Journal of Photochemistry and Photobiology A: Chemistry 356 (2018) 263–271

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Journal of Photochemistry and Photobiology A:

Chemistry
journal homepage: www.elsevier.com/locate/jphotochem

Solar-driven H2 evolution over CuNb2O6: Effect of two polymorphs

(monoclinic and orthorhombic) on optical property and photocatalytic
activity
Sunao Kamimuraa,b,c,* , Shungo Abea , Toshiki Tsubotaa , Teruhisa Ohnoa,c,d,*
a
Department of Applied Chemistry, Faculty of Engineering, Kyushu Institute of Technology, 1-1 Sensuicho, Tobata, Kitakyushu, 804-8550, Japan
b
PRESTO, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi-shi, Saitama, 322-0012, Japan
c
Research Center for Solar Light Energy Conversion, 1-1 Sensuicho, Tobata, Kitakyushu, 804-8550, Japan
d
ACT-C, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi-shi, Saitama, 322-0012, Japan

A R T I C L E I N F O A B S T R A C T

Article history:
Received 29 November 2017 We synthesized two different polymorphs (monoclinic and orthorhombic phases) of CuNb2O6 as a d0–d9
Received in revised form 26 December 2017 photocatalyst by a solid-state reaction route and performed photocatalytic H2 evolution from water
Accepted 27 December 2017 under AM 1.5G solar light irradiation. The monoclinic phase (P21/c) was transformed to the orthorhombic
Available online 5 January 2018 phase (Pcna) at ambient temperature (>700
C), and XRD data revealed that the direct environment of
octahedral sites was occupied by Cu2+ cations. The difference in the local crystal structure of the CuO6
Keywords: octahedral in the two polymorphs of CuNb2O6 was closely related to the optical absorption property. For
Photocatalyst monoclinic CuNb2O6, the optical band gap transition was a metal-to-metal charge transfer between Cu2+
Photocathode
and Nb5+, and d-d absorption of Cu2+ was a forbidden transition by the Laporte selection rule due to its
Water splitting
symmetric CuO6 octahedral. For orthorhombic CuNb2O6, d-d absorption of Cu2+ was partially allowed
Copper niobate
CuNb2O6 because of its distorted CuO6 octahedral. We experimentally revealed that d-d absorption of Cu2+
contributed a significant effect on the photocatalytic activity of both polymorphs of CuNb2O6; the
photocatalytic activity of the monoclinic phase was insensitive to d-d transition in Cu2+ ions, while the
photocatalytic activity of the orthorhombic phase was strongly influenced by d-d transition in Cu2+ ions
because an electron configuration as d9 readily induces structural distortion by Jahn-Teller effects in an
octahedral crystal field. The distortion was avoided by trapping photo-generated electrons, leading to a
decrease in photocatalytic activity. We discuss the photocatalytic activities of both polymorphs of
CuNb2O6 in conjunction with structural, optical and electrochemical properties. We also show that a
deposition of platinum nanoparticles on CuNb2O6 further improved the photocatalytic activity.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction large-scale manufacturing system for solar-driven H2 production

Hydrogen (H2) production from water is now an important
research subject from the viewpoints of usage of renewable energy
and next-generation energy carrier. Photocatalytic water splitting
and photoelectrochemical (PEC) water splitting utilizing semicon-
ductor materials have attracted considerable attention as a
potential means of converting solar energy into chemical energy
in the form of usable H2 from water [1–5]. Powdered photocatalytic
water splitting is a low-cost and a simple reaction system, [6] and a
* Corresponding author at: Department of Applied Chemistry, Faculty of
Engineering, Kyushu Institute of Technology, 1-1 Sensuicho, Tobata, Kitakyushu,
804–8550, Japan.
E-mail addresses: kamimura-sunao@che.kyutech.ac.jp (S. Kamimura),
tohno@che.kyutech.ac.jp (T. Ohno).
from water would thus be possible. Recent research in this field has
resulted in the development and fabrication of semiconductor
photocatalysts (also photoelectrodes) capable of absorbing visible
light, because almost 50% of the solar energy incident on the
earth's surface falls within the visible-light energy range [7–10].
Copper niobates with the chemical formula CuxNbyOz have
been widely studied as visible light-responsive photocatalysts and
photoelectrodes for water splitting [11–20]. Recent works on
copper niobates can be classified into two categories depending on
whether the oxidation state of copper is a monovalent (Cu+) or
divalent (Cu2+) state. Examples of the former are CuNbO3 and
CuNb3O8 that are composed of Cu+ with completely filled d-
orbitals (d10) and Nb5+ with empty d-orbitals (d0) [12,13]. These
compounds show a visible light bandgap originating from copper-
to-niobium charge transfer. Joshi and Maggard demonstrated PEC

