i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 4 9 0 e6 5 0 1

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Experimental investigation of various copper oxide

electrodeposition conditions on
photoelectrochemical hydrogen production

Yusuf Bicer*, Ghassan Chehade, Ibrahim Dincer

Clean Energy Research Laboratory, Faculty of Engineering and Applied Science, University of Ontario Institute of
Technology, 2000 Simcoe Street North, Oshawa, Ontario L1H 7K4, Canada

article info abstract

Article history: In this study, an experimental investigation of photosensitive material copper oxide
Received 2 October 2016 electrodeposition on various substances is performed under different experimental con-
Received in revised form ditions in order to evaluate the effects on photoelectrochemical hydrogen production
17 December 2016 system. The experimental setup consists of solar simulator, electrodeposition chemicals,
Accepted 18 December 2016 hydrogen sensor, pH meter, graphite and platinum electrodes, heating plate, stirrer, tem-
Available online 4 January 2017 perature sensors, cathode and anode plates, concentrating lens and potentiostat. The
overall aim is to optimize the efficiencies by generating higher currents and eventually
Keywords: hydrogen as light enhances the separation of water process. The results obtained in this
Hydrogen study are promising for photoelectrochemical hydrogen production under the solar
Photoelectrochemical simulator and concentrated light irradiation conditions. Furthermore, an electrolysis setup
Copper oxide using the coated metals and graphite rod is built to investigate the amount of photocurrent
Electrodeposition production. The characterization is also conducted under light and no-light conditions,
Photocurrent where the amount of produced current and hydrogen increased in light compared to no-
light condition. At the applied voltage of
0.6 V and
0.4 V vs. Ag/AgCl, the photocur-
rent densities of 0.8 mA/cm2 and 0.27 mA/cm2 are obtained with a solar conversion effi-
ciency of 0.86% and 0.24%, respectively.
2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

hydrogen from water using renewable resources. One of the

Introduction
Conventional energy resources (natural gas, coal and oil)
deplete fast day by day. Due to the magnitude of such deple-
tion, humans seek for alternative sources of energy. Solar en-
ergy is one of the best candidates for replacement as a
renewable energy source to fulfill all the requirements needed
for future generations. Since hydrogen is mostly abundant in
water, there are many processes used in the separation of
most environmental-friendly processes for hydrogen produc-
tion is the use of solar energy via photoelectrochemical (PEC)
water splitting where a potential difference of at least 1.23 V, in
addition to over potentials, is required. The value of over po-
tentials is mainly dependent on the materials and electrolyte
used. Summation of the potentials will result in the total po-
tential difference required to drive the redox reaction for
hydrogen production in a PEC cell. The required voltage can be
partly supplied by the potential difference created within the

* Corresponding author.
E-mail addresses: yusuf.bicer@uoit.ca (Y. Bicer), ghassan.chehade1@uoit.net (G. Chehade), ibrahim.dincer@uoit.ca (I. Dincer).
http://dx.doi.org/10.1016/j.ijhydene.2016.12.067
0360-3199/ 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 4 9 0 e6 5 0 1
photoelectrode (photocathode or photoanode depending on
the photosensitive material) when there is sun light illumi-
nation. Nevertheless, based on the material, the PEC can only
produce 0.6 V of the required voltage. For the additional voltage
which is needed to drive water splitting, additional power
supplies can be used. In this case, employing solar PV cells
integrated to PEC cells results in a sustainable and environ-
mentally friendly solution. The copper oxide is one of the
alternative materials for PEC hydrogen production applica-
tions. In the following section, we review the current open
literature, particularly on the copper oxide electrodeposition
for photochemical hydrogen production, as outlined in Table 1.
Various studies have been conducted in the literature for
CuO/Cu2O photo-sensitive material electrodeposition [1e18].
Electrodeposition process to obtain cuprous oxide is quite
cheap with a possibility of making large area coatings. Zhao
et al. [7] reported that electrodeposition conditions of the Cu2O
thin films have important effects on the surface morphology,
crystal quality, photocatalysis and photoelectric properties.
However, the response to sun light of Cu2O thin films has been
rarely reported. According to their results, the deposition po-
tential has an important effect on the crystallographic orien-
tation and particle size. They used different morphologies of
cuprous oxide (Cu2O) thin film electrodes which were electro-
deposited on indium-doped tin oxide (ITO) substrates. Their
study identified the dendritic morphology as superior to the
granular morphology in producing photoelectrodes with good
electrical continuity at a temperature of 20  C, slightly acidic
medium and photocurrent density of 0.061 mA/cm2. The
photo-energy conversation efficiency was about 0.01% under
the visible illumination. Amano et al. [8] used indirect photo-
electrochemical water splitting achieved by using a Cu2O
electrode, catalyst and redox couple as an electron mediator
from the electrode to the catalyst. The study highlighted the
crystalline composition of the outermost surface of Cu2O films
as important factor in regulating photoecathodic reactions.
Cu2O may only be deposited electrochemically in a
restricted voltage limits, at pH 9e11 between approximately

