Article

pubs.acs.org/JPCC

Which is an Intermediate Species for Photocatalytic Conversion of

CO2 by H2O as the Electron Donor: CO2 Molecule, Carbonic Acid,
Bicarbonate, or Carbonate Ions?
Kentaro Teramura,*,, Kazutaka Hori, Yosuke Terao, Zeai Huang, Shoji Iguchi, Zheng Wang,
Hiroyuki Asakura,, Saburo Hosokawa,, and Tsunehiro Tanaka*,,

Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyotodaigaku Katsura, Nishikyo-ku,
Kyoto 615-8510, Japan

Elements Strategy Initiative for Catalysts & Batteries (ESICB), Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto 615-8245,
Japan
*
S Supporting Information

ABSTRACT: In the photocatalytic conversion of CO2 using H2O as

the electron donor, there are four candidates of the intermediate
species in the solution: hydrated CO2 molecule (CO2(aq)), carbonic
acid (H2CO3), bicarbonate (HCO3), and carbonate (CO32) ions.
The concentrations of all four species in the system at equilibrium
can be controlled by controlling the temperature, pH value, and
concentration of the countercation. According to our experiments
conducted under dierent conditions, we narrowed the possible
intermediates down to two: CO2(aq) and HCO3. The isotopic
experiment using 13CO2 and in situ infrared spectroscopy revealed
that CO2(aq) reacts with the hydroxyl group anchored on the Ga
atom on the surface of ZnGa2O4/Ga2O3 to form bidentate HCO3
Ga, followed by the formation of bidentate HCOOGa via
monodentate HCO3Ga. We conclude that bidentate HCOOGa is the real intermediate species for the photocatalytic
conversion of CO2 by H2O as the electron donor over Ag/ZnGa2O4/Ga2O3 catalyst, and it decomposes into CO as a product.

INTRODUCTION
To counter global climate change, many countries have taken
measures to reduce the emission of CO2. Articial photosyn-
thesis, especially the photocatalytic conversion of CO2 into
valuable compounds using water as the electron donor, is a
chemical process much sought after for energy conversion and
chemical feedstock production.15 Since the early reports by
Herrman et al.6 and Honda et al.,7 many research groups have
observed the conversion of CO2 into reduction products such
as carbon monoxide (CO), formic acid (HCOOH), form-
aldehyde (HCHO), methanol (CH3OH), and methane (CH4).
In many cases, only the reduction products of CO2 were
focused upon, meaning that all electrons generated by charge
transfer are used for the reduction of CO2, although the overall
water splitting can occur with many kinds of photocatalysts.813
That is to say, when H2O is used as the electron donor, the
reduction of CO2 (eq 1 in the case of producing CO) invariably
competes with the production of H2 from the overall water
splitting (eq 2).14
+
CO2 + 2H + 2e CO + H 2O (1)
+ Revised: March 8, 2017
2H + 2e H 2 (2)
It is therefore necessary to monitor the evolution of H2 and
determine the selectivity of the generated electrons toward the
reduction products. In addition, the stoichiometry of O2 is one
of the strongest pieces of evidence that H2O functions as the
electron donor and undergoes a four-electron oxidation
reaction (eq 3).15
2H 2O O2 + 4H+ + 4e (3)
The number of holes (h+) generated and consumed is
consistent with that of electrons (e), thereby essentially
achieving the photocatalytic conversion of CO2 using H2O as
the electron donor. If CO is also evolved as a reduction
product, the selectivity toward it and the balance between the
consumed electrons and holes can be expressed as follows:
selectivity toward CO evolution (%)
= 2R CO/(2R CO + 2R H2) 100 (4)
Received: December 21, 2016
Published: April 11, 2017

2017 American Chemical Society 8711 DOI: 10.1021/acs.jpcc.6b12809

J. Phys. Chem. C 2017, 121, 87118721
The Journal of Physical Chemistry C Article

(2R CO + 2R H2) [H+][HCO3 ]

consumed e/h+ = K1 =
4R O2 (5) [H 2CO3*] (12)

where Rx is the formation rate of species x. Recently, Kudo and [H+][CO32 ]

co-workers opened the gate to the next stage of the K2 =
[HCO3 ] (13)
photocatalytic conversion of CO2 by H2O as the electron
donor. The photocatalyst ALa4Ti4O15 (A = Ca, Sr, and Ba) with It is well-known that K1 and K2 depend on the solution
Ag nanoparticles exhibited good activity with a rate of CO temperature with the following empirical expressions according
formation higher than that of H2 evolution together with a to Plummer and Busenberg27
stoichiometric rate of O2 formation.16 Therefore, all of the 21834.37
requirements mentioned above for the photocatalytic con- log K1 = 356.3094 0.06091964T +
version of CO2 using H2O as the electron donor were satised. T
Their work inspired our group to switch the electron donor 1684915
+ 126.8339log T
from H2 to H2O. Kudo et al. also reported that KCaSrTa5O15 T2 (14)
with Ag nanoparticles functions as a photocatalyst for the
5151.79
photocatalytic conversion of CO2 by H2O.17,18 Their isotope log K 2 = 107.8871 0.03252849T +
experiment using 13CO2 revealed that CO was generated from T
the introduced CO2. Meanwhile, we succeeded in designing 563713.9
+ 38.92561log T
highly selective photocatalytic conversion of CO2 by H2O as T2 (15)
the electron donor by the simultaneous use of an inhibitor
where T is the temperature of the solution. Substituting eqs 12
against the production of H2 and a material for CO2 capture
and 13 into 11 results in
and storage such as ZnGa2O4/Ga2O3,19,20 La2Ti2O7,21 SrO/
Ta2O5,22 ZnGa2O4,23 ZnTa2O6,24 and Sr2KTa5O1525 with the K1[H+]
modication of Ag cocatalyst. Ag/ZnGa2O4/Ga2O319,20 is [HCO3 ] = S
[H+]2 + K1[H+] + K1K 2 (16)
remarkable for suppressing the H2 evolution by forming
ZnGa2O4 on the surface of Ga2O3, resulting in high selectivity K1K 2
toward CO evolution.23 [CO32 ] = S
[H ] + K1[H+] + K1K 2
+ 2
(17)
To enhance the CO formation rate, it is very important to
identify the intermediate species with multiple characterization Eventually,[HCO3] 2
and [CO3 ] are represented using S and
methods as well as the reaction mechanism. In this study, we [H+]. [H+] is easily determined from the pH value recorded
examine the intermediate species of CO2 reduction in aqueous during the reaction. Because [H2CO3*] is almost equal to
solutions. It is known that gaseous CO2 can dissolve in [CO2(aq)], [CO2(aq)] can be estimated as follows:
H2O.26,27 The hydrated CO2 molecule (CO2(aq)) reacts with
H2O to form carbonic acid (H2CO3). Dissociation of H2CO3 [H+]2
[CO2 (aq)] = S
produces bicarbonate (HCO3) and carbonate ions (CO32) in [H+]2 + K1[H+] + K1K 2 (18)
two stages, depending on the pH value. These four reactions
reach equilibria during the photocatalytic reaction: On the other hand, S is constrained by the electrical neutrality
when CO2 dissociates in a solution containing Na+ ions from a
CO2 (g) CO2 (aq) (6) buer such as NaOH, NaHCO3, and Na2CO3:

