromatic rings (N-C═N), which represent the major carbon species in
the g-C3N4 [41]. The corresponding binding energies of N 1s spectra are determined
to be 398.9 eV, 400.1 eV, and 401.4 eV (Fig. 6c). The main peak centered at 398.9 eV
originates from the sp2-bonded N involved in the triazine rings (C-N═C) dominated in
g-C3N4. While the weak peak at 400.1 eV is caused by the tertiary nitrogen N-(C)3

12
groups, and another weak peak at 401.4 eV indicates the presence of amino groups
(C-N-H) [42,43]. Fig. 6d shows the characteristic peaks of the Cu 2p at 932.7 and
952.9 eV which are attributed to the binding energy of Cu 2p3/2 and Cu 2p1/2,
respectively. Peaks of the Cu 2p assigned to Cu2O or Cu (Cu+1 or Cu0) due to absence
of satellite structure (Fig. 6d). However, it is difficult to differentiate Cu2O and Cu by
the XPS feature of Cu 2p3/2 and Cu 2p1/2 because their binding energies are very
close. According to a previous reports [44,45], the Cu LMM peak region provides a
clear means to distinguish the two oxidation states. Fig. 6e shows that the Cu LMM
peaks of the sample occur at 568 and 571.2 eV which consist with Cu0 and Cu2O. It
indicates that composites contain Cu and Cu2O at the same time, which can also be
proved by XRD patterns.
<Fig. 6.>
The BET specific surface area (SBET) and pore structure of the as-prepared
samples were investigated using adsorption-desorption measurements. The BET
specific surface area, pore volume and average pore size of those samples are shown
in Table 1. It can be seen that composite E shows the highest SBET among the six
samples and this phenomenon can be explained as follows. Cu-Cu2O nanoparticles are
smaller than porous g-C3N4 when Cu2+ content is minor and Cu-Cu2O nanoparticles
loaded on the surface of g-C3N4 could increase surface area. As content of Cu2+
increase gradually, Cu-Cu2O NPs may aggregate into bigger particles and fill more
pores which could decrease surface area. The large surface area of the
nanocomposites can supply more surface active sites and make charge carrier
transport easier, resulting in an enhancement of the photocatalytic performance [46].
In the meantime, the average pore diameters of the samples were analyzed from the
Barrett-Joyner-Halenda (BJH) pore size distribution. The average pore diameter and
pore volume of composites have a slight decrease with increasing Cu2+ because
Cu-Cu2O NPs fill some pores of g-C3N4.
<Table 1>
Molar ratio between Cu and Cu2O was determined by atomic absorption

13
spectroscopy and results are shown in table 1. The amount of Cu2O decreases
monotonously with the increasing weight of Cu2+. This phenomenon could explain as
follow. Cu NPs are small and most are oxidized when content of Cu2+ is tiny. As
content of Cu2+ increase gradually, Cu NPs aggregate into bigger NPs and oxidation
occurred mainly on the surface of Cu NPs. So the content of Cu2O decreases stepwise
with increasing weight of Cu2+. More Cu-Cu2O NPs on the surface of g-C3N4 could
make them agglomeration and have a negative effect on photocatalysis.
Cu2+ changes to Cu NPs by the reduction reaction of NaBH4 and then is oxidized
partially to Cu2O in the air. Surface oxidation of fresh copper metal NPs will take
place in air. Cupric oxide (CuO) or cuprous oxide (Cu2O) of copper oxide phases
depend on the temperature and oxygen concentration. At room temperature and in air,
Cu2O is the dominant product of oxidation [47,48]. Reduction reaction was carried
out in an ice bath and air in this experiment, so the product is Cu2O rather than CuO.
Moreover, Cu2O will not react with oxygen to produce CuO at room temperature,
because the reaction needs to be heated. This result is also proved by XRD, FTIR,
XPS and TEM. In addition, Cu2O is a stable catalyst for H2 evolution under visible
light irradiation and has few changes after photocatalytic reaction [49-51].
Disproportionation reaction of Cu2O will be occured under acid condition, but
photocatalytic reaction is carried out under alkaline conditions due to the existence of
triethanolamine. So Cu2O does not change under photocatalytic reaction. Moreover,
photocatalytic reaction was investigated under vacuum and further oxidation of Cu
and Cu2O NPs were avoided. Summarily, the results discussed above indicate that the
composites of Cu-Cu2O/g-C3N4 are successfully prepared by chemical reduction
method.

2.2. Photocatalytic hydrogen evolution

The actual photocatalytic activities for hydrogen evolution of the g-C3N4 and
composites with various weight ratio of Cu2+ have been evaluated in aqueous solution