0.1 to
0.6 V vs. SCE as reported by Jongh et al. [12]. The pH of
the electrodeposition mixture carried a solid impact on the
characteristics of the layers. At pH 7 and 8, copper was made
at upper current densities. For pH 9e12, well-defined layers of
faceted Cu2O crystals can be obtained. Georgieva and Ristov
[13] performed the study by preparing semi-conductor copper
oxide layers with electro-deposition onto viable conducting
glass covered with indium tin oxide coated by spraying
Table 1 e Brief review of electrodeposition literature and comparison with the current study.
Ref. Year Max photocurrent density Efficiency (%)
(mA/cm2)
[7] 2011 0.061 0.01%
[8] 2014 0.1 e 90
[13] 2002 0.57 0.0234
[14] 2008 0.75 0.41
[15] 2012 1.4 e 50
[16] 2012 1.20 0.91
[17] 2012 e 0.3
[18] 2016 e e
This study 2016 1.5 0.86
6491
method. The copper oxide layers were electrodeposited with a
galvanostatic process from an alkaline CuSO4 bath comprising
lactic acid and sodium hydroxide at a temperature of 60  C.
The film thickness was around 4e6 mm. The best values of
Voc 340 mV and Isc 245 mA/cm2 were obtained by depos-
iting graphite paste and illumination by an artificial white
light source of 100 mW/cm2. The total cell active area was
1 cm2 with current density of 0.57 mA/cm2. The efficiency of
the cell was found to be 0.0234%. The cell showed photovoltaic
features after heat management of the layers for 3 h at 130  C.
ZnO/Cu2O heterojunction solar cells were made by consec-
utive cathodic electrodeposition of ZnO and Cu2O on glass
plates covered with a SnO2 transparent conductive oxide layer
(Asahi glass) in the study by Jeong et al. [14]. The impact of the
electrodeposition situations (pH/temperature) on the perfor-
mance of the cell has been examined with film thickness
changing between 2 and 4 mm. The cells made with a Cu2O layer
deposited at high pH about 12 and moderate temperature about
50  C and current density 0.75 mA/cm2 for Cu2O and 1 mA/cm2
for ZnO shown conversion efficiency as high as 0.41%.
Bao et al. [15] deposited Cu2O films using a ZF-8 potentio-
stat, completed with a standard three-electrode electro-
chemical cell. A platinum piece and a saturated calomel
electrode (SCE) were utilized as a counter electrode and a
reference electrode, respectively. A well-polished stainless
steel with a 2 cm2 surface area was used as a work electrode.
The Cu2O films were deposited electrochemically at a persis-
tent deposition potential of
0.1 and
0.2 V, measured with
respect to SCE. The chemical solution confined 0.1 M Cu (II) salt
and 0.75 M lactic acid as chelating mediator to alleviate the
Cu2 ion. Its pH was set to 9 with sodium hydroxide. The
temperature of the bath was 50  C. Three or more films were
deposited under each deposition circumstance to confirm
reproducibility. The electrodeposition conditions include a pH
of 9 and a temperature of 50  C where they recorded a photo-
current density of 0.57 mA/cm2. However, the efficiency and
the electrodeposition current values were neither specified nor
provided. CuO nanoparticles were deposited by Chiang et al.
[16] in a solution based process and used to prepare photo-
active porous nanostructured CuO thin film electrodes for
hydrogen generation via a photoelectrochemical cell. The
particle and film morphologies were well controlled in the
processes. The porous structure of the CuO film made by this
process (powder prepared at 60  C and sintered at 600  C for 1 h)
had increased surface area and a high photocurrent and charge
carrier density. These films were demonstrated to have 0.91%
Electrodeposition Electrodeposition Electrodeposition
Temperature ( C) pH Potential (V)
20 Slightly acidic
0.2 vs. SCE
5
0.5 vs. Ag/AgCl
60 9 e
50 12
0.26 vs. Ag/AgCl
9
0.1 and
0.2 V
60 14
0.55 vs. Ag/AgCl
60 12.5
0.9 vs. MSE
55 e
0.25 vs. Ag/AgCl
55 10
0.30 vs. Ag/AgCl
6492 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 4 9 0 e6 5 0 1
solar conversion efficiency at applied voltage of
0.55 V vs. Ag/
AgCl in 1 M KOH electrolyte with 1 sun (AM1.5G) illumination.
Electrodeposition of Cu2O was also investigated by Haller et al.
[17] for potentials of deposition ranging from
0.7 to
1.05 V vs.
MSE with electrolyte at pH 9 and 12.5. The effect of chloride
addition either from CuCl2 or KCl and hence annealing has also
been studied. Crystal quality was found to depend on the po-
tential of deposition and an optimum was found for deposition
at
0.9 V vs. MSE in an electrolyte at pH 12.5 and free of chlo-
ride. In the best conditions, ZnOeCu2O heterojunction could
reach efficiency up to 0.33%. Casallas et al. [18] also conducted
electrodeposition to obtain a photocathode by deposition of
copper oxide semiconductors on the surface of the cathode of a
membrane electrode assembly consisting of a NAFION
membrane with two faces of which were coated with carbon
layers and doped with electro-catalysts.
Because of having higher absorption coefficient in the visible
region of the solar light spectrum, Cu2O is preferred in appli-
cations for solar energy conversion and photoelectrochemical
hydrogen production applications. Cu2O is a p-type semi-
conductor with direct band-gap of 1.9e2.2 eV. However, there
are some potential drawbacks of copper oxide coatings, such as
probability of photo-corrosion which might be caused since
oxidation and reduction potentials of Cu2O and CuO drop
within the bandgap [19]. The other drawback may be the
diffusion length of photo-generated charge carriers due to
having shorter than light absorption depth. In order to over-
come the photo-corrosion, different techniques have been
proposed in the literature such as formation of composite
coatings or deposition of thin protective layers such as the one
performed by Tran et al. [20] by applying a composite with
reduced graphene oxide.
There are various ways for photosensitive material coating
in the literature such as chemical bath deposition (CBD),
electro-deposition (ED) and thermal evaporation [21,22].
Nevertheless, some of the methods require harsh coating en-
vironments, such as a ultra-high vacuum, higher tempera-
tures, quite lengthy period of time, and complex phases.
Consequently, considering large scale hydrogen production
plants from photoelectrochemical methods will necessitate to
develop lower temperature, atmospheric, and modest
solution-based techniques for Cu2O coatings. Hence, electro-
deposition technique is a promising method to make photo-
electrochemical cells and also dye sensitized solar cells.
Because, this method is a low cost, simple, and environmen-
tally friendly [23]. Kelly et al. [24] measured the light focusing
properties of two types of PEC reactors with curved surfaces
and holding a clear aqueous fluid that resulted in the focusing
of solar irradiance within the reactor. One reactor was a tear-
drop shaped plastic-film bag reactor, and the other was an
acrylic spherical tank reactor. They concluded that a Fresnel
lens could increase the photo enhancement in either the bag
reactor or the spherical tank reactor. Increasing the solar
irradiance on the PEC photoelectrode which is evaluated as the
most expensive part of the overall system, can help reducing
the system cost, therefore a light-focusing reactor is an