https://doi.org/10.1016/j.jphotochem.2017.12.039
1010-6030/© 2018 Elsevier B.V. All rights reserved.
264 S. Kamimura et al. / Journal of Photochemistry and Photobiology A: Chemistry 356 (2018) 263–271
H2 evolution by using CuNbO3 and CuNb3O8 photocathodes with
an external applied bias under visible light irradiation [12,13].
Thus, H2 evolution activity of copper niobates with a Cu+ (d10)
electronic configuration has been extensively studied, and a d0–d10
photocatalyst is considered to be potentially effective for water
splitting.
On the other hand, copper niobates composed of Cu2+ with
partly filled d-orbitals (d9) have also attracted much attention due
to their photocatalytic activity under visible light irradiation. For
example, Zhang et al. reported photocatalytic decomposition of a
methyl orange dye in the presence of CuNb2O6 powder under
visible light irradiation [10]. Papa et al. studied the PEC properties
of a CuNb2O6 electrode, and they first described its photocathodic
property [17]. Moreover, Korma’nyos et al. performed PEC CO2
reduction by using a CuNb2O6 electrode in an aqueous electrolyte
under AM 1.5G irradiation [20]. However, H2 evolution over a
CuNb2O6 electrode was not observed in previous works because
the CuNb2O6 electrode suffered from degradation ascribed to the
self-reduction of Cu2+ to Cu+ in the electrode [17,20]. According to
theoretical band calculation, the conduction band minimum (CBM)
of CuNb2O6 is located at 1.73 V vs. Ag/AgCl (pH 7) [20]. Thus, the
CBM potential of CuNb2O6 lies more negative than the H+/H2
potential, being thermodynamically favorable for hydrogen
evolution.
We are interested in exploring the potential of powdered state
CuNb2O6 as a d0–d9 photocatalyst for H2 evolution from water. For
this compound, two polymorphs, monoclinic and orthorhombic
phases, have been reported [21]. However, each polymorph has
been studied independently for photocatalytic activity, and it is
therefore not clear whether a monoclinic phase is better than an
orthorhombic phase. In the present study, we synthesized two
polymorphs of CuNb2O6 by a solid-state route and performed
photocatalytic H2 evolution from water under AM 1.5 G solar light.
The photocatalytic activity of CuNb2O6 was strongly dependent on
the type of polymorph; the rate of photocatalytic H2 evolution over
monoclinic CuNb2O6 was greater than that over orthorhombic
CuNb2O6. Furthermore, we experimentally revealed that d-d
transition in Cu2+ ions contributed to a significant effect of
photocatalytic water splitting. We discuss the photocatalytic
activity of CuNb2O6 as a d0–d9 photocatalyst in conjunction with
structural, optical and electrochemical properties. Finally, we show
that deposition of platinum (Pt) nanoparticles on CuNb2O6
improved the photocatalytic activity.
2. Experimental
2.1. Synthesis of CuNb2O6 powder
CuNb2O6 powder was synthesized by a solid-state reaction
method. First, Nb2O5 (purchased from Kojundo Chemical, >99.9%)
and CuO (Wako, 99.0%) were weighed stoichiometrically and
mixed together thoroughly in the presence of a small amount of
ethanol. The mixture was put into a platinum crucible and calcined
at 600  1000
C for 24 h in air. Then CuNb2O6 powder was
obtained. It should be noted that the crystal phase of Nb2O5 used as
a starting reagent was monoclinic phase (H-Nb2O5). Incomplete
reaction occurs if commercially available Nb2O5 (mainly T-Nb2O5)
is used as a starting material and it is absolutely essential that this
first be converted into H-Nb2O5 by high-temperature treatment
( >1100
C).
2.2. Deposition of platinum over CuNb2O6 powder
Pt was loaded on CuNb2O6 by a photo-reduction method. First,
0.25 g CuNb2O6 powder was dispersed in distilled water (30 mL)
