Chemical Physics Letters 703 (2018) 56–62

Contents lists available at ScienceDirect

Chemical Physics Letters

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

A high performance p-type nickel oxide/cuprous oxide nanocomposite

with heterojunction as the photocathodic catalyst for water splitting to
produce hydrogen
Aijuan Liu a, Yongcheng Zhu a, Kezhen Li a, Dongmei Chu a, Jie Huang a,b, Xia Li a, Chunyong Zhang a,
Ping Yang a,⇑, Yukou Du a
a
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
b
Key Laboratory of Nano-Bio Interface, Division of Nanobiomedicine, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, China

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

Article history: An efficient and robust p-type NiO/Cu2O nanocomposite was developed as photocathodic catalyst of a
Received 29 January 2018 photoelectrochemical cell. The nanocomposite with heterojunction demonstrates enhanced photoelec-
In final form 9 May 2018 trochemical (PEC) properties and considerable photocatalytic hydrogen generation ability. When ca. 6
Available online 16 May 2018
wt.% Cu2O was loaded on the surface of NiO, the sample exhibited the highest photocatalytic activity.
The amount of hydrogen evolved from the cathodic chamber of the PEC cell up to 17.6 lmol under 2 h
Keywords: simulated sunlight irradiation with
0.0455 V vs. RHE (reversible hydrogen electrode) bias.
NiO/Cu2O nanocomposite
Ó 2018 Elsevier B.V. All rights reserved.
Heterojunction
Photocathode
Hydrogen production

1. Introduction conduction band level (
0.28 V vs. RHE) is beneficial to the

It is well known that hydrogen is an economic and environmen-
tally friendly energy source [1]. Photoelectrochemical (PEC) water
splitting to produce hydrogen is one of the most attractive and
challenging tasks for a sustainable society [2,3]. In a PEC water
splitting system, the photocathode for hydrogen evolution should
be made of a p-type semiconductor, such as CuI, SnS, InP, ZnFe2O4
and NiO etc [4–8]. Among these semiconductors, nickel oxide is a
nonstoichiometric p-type semiconductor with good thermal and
chemical stability [9], which makes NiO one of the most appropri-
ate semiconductor substrates for water splitting to produce hydro-
gen. However, pristine NiO has some intrinsic weakness, such as
the large overpotential for hydrogen evolution and low photocat-
alytic activity [10,11], hindering its practical applications. Modify-
ing NiO with quantum dots is an effective method to improve the
photocatalytic properties of the semiconductor [12].
Recently, p-type Cu2O has been widely reported as a typical
photocatalyst because of its low production cost and excellent
photovoltaic properties [13]. Besides, its appropriate direct band
gap (2.2 eV) enables efficient visible light absorption and its high
⇑ Corresponding author.
E-mail addresses: jhuang2008@sinano.ac.cn (J. Huang), pyang@suda.edu.cn
(P. Yang).
reduction of the protons in the aqueous solution [14]. However,
the photocatalytic system consisting of single Cu2O is less efficient
for water splitting to produce hydrogen because of some of its
intrinsic defects [15].
In this paper, we report a novel and robust p-type composite
semiconductor consisting of NiO and Cu2O. The composite with
heterojunction was prepared by deposition copper precursor on
the surface of NiO nanoparticles followed by a low temperature
solid reaction. The composite photocathode fabricated by immobi-
lizing composite on the surface of fluorine-doped tin oxide glass
demonstrated excellent photocatalytic activity. This work provides
a new approach to prepare effective and cost-effective semicon-
ductor catalysts with heterojunction for photocatalytic water split-
ting to produce hydrogen in a tandem cell.
2. Experimental
2.1. Materials
Nickel chloride hexahydrate (NiCl26H2O), sodium hydroxide
(NaOH), copper (II) nitrate trihydrate (Cu(NO3)23H2O), sodium
sulfate anhydrous (Na2SO4), sodium dihydrogen phosphate dihy-
drate (NaH2PO42H2O), disodium hydrogen phosphate dodecahy-
drate (Na2HPO412H2O) and ethanol (C2H5OH) were purchased in
analytical grades from Sinopharm Chemical Reagent Company