important system component. Wu et al. [25] experimentally
investigated the effects of various parameters such as tem-
perature and solar intensity, different ambient air tempera-
tures, and natural and forced convection on the system. They
mainly analyzed the thermal behavior of Fresnel lens and PV
with respect to various ambient conditions where the solar
intensity was varied between 200 W/m2 and 1000 W/m2. Some
researchers performed electrodeposition of different chem-
icals, such as Fe3O4 [26] where they highlighted the advantage
of using low-temperature electrochemical deposition methods
to make high-performance Fe3O4 electrodes. Dubal et al. [27]
studied copper oxide multilayer nano-sheets for synthesizing
in a simple and inexpensive chemical bath deposition method.
They resulted that the chemically deposited copper oxide thin
films appear to be promising electrode material for electro-
chemical capacitors. Daltin et al. [28] deposited in potentio-
static way cuprous oxide nanowires in polycarbonate
membrane by cathodic reduction of alkaline cupric lactate
solution where they defined the optimum parameters for the
deposition of nanowires as temperature of 70  C, pH of 9.1, and
applied potential of 0.9 V vs. SSE. Zhou and Switzer [29] con-
ducted polycrystalline copper (I) oxide films on stainless steel
substrate by galvanostatic electrodeposition method where
the substrates, which were used as cathodes, were disks of 430
stainless steel with 15 mm in diameter.
As reported in the literature, there are different types of
deposition methods where some of them require the moderate
and high temperatures above 100  C. In addition, the literature
studies mainly performed electrodeposition on FTO glass
substrates having a very small surface area. Therefore, there is
a gap in the open literature to investigate copper oxide elec-
trodeposition on large surface metal plates for practicability
under different conditions comparatively such as under solar
simulator light and concentrated light. Furthermore, the
electrodeposition of copper oxide has not been conducted on
such a large area stainless steel plate and characterized under
concentrated light for hydrogen production. In this study,
copper oxide is deposited on large area steel and stainless steel
metals under different experimental conditions by changing
the temperature, pH and durations. Furthermore, the effects of
these conditions are investigated for photoelectrochemical
hydrogen production system under concentrated light, solar
simulator light and no-light conditions. The main aim of this
study is to apply electrodeposition of copper oxide on large
scale steel plates for photoelectrochemical hydrogen produc-
tion applications and to investigate the effects of various pa-
rameters of copper oxide deposition under different scenarios
such as concentrated light for photoelectrochemical hydrogen
production as follows:
 concentrated light and no-light conditions,
 stainless steel and steel plates,
 smaller surface area and larger surface area,
 duration of electrodeposition process, and
 electrodeposition temperature (25  C and 55  C).
Experimental investigation
In the present study, the electrochemical deposition of Cu2O
films was conducted in an electrolyte solution consisting of
0.4 M CuSO4$5H2O and 3 M lactic acid which were purchased
from Sigma Aldrich. By complexing with lactate ion, the
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 4 9 0 e6 5 0 1
Fig. 1 e Electrodeposition setup for the stainless steel plate.
copper is stabilized and the pH can be raised to alkaline
values. The dark blue solution has been prepared and
continuously stirred during electrodeposition. The electrode-
position setup is illustrated in Fig. 1 where the green wire is
working electrode, which is connected to the stainless steel
plate, while the red wire is the counter electrode which is
connected to the graphite rod with platinum winding. The
white wire is connected to the reference electrode which is the
Ag/AgCl in this study. It is placed in the electrodeposition
solution perpendicularly.
The pH of the solution was adjusted between 9 and 10 by
the addition of sodium hydroxide pellets. Two different elec-
trodeposition solutions were prepared for smaller area steel
plate and larger area stainless steel plate. In the first solution,
a total of 9.58 g of CuSO4$5H2O was dissolved in 21.4 mL of
lactic acid to form the copper lactate complex. In the second
solution for the larger area stainless steel plate, a total of
151.9 g of CuSO4$5H2O was dissolved in 340 mL of lactic acid to
form the copper lactate complex. For both solutions, NaOH
Fig. 2 e Stainless steel plate before (A) and after (B) the electrodeposition process.
6493
pellets were added in small portions to the copper solution to
keep the pH between 9 and 10. The amount of added NaOH
was about 150 g for the second solution. The exact pH of the
second solution was 9.97 measured by the pH meter.
The solution temperature was kept constant during depo-
sition by temperature controller. Deposition temperatures are
set to 25  C or 55  C. The exact solution temperature was
55.5  C for the stainless steel plate electrodeposition.
Copper oxide was deposited onto either larger area stain-
less steel (see Fig. 2) or smaller area steel substrates, which
were placed in the solutions graphite counter electrode with
platinum winding and Ag/AgCl reference electrode. All volt-
ages in this study are reported versus the Ag/AgCl reference
electrode. Electrochemical deposition was controlled by
Gamry Reference 3000 Potentiostat with a 30 K booster
potentiostat. Electrodeposition of Cu2O was carried out in a
three-electrode setup consisting of graphite counter electrode
with platinum winding, Ag/AgCl reference electrode, and
metal substrate as a working electrode. A series of pre-
samples consisting of metal washers were deposited at 10,
20 and 30 min before actual plate deposition. The photo-
responses were tested under solar simulator light (OAI Trisol
TSS-208 Class AAA) in an electrolyte. After the pre-tests to find
the optimal temperature, pH and duration, smaller area steel
plate was deposited in 20 min. Larger area stainless steel plate
required 4 runs of 20 min in order to have full coating as
shown in Fig. 2. In addition to time, two other significant
experimental conditions were the pH and the temperature of
the electrodeposition solution. The applied voltage for the
electrodeposition process was
0.3 V vs. Ag/AgCl and
0.4 V
vs. Ag/AgCl for larger area stainless steel plate and smaller
area steel plate, respectively.
Note that the literature studies have not yet focused on the
characterization of copper oxide electrodeposition under
concentrated light which can drastically affect the copper
oxide performance. In this regard, we establish an experi-
mental setup to concentrate the light and investigate the
impacts. Concentrated light measurements were also con-
ducted using a Fresnel lens. Fresnel lenses consist of a series
of concentric grooves imprinted into plastic. A Fresnel lens
can be combined into a projection lens structure to diminish
6494 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 4 9 0 e6 5 0 1

