Article

pubs.acs.org/IECR

Cobalt Phosphate−ZnO Composite Photocatalysts for Oxygen

Evolution from Photocatalytic Water Oxidation
Yabo Wang,† Yongsheng Wang,‡ Rongrong Jiang,† and Rong Xu*,†
†
School of Chemical & Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore 637459
‡
School of Mechanical & Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798
*
S Supporting Information

ABSTRACT: Cobalt based oxygen evolution catalysts (Co−Pi) were loaded on the surface of ZnO by photochemical
deposition in a neutral phosphate buffer solution containing Co2+ ions. Structural, morphological, and optical properties of the
samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission
electron microscopy, X-ray photoelectron spectroscopy, and UV−vis diffuse reflectance spectra techniques. The Co−Pi phase
formed was amorphous and was deposited on the surface of ZnO uniformly as a layer of nanoparticles. The enhanced activity for
oxygen evolution was directly observed from photocatalytic water oxidation over Co−Pi loaded ZnO. The oxygen produced in
the first hour was more than 4 times of that obtained over ZnO alone. The results suggest that Co−Pi played the role of
cocatalyst, which can trap photogenerated holes, leading to the enhancement of electron and hole separation efficiency. Further
studies showed that the mixture of cobalt phosphate and ZnO exhibited similar enhancement in activity for oxygen evolution
which could be due to the oxidation of nonactive cobalt(II) phosphate to active Co−Pi with higher oxidation states of cobalt
upon light illumination during photocatalytic water oxidation process. In both systems, ZnO photocorrosion was observed based
on inductively coupled plasma, XRD, and FESEM analyses.

1. INTRODUCTION for water oxidation. Recently, some new semiconductor

Conversion of solar energy to chemical energy by water photocatalysts were reported to be active for oxygen evolution
splitting represents an attractive process to solve the global from water, such as BiCu2VO6,24 BiZn2VO6,25 TiNxOyFz,26 and
energy and environmental challenges, as sunlight and water are nitrogen-doped CsCa2Ta3O10,27 with the oxygen evolution
abundant and renewable. Many efforts have been devoted to rates ranging from about 3−70 μmol h−1. Layered double
the searching of efficient photocatalysts to produce hydrogen hydroxides (LDHs) were also reported capable of photo-
and oxygen from water under solar energy in the past few catalytic water oxidation.28 Ag3PO4 crystals developed by Ye’s
decades.1−5 So far, only a limited number of semiconductor group showed rather good activity (1.6 and 7.8 times higher
photocatalysts have been reported capable for overall water than that of BiVO4 and WO3, respectively) and a high quantum
splitting,6−9 because semiconductor materials with suitable efficiency (about 90% at 420 nm) for oxygen evolution in the
redox potentials and band gap for simultaneous water reduction presence of AgNO3 as a sacrificial reagent.29 Nevertheless, it is
and oxidation are not commonly available. Most research still a great challenge in developing efficient and stable
activities are focused on half reactions, that is, separate water photocatalysts and understanding the mechanisms for water
reduction and water oxidation involving sacrificial reagents as oxidation.
electron donors and acceptors, respectively. The combination A novel earth-abundant cobalt-based oxygen evolution
of a hydrogen evolution photocatalyst and an oxygen evolution catalyst was first reported by Kanan and Noreca in 2008.
photocatalyst may lead to overall water splitting, such as the This amorphous catalyst can be readily formed in neutral
construction of a Z-scheme reaction system.10,11 Compared phosphate buffer solution containing Co2+.12 Although the
with hydrogen production from water reduction which requires exact structure and composition of the cobalt based phosphate
two electrons, water oxidation for oxygen production is more catalyst (Co−Pi) has not been fully understood, it is suggested
challenging since it requires four holes for generation of two that Co2+ was oxidized to Co3+ during photodeposition and
oxygen−oxygen bonds in one oxygen molecule.12 precipitated in the forms of amorphous oxide and hydroxide
To date, many efficient photocatalysts for hydrogen containing phosphate.30 Electrochemical, extended X-ray
production have been developed, including doped and undoped absorption fine structure (EXAFS), and electron paramagnetic
metal oxides, metal sulfides, and their solid solutions.13−20 It resonance (EPR) results indicated that the catalytic ability of
has been generally found that cocatalysts on the surface of base
semiconductor particulates improve the separation and trans-
Special Issue: APCChE 2012
portation of photogenerated electrons and holes which leads to
improved photocatalytic activities.16,17 Compared with hydro- Received: November 25, 2011
gen evolution photocatalysts, the reported active photocatalyst Revised: March 24, 2012
systems for oxygen evolution from water oxidation are much Accepted: April 3, 2012
fewer. So far, WO321,22 and BiVO423 are typical photocatalysts