https://doi.org/10.1016/j.cplett.2018.05.020
0009-2614/Ó 2018 Elsevier B.V. All rights reserved.
 A. Liu et al. / Chemical Physics Letters 703 (2018) 56–62
(Shanghai, China). All reagents were used without further
purification.
2.2. Sample preparation
NiO nanoparticles were synthesized by a modified method
reported in previous research [16]. In a typical synthesis, 10 mL
of NaOH solution (8 mol L
1) was added dropwise into 20 mL of
NiCl2 solution (0.2 mol L
1) under magnetic stirring. The light
green NiO precursor can be seen in the process. The mixture was
heated to 80 °C and maintained at that temperature for 3 h. The
suspension was naturally cooled down to room temperature, and
NiO solid was isolated by centrifugation. The product was washed
with deionized water and ethanol three times, and then was dried
at 60 °C for 12 h. The obtained solid was calcined at 400 °C in air for
2 h, obtaining desired NiO sample.
NiO/Cu2O nanocomposite was prepared by a low temperature
solid reaction method [17,18]. In a typical experiment, the NiO
nanoparticles were dispersed in 10 mL of anhydrous ethanol and
Fig. 1. TEM images of (A) NiO and (B) NiO/Cu2O-6; (C) XRD patterns of the samples of (a) NiO, (b) NiO/Cu2O-3, (c) NiO/Cu2O-6 and (d) NiO/Cu2O-9; D) HRTEM of NiO/Cu2O-6.
Inset: the magnified image of labeled area.
57
stirred at room temperature for 1 h. Then, the calculated amount
of Cu(NO3)2 ethanol solution (0.04 mol L
1) was added into the
NiO suspension under vigorous stirring. The mixture was stirred
at room temperature for 2 h. The solvent was removed by vacuum
evaporation. The solid was dried at 80 °C for 6 h and then was cal-
cined in air at 350 °C for 2 h, resulting in Cu2O modified NiO
nanocomposite. The samples were labeled NiO/Cu2O-x, where x
stands for the weight percent of Cu2O in the sample.
2.3. Photoelectrode preparation
To 5 mL of the solution consisting of ethanol-ethylene glycol-
polyvinyl pyrrolidone (4 mL: 1 mL: 1.5 mg), 20 mg of the as-
prepared NiO nanoparticles or NiO/Cu2O composite was added
under ultrasonic treatment to form a suspension. The suspension
was spin-coated on the surface of a clean fluorine-doped tin-
oxide (FTO) substrate. The FTO plate with the deposited sample
was dried on a heating plate at 50 °C for 20 min and was then sin-
tered in Ar at 400 °C for 0.5 h.
58 A. Liu et al. / Chemical Physics Letters 703 (2018) 56–62
2.4. Characterization
The crystal structure of the samples was analyzed by X-ray
diffraction (XRD) (Japan, XD-3A) using Cu Ka radiation in the 2h
range of 20–80°. The transmission electron microscopy (TEM)
was performed on a TECNAI-G20 electron microscope operation
at an accelerating voltage of 200 kV. The X-ray photoelectron spec-
troscopy (XPS) measurements were carried out with an AXIS Ultra
DLD system (Kratos Analytical Inc). The UV–vis absorption spec-
trum of the as-prepared nanocomposite was recorded on a
UV3600 Spectrophotometer.
2.5. Photocatalytic reactions of the samples
The photoelectrochemical (PEC) performance of the samples
was measured in a three-electrode system composed of a working
electrode, a saturated calomel electrode (SCE) as the reference
electrode, and a platinum plate as the counter electrode. The elec-
trodes were immersed in 0.2 M of a phosphate buffer solution
(pH = 7). The system was connected with a CHI 660D potentiostat/
galvanostat electrochemical analyser. A 300 W sunlight simulator
(Ultra-vitalux) was positioned ca.18 cm away from the optical
entry window of the reactor as the visible light source. The pro-
duced gases were analyzed with an online gas chromatograph
Fig. 2. (A) XPS spectra survey of NiO nanoparticle and NiO/Cu2O-6; (B) comparison between the Ni 2p peaks of the NiO nanoparticle and NiO/Cu2O-6; (C) Cu 2p peaks of NiO/
Cu2O-6; (D) Cu LMM of NiO/Cu2O-6.
(GC1650) equipped with a thermal conductivity detector (TCD),
and argon was used as carrier gas. The standard H2-Ar gas mixtures
of known concentrations were used for GC signal calibration. The
Nernst equation:
RRHE ¼ ESCE þ 0:059pH þ EoSCE
is used for converting the measured potential vs. SCE to the poten-
tial vs. reversible hydrogen electrode (RHE), where ERHE is the
potential vs. RHE, ESCE is the measured potential vs. SCE, and
EoSCE = 0.2415 V at 25 °C.
3. Results and discussion
3.1. Morphology and structure of the samples
Fig. 1 shows TEM images of NiO and NiO/Cu2O-6. It can be
observed that the as-prepared NiO sample is consisted of nanopar-
ticles in an irregular shape (Fig. 1A). The diameter of the nanopar-
ticles is in the range of 4–6 nm. The NiO/Cu2O-6 sample
demonstrates almost the same morphology of the NiO nanoparti-
cles (Fig. 1B) with a slight increase in the size of the particles.
Fig. 1C shows the XRD patterns of the as-prepared samples. For
the NiO sample, four diffraction peaks at 37.14°, 43.12°, 62.47°
 A. Liu et al. / Chemical Physics Letters 703 (2018) 56–62 59