(S)

Fig. 3 e Comparison of Cu2O deposited photocathode steel plate and nickel rod counter electrode under solar simulator light
and no-light conditions in NaHCO3 electrolyte solution at 5 V.

the number of apparatuses, cost, dimension, and mass cost. In
order to evaluate the irradiation at the time of photocurrent
measurements, a pyranometer (Vernier PYR-BTA) was placed
on the focal area before and after the test.
Results and discussion
Photoelectrochemical (PEC) hydrogen production setups were
constructed using Cu2O coated metals as photo cathodes,
graphite rod and an Ag/AgCl reference electrode as counter
and reference electrodes, respectively. The area of the various
type metals used in the present study was between 5 cm2 to
820 cm2. The results presented here are for the stainless steel
plate which has an area of 820 cm2 in total and smaller area
steel plate which has an area of 20 cm2. The photocurrent
characteristics of the built PEC system were studied under
solar simulator light and actual concentrated sun light in
comparison with dark measurements using Gamry Reference
3000 Potentiostat with a 30 K booster potentiostat. The Cu2O

Fig. 4 e Comparison of Cu2O deposited photocathode steel plate and copper rod counter electrode under solar simulator
light and no-light conditions in NaHCO3 electrolyte solution at 5 V.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 4 9 0 e6 5 0 1 6495

Fig. 5 e Comparison of Cu2O deposited photocathode steel plate and graphite rod counter electrode under solar simulator
light and no-light conditions in an electrolyte of 0.05 M NaOH solution at 5 V.

coated plates are tested for photoelectrochemical character-

i E0rev
Vbias
ization in solutions of NaHCO3 and NaOH with a graphite rod hPEC (1)
Io
or stainless steel as the counter electrodes. In order to
compare the results with different counter electrodes, various where i is photocurrent density (mA/cm2) at a certain applied
types of metals were used namely; nickel, copper and graphite. voltage, E0rev is the standard water splitting reaction potential
The conversion efficiencies of PEC cells can be calculated by given reference to NHE at pH 0, Io is the light intensity (mW/
solar conversion efficiency which is the ratio of the power used cm2), and Vbias is the applied external potential given reference
for water splitting to the input light power [for example, 16,30]: to RHE.