14
with triethanolamine used as sacrificial reagent with visible light. Before the actual
photocatalytic experiment was performed, control experiments were carried out using
a pure triethanolamine solution in the absence of either a photocatalyst or irradiation.
No appreciable H2 evolution was detected, indicating that H2 was produced from the
triethanolamine solution by photocatalytic reactions on a photocatalyst. The average
rate of hydrogen evolution of composites within 5 h was illustrated in Fig. 7a. g-C3N4
presents a relative low hydrogen evolution rate (140 μmol g-1 h-1) because of the fast
recombination of the photoinduced electrons and holes. The average H2 evolution rate
of all the composites are higher than pure g-C3N4 due to modification with Cu-Cu2O
NPs. Heterojunction between semiconductors and Cu NPs co-catalyst could improve
the separation and transportation of electronic-holes efficiently. Comparing with
various weight ratio of Cu2+, composite E exhibits the highest H2 evolution rate at 400
μmol g-1 h-1, which is about triple of the pure g-C3N4. This result indicates that
appropriate amount of Cu-Cu2O NPs could form an efficient interaction between
components, and thus promote photoinduced charges separation. On the contrary,
inappropriate amount would make an agglomerating state, thus forming
recombination centers and reducing the contact area [52,53].
<Fig. 7.>
Furthermore, the repeatability of composite E was tested in six consecutive runs
of accumulatively 30h under the same conditions (Fig. S4). After six recycles, little
deactivation of the catalyst occurs upon repeated use, implying that it exhibits good
stability and has sustaining photostability. In particular, a comparison of the XRD
patterns (Fig. S5) of composite E before and after the stability test is presented. There
are no obvious changes in the positions of the peaks about Cu-Cu2O/g-C3N4,
suggesting that its crystal phase doesn′t change after photocatalytic reaction. In
addition, surface element composition of composite E before and after recycling
photocatalytic reaction is presented in Table S1. Few changes are observed in
composition, indicating that surface structures remain unchanged.
In order to further optimize the system, photocatalytic H2 evolution of g-C3N4

15
modified with Cu and Cu2O NPs were investigated respectively. The experimental
section and the results of H2 evolution were shown in supporting information. As
shown in Fig. S6a, the H2 evolution of the catalysts which contain Cu NPs are much
higher than not and the highest H2 evolution rate is 300 μmol g-1 h-1 with content of
Cu 3 wt%. The result indicates that co-catalyst of Cu NPs indeed enhanced
photocatalytic H2 evolution from water, but H2 evolution rate is still below 400 μmol
g-1 h-1 due to lack of heterojunctions with Cu2O. Cu/g-C3N4 composite was
characterized by XRD (Fig. S6b) and it revealed the existence of Cu and g-C3N4. Fig.
S7a shows the H2 evolution rate of Cu2O/g-C3N4 and the highest H2 evolution rate is
220 μmol g-1 h-1 with Cu2O is 0.03 wt%. This result illustrated that heterojunctions
were formed between g-C3N4 and Cu2O which would promote separation of
electron-holes. Cu2O/g-C3N4 composite was characterized by XRD (Fig. S7b) and
FTIR spectrum (Fig. S7c). As shown in Fig. S7b, there is only two peaks for g-C3N4
and no peaks for Cu2O because the Cu2O contents are quite low [54,55]. However, the
existence of Cu2O is proved by FTIR spectrum (Fig. S7c). The band at about 622 cm-1
corresponds to the stretching vibration of Cu(I)-O bond [36]. Therefore, XRD patterns
and FTIR spectrum reveal the existence of Cu2O and g-C3N4.
In addition, Cu/Cu2O nanocomposites were prepared by the same processes for
Cu-Cu2O/g-C3N4 composites except the existence of g-C3N4. Various amount of Cu2+
were invested in reduction reaction experimental and H2 evolution rate was shown in
Fig. S8a. The highest H2 evolution rate is 230 μmol g-1 h-1 with 10mg Cu2+ which is
lower than Cu-Cu2O/g-C3N4 due to lack of heterojunctions with g-C3N4. As shown in
Fig. S8a, H2 evolution rates decrease gradually when amount of Cu2+ over 10 mg due
to the aggregation of particles. Cu/Cu2O nanocomposite was characterized by XRD
(Fig. S8b) and peaks of Cu and Cu2O all appears. In summary, we can find that single
Cu or Cu2O NPs modified g-C3N4 and Cu/Cu2O nanocomposites are lower active for
H2 evolution than Cu-Cu2O/g-C3N4. Therefore, the existences of g-C3N4, Cu and
Cu2O NPs are important for H2 evolution in the catalytic system.
ErB was chosen to sensitize composite E due to its extended light absorption in

16
the dye sensitization experiments. Fig. 7b shows H2 evolution rate over the samples of
E/ErB (E represent composite E and ErB represent Erythrosin B dye) system within 5
h under visible light irradiation. Control experiments were investigated before
sensitization experiments. No H2 evolution was detected in the absence of either
photocatalyst or irradiation in triethanolamine solution with ErB, indicating that
hydrogen was produced on a photocatalyst with photocatalytic reactions. Without
addition of ErB, composite E showed a low H2 evolution rate with 400μmol g-1 h-1
(Fig. 7a). However, H2 evolution rate was enhanced remarkably in the presence of
ErB dye into the reaction solution. As shown in Fig. 7b, H2 evolution rate in different
sensitization experiments were all higher than not sensitization, suggesting the
sensitization effect of ErB dye on composite E was positive for H2 evolution. H2
evolution rate is heavily rely on the amount of ErB dye in photocatalytic reaction
solution and the highest H2 evolution rate is obtained (5000 μmol g-1 h-1) when 5 mg
ErB was added into reaction system. However, the further increasing amount of ErB
dye results in a decreased H2 evolution rate. This phenomenon should be caused by
competitive effect of ErB adsorption on composite E. Dynamically non-touched ErB
dyes in the suspension can act as competitive light-absorbing molecules over touched
ErB dyes on composite E and thereby makes light utility efficiency decrease for H2
evolution. The repeatability of ErB-sensitized composite E was tested in six
consecutive runs (Fig. 7c). After six recycles of photoreactions, H2 evolution activity
still keeps over 85%, indicating the excellent repeatability of photocatalytic H2
evolution system. A partially decrease of H2 evolution occurs upon dye-sensitization
system, which could be attributed to the ErB instability and consumption of TEOA as
a sacrificial agent. ErB dye has xanthene ring substituted with four iodide groups
which could be cleaved under long time visible light irradiation to low-activity
halogen-free analog for photocatalytic H2 evolution [56,57]. A comparison of XRD
patterns (Fig. S9) and surface element composition (Table S2) of sample E/ErB-5mg
(composite E denoted E, the number 5 indicates the amount of added ErB dye) are
presented before irradiation and after irradiation for 30 h. No significant difference in