containing methanol (0.3 mL). Then 10 mM hydrogen
hexachloroplatinate (IV) hexahydrate (Wako, 98.5%) was added
to the mixed solution after N2 bubbling for 30 min, and the mixed
solution was irradiated with UV light. Then Pt-deposited CuNb2O6
powder (denoted as Pt-CuNb2O6 hereafter) was obtained.
2.3. Fabrication of a CuNb2O6 electrode
To estimate the flat band potential, we fabricated a CuNb2O6
electrode by an electrophoretic deposition method on a fluorine-
doped tin oxide (FTO) substrate (Asahi Glass Co.). Electrophoretic
deposition was carried out in acetone containing CuNb2O6 powder
(80 mg) and iodine (30 mg), which was dispersed by sonication for
30 min. Two FTO electrodes (15 mm  30 mm) were immersed
parallel in the solution with a distance between them of 10 mm,
and 6 V of bias was then applied between the electrodes for 3 min.
The electrodes were then annealed at 400
C for 1 h in air.
2.4. Characterization
The crystalline phases were characterized by using a powder
Xray diffraction (XRD) instrument (MiniFlex II, Rigaku Co.) with
CuKa (l = 1.5418 Å) radiation (cathode voltage: 30 kV, current:
15 mA). The absorbance of CuNb2O6 (powder state) was measured
by the diffuse reflection method with a UV–vis spectrometer (UV-
2600, SHIMAZU. Co.) attached to an integral sphere at room
temperature. Mott-schottky analysis was carried out by using an
electrochemical analyzer (604D, ALS Co.) with a CuNb2O6
electrode, platinum wire, Ag/AgCl electrode and 0.1 M NaHCO3
solution (pH = 8.2) used as a working electrode, counter electrode,
reference electrode and electrolyte, respectively. Xray photo-
electron spectroscopy (XPS) measurements were performed by
using a Kratos AXIS Nova spectrometer (Shimazu Co.) with a
monochromatic Al Ka Xray source. The binding energy was
calibrated by taking the carbon (C) 1 s peak of contaminant carbon
as a reference at 284.6 eV.
2.5. Analysis of products
Photocatalytic H2 evolution was performed in a gas-closed cell.
Briefly, CuNb2O6 powder (10 mg) and 10 vol% CH3OH as a sacrificial
agent were added to distilled water (10 mL, pH 7) while being
suspended using a magnetic stirrer. Nitrogen gas was bubbled into
the system for deaeration. AM 1.5G solar light was used as a light
source. To prevent a temperature rise of water during photo-
irradiation, a reaction tube is always exposed by a cooling air from
the electric fun. Evolved H2 gas was detected by an online gas
chromatograph (GC) with a thermal conductivity detector (Agilent
Technology Co. MicroGC) equipped with an MS5A column. The
column temperature and column pressure were fixed at 100
C and
170 kPa, respectively. He gas was used as the carrier gas. Action
spectrum at each wavelength was calculated from the rate of H2
evolution, which was measured by using a Xe lamp equipped with
a band-pass filter centered at 400 nm, 450 nm, 470 nm, 500 nm,
550 nm and 600 nm (All band-pass filters were purchased from
Asahi Spectra Co., Ltd., and full width at half maximum was 10 nm).
3. Results and discussion
3.1. Structural and optical properties of CuNb2O6
Fig. 1a and b show XRD patterns of CuNb2O6 at various
calcination temperatures. The diffraction peaks of the sample
calcined at 650
C coincided with those of the monoclinic phase of
CuNb2O6 (JCPDS 01-083-0369), indicating that a pure monoclinic
phase could be synthesized. On the other hand, orthorhombic
phase appeared with an increase of calcination temperature; a
 S. Kamimura et al. / Journal of Photochemistry and Photobiology A: Chemistry 356 (2018) 263–271
Fig. 1. (a) Calcination temperature dependence of XRD patterns for CuNb2O6 polycrystals. (b) Enlarged figure of Fig. 1a ranging between 27 and 33
. (c) Crystal structures of