© XXXX American Chemical Society A dx.doi.org/10.1021/ie2027469 | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

Co−Pi is related to the oxidation of Co2+ to Co3+ and Co4+, and 10 mA) in the range of 10°−70° with a scan speed of 0.04°
leading to the formation of high valence Co4+−O intermedi- s−1. UV−visible diffuse reflectance spectra (UV−vis DRS) were
ates.31−34 Furthermore, when deposited on photoelectrodes, recorded on a UV−visible spectrophotometer (UV-2450,
such as ZnO, WO3, and α-Fe2O3, Co−Pi nanoparticles Shimadzu). The morphologies of samples were observed on
enhanced photocurrent and photoanode efficiencies.30,35−39 It field emission scanning electron microscopy (FESEM, JEOL
was commonly suggested that photogenerated holes can be JSM 6700F) equipped with an energy dispersive spectroscopy
trapped by Co−Pi catalyst where water oxidation occurs, (EDS) and transmission electron microscopy (TEM, JEOL
leading to the efficient charge separation and enhanced 3010). The concentrations of Zn2+ and Ag+ in the reaction
photoelectrochemical activities. Barroso et al. employed solution were determined using inductively coupled plasma
transient absorption spectroscopy to study Co−Pi deposited (ICP) optical emission spectrometer on a Perkin-Elmer ICP
α-Fe2O3 photoelectrode. It was observed that the lifetime of Optima 2000DV machine. X-ray photoelectron spectroscopy
photogenerated holes can be increased by more than 3 orders (XPS) analysis was conducted on an Axis Ultra spectrometer
of magnitude with retarded electron−hole recombination (Kratos Analytical) using a monochromated Al Kα X-ray source
because of the formation of a Schottky-type heterojunction.39 (1486.7 eV) operating at 15 kV. The binding energy was
Despite the above progress achieved, almost all the studies calibrated using the C1s peak at 284.6 eV.
were focused on the photoelectrochemical performances by 2.3. Photocatalytic Reaction. The photocatalytic water
using photoelectrode devices. Herein, we for the first time splitting reaction was conducted in a top window Pyrex cell
employed photocatalytic water oxidation process to evaluate connected to a closed gas circulation and evacuation system as
the activities of Co−Pi/ZnO photocatalysts for oxygen shown in Scheme 1. A 300 W xenon lamp (Newport) was
evaluation. The photocatalytic reaction was carried out in a
closed circulation system with online gas chromatography for Scheme 1. Schematic Diagram of Photocatalytic Reaction
an accurate measurement of the oxygen gas produced. In System for Water Oxidation
addition, it was observed that the mixture of cobalt phosphate
and ZnO exhibited similar enhancement in activity for oxygen
production as compared to Co−Pi/ZnO composites.