17
the elemental concentration and locations of the peaks was observed, indicating that it
has excellent photostability. Element composition is shown in Table S2, the
percentage of iodine atoms has some decline due to decomposition of ErB dye. Other
elements have few differences.
To confirm that ErB dye contacts with composite E is benefits for photocatalytic
H2 evolution, UV-Vis, XRD, FTIR and photo-luminescence (PL) spectral were
obtained. The sample E/ErB-5mg catalyst was obtained through centrifugation (10000
rpm, 20 min) of reaction solution after irradiation 5 h which contains 5 mg ErB dye.
As shown in Fig. 8a, the FTIR spectra of sample E/ErB-5mg and ErB are similar in
two regions which are marked by blue and green dash line although locations of peaks
have some differences due to interaction of ErB and composite E. This indicates ErB
is adsorbed by composite E. Wavenumber from 2000 to 1000 cm-1 of sample
E/ErB-5mg spectrum can be attributed to g-C3N4 peaks as shown in Fig. S2. Fig. 8b
exhibits XRD patterns of sample E/ErB-5mg and ErB. No peak for ErB is observed
due to its amorphous phase. The intensity of peaks about sample E/ErB-5mg declines
in some degree and only two peaks for Cu and Cu2O are observed significantly. This
phenomenon could attribute to interaction of composite E and ErB. Combined with
Fig. 8a, they can fully prove existence of ErB and composite E at the same time.
Electron transfer between the ErB and composite E was measured by
photoluminescence (PL) spectra of ErB and sample E/ErB-5mg under an excitation of
490 nm light. As shown in Fig. 8c, a strong emission peak of ErB occurs at 553 nm
and a relatively weak emission peak of sample E/ErB-5mg occurs at 558 nm. The PL
quenching of ErB happens in the presence of composite E because of rapid electron
transfer from the ErB to composite E. Meanwhile, a slight red shift (~5 nm) of sample
E/ErB-5mg emission peak is observed, which attribute to Van Der Waals interactions
and non-bonded π-π stacking between ErB and composite E [25]. Hence, electrons
transfer from ErB to composite E happen effectively indeed. UV-Vis diffuse
reflectance spectra of composite E and sample E/ErB-5mg are shown in Fig. 8d.
Sample E/ErB-5mg exhibits a stronger absorption than composite E in the region of

18
480-580 nm, which efficiently extends the light harvesting ability.
<Fig. 8.>
In addition, morphology comparison of composite E and sample E/ErB-5mg
were investigated by HRTEM and shown in Fig. S10. As shown in Fig. S10a,
composite E exhibits obvious lattice of Cu and Cu2O. After the sensitization with ErB
(Fig. S10b), no significant lattice was observed for Cu and Cu2O because it was
covered by lots of ErB dyes. This phenomenon could also confirm the effective
attractions between composite E and ErB dyes. Moreover, EDX spectrum of sample
E/ErB-5mg was obtained and it was shown in Fig. S11. It indicates C, N, O, Cu and I
elementals exist in sample E/ErB-5mg. Elemental mapping patterns (Fig. S12) of
sample E/ErB-5mg is consistent with the EDX spectrum.

2.3.Mechanism

Fig. S13 schematically illustrates a possible mechanism for the visible-light-driven

photocatalysis of Cu-Cu2O/g-C3N4 to produce hydrogen before sensitization. Before
this, we should illustrate that the conduction band (CB) and valence band (VB) edge
potentials of g-C3N4 are at -1.12 and 1.57 eV [4], and Cu2O are at 1.4 and -0.6 eV [20],
respectively. Cu2O is a p-type semiconductor and its Fermi level is close to valence
band (marked by red dash line in Fig. S13) whereas g-C3N4 is an n-type
semiconductor and its Fermi level is close to conduction band (marked by red dash
line in Fig. S13) [58,59]. Obviously, it is inappropriate to form heterojunctions for
separating photoinduced electro-holes due to their straddling band-structure of g-C3N4
and Cu2O before contact. After g-C3N4 contact with Cu2O, holes would transfer from
Cu2O to g-C3N4 and electrons would transfer from g-C3N4 to Cu2O in their contacted
interface. Electrons and holes would form an internal electric field make the Fermi
levels of Cu2O and g-C3N4 reached same value [60,61]. Under visible light irradiation,
g-C3N4 and Cu2O were excited, and the electrons and holes were then generated.
Holes transferred to the negative field (p-Cu2O) and electrons transferred to the