monoclinic and orthorhombic CuNb2O6.
multiphase of monoclinic/orthorhombic CuNb2O6 was obtained at
temperatures ranging between 750 and 850
C. At calcication
temperatures over 900
C, a pure orthorhombic phase of CuNb2O6
could be synthesized. Thus, the monoclinic phase was easily
converted to orthorhombic phase by increasing the calcination
temperature, and both phases were stable at room temperature.
The reverse phase transition (i.e., orthorhombic to monoclinic)
could not be achieved by annealing the orthorhombic phase. Fig. 1c
shows the crystal structures of monoclinic CuNb2O6 and ortho-
rhombic CuNb2O6. The unit cell for monoclinic CuNb2O6
(a = 4.9991, b = 14.1566, c = 5.7540 Å, b = 91.718, space group P21/
c) was reduced along the a axis and expanded along the b and c
axes, compared to that for orthorhombic CuNb2O6 (lattice
parameter a = 5.12375, b = 14.10380, c = 5.60728 Å, space group
Pcna). Such a discrepancy in crystal structure leads to a significant
effect on the optical property and photocatalytic activity, as will be
discussed later.
Fig. 2 shows SEM photographs of CuNb2O6 at various
calcination temperatures. As can be seen in these photographs,
the shape of CuNb2O6 varied depending on the polymorph; the
monoclinic phase (650
C) was a random aggregate of nano-
particles, while the orthorhombic phase (900
C) was corn-like
particles with dimeters of ca. 0.5  1 mm. In addition, particle size
became larger with increase in calcination temperature due to
particle growth at a high temperature.
Fig. 3 shows UV–vis spectra for monoclinic CuNb2O6 (650
C)
and orthorhombic CuNb2O6 (900
C). According to previous
reports, CuNb2O6 is an indirect energy gap material [28,29]. The
optical absorption edge of CuNb2O6 could be estimated from a Tauc
plot ((F(R1)hv) n vs. hv, where n = 0.5 for an indirect bandgap, and
265
the optical band gaps of both samples were estimated to be ca.
2.7 eV, which is consistent with a previous report by Choi et al. [17].
Importantly, in an orthorhombic sample, two broad bands were
observed in the near-infrared (NIR) region, being ascribed to d-d
transitions in Cu2+ ions in a distorted ‘octahedral’ ligand field [21–
24]. As shown in the top half of Fig. 4a and b, the two axial Cu–O
distances for an orthorhombic sample increased simultaneously
along the a axes, compared to that of the monoclinic phase. The
d-orbitals that interact most strongly with the two axial ligands
decrease in energy due to a decrease in electrostatic repulsions
between the electrons in these orbitals and the negative ends of
the ligand dipoles (O 2p orbital); the affected d-orbitals are those
with components  dz2, dxz, and dyz. Thus, an electron configura-
tion of Cu2+ in the orthorhombic phase readily induced structural
distortion by Jahn-Teller effects in an octahedral crystal field,
resulting in the appearance of some d-d absorption bands of Cu2+
ions. Generally, d-d transition bands have weak intensity because
they are a forbidden transition by the Laporte selection rule [25].
This is why monoclinic CuNb2O6 showed a weak d-d transition in
the NIR region, as can be seen in Fig. 4c. However, forbidden
transitions are allowed if the center of symmetry is disrupted for
various reasons, such as the Jahn-Teller effect and asymmetric
vibrations. Through such Jahn-Teller effects of orthorhombic
CuNb2O6, d-d transition, which would theoretically be forbidden,
is considered to be allowed.
3.2. Electrochemical analysis of CuNb2O6 electrode
For clarifying the flat band potential (Vfb) of CuNb2O6, Mott–
Schottky analysis was carried out by using an alternating current
266 S. Kamimura et al. / Journal of Photochemistry and Photobiology A: Chemistry 356 (2018) 263–271