2. EXPERIMENTAL SECTION
2.1. Co−Pi Loading on ZnO. All reagents were of
analytical grade and used without any purification. Co−Pi
nanoparticles were deposited on the surface of ZnO particulates
by a similar photochemical method as described by Steinmiller
and Choi.30 Typically, 0.3 g of ZnO (>99.0%, KANTO
Chemical) was dispersed in 50 mL of sodium phosphate buffer
solution (0.01 M, pH = 7.0) prepared from sodium phosphate
monobasic (NaH2PO4·H2O, ∼99%, USB corporation) and
disodium hydrogen phosphate (Na2HPO4, > 99.0%, KANTO
Chemical) followed by ultrasonication for 3 min. To this
suspension, 1.25 mL of 0.02 M cobalt nitrate (Co-
(NO3)2·6H2O, > 97.0%, GCE) aqueous solution was added
under stirring. The mixture was subjected to UV light
illumination for 30 min by using a UV lamp (8 W, λ = 302
nm, UVP). The precipitate was collected by centrifugation and
washed with deionized water thoroughly before drying at 60 °C applied as the light source. In a typical run, 0.1 g of the catalyst
overnight. This sample was named as Co−Pi/ZnO. was well dispersed with constant stirring in 100 mL of AgNO3
For comparison purposes, cobalt phosphate (CoP) and zinc aqueous solution at 5 mM. Before the reaction, the system was
phosphate (ZnP) in the absence of ZnO were prepared by evacuated and refilled with argon gas for several times to
slowly adding 18 mL of 0.5 M Co(NO3)2 or Zn(NO3)2 remove the air inside and finally filled with argon to
aqueous solution to 60 mL of phosphate buffer solution (0.1 approximately 30 Torr. The temperature of photoreaction
M, pH = 7.0). After stirring for 30 min at room temperature, cell was kept at about 20 °C by a cooling water jacket. The
the precipitates were collected, washed with deionized water, produced oxygen gas was analyzed with an online gas
and dried at 60 °C overnight. Silver phosphate (AgP) was also chromatography (Agilent 6890N, TCD detector, argon as
prepared according to the method reported in the literature.29 carrier gas, 5 Å molecular sieve column). Before and after the
In a typical synthesis, 3 mmol of Na2HPO4 was thoroughly reaction, the pH of the solution was measured to be almost
mixed with 9 mmol of AgNO3 (>99.0%, Sigma) in a rotator constant and close to neutral at 6.6.
(labroller II, Labnet corporation) overnight. Then the mixture
was washed with deionized water thoroughly and dried at the 3. RESULTS AND DISCUSSION
same condition. The samples consisting of a physical mixture of 3.1. Materials Properties of Co−Pi/ZnO. Figure 1
CoP and ZnO (CoP+ZnO) were prepared by grinding a certain displays the XRD patterns of cobalt phosphate (CoP), Co−
amount of as-prepared CoP and the commercial ZnO powder Pi loaded ZnO (Co−Pi/ZnO), mixture of CoP and ZnO (CoP
in an agate mortar. +ZnO), and pristine ZnO. The pristine ZnO (curve d) shows
2.2. Characterization. The X-ray diffraction (XRD) good crystallinity with a hexagonal structure (JCPDS card no.
patterns of the as-prepared samples were obtained on a X-ray 36-1451). The characteristic peaks shown in curve a can be well
diffractometer (Bruker D2 Phaser, Cu Kα, λ = 1.5406 Å, 30 kV indexed to Co3(PO4)2·8H2O (JCPDS card no. 33-0432) which
B dx.doi.org/10.1021/ie2027469 | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

Figure 1. (A) Wide-range and (B) narrow-range powder XRD patterns of (a) cobalt phosphate (CoP), (b) Co−Pi loaded ZnO, Co−Pi/ZnO, (c)
CoP and ZnO physical mixture, CoP+ZnO, and (d) ZnO. The peaks labeled with the asterisk (∗) in curve B-b can be indexed to Zn3(PO4)2·4H2O
(JCPDS card no. 33-1474). The peaks labeled with the triangle (Δ) in curve B-c can be indexed to Co3(PO4)2·8H2O (JCPDS card no. 33-0432).