and 75.18° (Fig. 1C, curve a) corresponding to (1 1 1), (2 0 0), (2 2 0)
and (3 1 1) crystal planes of cubic NiO phases (JCPDS, No. 65-2901),
respectively, can be observed. The half peak width is relatively
wide, indicating that the crystalline grain of the obtained sample
is in nanometer scale. All diffraction peaks of the NiO/Cu2O sam-
ples in different compositions (Fig. 1C, curve b–d) can be indexed
to NiO unambiguously. No typical diffraction peaks belonging to
Cu2O can be found in the curves, which may owe to the low con-
tent and relatively low diffraction intensity of Cu2O. The HRTEM
image of NiO/Cu2O-6 (Fig. 1D) displays two different lattice fringes.
The inset of the figure demonstrates the magnified labeled area,
from which the lattice fringes with d-spacing of 0.208 nm corre-
sponding to the (2 0 0) planes of NiO and other ones with d-
spacing of 0.24 nm relating to the (1 1 1) planes of Cu2O (JCPDS
No. 050667) can be clearly observed. These results indicate
that Cu2O has been successfully decorated on the surface of the
NiO nanoparticles, forming a composite with heterojunction
structure.
Fig. 2 displays the XPS spectra of the samples. The survey spec-
tra of NiO and NiO/Cu2O-6 (Fig. 2A) indicate that both samples con-
tain the elements of the relevant compound: i.e., Ni and O, or Ni,
Cu, and O. The high-resolution Ni XPS spectra of NiO and NiO/
Cu2O-6 are demonstrated in Fig. 2B. Four obvious binding energy
peaks can be found in the XPS spectrum of NiO: two binding
energy peaks located at 853.6 and 860.9 eV are assigned to Ni2+
2p3/2 and its satellite peak, respectively, and two other peaks at
872.6 and 879.5 eV are assigned to Ni2+ 2p1/2 and its satellite peak
[19]. Moreover, there is also a peak with low intensity at 855.6 eV,
which may be caused by trace amounts of Ni3+ in the sample [20].
Compared with the spectrum of NiO, the Ni XPS peak positions of
the NiO/Cu2O-6 composite have no obvious changes. The XPS spec-
trum of Cu 2p about NiO/Cu2O-6 is demonstrated in Fig. 2C. The
characteristic peaks located at 932.7 and 952.9 eV are assigned to
Cu+ 2p3/2 and Cu+ 2p1/2 [21,22]. The presence of the peak with very
low intensity in Fig. 2C may attribute to the trace amounts of Cu2+.
The amount of Cu2O in NiO/Cu2O-6, calculated from the peak areas,
is approximately 5.6 wt.%, which is basically the same as the value
estimated from the quantities of the starting materials of the syn-
thetic process. The Cu LMM XPS spectrum of NiO/Cu2O-6 is shown
in Fig. 2D. The peak located at 570.2 eV is assigned to Cu+, which
provides further evidence of forming Cu2O modified NiO nanocom-
posite [22].
3.2. Optical and photoelectrochemical properties
As shown in Fig. 3A, the dark NiO sample shows strong absor-
bance in the UV–visible region. The absorption peak located at
276 nm is assigned to the direct interband transition of NiO

Fig. 3. (A) UV–vis absorption spectra of NiO, NiO/Cu2O-3, NiO/Cu2O-6 and NiO/Cu2O-9; (B) Photocurrent of NiO, NiO/Cu2O-3, NiO/Cu2O-6 and NiO/Cu2O-9 electrode under
UV–visible light irradiation at
0.0045 V vs. RHE; (C) Linear sweep voltammetry of NiO, NiO/Cu2O-3, NiO/Cu2O-6 and NiO/Cu2O-9 electrode under UV-visible light irradiation
in 0.2 M Na2SO4 (pH = 6) solution; (D) EIS spectra of NiO, NiO/Cu2O-3, NiO/Cu2O-6 and NiO/Cu2O-9 electrode at a potential of 0.3955 V vs. RHE.
60 A. Liu et al. / Chemical Physics Letters 703 (2018) 56–62