19
positive field (n-g-C3N4) under the action of the internal electric field. As a result,
photoinduced electrons and holes would accumulate in the g-C3N4 and Cu2O region,
respectively. Then the photoinduced electrons transfer to Cu NPs rapidly. The trapped
electrons at the Cu NPs could easily reduce the bonded H+, leading to H2 generation.
Cu NPs could collect electrons from the conduction band of Cu2O and g-C3N4 and
preventing electron-hole pairs from recombining. In addition, a Schottky barrier is
created on Cu NPs by accumulation of electrons that could also prevents the
recombination of photo-generated electrons and holes. As a result, the recombination
of photogenerated electrons and holes on g-C3N4 and Cu2O were obviously prevented.
To verify the proposed mechanism, photocurrent-time curves and
electrochemical impedance spectra (EIS) were acquired to study the charge transfer
and recombination behavior of composite A, composite E and sample E/ErB-5mg. Fig.
9a shows the photocurrent-time curves of samples with three on-off intermittent
visible light irradiation cycles (λ > 420 nm). Apparently, the photocurrent value
rapidly decreases to zero as soon as light is turned off and then increases when light is
turned on again, exhibiting good repeatability. The photoelectrode of sample
E/ErB-5mg shows highest value compared with others, which indicated the efficient
photogenerated charge transfer between ErB and Cu-Cu2O/g-C3N4. In addition,
composites were evaluated by electrochemical impedance spectra (EIS) and an
evidently decreased EIS radius (Fig. 9b) was revealed for sample E/ErB-5mg. This
indicates that electronic impedance is reduced and charge separation is enhanced. All
catalysts show decreased EIS radius compared with the pure g-C3N4. Actually, all of
the electrochemical experiments illustrate that the charge separation and transfer of
the modified g-C3N4 are strengthened, which are attributed to the formation of
semiconductor heterojunctions, existence of co-catalysts and dye sensitization.
<Fig. 9.>
Based on the above discussions and references [24-27], a possible mechanism
over ErB sensitized Cu-Cu2O/g-C3N4 for H2 evolution is proposed and shown in Fig.
10. HOMO and LUMO potential of ErB are about 1.4 and -0.9 eV vs NHE,

20
respectively [25]. CB edge potentials of Cu2O is -0.6 eV vs NHE. CB edge potentials
of g-C3N4 is more negative than -0.6 eV vs NHE due to the change of Fermi levels in
heterojunction. Hence, electron transfer is thermodynamically favorable from the
photoexcited ErB dye to Cu2O and g-C3N4 which have been illustrated by PL spectral
in Fig. 8c, and then to Cu NPs for H2 evolution. In aqueous solution with presence of
ErB, the state of excited triplet 3*ErB forms when EB is irradiated by visible light.
Electrons released from adsorbed 3*ErB and then injected to the CB of g-C3N4 and
Cu2O. Meanwhile, the 3*ErB becomes oxidized ErB+ and it can be regenerated to ErB
by sacrificial reagent triethanolamine next. The following electrons transfer is the
same as above description. After sensitization with ErB, H2 evolution rate was
enhanced remarkably due to efficient charge transfer and the wide light absorption.
<Fig. 10.>

3. Conclusions

In summary, a novel photocatalyst of Cu-Cu2O/g-C3N4 was designed, synthesized and

characterized. The photocatalytic H2 evolution activity for g-C3N4 was significantly
enhanced after modification with Cu-Cu2O NPs. Then, Cu-Cu2O/g-C3N4 was
sensitized by ErB and a significant improvement of hydrogen evolution was realized.
This work may be important to provide an insight into preparing g-C3N4 based
photocatalytic system, with high activities for applications in solar energy utilization
and conversion.
Acknowledgements

We are grateful to the National Natural Science Foundation of China (No. 21371060,
21571064), the Pearl River S&T Nova Program of Guangzhou (No. 2014J2200047),
the Fundamental Research Funds for the Central Universities(No.2015ZM162) and
the research fund of the Key Laboratory of Fuel Cell Technology of Guangdong
Province for financial support.