was formed due to precipitation of Co2+ ions by the phosphate bound to oxygen, hydroxyl, or phosphate groups, which is
anions. The grain size of this sample was estimated to be about consistent with that reported by others.12,30 The P 2p peak at
54 nm by using the Scherrer equation and on the basis of the 133.6 eV can be ascribed to phosphate in the Co−Pi phase,
strongest peak at 2θ of 13.25°. As shown in Figure 1B, some while the peak at 139.4 eV could belong to phosphate in the
weak diffraction peaks can be observed in curves b and c in the zinc phosphate phase as detected in the XRD pattern. Similar
range of 10°−25°, which are labeled by an asterisk (*) and observations were reported in the electrodeposited Co−Pi
triangle (Δ), respectively. The peaks present in curve b can be catalyst on ZnO electrode.30
assigned to Zn3(PO4)2·4H2O (JCPDS card no. 33-1474). The morphologies of ZnO and Co−Pi/ZnO are shown in
During the photochemical deposition of Co−Pi on the surface Figure 3 and Figure 4. The pristine ZnO (Figure 3a) consists of
of ZnO, UV light was applied. Photocorrosion of ZnO may
occur to a certain extent due to UV illumination. The leached
Zn2+ was precipitated by the phosphate ions out in the form of
zinc phosphate. The presence of Zn3(PO4)2·4H2O was further
confirmed by FESEM results, which will be discussed shortly.
The small peaks in curve c should be ascribed to the presence
of a small portion of Co3(PO4)2·8H2O (CoP) as this sample is
a physical mixture of CoP and ZnO. The above results indicate
that the Co−Pi phase photochemically deposited on ZnO is
amorphous, and its presence in sample Co−Pi/ZnO is not
detectable by XRD as shown in Figure 1b. This is consistent
with the findings reported by others about the formation of the
amorphous Co−Pi thin film on various electrodes.12,30,31,33,40
In fact, the formation of cobaltate clusters of molecular
dimension have been proposed in Co−Pi structures based on
EXAFS studies by Nocera and co-workers.33
XPS spectra of Co 2p and P 2p of sample Co−Pi/ZnO are
shown in Figure 2. The signal of Co 2p is rather weak due to its
low percentage in the sample (<0.1% on metal basis). The Co
2p3/2 peak located at 780.7 can be assigned to Co2+ or Co3+
Figure 3. FESEM images of (a) ZnO and (b−d) Co−Pi/ZnO at
different magnifications.

submicrometer-sized particles with generally a rod-like

morphology despite of the existence some irregular particles.
After Co−Pi loading, it can be observed from Figure 3b that
additional micrometer sized plate-like crystals appear in Co−
Pi/ZnO. The plate-like structure should belong to
Zn3(PO4)2·4H2O due to photocorrosion of Zn2+ ions, which
was also confirmed by EDS data (Supporting Information,
Figure S1) and XRD patterns (Figure 1B). At higher
magnifications (Figure 3c,d), it can be clearly seen that the
Figure 2. High resolution XPS spectra of Co 2p and P 2p of sample surface of ZnO became rougher compared to that of pristine
Co−Pi/ZnO. ZnO due to the deposition of nanoparticles. Most of these
C dx.doi.org/10.1021/ie2027469 | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

the pristine ZnO, indicating that the structure of ZnO was not
affected by Co−Pi loading. On the other hand, the absorption
in the range of 400−700 nm was slightly enhanced (Figure 5b)
owing to the deposition of Co−Pi on the surface of ZnO.
3.2. Oxygen Production Activity. The photocatalytic
water oxidation was conducted under a 300 W Xe lamp using
AgNO3 as the sacrificial reagent in a photoreactor system as
shown in Scheme 1. The time courses of oxygen production
over different samples are displayed in Figure 6. ZnO alone

Figure 4. (a) TEM and (b) HRTEM images of Co−Pi/ZnO. The

arrows indicate a layer of amorphous Co−Pi on the surface of ZnO.