Fig. 6 e Linear sweep voltammetry results of Cu2O deposited at 0.4 V and 25  C (vs. Ag/AgCl reference electrode) 20 min on
steel electrode in an electrolyte of 0.05 M NaOH solution under solar simulator light (1000 W/m2) and no-light conditions.
6496 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 4 9 0 e6 5 0 1

In order to convert Ag/AgCl reference electrode to the
reversible hydrogen electrode (RHE) [31], the applied external
potential and the effect of pH of electrolyte can be converted
into the potential vs. RHE as follows:
ERHE EAgCl E0AgCl 0:059 pH
Here, E0AgCl is 0.197 at 25  C and the pH of the electrolyte is 9.
In Fig. 3, initial metal plate was tested under 1000 W/m2
irradiance in the solar simulator. An electrolyte solution of
NaHCO3 was prepared. The working electrode is Cu2O elec-
trodeposited plate and counter electrode is a nickel rod. The
solar simulator light was shut off to obtain the no-light con-
ditions and the tests were repeated in sequence to avoid any
external effect. The total accumulated charge and average
current within 3 min were
57.71 C and
322.2 mA,
58.86 C
and
328.7 mA, for no-light and light conditions, respectively.
Copper has higher conductivity leading higher currents as
seen in Fig. 4. Here, the counter electrode was switched to
copper rod. The total accumulated charge and average current
within 2 min were
52.95 C and
444.7 mA,
54.41 C and

457 mA, for no-light and light conditions, respectively. The
difference in current between light and no-light conditions is
attributed to photocurrent which was about 0.61 mA/cm2 for
the active area of 20 cm2 steel plate.
Fig. 5 presents the current characteristics of coated metal
plate where graphite rod is used as counter electrode. In this
(2) case, the total current decreases because of lower conductivity
of graphite rod compared to nickel and copper electrodes. The
total accumulated charge and average current within 5 min
were
28.52 C and
95.36 mA,
39.52 C and
132.1 mA, for no-
light and light conditions, respectively. The photocurrent in
this case was calculated to be about 1.1 mA/cm2 for the active
area of 20 cm2 steel plate.
Fig. 6 illustrates the linear sweep voltammetry of coated
steel electrode between applied potential of 0e5 V. The figure
reveals the currentepotential responses of the Cu2O coated
metal plate to a linear potentiodynamic scan with a rate of
100 mV/s. The graphite rod is used as the counter electrode in
a 0.05 M NaOH electrolyte. Essentially, the current was
improved by the effective transference of the majority holes
from Cu2O towards the external circuit to combine with the
majority electrons. The test was conducted under solar

Fig. 7 e (a) Cyclic voltammetry results of Cu2O deposited at 0.4 V and 25  C (vs. Ag/AgCl reference electrode) 20 min on steel
electrode under solar simulator light (1000 W/m2) and no-light conditions, (b) Current density-potential (JeV) characteristics
of Cu2O deposited stainless steel photocathode under solar simulator light illumination at 1000 W/m2.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 4 9 0 e6 5 0 1 6497

Fig. 8 e Linear sweep voltammetry results of Cu2O deposited at 0.30 V and 55  C (vs. Ag/AgCl reference electrode) on a
stainless steel plate electrode under solar simulator chopped light of 1000 W/m2.

simulator light with an irradiation of 1000 W/m2. The plate
was electrodeposited at
0.4 V and 25  C during 20 min.
Fig. 7a presents the cyclic voltammetry curves obtained in
0.05 M NaOH aqueous solution using the Gamry potentiostat
device whereas counter electrode was graphite rod. For com-
parison purposes, the cyclic voltammetry curves obtained in
the presence and absence of light were also shown in the
figure where the scan rate was 100 mV/s. The curves are
similar in the positive region however, in the presence of light
at the negative applied voltage, there is important difference
in the current values. These results indicate the additional
photocurrent and the Cu2O coated electrode shows enhanced
electro-catalytic current response.
After the smaller area steel plate, a larger area (820 cm2)
stainless steel plate was coated with Cu2O which is one of the
main contributions in this study. The tests were conducted
both under solar simulator light and concentrated light con-
ditions. The concentrated light conditions may affect the
performance and durability of the coated plate which was not
reported in the open literature. Hence, the current experi-
mental tests are comparatively performed. Initially, the
coated stainless steel plate was tested under solar simulator