21
References
[1] X.C. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J.M. Carlsson, K.
Domen, M. Antonietti, A metal-free polymeric photocatalyst for hydrogen
production from water under visible light, Nat. Mater. 8 (2008) 76-80.
[2] X.C. Wang, S. Blechert, M. Antonietti, Polymeric graphitic carbon nitride for
heterogeneous photocatalysis, ACS Catal. 2 (2012) 1596-1606.
[3] S. Cao, J. Low, J. Yu, M. Jaroniec, Polymeric photocatalysts based on graphitic
carbon nitride, Adv. Mater. 27 (2015) 2150-2176.
[4] Z. Zhao, Y. Sun, F. Dong, Graphitic carbon nitride based nanocomposites: a
review, Nanoscale 7 (2015) 15-37.
[5] S. Cao, J. Yu, g-C3N4-based photocatalysts for hydrogen generation, J. Phys.
Chem. Lett. 5 (2014) 2101-2107.
[6] S. Cao, J. Yu, Carbon-based H2-production photocatalystic materials, J.
Photochem. Photobiol. C: Photochem. Rev. (2016)
http://dx.doi.org/10.1016/j.jphotochemrev.2016.04.002.
[7] S. Ye, R. Wang, M. Wu, Y. Yuan, A review on g-C3N4 for photocatalytic water
splitting and CO2 reduction, Applied Surface Science 358 Part A (2015) 15-27.
[8] K. Maeda, X.C. Wang, Y. Nishihara, D. Lu, M. Antonietti, K. Domen,
Photocatalytic activities of graphitic carbon nitride power for water reduction
and oxide under visible light, J. Phy. Chem. C 113 (2009) 4940-4947.
[9] S.C. Yan, Z.S. Li, Z.G. Zou, Photodegradation performance of g-C3N4 fabricated
by directly heating melamine, Langmuir 25 (2009) 10397-10401.
[10] J.Y. Qin, J.P. Huo, P.Y. Zhang, J. Zeng, T.T. Wang, H.P. Zeng, Improving the
photocatalytic hydrogen production of Ag/g-C3N4 nanocomposites by
dye-sensitization under visible light irradiation, Nanoscale 8 (2016) 2249-2259.
[11] S. Liang, Y. Xia, S. Zhu, S. Zheng, Y. He, J. Bi, M. Liu, L. Wu, Au and Pt
co-loaded g-C3N4 nanosheets for enhanced photocatalytic hydrogen production
under visible light irradiation, Applied Surface Science 358 Part A (2015)

22
 304-312.
[12] J. Lang, M. Liu, Y. Su, L. Yan, X. Wang, Fabrication of the heterostructured
CsTawO6/Au/g-C3N4 hybrid photocatalyst with enhanced performance of
photocatalytic hydrogen production from water, Applied Surface Science 358 Part
A (2015) 252-260.
[13] Y.L. Zhou, S.Z. Kang, X.Q. Li, L.X. Qin, J. Mu, TiO2 nanosheets loaded with Cu:
A low-cost efficient photocatalytic system for hydrogen evolution from water, J.
Int. Hydrogen Energy 39 (2014) 15403-15410.
[14] E.Z. Liu, L.L. Qi, J.J. Bian, Y.H. Chen, X.Y. Hu, J. Fan, H.C. Liu, C.J. Zhu, Q.P.
Wang, A facile strategy to fabricate plasmonic Cu modification TiO2 nano-flower
films for photocatalytic reduction of CO2 to methanol, Mater. Res. Bull. 68 (2015)
203-209.
[15] S.C. Yan, S.B. Lv, Z.S. Li, Z.G. Zou, Organic-inorganic composite photocatalyst
of g-C3N4 and TaON with improved visible light photocatalytic activities, Dalton
T. 39 (2010) 1488-1491.
[16] Y. Wang, R. Shi, J. Lin, Y. Zhu, Enhancement of photocurrent and photocatalytic
activity of ZnO hybridized with graphite-like C3N4, Energ. Environ. Sci. 4 (2011)
2922-2929.
[17] M.S. Akple, J. Low, S. Wageh, A.A. Al-Ghamdi, J. Yu, J. Zhang, Enhanced
visible light photocatalytic H2-production of g-C3N4/WS2 composite
heterostructures, Applied Surface Science 358 Part A (2015) 196-203.
[18] J. Zhang, F. Huang, Enhanced visible light photocatalytic H2 production activity
of g-C3N4 via carbon fiber, Applied Surface Science 358 Part A (2015) 287-295.
[19] S. Cao, Y. Yuan, J. Barber, S.C.J. Loo, C. Xue, Noble-metal-free
g-C3N4/Ni(dmgH)2 composite for efficient photocatalytic hydrogen evolution
under visible light irradiation, Applied Surface Science 319 (2014) 344-349.
[20] L. Liu, Y. Qi, J. Hu, Y. Liang, W. Cui, Efficient visible-light photocatalytic
hydrogen evolution and enhanced photostability of core@shell Cu2O@g-C3N4
octahedra, Applied Surface Science 351 (2015) 1146-1154.