Fig. 2. Calcination temperature dependence of SEM photographs for CuNb2O6. (a) 650
C, (b) 700
C, (c) 800
C, and (d) 900
C.

Fig. 3. (a) UV–vis spectra for monoclinic and orthorhombic CuNb2O6 samples. (b) Photographs of prepared monoclinic and orthorhombic CuNb2O6 samples.

(AC) electrochemical impedance method at 0.5 kHz, 1 kHz and
2 kHz with AC 5 mV of amplitude in 0.1 M NaHCO3 solution (pH
8.2). Fig. 5a shows Mott–Schottky plots for monoclinic CuNb2O6.
Negative slopes were observed at all AC frequencies, suggesting
that monoclinic CuNb2O6 behaves as p-type semiconductors. In the
case of p-type semiconductors, Vfb is generally located near the
valence band (VB), [26–28] and it can be estimated from the
intersection of a plot of 1/C2 against E by the following equation
[29]:
 
1 2 kT
¼ V  Vf b  ; oxidation. In general, the VBM of metal oxides is mainly composed
C 2 eee0 N e
where C is capacitance, e is the electron charge, e is the dielectric
constant, e0 is permittivity of vacuum, N is an acceptor density, V is
the electrode potential, Vfb is the flat band potential, k is the
Boltzmann constant, and T is temperature. The x-axis intersection
was +0.53 V vs. Ag/AgCl for all frequencies (0.5 kHz, 1 kHz and
2 kHz) and can be used to determine Vfb from the above equation
V = Vfb  kT/e. By correcting the solution pH using the relation
Vcorrect = V  0.059V(pH), the valence band maximum (VBM) of
monoclinic CuNb2O6 was estimated to be +1.19 V vs. NHE (pH 0).
The resulting band energy diagram is plotted in Fig. 5b, which
shows the CBM and VBM to be suitably located with respect to the
relevant redox couples. The CBM potential and VBM potential of
monoclinic CuNb2O6 lie at 1.51 V and +1.19 V vs. NHE (pH 0),
respectively, being suitable for water reduction but not for water
of an O 2p orbital, and it is located around +3 V vs. NHE (pH 0) [30].
The fact that the VBM of CuNb2O6 is more than ca. 1.8 V negative of
the typical metal oxides rules out the possibility of an O 2p orbital
on the VBM in monoclinic CuNb2O6. Taking into consideration the
fact that the VBM potentials of other copper oxides (e.g., Cu2O and
 S. Kamimura et al. / Journal of Photochemistry and Photobiology A: Chemistry 356 (2018) 263–271 267

Fig. 4. Local structures around Cu for (a) monoclinic and (b) orthorhombic CuNb2O6. (c) Crystal field splitting of Cu 3d-orbital for monoclinic (left) and orthorhombic (right)
CuNb2O6.

Fig. 5. (a) Mott–Schottky plots at 0.5 kHz, 1 kHz and 2 kHz measured under dark conditions. (b) Positions of the conduction band and valence band of monoclinic CuNb2O6
together with the redox couples for water reduction/oxidation potential.