CO2 (aq) + H 2O(l) H 2CO3(aq) [Na +] + [H+] = [HCO3 ] + 2[CO32 ] + [OH] (19)
(7)
K w = [H+][OH] (20)
H 2CO3(aq) HCO3 (aq) + H+(aq) (8)
where Kw = 1.0 1014 is the self-ionization constant of water.
HCO3 (aq) CO32 (aq) + H+(aq) (9) When eqs 16, 17, and 20 are introduced into 19, we obtain the
following equation:
From the low hydration equilibrium constant of carbonic acid
in pure water (eq 7, Kh = [H2CO3]/[CO2(aq)] 1.7 103), K w [H+]2 + K1[H+] + K1K 2
S = [Na +] + [H+]
the dissolved CO2 consists of mostly CO2(aq) together with a [H+] K1[H+] + 2K1K 2
small amount of H2CO3; therefore, H2CO3* is used to (21)
represent the two species of CO2(aq) and H2CO3 in writing
the aqueous chemical equilibrium equation. Eqs 7 and 8 are Therefore, we can estimate the concentrations of all CO2-
rewritten as follows related species in the aqueous solution from the amount of
buer, the temperature, and the pH of the solution. Figure 1
H 2CO3* HCO3 + H+ (10) shows [CO2(aq)], [HCO3], and [CO32] under the typical
reaction conditions in this study (303 K, 0.10 M added
We dene S as the total concentration of all CO2-related NaHCO3). On the basis of this gure, the fractions of CO2-
species (H2CO3* (i.e., CO2(aq) + H2CO3), HCO3, and related species at equilibrium (the so-called Bjerrum plot) are
CO32): often used as an example in textbooks of analytical chemistry
S = [H 2CO3*] + [HCO3 ] + [CO32 ] (11)
(Figure S1). In this study, the measured pH values were 4.0
8.0, a range in which [CO32] is vanishingly small, as shown in
On the basis of eqs 9 and 10, the rst and second dissociation Figure 1. On the other hand, [HCO3] changes very little
constants of carbonic acid can be denoted by the following within this pH range. [CO2(aq)] dramatically decreases with
equations, respectively: increasing pH, vanishing at around 8.0 under our typical
8712 DOI: 10.1021/acs.jpcc.6b12809
J. Phys. Chem. C 2017, 121, 87118721
The Journal of Physical Chemistry C
Figure 1. Calculated concentrations of CO2(aq) (circle), HCO3
(triangle), and CO32 (square) in 0.10 M aqueous solution of
NaHCO3 at 303 K under 101.325 kPa of CO2.
experimental conditions (pressure of CO2: 101.325 kPa,
[NaHCO3]: 0.10 M, T: 303 K), although it is dominant in
acidic conditions. As mentioned above, [H2CO3] is also
negligible because the CO2 hydration equilibrium constant is
very small. As a result, we focus on CO2(aq) and HCO3 as
candidate intermediate species for the reaction (i.e., photo-
catalytic conversion of CO2 by H2O as the electron donor) with
Ag/ZnGa2O4/Ga2O3 and discuss the reaction mechanism,
including the determination of the intermediate species.
EXPERIMENTAL SECTION
Ga2O3 was fabricated by a typical precipitation method using a
gallium nitrate precursor (Ga(NO3)nH2O).19,20 An aqueous
solution of ammonia (28%) was added dropwise into an
aqueous solution of Ga(NO3)nH2O until the pH value reached
approximately 8.9. The gallium hydroxide (Ga(OH)3) was
centrifuged, washed with milli-Q water, and dried aerially at 353
K in an oven, followed by calcination at 1273 K for 6 h to
obtain -Ga2O3. ZnGa2O4-modied Ga2O3 (ZnGa2O4/Ga2O3)
was fabricated by an impregnation method, as reported by us
elsewhere.19,20 The as-prepared -Ga2O3 was dispersed in an
aqueous solution of Zn(NO3)26H2O by ultrasonication. After
impregnation, the sample was dried under vacuum with
ultrasonication at 313323 K and then calcined at 1223 K
for 6 h. Ag-loading onto the ZnGa2O4-modied Ga2O3 to form
Ag/ZnGa2O4/Ga2O3 was carried out by a well-known photo-
deposition method.19,20 The amount of loaded Ag cocatalyst
was xed at 1.0 wt % in this study. Specically, the prepared
ZnGa2O4/Ga2O3 was dispersed in an aqueous solution of
AgNO3. The suspension was deaerated using CO2 gas (not
inert gases like N2 or Ar) for 30 min and then illuminated
under a 400 W high-pressure mercury lamp (SEN LIGHTS Co,
Ltd.) through a quartz lter equipped with a water cooling
system. After 2 h, the suspension was ltered, and the ltrate
was washed with distilled water several times and dried in an
oven at 353 K overnight.
The X-ray diraction (XRD) patterns of Ag/ZnGa2O4/
Ga2O3 were recorded using an Ultima IV powder dirac-
tometer (Rigaku Corporation). The UVvis diuse reectance
spectra (DRS) were measured with a V-670 spectrometer
(JASCO Corporation) equipped with an integrating sphere.
Spectralon (Labsphere Inc.) was used as a standard reection
sample like BaSO4. The X-ray photoelectron spectra (XPS)
were acquired using an ESCA 3400 X-ray photoelectron
spectrometer (Shimadzu Corporation) using a Mg K source
in a vacuum chamber in 0.1 eV steps. A pellet sample was
8713
Article
mounted on the sample holder by using conductive carbon
tape. The position of the C 1s carbon peak at 284.6 eV was
used to calibrate the binding energies for all the samples. The
surface atomic ratio was estimated from the areas of Ga 2p and
Zn 2p peaks using the corresponding relative sensitivity factors.
Fourier transform infrared (FT-IR) spectra of the ZnGa2O4/
Ga2O3 sample and adsorbed CO2 species were observed with
an FT/IR-4200 spectrometer (JASCO Corporation) equipped
with a mercurycadmiumtellurium (MCT) detector cooled
by liquid N2 in a transmission mode at 303 K. Approximately
50 mg of ZnGa2O4/Ga2O3 sample was pressed into a wafer 10
mm in diameter at the pressure of 15 MPa. The wafer was
placed in a cylindrical glass cell equipped with CaF2 windows.
The cell allowed us to perform heating, O2 treatment,
introduction of various gases, photoirradiation, and in situ
spectral measurement. The wafer was evacuated at 673 K for 3
h before measurement, followed by treatment with 5 kPa of O2
for 30 min and evacuation for 10 min at 673 K. For each
spectrum, data from 100 scans were accumulated at a resolution
of 4 cm1.