[23,24]. According to the Tauc plot of NiO shown in Fig. S1A, the
band gap of NiO is 3.8 eV. The enhanced absorption in the visible
region of NiO is due to the vacant 3d states of Ni above the valence
band [25]. Modifying NiO with Cu2O enhances the absorbance in
visible range. As the content of Cu2O in the NiO/Cu2O composite
increases, the absorbance intensity also increases, indicating that
forming the composite is beneficial to light harvesting. The sample
exhibits the highest absorbance intensity when the content of
Cu2O in the composite reaches 6 wt.%. Fig. 3B shows the result of
the photocurrent test under chopped light irradiation. The NiO
sample demonstrates a weak cathodic photocurrent (
0.3 lA
cm
2). After coupling NiO with Cu2O, cathodic photocurrent
explicitly increases. The cathodic photocurrent of the NiO/Cu2O-3
electrode increases to
1.25 lA cm
2; while the NiO/Cu2O-6 elec-
trode reaches
3 lA cm
2, which is ca. 10 times as high as that of
the pristine NiO electrode. The enhanced photocurrent density of
the composite electrode proves that the heterojunction formed
between NiO and Cu2O facilitates the charge transfer and separa-
tion. However, when the content of Cu2O in the composite
increases to 9 wt.%, the photocurrent decreases (
2.25 lA cm
2),
which may be owed to that the excess Cu2O in the composite
blocks the active sites [26,27]. The linear scan voltammetry (LSV)
of the samples is demonstrated in Fig. 3C. NiO shows a weak catho-
dic current under illumination. For the NiO/Cu2O-3 electrode, the
photocurrent density turns from 0.0064 to
0.1017 mA cm
2
when applied bias changes from 0.3 V to
0.5 V vs. RHE. Moreover,
the photocurrent density of the NiO/Cu2O-6 electrode reaches

0.2217 mA cm
2 at the bias of
0.5 V vs. RHE. However, the
NiO/Cu2O-9 electrode demonstrates a lower photocurrent density
compared to the NiO/Cu2O-3 electrode. The LSV results are well
coincident to those of the photocurrent test. Fig. 3D demonstrates
electrochemical impedance spectra (EIS) of the prepared samples
shown as Nyquist plots. The diameter of the Nyquist plot is
equivalent to the charge transfer resistance across the interface
of the electrode and electrolyte. It can be seen that the diameter
of the Nyquist curves change in the following order: NiO > NiO/ Fig. 4. (A) Comparison of the amount of H2 evolution under 2 h simulated sunlight
illumination at
0.0455 V vs. RHE in 0.2 M phosphate buffer solution (pH = 7). (a)
Cu2O-3 > NiO/Cu2O-9 > NiO/Cu2O-6. The fact that the NiO/Cu2O-6
pure NiO, (b) NiO/Cu2O-3, (c) NiO/Cu2O-6 and (d) NiO/Cu2O-9 photocathode; (B)
electrode possesses the smallest slope indicates that the optimal Current-time curves of NiO, NiO/Cu2O-3, NiO/Cu2O-6 and NiO/Cu2O-9 photocath-
composite electrode has the lowest resistance and the highest ode under light illumination at
0.0455 V vs. RHE in 0.2 M phosphate buffer
transfer charge efficiency at the interface of the solution (pH=7).
electrode/electrolyte.
Fig. S1B shows the Mott-Schottky plot of the NiO sample. The
negative slope of the curve indicates that the as-prepared NiO photocatalytic activity of the composite electrode starts to
belongs to a p-type semiconductor [8]. The flat band potential of decrease when the content of Cu2O in the composite exceeds 6
NiO, derived by extrapolating the linear region of the curve to V wt.%. The amount of H2 decreases to 9.5 lmol from the chamber
axis, is 1.875 V vs. RHE. Since the flat potential of p-type semicon- of the NiO/Cu2O-9 electrode, which may be due to that the exces-
ductor can be treated approximately as of the value of the valence sive amount of Cu2O in the nanocomposite may introduce charge
band edge, combining with the band gap of NiO (3.8 eV), we can
draw the conclusion that the conduction band of NiO is
1.925 V
vs. RHE.