23
[21] J. Chen, S.H. Shen, P.H. Guo, M. Wang, P. Wu, X.X. Wang, L.J. Guo, In-situ
reduction synthesis of nano-sized Cu2O particles modifying g-C3N4 for enhance
photocatalytic hydrogen production, Appl. Catal. B-Environ. 152-153 (2014)
335-341.
[22] B.Y Peng, S.G. Zhang, S.Y. Yang, H.J. Wang, H. Yu, S.Q. Zhang, F. Peng,
Synthesis and characterization of g-C3N4/Cu2O composites catalyst with
enhanced photocatalytic activity under visible light irradiation, Mater. Res. Bull.
56 (2014) 19-24.
[23] A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo, H. Pettersson, Dye-Sensitized solar
cells, Chem. Rev. 110 (2010) 6595-6663.
[24] Z.Y. Li, Y.L. Fang, X.Q. Zhan, S. Xu, Facile preparation of squarylium dye
sensitized TiO2 nanoparticles and their enhanced visible-light photocatalytic
activity, J. Alloy. Compd. 564 (2013) 138-142.
[25] Y.P. Yuan, L.S. Yin, S.W. Cao, G.S. Xu, C.H. Li, C. Xue, Improving
photocatalytic hydrogen production of metal-organic framework UiO-66
octahedrons by dye-sensitization, Appl. Catal. B-Environ. 168-169 (2015)
572-576.
[26] Y. Wang, J.D. Hong, W. Zhang, R. Xu, Carbon nitride nanosheets for
photocatalytic hydrogen evolution: remarkably enhanced activity by dye
sensitization, Catal. Sci. Technol. 3 (2013) 1703-1711.
[27] J.Y. Xu, Y.X. Li, S.Q. Peng, Photocatalytic hydrogen evolution over Erythrosin
B-sensitized graphitic carbon nitride with in situ grown molybdenum sulfide
cocatalyst, Int. J. Hydrogen Energ. 40 (2015) 353-362.
[28] J.P. Huo, H.P. Zeng, A novel triphenylamine functionalized bithizaole-metal
complex with C60 for photocatalytic hydrogen production under visible light
irradiation, J. Mater. Chem. A 3 (2015) 6258-6264.
[29] J.P. Huo, H.P. Zeng, Copper nanoparticles embedded in the triphenylamine
functionalized bithizaole-metal complex as active photocatalysts for visible
light-driven hydrogen evolution, J. Mater. Chem. A 3 (2015) 17201-17208.

24
[30] H.Y. Liu, T.T. Wang, H.P. Zeng, CuNPs for efficient photocatalytic hydrogen
evolution, Part. Part. Syst. Char. 32 (2015) 869-873.
[31] T. Song, J.P. Huo, T. Liao, J. Zeng, J.Y. Qin, H.P. Zeng, Fullerene modified
Cr2-xFexO3 nanocomposites for enhanced photocatalytic activity under visible
light irradiation，Chem. Eng. J. 287 (2016) 359-366.
[32] J.P. Huo, L.T. Fang, Y.L. Lei, G.C. Zeng, H.P. Zeng, Facile preparation of
yttrium and aluminum co-doped ZnO via a sol-gel route for photocatalytic
hydrogen production, J. Mater. Chem. A 2 (2014) 11040-11044.
[33] M.J. Bojdys, J.O. Müller, M. Antonietti, A. Thomas, Ionothermal synthesis of
crystalline, condensed, graphitic carbon nitride, Chem. Eur. J. 14 (2008)
8177-8182.
[34] G. Liao, S. Chen, X. Quan, H. Yu, H. Zhao, Graphene oxide modified g-C3N4
hybrid with enhanced photocatalytic capability under visible light irradiation, J.
Mater. Chem. 22 (2012) 2721-2726.
[35] F. Dong, L. Wu, Y. Sun, M. Fu, Z. Wu, S.C. Lee, Efficient synthesis of polymeric
g-C3N4 layered materials as novel efficient visible light driven photocatalysts, J.
Mater. Chem. 21 (2011) 15171-15174.
[36] C.C. Yec, H. Zeng, Synthetic architecture of multiple core-shell and structures of
(Cu2O@)nCu2O (n=1-4) with centricity and eccentricity, Chem. Mater. 24 (2012)
1917-1929.
[37] L. Xiong, F. Yang, L. Yan, N. Yan, X. Yang, M. Qiu, Y. Yu, Bifunctional
photocatalysis of TiO2/Cu2O composites under visible light: Ti3+ in organic
pollutant degradation and water splitting, J. Phys. Chem. Solids 72 (2011)
1104-1109.
[38] L. Gou, C.J. Murphy, Controlling the size of Cu2O nanocubes from 200 to 25 nm,
J. Mater. Chem. 14 (2004) 735-738.
[39] S.H. Shen, P.H. Guo, L. Zhao, Y.C. Du, L.J. Guo, Insights into
photoluminescence property and photocatalytic activity of cubic and
rhombohedral Znln2S4, J. Solid State Chem. 184 (2011) 2250-2256.