The photocatalytic conversion of CO2 by H2O was carried
out in a quartz inner-irradiation-type reaction vessel (1.0 L) in a
quasi-owing batch system. The synthesized Ag/ZnGa2O4/
Ga2O3 was dispersed in an aqueous solution of NaHCO3 or
other buers. CO2 gas (99.999%) was bubbled into the solution
at a ow rate of 30 mL min1. The suspension was irradiated
using the same mercury lamp system as that used in the
photodeposition process. The produced H2 and O2 were
analyzed by using a GC-8A gas chromatograph (GC)
(Shimadzu Corporation) equipped with thermal conductivity
detector (TCD) and a Molecular Sieve 5A column (carrier gas:
Ar). On the other hand, the main product CO and the substrate
CO2 were monitored by using a GC-8A system equipped with
ame ionization detector (FID), a methanizer, and a
SHINCARBON ST column (carrier gas: N2). The initial
formation rate of each product was estimated every hour by
linear tting during the 5 h of photoirradiation. In the isotopic
experiment with 13CO2, the formed 13CO and 12CO were
observed by using a quadrupole-type mass spectrometer (MS,
MicrotracBEL, BEL Mass).
RESULTS AND DISCUSSION
The prepared Ga2O3, ZnGa2O4/Ga2O3, and Ag/ZnGa2O4/
Ga2O3 samples were characterized by XRD and UVvis DRS.
Their crystal phase and estimated band gap energy were
conrmed to be similar to those we reported before.19,20 The
as-prepared Ga2O3 exhibited the typical XRD pattern of -
Ga2O3 (Figure S2). A peak at 35.7 appeared after the
modication by Zn(NO3)2 and calcination at high temperature
and was assigned to the (311) facet of the ZnGa2O4 structure.
On the other hand, there was no peak assignable to Ag after the
photodeposition of Ag cocatalyst, indicating that Ag existed on
the surface of ZnGa2O4/Ga2O3 as relatively small nanoparticles.
The absorption edge of bare Ga2O3 was observed at 265 nm,
and the band gap energy was estimated as 4.6 eV according to
the DavisMott eq (Figure S3). The edge was not changed by
the modication of ZnGa2O4. However, the loading of Ag
aorded a new broad band at 270330 nm, which was derived
from surface plasmon resonance (SPR) of the Ag nano-
particles.2830 This result agrees well with the absence of Ag
peaks in the XRD measurement. In this study, the ratio of Zn/
(Zn + Ga) in the starting material was xed to 3.0 mol %
because the selectivity toward CO evolution becomes saturated
DOI: 10.1021/acs.jpcc.6b12809
J. Phys. Chem. C 2017, 121, 87118721
The Journal of Physical Chemistry C
when the amount of added Zn(NO3)2 precursor exceeds this
ratio (Figure S4).
Figure 2 shows the temperature-dependent formation rates
of CO and H2 as reduction products, the evolved O2 as an
Figure 2. Temperature-dependent (A) formation rates of CO (circle),
H2 (triangle), and O2 (square), and selectivity toward CO evolution
(open diamond), and (B) p[CO2] (diamond) and pH (open circle)
values for the photocatalytic conversion of CO2 by H2O. Catalyst: Ag
(1.0 wt %)/ZnGa2O4 (3.0 mol %)/Ga2O3 (0.5 g); solution: H2O (1.0
L); buer: 0.10 M NaHCO3; ow rate of CO2: 30 mL min1.
oxidation product, the selectivity toward CO evolution,
p[CO2], which is dened aslog[CO2(aq)], and pH value
when using Ag (1.0 wt %)/ZnGa2O4 (3.0 mol %)/Ga2O3. The
formation rate of CO decreased with increasing reaction
temperature. However, that of H2 evolution showed the
opposite trend, which means that a higher reaction temperature
promotes H2 evolution and inhibits CO evolution. Interest-
ingly, the number of electrons involved in the photocatalytic
reaction, as estimated by the formation rates of CO and H2,
remained approximately constant with temperature. Addition-
ally, the formation rate of O2, which was monitored
stoichiometrically, was also constant at all reaction temper-
atures. This indicates that the total number of electrons and
holes generated by charge transfer remains the same in the
entire temperature range. The selectivity toward CO evolution
clearly depends on p[CO2]. In general, x2, the mole fraction of
CO2 in H2O (mole of solute per mole of solvent), which is
related to its solubility, can be calculated by the following
formula:26
8742.4 T 0.1103 T
ln x 2 = 60.069 + + 21.671 ln
T 100 100
(22)
The value of x2 decreases with increasing solution temperature
(T). In our case, the concentration of HCO3 was much higher
than that of CO2 for the entire temperature range. Note that
the concentration of CO2 is temperature-dependent. Therefore,
p[CO2] decreased with decreasing temperature of the solution.
On the other hand, the pH value remained constant (6.76.8)
in this temperature range, as shown in Figure 2. The
equilibrium in eq 7 between CO2 and H2CO3 in aqueous
8714
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solutions goes strongly toward to the reactant. Therefore, most
of CO2 in the solution exists as CO2(aq), and the pH value
should not change even though p[CO2] becomes lower when
the solution temperature is lowered. To encourage the
reduction of CO2 and suppress the production of H2 (i.e.,
high selectivity toward CO evolution), the photocatalytic
reaction should be carried out at a lower temperature.
Figure 3 shows that the formation rate of CO increases
remarkably with the partial pressure of CO2, even though the
Figure 3. (A) Formation rates of CO (circle), H2 (triangle), and O2
(square), and selectivity toward CO evolution (open diamond), and
(B) p[CO2] (diamond) and pH (open circle) values with various
partial pressures of CO2 for the photocatalytic conversion of CO2 by
H2O. Catalyst: Ag (1.0 wt %)/ZnGa2O4(3.0 mol %)/Ga2O3 (0.5 g);
solution: H2O (1.0 L); buer: 0.10 M NaHCO3; ow rate of gases
(CO2 + Ar): 30 mL min1, reaction temperature: 303 K.
rate of H2 evolution is also slightly decreased at higher CO2
pressure. As a result, the selectivity toward CO evolution