nanoparticles are uniformly distributed on the surface of ZnO,

and their sizes are below 10 nm except for a few larger particles
of about 20 nm as shown in Figure 3d. Such observations are
similar to those reported for Co−Pi deposited ZnO photo-
anode.30 Further TEM observation clearly showed that a thin
layer of nanoparticles was deposited on the surface of ZnO
(Figure 4a). And the amorphous nature of those nanoparticles
was confirmed by the HRTEM image (Figure 4b). Compared
with the well-crystallized ZnO which shows clear lattice, there is
no lattice observed from the deposited layer of Co−Pi on the
surface of ZnO. The measured lattice spacing of ZnO (0.242
nm) is in good agreement with the interplanar distance of the
[100] plane (0.247 nm) obtained from the XRD result. In Figure 6. Time courses for oxygen production over samples (a) Co−
combination with the XPS result, it can be concluded that Co− Pi/ZnO, (b) ZnO, and (c) CoP. Reaction conditions: 0.1 g of catalyst,
Pi amorphous nanoparticles were successfully loaded on the 100 mL of aqueous solution with 5 mM AgNO3, 300 W Xe lamp.
surface of ZnO particles. On the other hand, the sample CoP
obtained by precipitation also presents a micrometer-sized
plate-like structure as shown in Supporting Information, Figure exhibited a low activity of producing 36.6 μmol of oxygen in the
S2. first hour. On the other hand, only a trace amount of oxygen
Figure 5 shows UV−visible diffuse reflectance spectra of gas was observed over cobalt phosphate (CoP) alone,
different samples. The spectrum of ZnO (Figure 5a) shows indicating that cobalt phosphate itself is inactive. After loading
Co−Pi on the surface of ZnO, the activity was remarkably
enhanced and 155.8 μmol of oxygen was produced in the first
hour. In their photoelectrochemical process, Steinmiller and
Choi observed that Co−Pi catalyst deposited on ZnO electrode
effectively enhanced the anodic photocurrent, demonstrating
the promising capability of such a system in photocatalytic
water oxidation.30 Herein, we directly observed more than four
times of enhancement in photocatalytic oxygen evolution over
Co−Pi/ZnO photocatalyst against ZnO. Such result is also
consistent with the observation of the prolonged lifetime of
photogenerated holes when Co−Pi cocatalyst was loaded on α-
Fe2O3 photoanode.39 It is believed that efficient electron−hole
separation and long lifetime of holes together contribute to the
higher activity of Co−Pi/ZnO in water oxidation. Figure 6
shows that the oxygen production activity decreased quickly
after 1.5 h of photocatalytic reaction and almost no oxygen gas
was produced after 2 h. Such a trend is reasonable because the
sacrificial reagent AgNO3 was consumed by photogenerated
Figure 5. UV−visible diffuse reflectance spectra of (a) ZnO, (b) Co− electrons, resulting in the formation of silver metal. The
Pi/ZnO, (c) CoP+ZnO, and (d) CoP.
generated silver metal was deposited on the surface of ZnO,
leading to retardation of light adsorption.
intense absorption edge at around 390 nm, corresponding to a During the photocatalytic water splitting reaction, an
band gap of 3.18 eV which is consistent with value in the interesting phenomenon was observed. After 3 h of reaction,
literature.41,42 Although the absorption edge of cobalt the total oxygen gas produced exceeded the theoretical value of
phosphate CoP (Figure 5d) is located at a wavelength of 125 μmol calculated according to the amount of AgNO3
around 280 nm, a broad absorption band in 400−700 nm sacrificial reagent. To explain this phenomenon, ICP method
indicates its visible light absorption ability. After loading Co−Pi was applied to monitor the concentration of metal ions in the
on ZnO, no absorption edge shift was observed comparing with solution during photocatalytic reaction and the results are
D dx.doi.org/10.1021/ie2027469 | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