25
[40] E.Z. Liu, L.M. Kang, Y.H. Yang, T. Sun, X.Y. Hu, C.J. Zhu, H.C. Liu, Q.P. Wang,
X.H. Li, J. Fan, Plasmonic Ag deposited TiO2 nano-sheet film for enhanced
photocatalytic hydrogen production by water splitting, Nanotechnology 25 (2014)
165401.
[41] S.W. Cao, Y.P. Yuan, J. Fang, M.M. Shahjamali, F.Y.C. Boey, J. Barber, S.C.
Joachim Loo, C. Xue, In-situ growth of CdS quantum dots on g-C3N4 nanosheets
for highly efficient photocatalytic hydrogen generation under visible light
irradiation, Int. J. Hydrogen Energ. 38 (2013) 1258-1266.
[42] A. Thomas, A. Fischer, F. Goettmann, M. Antonietti, J.O. Muller, R. Schlogl, J.M.
Carlsson, Graphitic carbon nitride materials: variation of structure and
morphology and their use as metal free catalysts, J. Mater. Chem. 18 (2008)
4893-4908.
[43] Q. Xiang, J. Yu, M. Jaroniec, Preparation and enhanced visible-light
photocatalytic H2-production activity of graphene/C3N4 composites, J. Phys.
Chem. C 115 (2011) 7355-7363.
[44] T. Ghodselahi, M.A. Vesaghi, A. Shafiekhani, A. Baghizadeh, M. Lameii, XPS
study of the Cu@Cu2O core-shell nanoparticles, Appl. Surf. Sci., 255 (2008)
2730-2734.
[45] C. Zhu, A. Osherov, M.J. Panzer, Surface chemistry of electrodeposited Cu2O
films studied by XPS, Electrochim. Acta 111 (2013) 771-778.
[46] M. Waki, Y. Maegawa, K. Hara, Y. Goto, S. Shirai, Y. Yamada, N. Mizoshita, T.
Tani, W.J. Chun, S. Muratsugu, M. Tada, A. Fukuoka, S. Inagaki, A solid
chelating ligand: periodic mesoporous organosilica containing 2,2-bipyridine
within the pore walls, J. Am. Chem. Soc. 136 (2014) 4003-4011.
[47] N. Cabrera, N.F. Mott, Theory of the oxidation of metals, Rep. Prog. Phys. 12
(1948) 163-184.
[48] J.H. Kim, S.H. Ehrman, T.A. Germer, Influence of particle oxide coating on light
scattering by submicron metal particles on silicon wafers, Appl. Phys. Lett. 84
(2004) 1278-1280.

26
[49] M. Hara, T. Kondo, M. Komoda, S. Ikeda, K. Shinohara, A. Tanaka, J.N. Kondo,
K. Domen, Cu2O as a photocatalyst for overall water splitting under visible light
irradiation, Chem. Commun. 3 (1998) 357-358.
[50] S. Ikeda, T. Takata, T. Kondo, G. Hitoki, M. Hara, J.N. Kondo, K. Domen, H.
Hosono, H. Kawazoe, A. Tanaka, Mechano-catalytic overall water splitting,
Chem. Commun. 20 (1998) 2185-2186.
[51] P.E. De Jongh, D. Vanmaekelbergh, J.J. Kelly, Cu2O: a catalyst for the
photochemical decomposition of water, Chem. Commun. 12 (1999) 1069-1070.
[52] X. Wang, Q. Wang, F. Li, W. Yang, Y. Zhao, Y. Hao, S. Liu, Novel BiOCl-C3N4
heterojunction photocatalysts: in situ preparation via an ionic-liquid-assisted
solven-thermal route and their visible-light photocatalytic activities, Chem. Eng.
J. 234 (2013) 361-371.
[53] C. Pan, J. Xu, Y. Wang, D. Li, Y. Zhu, Dramatic activity of C3N4/BiPO4
photocatalyst with core/shell structure formed by self-assembly, Adv. Funct.
Mater. 22 (2012) 1518-1524.
[54] W. Xu, X. Liu, J. Ren, P. Zhang, Y. Wang, Y.G. Guo, Y. Guo, G. Lu, A novel
mesoporous Pd/cobalt aluminate bifunctional catalyst for aldol condensation and
following hydrogenation, Catalysis Communications 11 (2010) 721-726.
[55] Z. Zhao, X. Lin, R. Jin, Y. Dai, G. Wang, High catalytic activity in CO PROX
reaction of low cobalt-oxide loading catalysts supported on nano-particulate
CeO2-ZrO2 oxides, Catalysis Communications 12 (2011) 1448-1451.
[56] W. Zhang, J.D. Hong, J.W. Zheng, Z.Y. Huang, J.R. Zhou, R. Xu,
Nickel-Thiolate complex catalyst assembled in one step in water for solar H2
production, J. Am. Chem. Soc. 133 (2011) 20680-20683.
[57] W. Zhang, R. Xu, Hybrid photocatalytic H2 evolution systems containing
xanthene dyes and inorganic nickel based catalysts, Int. J. Hydrogen Energy 37
(2012) 17899-17909.
[58] J. Zhang, J. Sun, K. Maeda, K. Domen, P. Liu, M. Antonietti, X. Fu, X. Wang,
Sulfur-mediated synthesis of carbon nitride: Band-gap engineering and improved

27
 functions for photocatalysis, Energy Environ. Sci. 4 (2011) 675-678.
[59] A. Paracchino, V. Laporte, K. Sivula, M. Grätzel, E. Thimsen, Highly active
oxide photocathode for photoelectrochemical water reduction, Nat. Mater. 10
(2011) 456-461.
[60] Z. Zhang, C. Shao, X. Li, C. Wang, M. Zhang, Y. Liu, Electrospun nanofibers of
p-Type NiO/n-Type ZnO heterojunctions with enhanced photocatalytic activity,
ACS Appl. Mater. Interfaces 2 (2010) 2915-2923.
[61] L. Chen, Q. Zhang, R. Huang, S. Yin, S. Luo, C.T. Au, Porous peanut-like
Bi2O3-BiVO4 composites with heterojunctions: one-step synthesis and their
photocatalytic properties, Dalton Trans. 41 (2012) 9513-9518.