Fig. 9 e Linear sweep voltammetry results (2 mV/s scan rate) of Cu2O deposited at 0.30 V (vs. Ag/AgCl reference electrode)
and 55  C on a stainless steel cathode electrode under chopped concentrated light (1420 W/m2).
6498 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 4 9 0 e6 5 0 1

Fig. 10 e Linear sweep voltammetry results (1 mV/s scan rate) of Cu2O deposited at 0.30 V (vs. Ag/AgCl reference electrode)
and 55  C on a stainless steel cathode electrode under chopped concentrated light (1335 W/m2).

light with an irradiance of 1000 W/m2 in the solution of NaOH.
Most of the relevant studies in the open literature regarding
copper oxide coating and photoelectrochemical hydrogen
production use dark and light characterizations [19,21,32,33].
In addition, the voltage range is between
0.7 V and 0 V in the
literature [19,21,32,33]. As being consistent with the literature,
the characterization of the electrodeposited stainless steel is
presented in Fig. 7b for the applied potentials between
0.6 V
and 0 V. Furthermore, light and dark measurements are car-
ried out by chopping the light under solar simulator light and
actual concentrated light conditions.
Fig. 8 illustrates the linear sweep voltagram of the coated
stainless steel plate under chopped light. The scan rate was
0.1 mV/s and the electrolyte was 0.05 M NaOH solution. The
illuminated area was about 255 cm2 and the maximum ob-
tained photocurrent was about 0.012 mA/cm2.
For the Cu2O coated stainless steel electrode at 55  C at the
applied voltage of
0.3 V vs. Ag/AgCl in NaHCO3 solution, the
maximum photocurrent was found to be 0.19 mA/cm2 as
shown in Fig. 9. The measured average ambient irradiance
was 452 W/m2 and concentrated irradiance was 1420 W/m2.
The illuminated active area was about 172.5 cm2. The

Fig. 11 e Linear sweep voltammetry results (1 mV/s scan rate) of Cu2O deposited at 0.30 V (vs. Ag/AgCl reference electrode)
and 55  C on a stainless steel cathode electrode under chopped concentrated light (1320 W/m2).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 4 9 0 e6 5 0 1 6499

measurements were based on the average of the several 737 cm2 whereas the full surface was not inside the
experimental results with high reproducibility. The counter electrolyte.
electrode for larger area stainless steel plate experiments was Fig. 10 shows the currentepotential responses of the
non-coated stainless steel plate with one side surface area of coated stainless steel plate to a linear potentiodynamic scan

Fig. 12 e (a) Current density and (b) hydrogen production rate comparison of Cu2O deposited stainless steel photocathode
plate under concentrated light and no-light conditions in NaHCO3 electrolyte solution at 5 V, (c) change of hydrogen
evolution rate with rising current density under concentrated light conditions.
6500 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 4 9 0 e6 5 0 1