shown in Figure 7. It can be seen that the concentration of Ag+ than that of ZnO. However, the O2 produced in the first 30 min
(Figure 7d) quickly decreased during the first hour due to its over sample Co−Pi/ZnO was much higher than that of sample
ZnO. Thus, it is suggested that the Co−Pi layer loaded on the
surface of ZnO played an important role during water
oxidation, leading to much higher activity for O2 production.
At 3 h of reaction time, the concentration of Zn2+ leached from
ZnO at 3 h (Figure 7b) was slightly lower than that from Co−
Pi/ZnO (Figure 7a). If no sacrificial reagent of AgNO3 was
present in the photoreaction solution, the leaching of Zn2+ over
sample Co−Pi/ZnO was dramatically suppressed as shown in
Figure 7c. The concentration of Zn2+ was only 3.9 mg L−1 after
3 h illumination. In the absence of Ag+ as an electron acceptor,
electrons and holes generated from Co−Pi/ZnO recombined
quickly. Photocatalytic water oxidation (eq 2) and photo-
corrosion of ZnO (eq 1) hardly happened, leading to a low
concentration of Zn2+.
Another interesting phenomenon observed was that when a
small amount of cobalt phosphate (CoP, 2 mg) was mixed with
ZnO (100 mg), the oxygen production rate was also greatly
enhanced as shown in Figure 8a. During the first hour, the
Figure 7. The concentrations of Zn2+ (a, b, c) and Ag+ (d) ions in the
photoreaction solutions. Photocatalytic reaction conditions: (a) Co−
Pi/ZnO in 5 mM AgNO3 aqueous solution, (b) ZnO in 5 mM AgNO3
aqueous solution, (c) Co−Pi/ZnO in H2O, and (d) Co−Pi/ZnO in 5
mM AgNO3 aqueous solution.

role as sacrificial electron acceptor. Only a trace amount of Ag+

was detected after 3 h of photocatalytic reaction. On the other
hand, the concentration of Zn2+ increased upon light
illumination. After 1 h, the concentration of Zn2+ reached a
more or less stable value of approximately 173 mg L−1 for Co−
Pi/ZnO (Figure 7a). Such a phenomenon can possibly be
explained by the photocorrosion of ZnO under light
illumination and the dissolution of ZnO by H+ ions produced
during water oxidation. The process of photoinduced
dissolution of ZnO can be represented by eq 1.43,44 Oxygen
gas produced from ZnO photocorrosion also contributed to the
total amount of oxygen gas in the current system. In fact, the
amount of oxygen produced over ZnO increased over the Figure 8. Time courses for oxygen production over the physical
reaction time although the initial oxygen production rate was mixture of ZnO (100 mg) and different amounts of cobalt phosphate
low as shown in Figure 6b. About 110 μmol of oxygen was (CoP), zinc phosphate (ZnP), or silver phosphate (AgP): (a) 2 mg of
produced during the third hour over ZnO. The accelerated CoP, (b) 5 mg of CoP, (c) 10 mg of CoP, (d) 20 mg CoP, (e) 2 mg of
oxygen production could be mainly contributed by more severe ZnP, (f) 2 mg of AgP, and (g) ZnO alone.
photocorrosion of ZnO after a period of light illumination.
Another factor that contributed to the high concentration of
Zn2+ in the reaction solution would be the dissolution of ZnO. amount of oxygen produced reached 216 μmol. As ZnO and
During photocatalytic water oxidation process, H+ ions were CoP alone only exhibited low or no activity (Figure 6), it is
produced according to eq 2 which would lead to the decrease of believed that the interface between ZnO and CoP phases in the
pH value of the solution. However, the pH value of the reaction physical mixture played an important role in charge transfer.
solution was measured to be almost constant at about 6.6 Upon light illumination, holes generated in the ZnO semi-
before and after 3 h light irradiation, indicating that the H+ ions conductor could migrate to CoP phase to oxidize Co2+ to
were consumed by ZnO according to eq 3. Co3+/Co4+. Thus, nonactive CoP can be transformed to active
Co−Pi cocatalyst which is similar to those loaded on the
1 surface of ZnO, leading to high activity of oxygen production
ZnO + 2h+ → Zn 2 + + O2
2 (1) over a mixture of CoP and ZnO. As shown in Figure 8, a larger
amount of CoP (5, 10, and 20 mg) resulted in lower activities.
hv 1
H 2O → 2H+ + O2 Although the interface between CoP and ZnO was only caused
2 (2) by physical contact initially, the observed synergistic effect
ZnO + 2H+ → Zn 2 + + H 2O suggested that light illumination during the reaction could
(3)
induce interfacial property change to favor the water oxidation
2+
It has also been observed that the Zn leaching amount was process. Similarly, it has been reported that the mixture of ZnO
almost the same for Co−Pi/ZnO and ZnO samples during the and C60 fullerene presented improved photocatalytic activity
initial 30 min of light illumination (Figure 7a,b). After that and photostability of ZnO due to better migration efficiency of
more Zn2+ was found in the solution of sample Co−Pi/ZnO the charge carriers.44 The exact mechanism of the above
E dx.doi.org/10.1021/ie2027469 | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