CuO) and copper niobates (e.g., CuNb3O8 and Cu2Nb8O21) are
mainly composed of a Cu 3d state, [31,32] it is possible that the
VBM of monoclinic CuNb2O6 also originated from the Cu 3d9 band.
In addition, the CBM potentials of other copper niobates are
composed of an Nb 4d state, [32] and the CBM of monoclinic
CuNb2O6 was thus considered to be composed of an Nb 4d state. On
the basis of above consideration, the energy band gap transition
(ca. 2.7 eV, see Fig. 3) of monoclinic CuNb2O6 is a metal-to-metal
charge transfer between Cu2+ and Nb5+, [13] and d-d transition in
Cu2+ is a forbidden transition due to its symmetric CuO6
octahedral. On the other hand, Mott–Schottky plots could not be
obtained from orthorhombic CuNb2O6. Although there is no clear
evidence, we speculated that a Schottky barrier was not formed at
the interface between orthorhombic CuNb2O6 and the electrolyte.
3.3. Photocatalytic H2 evolution over powdered CuNb2O6
Fig. 6a shows time courses of H2 evolution over monoclinic
CuNb2O6 powder under AM 1.5G solar light irradiation. Although
no H2 evolution was confirmed in pure water solvent, a relatively
268 S. Kamimura et al. / Journal of Photochemistry and Photobiology A: Chemistry 356 (2018) 263–271
Fig. 6. Time courses of H2 over (a) monoclinic and (b) orthorhombic CuNb2O6 samples under AM 1.5G solar light irradiation with and without 10 vol% CH3OH as a sacrificial
agent.
large amount of H2 was produced over monoclinic CuNb2O6 when
CH3OH was used a sacrificial agent. These results indicated that
photo-generated holes in the VB of CuNb2O6 are consumed during
the oxidation of CH3OH, allowing photo-excited electrons in the CB
of CuNb2O6 to reduce H2O and produce H2 effectively. The VBM
potential of CuNb2O6 lies more positive than the CH3OH/HCHO
potential, and our results obtained for the photocatalytic oxidation
of CH3OH are therefore reasonable. Similar results were confirmed
for the orthorhombic sample (see Fig. 6b). Thus, the two
polymorphs of CuNb2O6 have sufficient potential for water
reduction reaction, while their water oxidation ability is limited
due to a relatively negative VBM potential.
Table 1 shows the relationship between the polymorphs and
photocatalytic activity for H2 evolution. The photocatalytic activity
was measured in the presence of CH3OH under AM 1.5G solar light
irradiation. As clearly shown in this table, the rate of H2 evolution
over CuNb2O6 varied depending on the polymorph: the rate of
photocatalytic H2 evolution over the monoclinic sample was
greater than that over the orthorhombic sample. In addition, the
rate of photocatalytic H2 evolution gradually decreased with an
increase in calcination temperature of sample. These differences
were thought to be caused mainly by particle size because the
specific surface area of CuNb2O6 became smaller with an increase
in calcination temperature.
Importantly, d-d transition in Cu2+ ions contributed to a
significant effect on the photocatalytic H2 evolution of CuNb2O6.
To clarify the effect of d-d absorption on photocatalytic activity, we
irradiated two kinds of light having different wavelengths (see
Fig. 7a): AM 1.5G solar light or near-infrared (NIR) cutoff filter-
attached AM 1.5G solar light (it means visible light). The rate of
photocatalytic H2 evolution over monoclinic CuNb2O6 was
decreased to 80% of that under AM 1.5G solar light after mounting
the NIR cutoff filter. This decrease was caused by low transmittance
Table 1
Relationship between the polymorphs of CuNb2O6 and photocatalytic activity for H2 evolution.
Entry Temperature (
C) Crystal phase
1 <600 Unformed
2 650 Monoclinic
3 650 Monoclinic
4 700 Monoclinic + Orthohombic
5 800 Monoclinic + Orthohombic
6 900 Orthohombic
7 900 Orthohombic
a
Irradiated by AM 1.5G solar light.
b
10 vol% CH3OH added to water.
of the NIR cutoff filter in the visible region, suggesting that the
photocatalytic activity of monoclinic CuNb2O6 is insensitive to d-d
transition in Cu2+ ions. In contrast, the rate of photocatalytic H2
evolution over orthorhombic CuNb2O6 was decreased to 10% of
that under AM 1.5G solar light after mounting the NIR cutoff filter.
This behavior cannot be explained by transmittance of the NIR
cutoff filter. For orthorhombic CuNb2O6, it is clear that an electron
configuration as Cu 3d9 readily induces structural distortion by
Jahn-Teller effects in an octahedral crystal field. Such distortion
should be avoided by trapping an electron, similar to d-block
element-doped TiO2 [33]. In other words, the empty 3d orbitals of
Cu2+ ions actually work as deep traps for the electrons produced
under irradiation [34–36] and thus increase the recombination
rate of photo-generated electrons, resulting in a decrease in
photocatalytic activity after mounting the NIR cutoff filter (see
Fig. 7c). On the other hand, under AM 1.5G solar light irradiation,
the photo-generated electrons are filled 3d orbitals of Cu2+ ions via
d-d absorption, a state that inhibited the recombination of photo-
generated electrons in the CBM. Thus, the photocatalytic activity of
orthorhombic CuNb2O6 is strongly dependent on whether the
electrons are fully filled at Cu 3d-orbitals.
It should be noted that two polymorphs of CuNb2O6 powder
were stable under photocatalytic reaction. Fig. 8a–f shows XPS
spectra of monoclinic and orthorhombic samples before and after
24-h photocatalytic reaction. As shown in Fig. 8a and d, major
peaks at 934.2 eV and 954.2 eV were observed in both polymorphs,
and these peaks were attributed to typical values of Cu 2p3/2 and
2p1/2, respectively. Divalent copper Cu2+ compounds generally
exhibit strong satellite peaks with higher binding energy sides
compared with each of the Cu 2p3/2 and 2p1/2 lines [37,38]. As
clearly seen in this figure, strong satellite peaks were observed as
an indication of the presence of Cu2+ 3d9 species in CuNb2O6. There
was almost no difference in the XPS spectra for Cu 2p, Nb 3d and O
BET (m2/g) Light a
Sacrificial agent b
H2 activity (nmol h1)
– – – –
70.5 O O 4.8
70.5 O X N.D.
66.3 O 3.3
51.8 O O 3.7
12.4 O O 2.8
12.4 O X N.D.
 S. Kamimura et al. / Journal of Photochemistry and Photobiology A: Chemistry 356 (2018) 263–271 269