at 1 mV/s under chopped concentrated light illumination. The concentrated light measurements. Higher production rates
measured average ambient irradiance was 425 W/m2 and can be obtained using various electrolytes and counter
concentrated light was about 1335 W/m2. In the course of the electrodes.
cathodic scan the cathodic photocurrent showed a continuous
increase with the negative potential bias, indicating a p-type
signal of the coated metal which implies that there is a suffi- Conclusions
cient over potential for the reduction of water on illuminated
Cu2O. The active area which was illuminated was about This study presents the impacts of various electrodeposition
172.5 cm2. This shows that maximum photocurrent density conditions on the photocurrent density and photo-
was about 0.53 mA/cm2. electrochemical hydrogen production for Cu2O coated steel
Fig. 11 shows the currentevoltage diagram of the Cu2O plates. On the source of the cathodic photocurrent observed
coated stainless steel plate to a linear potentiodynamic scan and the equivalent hydrogen generation, the results in this
with a rate of 1 mV/s. In order to observe the photo response, a study prove that the photo-induced charges in the conduction
lower scanning rate was used. The test was conducted in band of p-type Cu2O are capable of reducing water to
concentrated light where the ambient irradiance was 420 W/ hydrogen. The magnitude of the photocurrent produced or
m2 and concentrated light was 1320 W/m2. The approximate hydrogen generated was a consequence of the electrodepo-
illuminated area was about 172.5 cm2 and the maximum sition temperature, duration, pH and surface area which
photocurrent density was measured as 0.31 mA/cm2. The impacted the overall performance. The substrates are steel
variations in the current density values are attributed to and stainless steel having different substrate areas. The
changing conditions of concentrated light since copper oxide electrodeposited plates present high photo-response under
is sensitive to changes in solar intensity and the experimental both solar simulator and concentrated light conditions. Using
setup is manually adjusted for the azimuth and zenith angles Fresnel lenses, the photocurrent generations and hydrogen
to face the sun. evolution are tested under concentrated light yielding higher
Fig. 12a shows the total current as a function of time for the photocurrent densities. The obtained photocurrent density at
coated stainless steel plate under no-light and concentrated
0.6 V is found to be 0.8 mA/cm2 corresponding to solar
light conditions. The ambient irradiance was 605 W/m2 and conversion efficiency of 0.86%.
the concentrated irradiance was measured as 1900 W/m2.
There are oscillations in the concentrated light measurements
because of the changing sun light conditions and sensitivity of
Cu2O. The average current was 313.5 mA and 689.8 mA for the Acknowledgement
no-light and concentrated light conditions, respectively. In
addition, the total accumulated charge was 18.44 C and 40.71 C The authors acknowledge the support by the Natural Sciences
for no-light and concentrated light conditions, respectively. and Engineering Research Council of Canada. The authors also
The illuminated area was about 250 cm2 of the Cu2O coated thank Janette Hogerwaard for assisting in measuring some
metal plate. Hence, this indicates an average photocurrent experimental data.
density of about 1.5 mA/cm2 as shown in Fig. 12a. The
generated photocurrent was maximum in this experiment Nomenclature
with the impact of higher concentrated irradiation. This
shows that concentrated light conditions may increase the C Coulomb (C)
overall performance of the photoelectrochemical hydrogen Erev Water splitting reaction potential (V)
production. Io Irradiance (W/m2)
At the applied voltage of
0.6 V vs. Ag/AgCl in NaHCO3 I Current (A)
electrolyte which yielded the maximum photocurrent of I Current density (mA/cm2)
0.8 mA/cm2 whereas the solar conversion efficiency is calcu- V Voltage (V)
lated to be 0.86% based on the above given equations. Simi-
Greek letters
larly, at the applied voltage of
0.4 V vs. Ag/AgCl in NaHCO3
h Efficiency
electrolyte, the conversion efficiency is calculated to be 0.24%
having about 0.27 mA/cm2. Acronyms
The related open literature has been reviewed in detail for MSE Mercury sulfate electrodes
a comparison purpose and the obtained results are tabulated PEC Photoelectrochemical
in Table 1. The obtained photocurrent densities and efficiency PV Photovoltaic
values are quite similar to the literature results. The evolution RHE Reversible hydrogen electrode
rates of hydrogen are determined for the concentrated light SCE Saturated calomel electrode
and no-light conditions as seen in Fig. 12b. The produced
hydrogen is at ambient pressure and temperature hence cor-
responding to about 160 mL/h hydrogen production rate under references
concentrated illumination. However, in dark measurements,
hydrogen production rate decreases to about 65 mL/h as a
consequence of lower current. The impact of changing current [1] Xue J, Shen Q, Liang W, Liu X, Bian L, Xu B. Preparation and
density on hydrogen evolution rate is shown in Fig. 12c for the formation mechanism of smooth and uniform Cu2O thin
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 4 9 0 e6 5 0 1
films by electrodeposition method. Surf Coatings Technol
2013;216:166e71.
[2] Altokka B, Yldrm AK. Effects of External Alternating
Magnetic Field on ZnO Films Obtained by Electrodeposition.
Arab J Sci Eng 2016;41(6):2345e51.
[3] Yang Y, Han J, Ning X, Su J, Shi J, Cao W, et al.
Photoelectrochemical stability improvement of cuprous