steadily increased with the partial pressure of CO2. The
behavior observed in Figure 3 is a bit dierent from that in
Figure 2. As expected, the stoichiometric formation rate of O2
could be also observed in this case. According to Henrys law,
the concentration of CO2 in an aqueous solution increases with
the CO2 partial pressure in the gas phase. Therefore, the
formation rate of CO is also increased.
On the other hand, we speculate that H2 evolution depends
not on the pH value but on the concentration of CO2 in the
liquid phase instead. The reason is that the formation rate of H2
changed very little with CO2 partial pressure compared to that
of CO (Figure 3A) but decreased with decreasing reaction
temperature (Figure 2A), which did not aect the pH value
(Figure 2B). It is somewhat counterintuitive that the rate of H2
formation does not depend on [H+]. Indeed, the evolution of
H2 is generally enhanced by very low pH values for overall
water splitting. For this reason, in many reports the overall
water splitting is carried out in the presence of strong acids like
H2SO4. In the current reaction (photocatalytic conversion of
CO2 by H2O as the electron donor over Ag/ZnGa2O4/Ga2O3),
however, the generated electrons are mainly used for the
reduction of CO2. Because p[CO2] is much lower than the pH
value in the solution, it is expected that the formation of H2 is
DOI: 10.1021/acs.jpcc.6b12809
J. Phys. Chem. C 2017, 121, 87118721
The Journal of Physical Chemistry C
regulated by the generation of electrons that are not used for
the reduction of CO2. When p[CO2] is relatively high, overall
water splitting preferentially takes place. Naturally, the
formation rate of H2 also increases with [H+]. However, the
pH value depends on p[CO2] in the solution, and the
production of H2 competes with the reduction of CO2. Overall,
the relationship between H+ and CO2 in this system is very
complex. We conclude that with Ag/ZnGa2O4/Ga2O3, the 2-
electron reduction of CO2 to CO with two protons is preferred
over the 2-electron reduction of H+ to H2. Therefore, the
formation rate of H2 in the presence of CO2 depends not on
the pH value but rather on p[CO2], which also aects the
formation rate of CO.
It is well-known that the pH value of a solution can be
adjusted by using a buer. Figure 4 displays the eect of
Figure 4. (A) Formation rates of CO (circle), H2 (triangle), and O2
(square), and selectivity toward CO evolution (open diamond), and
(B) p[CO2] (diamond) and pH (open circle) values at dierent
concentrations of NaHCO3, for the photocatalytic conversion of CO2
by H2O. Catalyst: Ag (1.0 wt %)/ZnGa2O4 (3.0 mol %)/Ga2O3 (0.5
g), solution: H2O (1.0 L), ow rate of CO2: 30 mL min1, reaction
temperature: 303 K.
NaHCO3 as a buer on the photocatalytic conversion of CO2
by H2O. The formation rates of H2, O2, and CO, the selectivity
toward CO evolution, and the pH and p[CO2] values all
depend exponentially on [NaHCO3]. As we have already
reported,19 the evolution of CO was hardly observed without
NaHCO3, although the amount of CO2 dissolved in the
aqueous solution (0.03 M as calculated by eq 19 at 303 K) was
high enough for the reduction reaction. The formation rate of
CO increased with [NaHCO3] due to the decrement of
p[CO2]. We obtained the same results in this case as those
achieved by changing the reaction temperature and the partial
pressure of CO2. Note that the formation rate of H2 does not
depend on pH, as explained earlier. Therefore, a high rate of H2
formation could be obtained at relatively low [H+]. This
tendency is the same as when the partial pressure of CO2 is
increased. The formation of H2 as a byproduct in the reduction
of H+ is not pH-dependent in the photocatalytic conversion of
CO2 by H2O, especially when using a photocatalyst with
suciently high activity for the evolution of CO. Rather, it is
8715
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very important to maintain high pH and low p[CO2] values to
obtain high photocatalytic activity and good selectivity toward
CO evolution.
The results discussed so far show that a low reaction
temperature, high partial pressure of CO2 , and high
concentration of NaHCO3 are important for achieving highly
selective photocatalytic conversion of CO2 by H2O. Figure 5
Figure 5. Time courses of evolved CO (circle), H2 (triangle), and O2
(square) for the photocatalytic conversion of CO2 by H2O. Catalyst:
Ag (1.0 wt %)/ZnGa2O4 (3.0 mol %)/Ga2O3 (0.5 g); solution: H2O
(1.0 L); buer: 1.2 M NaHCO3; ow rate of CO2: 30 mL min1;
reaction temperature: 303 K.
shows the time course of CO, H2, and O2 evolutions for this
reaction in 1.2 M aqueous NaHCO3 solution over Ag/
ZnGa2O4/Ga2O3. The formation rate of CO (165 mol h1)
was clearly higher than that of H2 (31.5 mol h1) with
stoichiometric formation rate of O2 (101 mol h1) at the
initial stage. These observations indicate that the charge
separation took place smoothly, the generated electrons
reduced not H+ into H2 but preferentially CO2 into CO, and
the generated holes oxidized H2O into O2. The selectivity
toward CO evolution reached 84.0%. The concentration of CO
evolved in the gas phase was estimated to be approximately
2300 ppm.
Interestingly, the photocatalytic activity depends on the kind
of buer. There was no visible dierence among NaOH,
NaHCO3, and Na2CO3 (Figure 6ac, respectively) in terms of
Figure 6. Formation rates of evolved H2 (blue), O2 (green), CO (red),
and pH value (black circle) in the photocatalytic conversion of CO2 by
H2O using dierent buers: (a) NaOH, (b) NaHCO3, (c) Na2CO3,
(d) Li2CO3, (e) K2CO3, (f) NaCl, (g) Na2SO4, and (h) NaNO3.
Catalyst: Ag (1.0 wt %)/ZnGa2O4 (3.0 mol %)/Ga2O3 (0.5 g);
solution: H2O (1.0 L); concentration of countercation: 0.10 M; ow