observations will be elucidated in our future work to design water oxidation process in the aqueous solution containing
more efficient and robust photocatalysts for oxygen production. AgNO3 sacrificial reagent. Co−Pi acted as cocatalyst to improve
To rule out the effect of possible contamination by ZnP and photogenerated electron and hole separation efficiency. Further
AgP, photocatalytic water oxidation over the mixture of ZnP (2 study showed that nonactive cobalt phosphate can be changed
mg) or AgP (2 mg) and ZnO (100 mg) was also conducted to active Co−Pi during a photocatalytic reaction when mixed
under the same reaction conditions. As shown in Figure 8e−g, with ZnO. However, photocorrosion of ZnO was also observed
it is found that these two samples exhibited almost the same in both systems. The investigation on the combination of Co−
trend of oxygen production as ZnO alone. Thus, ZnP and AgP Pi and other semiconductors for photocatalytic water splitting
did not contribute to the enhancement of oxygen production are undergoing.

■
activity.
The crystal structure and morphology of Co−Pi/ZnO and ASSOCIATED CONTENT
the mixture of CoP and ZnO (CoP+ZnO) after 3 h of
photocatalytic reaction were investigated by XRD and FESEM
*
S Supporting Information

analyses. As shown in Figure 9, both samples became less FESEM image and EDS results of sample Co−Pi/ZnO, and
FESEM image of CoP sample. This material is available free of
charge via the Internet at http://pubs.acs.org.

■ AUTHOR INFORMATION
Corresponding Author
*E-mail: [email protected]. Tel.: +65 67906713. Fax: +65
67947553.
Notes
The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
This work was supported by AcRF Grants ARC25/08
(T208B1215) and RG117/06 from the Ministry of Education,
Singapore. Y. B. Wang acknowledges the research scholarship
from Nanyang Technological University.