oxide (Cu2O) thin films in aqueous solution. Int J Energy Res
2016;40(1):112e23.
[4] Yilanci A, Ozturk HK, Dincer I, Ulu EY, Cetin E, Ekren O.
Exergy analysis and environmental impact assessment of a
photovoltaic-hydrogen production system. Int J Exergy
2011;8(2):227e46.
[5] Belhadi A, Nadjem I, Zaidat S, Boudjemaa A, Trari M.
Hydrogen evolution under visible light over the
heterojunction p-CuO/n-ZnO prepared by impregnation
method. Int J Energy Res 2015;39(14):1909e16.
[6] Nian J-N, Hu C-C, Teng H. Electrodeposited p-type Cu2O for
H2 evolution from photoelectrolysis of water under visible
light illumination. Int J Hydrogen Energy
2008;33(12):2897e903.
[7] Zhao W, Fu W, Yang H, Tian C, Li M, Li Y, et al.
Electrodeposition of Cu2O films and their
photoelectrochemical properties. CrystEngComm
2011;13(8):2871e7.
[8] Amano F, Ebina T, Ohtani B. Enhancement of photocathodic
stability of p-type copper(I) oxide electrodes by surface
etching treatment. Thin Solid Films 2014;550:340e6.
[9] Vequizo JJM, Zhang C, Ichimura M. Fabrication of Cu2O/FeeO
heterojunction solar cells by electrodeposition. Thin Solid
Films 2015;597:83e7.
[10] Cao D, Nasori N, Wang Z, Wen L, Xu R, Mi Y, et al. Facile
surface treatment on Cu2O photocathodes for enhancing the
photoelectrochemical response. Appl Catal B Environ
2016;198:398e403.
[11] Zhao M, Jiang Y, Lv J, Sun Y, Cao L, He G, et al.
Microstructure, morphology and sunlight response of
cuprous oxide thin films. J Mater Sci Mater Electron
2016;27(2):1799e804.
[12] de Jongh PE, Vanmaekelbergh D, Kelly JJ. Cu2O:
electrodeposition and characterization. Chem Mater
1999;11(12):3512e7.
[13] Georgieva V, Ristov M. Electrodeposited cuprous oxide on
indium tin oxide for solar applications. Sol Energy Mater Sol
Cells 2002;73(1):67e73.
[14] Jeong SS, Mittiga A, Salza E, Masci A, Passerini S.
Electrodeposited ZnO/Cu2O heterojunction solar cells.
Electrochimica Acta 2008;53(5):2226e31.
[15] Bao M, Wang D, Liu S, Kuang L, Sun J, Wang F, et al.
Electrodeposition and electrocatalytic activity of Cu2O film
on stainless steel substrate. Appl Surf Sci
2012;258(20):8008e14.
[16] Chiang C-Y, Shin Y, Aroh K, Ehrman S. Copper oxide
photocathodes prepared by a solution based process. Int J
Hydrogen Energy 2012;37(10):8232e9.
[17] Haller S, Jung J, Rousset J, Lincot D. Effect of electrodeposition
parameters and addition of chloride ions on the structural
and optoelectronic properties of Cu2O. Electrochimica Acta
2012;82:402e7.
[18] Casallas C, Dincer I, Zamfirescu C. Experimental
investigation and analysis of a novel photo-electrochemical
6501
hydrogen production cell with polymeric membrane
photocathode. Int J Hydrogen Energy 2016;41(19):7968e75.
[19] 
Juodkazyte_ J, Sebeka B, Savickaja I, Jagminas A,
Jasulaitiene_ V, Selskis A, et al. Study on copper oxide stability
in photoelectrochemical cell composed of nanostructured
TiO2 and CuxO electrodes. Electrochimica Acta
2014;137:363e71.
[20] Tran PD, Batabyal SK, Pramana SS, Barber J, Wong LH,
Loo SCJ. A cuprous oxide-reduced graphene oxide (Cu2O-
rGO) composite photocatalyst for hydrogen generation:
employing rGO as an electron acceptor to enhance the
photocatalytic activity and stability of Cu2O. Nanoscale
2012;4(13):3875e8.
[21] Zyoud A, AlKerm RS, Alkerm RS, Abdelhadi DH, Park D,
Helal MHS, et al. Enhanced PEC characteristics of pre-
annealed CuS film electrodes by metalloporphyrin/polymer
matrices. Sol Energy Mater Sol Cells 2016;144:429e37.
[22] Zyoud A, Saadeddin I, Khurduj S, Mm Marie, Hawash ZM,
Faroun MI, et al. Combined electrochemical/chemical bath
depositions to prepare CdS film electrodes with enhanced
PEC characteristics. J Electroanal Chem 2013;707:117e21.
[23] Mao Y, He J, Sun X, Li W, Lu X, Gan J, et al. Electrochemical
synthesis of hierarchical Cu2O stars with enhanced
photoelectrochemical properties. Electrochimica Acta
2012;62:1e7.
[24] Kelly NA, Gibson TL. Solar energy concentrating reactors for
hydrogen production by photoelectrochemical water
splitting. Int J Hydrogen Energy 2008;33(22):6420e31.
[25] Wu Y, Eames P, Mallick T, Sabry M. Experimental
characterisation of a Fresnel lens photovoltaic concentrating
system. Sol Energy 2012;86(1):430e40.
[26] Mitra S, Poizot P, Finke A, Tarascon JM. Growth and
electrochemical characterization versus lithium of Fe3O4
electrodes made by electrodeposition. Adv Funct Mater
2006;16(17):2281e7.
[27] Dubal DP, Dhawale DS, Salunkhe RR, Jamdade VS,
Lokhande CD. Fabrication of copper oxide multilayer
nanosheets for supercapacitor application. J Alloys Compd
2010;492(1e2):26e30.
[28] Daltin A-L, Addad A, Chopart J-P. Potentiostatic deposition
and characterization of cuprous oxide films and nanowires. J
Cryst Growth 2005;282(3e4):414e20.
[29] Zhou YC, Switzer JA. Galvanostatic electrodeposition and
microstructure of copper (I) oxide film. Material Res
Innovations 1998;2(1):22e7.
[30] Bak T, Nowotny J, Rekas M, Sorrell CC. Photo-electrochemical
hydrogen generation from water using solar energy.
Materials-related aspects. Int J Hydrogen Energy
2002;27(10):991e1022.
[31] Kay A, Cesar I, Gra tzel M. New benchmark for water
photooxidation by nanostructured a-Fe2O3 films. J Am Chem
Soc 2006;128(49):15714e21.
[32] Gannouni M, Ben Assaker I, Chtourou R.
Photoelectrochemical cell based on n-CuIn5S8 film as
photoanodes for photocatalytic water splitting. Int J
Hydrogen Energy 2015;40(23):7252e9.
[33] 
Juodkazyte_ J, Sebeka B, Savickaja I, Selskis A, Jasulaitiene_ V,
Kalinauskas P. Evaluation of electrochemically active surface
area of photosensitive copper oxide nanostructures with
extremely high surface roughness. Electrochimica Acta
2013;98:109e15.