rate of CO2: 30 mL min1; reaction temperature: 303 K.
DOI: 10.1021/acs.jpcc.6b12809
J. Phys. Chem. C 2017, 121, 87118721
The Journal of Physical Chemistry C
the formation rates of H2, O2, and CO, and the pH value. This
means that the equilibrium of CO2 dissolved in the solution
remains unchanged with these 3 buers because the pH,
concentration of Na+ countercation, and the partial pressure of
CO2 are all the same. As discussed previously, the conversion of
CO2 and selectivity toward CO evolution strongly depend on
the equilibrium amount of dissolved CO2, which is dened in
terms of eqs 69. This equilibrium is aected only by the type
of anion and not the type of countercations. For example, when
using Na2CO3, Li2CO3, or K2CO3, the same proles were
observed in the formation rates of H2, O2, and CO (Figure 6c
e, respectively). The pH value was not changed because of the
same concentration of the buer. Hence, the concentration of
the countercation, not its type, is important for obtaining high
conversion of CO2 and good selectivity toward CO evolution.
On the other hand, there was a huge change when anions
other than (bi)carbonates were present in the aqueous solution.
With NaCl (Figure 6f), the Cl ion is expected to act as a hole
scavenger rather than as an inhibitor for the reduction of CO2.
CO was generated as a reduction product together with H2 in
the presence of NaCl, indicating that Cl ion does not inhibit
the reduction of CO2. Note that the total formation rate of CO
and H2 is almost at the same order of magnitude when using
NaOH, NaHCO3, or Na2CO3; even though a portion of the
base sites should be poisoned by these buers. On the other
hand, we did not monitor the evolution of O2 as an oxidation
product, indicating that the generated holes do not oxidize H2O
to O2 but Cl to chlorine (Cl2) instead. Our research group has
already reported that the Cl ion works as a hole scavenger for
the photocatalytic conversion of CO2 in H2O over various
layered double hydroxide photocatalysts.31,32 Cl ion should be
oxidized into Cl2 by the generated holes, and then Cl2
decomposes by disproportionation into Cl and hypochlorite
(ClO) ions in the aqueous solution. In the cases of Na2SO4
and NaNO3 (Figures 6(g) and (h)), CO evolution was not
observed, and relatively tiny amounts of H2 and O2 were
generated stoichiometrically from overall water splitting due to
the low pH value (4.0). We expect the reduction of CO2 to be
more aected by sulde and nitrate ions than the pH value,
because the observed behavior was dierent from that with
NaCl even at the same pH (Figure 6(f)). In general, Na2SO4 is
used as a pH conditioning agent for overall water splitting to
maintain high [H+] (low pH value). On the other hand, the
SO42 ion behaves as a strong acid and easily poisons the base
sites where the CO2-derived species should be adsorbed and
then reduced to CO. Therefore, overall water splitting takes
place stoichiometrically. We conclude that, for highly selective
photocatalytic conversion of CO2 by H2O, it is very important
to maintain a high concentration of countercations in the
aqueous solution, and not to add anions other than CO2-related
species.
At the end of the Introduction section, we raised the
question of whether CO2, HCO3, or both of them in the
aqueous solution can function as intermediate species in the
photocatalytic conversion of CO2 by H2O as the electron
donor. As shown in Figure 1, [CO2(aq)] and [HCO3] are
almost the same at pH 6.7, where a relatively high formation
rate of CO was observed. FT-IR spectroscopy is known to be a
very powerful tool for investigating several species adsorbed on
the surface of heterogeneous catalysts and photocatalysts.
Previously, we used FT-IR spectroscopy to reveal that
bicarbonate and formate as intermediate species are generated
on the surfaces of ZrO2,33 MgO,34,35 and Ga2O3,36 which
8716
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exhibit relatively good CO evolution for the photoreduction of
CO2 in the presence of H2.
We measured the IR spectrum of ZnGa2O4/Ga2O3 in the
presence of CO2, as shown in Figure 7. The spectrum of
Figure 7. IR spectra of ZnGa2O4 (3.0 mol %)/Ga2O3 (a) before and
(b) after introduction of CO2 (2.0 kPa).
pretreated ZnGa2O4/Ga2O3 (Figure 7a) was used as the
background. A peak assigned to OH stretching [(OH)] of
isolated surface hydroxyl group on ZnGa2O4/Ga2O3 was
observed at 3684 cm1 after the pretreatment, which was
similar for that of Ga2O3 at 3685 cm1 (Figure S5). Many
bands related to CO2 were observed in the IR spectra (Figure
S6), and the dierence IR spectra (Figure S7) after the
introduction of CO2 over ZnGa2O4/Ga2O3. This is consistent
with the results of Knoezinger et al.,37 Morterra et al.,38,39 Busca
et al.,40 and Lavalley et al.,41,42 who reported adsorption of CO2
on the surface by in situ FT-IR spectroscopy. Four bands
between 1000 and 1800 cm1 were derived from bicarbonate
on Ga2O3. The bands at 1624 and 1228 cm1 are assigned to
asymmetric CO3 stretching [as(CO3)] and OH deformation
[(OH)], respectively. The symmetric CO3 stretching band
[s(CO3)] from 1350 to 1500 cm1 will be discussed later.
On the other hand, the typical bands assigned to molecular
CO2 adsorbed on surfaces were monitored between 2200 and
2600 cm1. The band with a peak located at 2342 cm1 is
slightly shifted in frequency from the standard vibration of
molecular CO2 at 2349 cm1. In fact, the IR spectra of adsorbed
CO2 is not consistent with that of CO2 gas at the same partial
pressure (Figure S8). Therefore, the CO2 molecules must
interact with surface Lewis sites, as mentioned by Lavalley et
al.41 Interestingly, the band at 2342 cm1 was decreased by the
photoirradiation, and then the bands between 2200 and 2600