Fig. 7. (a) AM 1.5G solar spectrum together with transmittance spectrum of the NIR cutoff filter. (b) The upper figure shows time courses of H2 evolution over monoclinic
CuNb2O6 under irradiation of AM 1.5G (solid circle) and NIR cutoff filter-attached AM 1.5G (open square). The lower figure shows time courses of H2 evolution over
orthorhombic CuNb2O6. (c) The photocatalytic process over orthorhombic CuNb2O6, where the upper (blue) and lower (green) bands are the conduction band (CB) and
valence band (VB), respectively. The black bar above the CB corresponds to the Cu 3d state. White and black circles indicate excited holes and electrons, respectively. Grey
circles are the electrons in the Cu 3d bands. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 8. XPS spectra of both polymorphs of CuNb2O6 before and after 24 h of photoirradiation (AM 1.5G solar light) in the presence of a CH3OH aqueous environment.
270 S. Kamimura et al. / Journal of Photochemistry and Photobiology A: Chemistry 356 (2018) 263–271

1 s before and after photocatalytic reactions, indicating that no
self-reduction (also oxidation) reaction occurred in powdered
CuNb2O6.
3.4. Effect of Pt deposition over CuNb2O6
As described above, the two polymorphs of CuNb2O6 powder
could reduce water to H2 in the presence of CH3OH, and the rate of
photocatalytic H2 evolution over monoclinic CuNb2O6 was greater
than that over orthorhombic CuNb2O6. For further improvement in
the rate of photocatalytic H2 evolution, we attempted to deposit Pt
nanoparticles on CuNb2O6 particles by the photo-deposition
method because co-catalysts such as noble metal nanoparticles
are believed to separate photogenerated electrons and holes.
Fig. 9a shows TEM photographs of 0.5 wt% Pt-deposited mono-
clinic CuNb2O6 particles. Black particles with sizes of less than
5 nm can be observed, and they should be platinum particles based
on the results of EDS (see Fig. 9b). Fig. 10 shows the time course of
H2 evolution over 0.5 wt% Pt-CuNb2O6 powder in the presence of
CH3OH under AM 1.5G solar light irradiation together with that
over a bare monoclinic sample. As can be seen in Fig. 10a, the rate of
H2 evolution over 0.5 wt% Pt-deposited monoclinic CuNb2O6 was
7-times larger than that over bare monoclinic CuNb2O6. This
improvement in the rate of H2 evolution was attributed to an
efficient separation of photoexcited carrier and a decrease of
activation energy for water reduction reaction over Pt nano-
particles [39,40]. It should be noted that the rate of H2 evolution is
strongly dependent on the amount of Pt, and 0.5 wt% of Pt shows
the highest photocatalytic activity. For orthorhombic (see Fig. 10b),
the rate of H2 evolution 0.5 wt% Pt-CuNb2O6 was increased up to ca.
14 nmol h1, which was 4.6-times greater than that over bare
CuNb2O6. The fact that the increasing rate of photocatalytic H2
evolution over Pt-deposited monoclinic sample was higher than
that over Pt- deposited orthorhombic sample indicated an efficient
charge separation of photo-generated carriers in monoclinic
sample.
Fig. 11 shows the relationship between the photocatalytic
activities for H2 evolution and the cutoff wavelength of incident
light for monoclinic and orthorhombic 0.5 wt% Pt-CuNb2O6
samples together with their diffuse reflectance spectra. The
absorption edge wavelength of the Pt-CuNb2O6 sample was
estimated to be approximately 600 nm, similar to that of bare
CuNb2O6. Photocatalytic H2 evolution was observed at wave-
lengths as long as 600 nm, although the activity was markedly
lower than that at 400 nm. Taking into consideration that
absorption band is observed at longer wavelength than band
gap of CuNb2O6, our results showing photocatalytic H2 evolution at
longer wavelength are reasonable. It should be noted that H2 was
not detected either under dark conditions or under AM1.5G
irradiation in the absence of Pt-deposited CuNb2O6. Therefore,
photocatalytic H2 evolution observed in Pt-CuNb2O6 is considered
to be induced by photoabsorption of CuNb2O6. In this system,
photoexcited electrons reduce water to H2, while photoexcited
holes oxidize CH3OH to HCHO (and CO2) under irradiation.
Consequently, it is concluded that the photo-reduction of water
proceeds via the band-gap absorption of CuNb2O6.