28
  g-C3N4  Cu  Cu2O


  
 
Intensity (a.u.) F
E
D
C
B

20 40 2 Theta 60 80

Fig. 1. XRD patterns of composite A (no Cu2+, pure g-C3N4), B (the Cu2+ content
which was invested in the experiment was 1 wt%), C (3 wt%), D (5 wt%), E (7 wt%),
F (9 wt%).

1.2

1.0

0.8
Abs (a.u.)

0.6
A
0.4 B
C
D
0.2 E
F

200 300 400 500 600 700 800

Wavelength / nm

Fig. 2. UV-visible diffuse reflectance spectra of composite A (no Cu2+, pure

g-C3N4), B (the Cu2+ content which was invested in the experiment was 1 wt%),
C (3 wt%), D (5 wt%), E (7 wt%), F (9 wt%).

29
 A
B

Intensity (a.u.)
C
D
F
E

450 500 550 600 650

Wavelength (nm)
Fig. 3. Photo-luminescence spectra of composite A (no Cu2+, pure g-C3N4), B (the
Cu2+ content which was invested in the experiment was 1 wt%), C (3 wt%), D (5
wt%), E (7 wt%), F (9 wt%).

Fig. 4. SEM images (a) composite A (no Cu2+, pure g-C3N4), (b) composite B (the
Cu2+ content which was invested in the experiment was 1 wt%), (c) composite C (3

30
wt%), (d) composite D (5 wt%), (e) composite E (7 wt%) and (f) composite F (9
wt%).

Fig. 5. Images of composite E: (a, e) TEM, (b) HRTEM, (c) EDX spectrum, (d)
elemental mapping patterns and (f) size distribution.

31
 N1s (a) C1s 284.7eV (b)

Intensity (a.u.) Cu LMM Cu2p

Intensity (a.u.)
O 1s Cu LMM2
C1s

288.1eV

200 400 600 800 1000 282 285 288 291

Binding Energy (eV) Binding Energy (eV)

N1s 398.9eV (c) 932.7eV Cu2p (d)

Intensity (a.u.)
Intensity (a.u.)

952.9eV
400.1eV
401.4eV

396 399 402 930 940 950 960

Binding Energy (eV) Binding Energy (eV)

Cu LMM 568ev (e)

Intensity (a.u.)

571.2ev

560 564 568 572

Binding Energy (eV)

Fig. 6. XPS spectral of composite E: (a) survey spectrum, (b) C1s, (c) N1s, (d) Cu2p
and (e) Cu LMM.

32
 5000 (b)
400 (a) 5000
400 373 4485
4300

Rate of H2 evolution
335

(mol g-1 h-1)

4000
Rate of H2 evolution

300 3323
mol g-1 h-1)

3000
217 2343
200
155 2000
140

100 1000

0
0 1 3 5 7 10
A B C D E F Amount of ErB (mg)
Composites

(c) 1st 2nd

25000 3rd 4th 5th 6th
Amounts of H2 evolution

20000
mol g-1)

15000

10000

5000

0
0 5 10 15 20 25 30
Irradiation time (h)

Fig. 7. (a) Photocatalytic H2 evolution of composites under visible-light irradiation,

(b) composite E photocatalytic H2 evolution over the systems with various amount of
ErB dye and (c) the cycling test of photocatalytic H2 evolution for sample E/ErB-5mg
(irradiation time=30 h).

33
 (a) (b)
E/ErB-5mg
g-C3N4
Transmittance (a.u.)

Intensity (a.u.)
Cu2O Cu

ErB E/ErB-5mg

ErB

1000 2000 3000 4000 20 40 60 80

Wavenumber (cm-1) 2 Theta

553 nm (c) (d)

excitation=490 nm Absorbance (a.u.)

ErB
Intensity (a.u.)

558 nm
E/ErB-5mg
E/ErB-5mg

Composite E

500 550 600 650 700 200 400 600 800

Wavelength (nm) Wavelength (nm)

Fig. 8 (a) FTIR spectra, (b) XRD patterns and (c) photo-luminescence (PL) spectra of
ErB and sample E/ErB-5mg, (d) UV-Vis diffuse reflectance spectra of composite E
and sample E/ErB-5mg.

40 (a) (b)
on
Photocurrent density (μA•cm2)

off 6000
E/ErB-5mg
30

4000
Z''()

20

E
10 2000
A E/ErB-5mg
E
0
A
0 50 100 150 200 0
Times (s) 0 2000 4000 6000 8000
Z' ()

Fig. 9. (a) Photocurrent response under visible light irradiation (λ > 420 nm) and (b)
electrochemical impedance spectroscopy plots of composite A, composite E and
sample E/ErB-5mg.

34
Fig. 10. Schematic of photocatalytic hydrogen evolution over ErB sensitized
Cu-Cu2O/g-C3N4.

35
Table 1 BET surface area, average pore diameter, pore volume and molar ratio
between Cu and Cu2O.
Sample SBET (m2 g-1) Pore Volume (cm3 g-1) Average pore diameter (nm) Cu : Cu2Oa

A 31.75 0.28 27.96

B 30.58 0.27 26.93 1 : 1.8
C 33.80 0.27 26.06 1 : 1.5
D 35.64 0.25 25.55 1 : 1.2
E 43.07 0.24 24.91 1 : 1.0
F 28.95 0.22 24.16 1 : 0.8

a
Cu : Cu2O is molar ratio.

36