cm1 became similar to those assigned to molecular CO2.
These observations mean that CO2 could be initially adsorbed
on the surface of ZnGa2O4/Ga2O3 and then desorbed into the
gas phase during photoirradiation due to the formation of H2O.
Generally, the information on surface hydroxyl groups is
obtained in the spectral range from 3200 to 3800 cm1.43 In
our case, it was dicult to observe the change after the
introduction of CO2 and photoirradiation because the band
assigned to OH stretching [(OH)] of isolated surface
hydroxyl group on ZnGa2O4/Ga2O3 (3684 cm1) was very
weak, as shown in Figure 7. To clarify the interaction between
the isolated surface hydroxyl group and CO2, the OH group on
ZnGa2O4/Ga2O3 was converted into OD by using D2O.
ZnGa2O4/Ga2O3 was pretreated in this manner, followed by
deuteration with 1.8 kPa of D2O for 30 min. Figure 8 shows the
dierence IR spectra of surface OD stretching on ZnGa2O4/
Ga2O3 after introducing CO2 under photoirradiation. The band
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The Journal of Physical Chemistry C
Figure 8. Dierence IR spectra of the stretching mode of surface OD
group of ZnGa2O4 (3.0 mol %)/Ga2O3 (a) before and (b) after
introducing CO2 (1.0 kPa) under photoirradiation for (c) 15 and (d)
30 min.
at 2691 cm1, which is assigned to OD stretching [(OD)] of
the isolated surface hydroxyl group on ZnGa2O4/Ga2O3,
became weaker upon the introduction of CO2. This indicates
that CO2 gas interacts with the isolated surface OD group. As a
result, the band assigned to OD stretching of bicarbonate
appeared at 2669 cm1. These two bands gradually became
weaker during the photoirradiation due to the generation of
CO and H2O. The broad band at 33003800 cm1 derived
from OH stretching increased after photoirradiation, which
indicates the generation of H2O by the photocatalytic reduction
of CO2 with the isolated surface hydroxyl group.
Figure 9 shows selected dierence IR spectra from 1350 to
1500 cm1 of adsorbed CO2 species on ZnGa2O4/Ga2O3 after
Figure 9. Dierence IR spectra of adsorbed CO2 species on ZnGa2O4
(3.0 mol %)/Ga2O3 under photoirradiation for (a) 0, (b) 0.5, and (c)
1 h.
introducing CO2 under photoirradiation. Two typical bands
were observed at 1460 and 1430 cm1 and are respectively
assigned to the symmetric CO3 stretching [s(CO3)] of
bidentate bicarbonate and monodentate bicarbonate species
by comparison to a Ga2O3 reference.44,45 A new shoulder peak
appeared at 1412 cm1 in the case of ZnGa2O4/Ga2O3,
although it was not observed on the surface of bare Ga2O3
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(Figure S9). This band, which can be better understood after
deconvolution, is derived from monodentate bicarbonate
species anchored on the Zn atom because ZnO produces a
s(CO3) band of monodentate bicarbonate species at the same
position.41,46,47 In short, there are three kinds of bicarbonate
species on ZnGa2O4/Ga2O3 after introducing CO2 gas: (i)
bidentate bicarbonate species anchored on Ga (b-HCO3Ga),
(ii) monodentate bicarbonate species anchored on Ga (m-
HCO3Ga), and (iii) monodentate bicarbonate species
anchored on Zn (m-HCO3Zn). It is reasonable to assume
that the bidentate bicarbonate species anchored on Zn (b-
HCO3Zn) is also present on ZnGa2O4/Ga2O3. However, it
could not be observed in the spectra because the corresponding
band is expected to be buried within the two bands at 1460 and
1430 cm1. The behaviors of the three bands under
photoirradiation are totally dierent from each other, as
shown in Figure 9. The band at 1430 cm1 (m-HCO3Ga)
became stronger with the photoirradiation time, in association
with the decreasing intensity of the 1460 cm1 band (b-HCO3
Ga), indicating that bidentate bicarbonates should be converted
to monodentate bicarbonates on the Ga atom. On the other
hand, the band at 1412 cm1 (m-HCO3Zn) was not changed
by photoirradiation at all.
As the photoirradiation continues, the band at 1430 cm1
(m-HCO3Ga) decreased, shifted to a much lower wave-
number, and then vanished after 56 h, as shown in Figure 10.
Figure 10. Dierence IR spectra of adsorbed CO2 species on ZnGa2O4
(3.0 mol %)/Ga2O3 under photoirradiation for (a) 1, (b) 3, (c) 6, (d)
12, (e) 56, (f) 152, and (g) 180 h.
The same behavior was observed in the case of Ga2O3 (Figure
S10). However, the band of Ga2O3 decreased with photo-
irradiation time at a rate slower than that of ZnGa2O4/Ga2O3.
The band at 1228 cm1, assigned to the deformation of
bicarbonate [(OH)], also became weaker with photo-
irradiation time, meaning that m-HCO3Ga was converted
into another species. Note that the new bands at 1579, 1390,
and 1356 cm1 (asymmetric CO2 stretching [as(CO2)], CH
deformation [(CH)], and symmetric CO 2 stretching
[s(CO2)] of bidentate formate (b-HCOOGa), respectively)
gradually appeared at the same time when the band of m-
HCO3Ga at 1430 cm1 was reduced.36,44,45 When D2 was
used for exchange of the OH group, only the band assigned to
(CH) was shifted, although the as(CO2) and s(CO2) bands
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J. Phys. Chem. C 2017, 121, 87118721
The Journal of Physical Chemistry C
remained in the range from 1200 to 1600 cm1 (Figure S11).
These bands completely disappeared after 180 h of photo-
irradiation. According to the time course of the integrated
absorbance of the characteristic bands, both long-term (Figure
11) and in the early stages (inset), the amount of m-HCO3Ga
Figure 11. Time course of integrated absorbance of bands at (a) 1430
cm1 (m-HCO3Ga, circle), 1460 cm1 (b-HCO3Ga, triangle), and
1579 cm1 (b-HCOOGa, square) in the dierence IR spectra of the
adsorbed CO2 species on ZnGa2O4 (3.0 mol %)/Ga2O3. Inset: time
course during 0360 min.
increased while that of b-HCO3Ga decreased, as mentioned