3.3. Photocatalytic hydrogen evolution

The properties of the photocatalytic hydrogen evolution of the

as-prepared samples were explored in a three-electrode PEC tan-
dem cell under irradiation of a 300 W sunlight simulator. As shown
in Fig. 4A, the NiO electrode demonstrates no detectable hydrogen
production activity at bias of
0.0455 V vs. RHE during the 2 h
reaction. Coupling Cu2O with NiO obviously shows positive effects
for hydrogen evolution under the same reaction conditions. For the
photocell using the NiO/Cu2O-3 composite as the photocathode,
the amount of hydrogen collected from the cathodic chamber is
8.9 lmol during a 2 h reaction. When the content of Cu2O in the
composite increases to 6 wt.%, the hydrogen amount augments to
17.6 lmol during a 2 h reaction, which is approximately 2 times Fig. 5. The possible mechanism of for the sunlight-driven photocatalysis of the NiO/
higher than that of the NiO/Cu2O-3 electrode. However, the Cu2O sample in a PEC tandem cell.
 A. Liu et al. / Chemical Physics Letters 703 (2018) 56–62
Fig. 6. The incident photocurrent conversion efficiency (IPCE) of NiO/Cu2O-6 under
light illumination at
0.0455 V vs. RHE in 0.2 M phosphate buffer solution (pH = 7).
recombination sites, thus decreasing the photocatalytic activity
[27,28]. Fig. 4B shows the results of the photocurrent-time of the
photocathode in different compositions under the light illumina-
tion in the 0.2 M phosphate buffer solution (pH = 7) with a bias
of
0.0455 V vs. RHE. In 2 h of simulated sunlight illumination,
the photoinduced current density produced by the NiO electrode
is basically stabilized at
4 lA cm
2, while the photocurrent den-
sity of the NiO/Cu2O-3 electrode is
53 lA cm
2. This result
demonstrates the obviously positive effect of the heterojunction
formed between NiO and Cu2O on the photocatalytic activity and
stability. The photocurrent density produced by the NiO/Cu2O-6
electrode reaches
70 lA cm
2, while the one produced by the
NiO/Cu2O-9 electrode becomes
57 lA cm
2. These results corre-
spond very well with the hydrogen production results of the PEC
cell.
Fig. 5 illustrates a possible mechanism for the sunlight-driven
photocatalysis of the NiO/Cu2O-based photocathode. Under the
simulated sunlight irradiation, NiO nanoparticles of the NiO/Cu2O
composite absorb visible-light and the electrons are photoexcited
from the valence band of NiO (1.875 V vs. RHE) to its conduction
band (
1.925 V vs. RHE), then transfer to the conduction band
(
0.28 V vs. RHE) of Cu2O, where H+ is reduced by the electron
to form H2. Meanwhile, the holes in NiO nanoparticles capture
the electrons transferred through external circuit from Pt elec-
trode, where water is oxidized to produce O2 and protons, under
bias and the electric potential gradient of the photocathode. The
heterojunction existing in the NiO/Cu2O nanocomposite enhances
the transfer and separation of photoexcited charges.
Fig. 6 shows the incident photon to electron conversion effi-
ciency (IPCE) spectrum of the NiO/Cu2O-6 photocathode. It can
be seen that the average value of IPCE under visible light illumina-
tion (410 to 560 nm) is approximately 9%. This result further indi-
cates that the NiO/Cu2O-based material is a promising candidate
for fabricating a photocathode.
4. Conclusions
In summary, this study provides a promising and simple
approach to construct highly efficient, visible-light-driven cathodic
catalysts for hydrogen evolution. The nanocomposite was highly
efficient for the photocatalytic H2 evolution under simulated sun-
light irradiation. The heterojunction formed between NiO and
Cu2O moieties enhances the photoexcited charges transfer, separa-
tion and the photocatalytic performance greatly. Our study
61
introduces a new approach for the development of an effective
and robust catalyst for photocatalytic water splitting to produce
hydrogen in a tandem cell.
Acknowledgements
The authors gratefully acknowledge financial support of this
research by the National Natural Science Foundation of China
(21373143), the Priority Academic Program Development of
Jiangsu Higher Education Institutions (PAPD) and the project of sci-
entific and technologic infrastructure of Suzhou (SZS201708).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.cplett.2018.05.020.
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