Fig. 9. (a) TEM images of 0.5 wt% Pt-loaded CuNb2O6 particles (monoclinic phase). (b) EDS of Fig. 9a area.

Fig. 10. (a) Time courses of H2 evolution for 0.5 wt% Pt-loaded CuNb2O6 (monoclinic phase) and a bare monoclinic sample in 10 vol% CH3OH aqueous solution under AM 1.5G
solar light irradiation. The insets show the dependence of the amount of Pt on the rate of photocatalytic H2 evolution. (b) Time courses of H2 evolution for orthorhombic
CuNb2O6 and Pt-deposited CuNb2O6.
 S. Kamimura et al. / Journal of Photochemistry and Photobiology A: Chemistry 356 (2018) 263–271
Fig. 11. Dependence of initial H2 evolution rate on cutoff wavelength of incident light for (a) monoclinic and (b) orthorhombic 0.5 wt% Pt-CuNb2O6. UV–vis spectra of
monoclinic and orthorhombic Pt-CuNb2O6 samples are also shown.
4. Conclusions References
We demonstrated that powdered CuNb2O6 with two different [1]
[2]
polymorphs (monoclinic and orthorhombic phases) evolved H2 [3]
from water in the presence of CH3OH under AM 1.5G solar light [4]
irradiation. Both polymorphs of CuNb2O6 have a visible light- [5]
responsive band gap (2.7 eV) due to a metal-to-metal charge [6]
transfer between Cu2+ and Nb5+, and the CBM (1.51 V vs. NHE) of [7]
monoclinic CuNb2O6 lies more negative than the water reduction
[8]
potential, allowing thermodynamically favorable H2 evolution. We [9]
successfully improved the photocatalytic activity by depositing Pt
nanoparticles over monoclinic CuNb2O6 particles, and the rate of [10]
H2 evolution Pt-CuNb2O6 was increased up to ca. 32 nmol h1, [11]
[12]
which was 7-times greater than that over bare CuNb2O6. Similar
results were confirmed for the orthorhombic CuNb2O6 and Pt- [13]
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[15]
candidates as visible light-responsive photocatalysts for H2
evolution from water, despite their d0-d9 oxides. In addition, the [16]
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[17]
more negative than that of conventional oxides indicated the [18]
possibility of a Z-scheme photocatalyst for H2 evolution.
Furthermore, we experimentally revealed the effects of d-d [19]
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activity. For monoclinic CuNb2O6, d-d absorption of Cu2+ was a
forbidden transition due to its symmetric CuO6 octahedral. For [21]
orthorhombic CuNb2O6, two axial Cu-O distances in the CuO6
[22]
octahedral increased simultaneously along the Z axes by Jahn-
Teller effects, and strong d-d absorption of Cu2+ appeared. Such d-d [23]
[24]
absorption of Cu2+ of CuNb2O6 contributed to a significant effect on
the photocatalytic activity; the recombination probability of [25]
photo-generated carriers was strongly dependent on whether
the electrons are fully filled at Cu 3d-orbitals via d-d absorption. [26]
The present work extends the possibility of the d0-d9 photocatalyst [27]
series for solar-driven H2 evolution from water and thus should [28]
help in the design and development of a highly active photo-
[29]
catalyst with a 3d-block element through control of the symmetry
of the crystal field. Although the proposed model partially explains [30]
the difference of the photocatalytic activity between monoclinic [31]
and orthorhombic CuNb2O6, other aspects such as the relationship [32]
between the band potential and photocatalytic activity are not yet [33]
clear. Further research is required to improve the present model
[34]
and understand the photocatalytic mechanism in depth.
[35]
[36]
Acknowledgements
[37]
[38]
This research was supported by the PRESTO program (Grant [39]
Number JPMJPR16P4) from Japan Science and Technology Agency
(JST), a Grant-in-Aid for Young Scientists (B) (16K17895) and [40]
Advanced Catalytic Transformation program for Carbon utilization
(ACTC Grant Number JPMJCR12Y5).
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