above. When b-HCO3Ga vanished, the amount of m-HCO3
Ga was also reduced. The amount of b-HCOOGa rst
increased and eventually declined, indicating that it acted as an
intermediate species in the reaction.
In the above discussion, we monitored the decrement of
formate during the reaction, as indicated in Figures 10 and 11.
One obvious question here is why the band assigned to the
reaction intermediate b-HCOOGa decrease after photo-
irradiation (Figure 11, green squares), even though the
conversion of CO2 by H2O proceeded catalytically. This
would mean that b-HCOOGa was not provided from m-
HCO3Ga continually. There are two reasons for this. (1) The
absence of Ag cocatalyst. We previously reported the
importance of surface Ag cocatalyst on ZnGa2O4/Ga2O3 for
obtaining a high rate of CO formation.19,20 Without it, overall
water splitting dominantly proceeds over ZnGa2O4/Ga2O3.
Here, we chose to use unmodied ZnGa2O4/Ga2O3 to observe
changes in the intermediate species (such as b-HCO3Ga, m-
HCO3Ga, and b-HCOOGa). These intermediate species
will persist in the presence of Ag cocatalyst, which indicates that
formate is generated as the intermediate species stably, and the
reaction proceeds catalytically. Further investigations are
needed to better understand this. (2) It is well-known that
bicarbonate on the surface easily desorbs into the gas phase in
the presence of H2O. Thus, at the beginning of the
photoirradiation, a part of bicarbonate could be converted
into formate as the real intermediate species. Afterward, a large
amount of bicarbonate would be desorbed due to the formation
of H2O under photoirradiation (as discussed earlier). Hence,
the amount of b-HCOOGa is lowered later.
As mentioned earlier, we have four candidates of
intermediate species in the aqueous solution of NaHCO3 for
the photocatalytic conversion of CO2 by H2O as the electron
donor. They are hydrated CO2 molecule (CO2(aq)), carbonic
acid (H2CO3), bicarbonate (HCO3), and carbonate ions
(CO32). In the earlier discussion, we suppose that CO2(aq) is
an intermediate species for the reaction. Thus, bicarbonate
species derived from CO2(aq) are generated on the surface of
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ZnGa2O4/Ga2O3, and then reduced into CO via formate upon
photoirradiation.
For a more concrete discussion of the intermediate species,
we carried out the photocatalytic conversion of CO2 by H2O
using isotopic NaH13CO3. Figure 12 represents the time course
Figure 12. Time course of (A) 13CO (closed circle) and 12CO (closed
triangle) determined by MS, CO (closed square) determined by FID-
GC, and pH value (open diamond) in the solution, and (B) 13CO2
(open circle) and 12CO2 (open triangle) determined by MS, CO2
(open square) determined by FID-GC, and pH value (cross) in the
solution for the photocatalytic conversion of CO2 by H2O. Catalyst:
Ag (1.0 wt %)/ZnGa2O4 (3.0 mol %)/Ga2O3 (1.0 g); solution: H2O
(1.0 L); buer: 0.10 M NaH13CO3; ow rate of CO2: 30 mL min1.
of carbon-containing species detected by MS (12CO, 13CO,
12
CO2, and 13CO2) and GC (CO and CO2). The amount of
CO estimated by GC is consistent with the total amount of
12
CO and 13CO determined by MS, the same for CO2. The CO
formation rate steadily increased with decreasing solution pH
and became constant after 60 min because CO2 gas gradually
dissolved in the solution and increased the concentration of
CO2(aq). Note that 13CO was initially generated as the main
product. However, the formation rate of 12CO steadily rose and
surged past that of 13CO after 90 min. Finally, 13CO vanished,
and only 12CO was produced. This result strongly suggests that
the formation rate of CO (12CO + 13CO) depends not on the
concentration of HCO3 but on that of CO2(aq). If HCO3
acts as an intermediate species, the highest formation rate of
13
CO would be achieved as soon as the lamp was turned on. In
fact, we observed that H2 and O2 derived from the overall water
splitting were generated in aqueous NaHCO3 solution together
with a tiny amount of CO without the bubbling of CO2 gas.19
At the initial stage where a large fraction of CO2 gas molecules
was not dissolved in the solution, 13CO2(aq) was produced
from NaH13CO3 on the basis of the equilibrium in eq 10,
causing 13CO to be preferentially evolved. With the continuous
bubbling of 12CO2, the concentration of CO2(aq) reached
equilibrium with that of HCO3 after 60 min. At this point, the
formation rate of 13CO decreased while that of 12CO increased.
Finally, only 12CO was generated as the main product as 12CO2
was continuously supplied from the gas to the liquid phase. On
the other hand, CO2 in the gas phase displayed the same
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J. Phys. Chem. C 2017, 121, 87118721
The Journal of Physical Chemistry C
tendency in isotope composition as CO evolved. The
concentration of 13CO2 increased until 60 min and then
tapered o, while that of 12CO2 gradually increased with
photoirradiation time. In this study, 12CO2 was owed at the
rate of 30 mL min1, which is approximately 1.3 103 mol
min1, a value consistent with the rate of CO2 detected by GC
and the total rate of 12CO2 and 13CO2 estimated by MS. In
addition, the integrated amount of 13CO2 from 0 to 600 min
was 0.093 mol, which is very similar to the initial amount of
NaH13CO3 (0.1 M in 1.0 L of aqueous solution). Therefore, the
13
C-labeled species in the solution, derived from NaH13CO3,
was gradually released into the gas phase as 13CO2. Our results
indicate that this reaction is in a state of dynamic equilibrium
with the rapid interconversion of CO2-related molecules (e.g.,
CO2(aq), H2CO3, HCO3, and CO32) in the solution. When
CO2 was bubbled in the dark for 120 min and the suspension
was then illuminated, the steady formation rate of CO was
initially monitored, and the formation rates of 12CO and 13CO
depended on the concentrations of 12CO2 and 13CO2 in the gas
phase, respectively (Figure S12). The time course completely
agrees with that in Figure 12. Therefore, the ratio of evolved
13
CO/12CO is similar to that of 13CO2(aq)/12CO2(aq).
Although we could not rule out the possibility that CO2(aq)
and HCO3 work cooperatively as the intermediate species, it is
clear that CO2(aq) is reduced to CO in the photocatalytic
conversion of CO2 when using H2O as the electron donor in
the aqueous solution of NaHCO3 with Ag/ZnGa2O4/Ga2O3.
Under the current circumstances, we propose the formation
mechanism of several intermediate species as shown in Scheme
1. Dissolved CO2 molecules (CO2(aq)) react with the hydroxyl
Scheme 1. Proposed Mechanism of the Formation of
Intermediate Species in the Photocatalytic Conversion of
CO2 by H2O as the Electron Donor over ZnGa2O4/Ga2O3
group anchored with Ga atom on the surface of ZnGa2O4/
Ga2O3 to form b-HCO3Ga. b-HCO3Ga is further converted
to b-HCOOGa via m-HCO3Ga. Finally, b-HCOOGa is
decomposed into CO.
Interestingly, photoirradiation is not exactly necessary in this
process, except for the formation of b-HCO3Ga. The
following charge transfer takes place during the conversion of
m-HCO3Ga to b-HCOOGa:
HCO3 + 2H+ + 2e HCOO + H 2OE 0 = 0.41 eV
(23)
On the other hand, the other two processes, namely the
transformation of b-HCO3Ga to m-HCO3Ga and the
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decomposition of b-HCOOGa, do not involve any generated
electrons. The former is either a kind of light switching of
molecules on the surface or photoabsorption. We already
reported that b-HCO3Ga is converted to m-HCO3Ga when
the pressure of introduced CO2 is increased.36 The reaction is
irreversible, so there is no conversion from m-HCO3Ga back
to b-HCO3Ga. This means that the transformation from the
quasi-stable b-HCO3Ga to the more stable m-HCO3Ga
occurs by fractional driving force such as the pressure and
photoirradiation. The latter is the so-called photolysis. It is well-
known that formate is an intermediate species in the water gas-
shift (WGS) reaction:
CO + H 2O CO2 + H 2 (24)
Generally, the equilibrium in eq 24 strongly leans toward the
reactant side, meaning that formate is easily decomposed into
CO and H 2 O upon heating (the so-called backward
decomposition of formate intermediate in WGS). Hirose et
al.48 found that the decomposition of formate on NiO(111)
lm grown on Ni(111) surface can produce both H2 and CO2
via dehydrogenation and CO and H2O by dehydration. In our
case, b-HCOOGa, which is a formate intermediate on the
surface of ZnGa2O4/Ga2O3, should decompose into the
product CO to leave GaOH on the surface. Calatayud et
al.49 reported that very stable formate species are generated by
CO insertion into the surface hydroxyl groups on a wide range
of hydroxylated metal oxides (including Ga2O3) at high
temperatures. Therefore, the backward reaction (formate
decomposition) can easily take place on Ga2O3, as suggested
in our proposed reaction mechanism. To enhance the
conversion of CO2 and selectivity toward CO evolution, it is
very important to adjust the pH to ensure a sucient quantity
of CO2(aq) in the solution and to produce suitable CO2
adsorption sites such as the hydroxyl group, which functions
as a Brnsted solid base.
CONCLUSION
CO2 dissolved in aqueous solution of NaHCO3 is determined
to be the intermediate species for the photocatalytic conversion
of CO2 by H2O as the electron donor. At the typical pH values
in this study, H2CO3 and CO32 are present only at very low
concentrations in the solution. HCO3 derived from NaHCO3
does not contribute to the reduction of CO2 but functions as a
buer to enable the dissolution of much more CO2 into the
solution, even though the concentration of HCO3 is higher
than that of the CO2 molecule. The conversion of HCO3 into
dissolved CO2 does not occur in equilibrium due to the
extremely low equilibrium constant (K1) and the continuous
feeding of CO2 from the gas phase. The dissolved CO2
molecules bind to the hydroxyl groups on the surface of
ZnGa2O4/Ga2O3 to form several bicarbonate species. Among
them, the monodentate bicarbonate is reduced by the electrons
generated under photoirradiation into a bidentate formate
intermediate via the bidentate bicarbonate. The main product
CO is evolved from the introduced CO2 gas through the
decomposition of formate.
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.6b12809.
DOI: 10.1021/acs.jpcc.6b12809
J. Phys. Chem. C 2017, 121, 87118721
The Journal of Physical Chemistry C
Bjerrum plot, XRD patterns, UVvis, DRS, XP spectra,
several IR spectra, and time course of 12CO and 13CO
(PDF)
AUTHOR INFORMATION
Corresponding Authors
*E-mail: teramura@moleng.kyoto-u.ac.jp
*E-mail: tanakat@moleng.kyoto-u.ac.jp.
ORCID
Kentaro Teramura: 0000-0003-2916-4597
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
This study was partially supported by a Grant-in-Aid for
Scientic Research(B) (KAKENHI Grant 15H04187) of the
Ministry of Education, Culture, Sports, Science, and Technol-
ogy (MEXT) of Japan; a Grant-in-Aid for Scientic Research
on Innovative Areas, All Nippon Articial Photosynthesis
Project for Living Earth (no. 2406) of the MEXT of Japan; the
Precursory Research for Embryonic Science and Technology
(PRESTO) program, supported by the Japan Science and
Technology Agency (JST); and the Program for Elements
Strategy Initiative for Catalysts & Batteries (ESICB),
commissioned by the MEXT of Japan.
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8721 DOI: 10.1021/acs.jpcc.6b12809

J. Phys. Chem. C 2017, 121, 87118721