■
Figure 9. XRD patterns of (a) pristine ZnO, (b) Co−Pi/ZnO, and (c)
CoP+ZnO after 3 h photocatalytic reaction (the peaks labeled with an REFERENCES
asterisk (∗) can be indexed to Ag metal (JCPDS card no. 89-3722)),
and FESEM images of (d) Co−Pi/ZnO and (e) CoP+ZnO after 3 h (1) Fujishima, A.; Honda, K. Electrochemical photolysis of water at a
photocatalytic reaction. semiconductor electrode. Nature 1972, 238, 37.
(2) Darwent, J. R.; Mills, A. Photo-oxidation of water sensitized by
WO3 powder. J. Chem. Soc., Faraday Trans. 1982, 78, 359.
crystalline after reaction compared with pristine ZnO, which (3) Zou, Z.; Ye, J.; Sayama, K.; Arakawa, H. Direct splitting of water
should be ascribed to the photocorrosion of ZnO. The under visible light irradiation with an oxide semiconductor photo-
catalyst. Nature 2001, 414, 625.
additional peaks (labeled with the asterisk (∗) belong to
(4) Osterloh, F. E. Inorganic materials as catalysts for photochemical
metallic silver formed by the reduction of the AgNO3 sacrificial splitting of water. Chem. Mater. 2008, 20, 35.
reagent. The color of both samples turned dark gray after the (5) Kudo, A.; Miseki, Y. Heterogeneous photocatalyst materials for
reaction. Compared to the FESEM images of Co−Pi/ZnO water splitting. Chem. Soc. Rev. 2009, 38, 253.
before the reaction (Figure 3), Figure 8d shows the distinct (6) Yamasita, D.; Takata, T.; Hara, M.; Kondo, J. N.; Domen, K.
difference in morphologies of Co−Pi/ZnO after the photo- Recent progress of visible-light-driven heterogeneous photocatalysts
reaction. The original rod-like ZnO became particles with for overall water splitting. Solid State Ionics 2004, 172, 591.
irregular sizes and shapes due to the occurrence of photo- (7) Zou, Z. G.; Ye, J. H.; Sayama, K.; Arakawa, H. Direct splitting of
corrosion and dissolution. Many nanoparticles with sizes water under visible light irradiation with an oxide semiconductor
around 50−100 nm can be observed on the surface or in the photocatalyst. Nature 2001, 414, 625.
(8) Maeda, K.; Takata, T.; Hara, M.; Saito, N.; Inoue, Y.; Kobayashi,
vicinity of ZnO particles which should be Ag metal reduced by
H.; Domen, K. GaN:ZnO solid solution as a photocatalyst for visible-
photogenerated electrons. In sample CoP+ZnO after photo- light-driven overall water splitting. J. Am. Chem. Soc. 2005, 127, 8286.
reaction (Figure 9e), some flake-like structures and the small (9) Maeda, K.; Domen, K. New non-oxide photocatalysts designed
fragments can be found besides ZnO. As CoP exhibits typical for overall water splitting under visible light. J. Phys. Chem. C 2007,
plate-like structure, they may be broken into smaller particles 111, 7851.
during the process of Co2+ oxidation and photoreaction. (10) Sayama, K.; Mukasa, K.; Abe, R.; Abe, Y.; Arakawa, H.
Further studies including the improvement of stability of ZnO Stoichiometric water splitting into H2 and O2 using a mixture of two
and the combination of Co−Pi with other semiconductors for different photocatalysts and an IO3−/I− shuttle redox mediator under
photocatalytic water oxidation are undergoing. visible light irradiation. Chem. Commun. 2001, 2416.

■
(11) Higashi, M.; Abe, R.; Takata, T.; Domen, K. Photocatalytic
CONCLUSIONS overall water splitting under visible light using ATaO2N (A = Ca, Sr,
Ba) and WO3 in a IO3−/I− shuttle redox mediated system. Chem.
A cobalt-based phosphate (Co−Pi) cocatalyst was loaded on Mater. 2009, 21, 1543.
the surface of ZnO by a photochemical method. Enhanced (12) Kanan, M. W.; Nocera, D. G. In situ formation of an oxygen-
oxygen evolution activity over Co−Pi loaded ZnO compared to evolving catalyst in neutral water containing phosphate and Co2+.
that over ZnO was directly observed from a photocatalytic Science 2008, 321, 1072.

F dx.doi.org/10.1021/ie2027469 | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

Industrial & Engineering Chemistry Research Article

(13) Zhang, F.; Maeda, K.; Takata, T.; Domen, K. Improvement of (31) Surendranath, Y.; Dincǎ, M.; Nocera, D. G. Electrolyte-
the photocatalytic hydrogen evolution activity of Sm2Ti2S2O5 under dependent electrosynthesis and activity of cobalt-based water oxidation
visible light by metal ion additives. J. Catal. 2011, 280, 1. catalysts. J. Am. Chem. Soc. 2009, 131, 2615.
(14) Liu, G.; Hua, G. Y.; Wang, X.; Cheng, L.; Pan, J.; Gao, Q. L.; (32) Lutterman, D. A.; Surendranath, Y.; Nocera, D. G. A self-healing
Cheng, H. M. Visible light responsive nitrogen doped anatase TiO2 oxygen-evolving catalyst. J. Am. Chem. Soc. 2009, 131, 3838.
sheets with dominant {001} facets derived from TiN. J. Am. Chem. Soc. (33) Kanan, M. W.; Yano, J.; Surendranath, Y.; Dincã, M.; Yachandra,
2009, 131, 12868. V. K.; Nocera, D. G. Structure and valency of a cobalt−phosphate
(15) Mukherji, A.; Marschall, R.; Tanksale, A.; Sun, C.; Smith, S. C.; water oxidation catalyst determined by in situ X-ray spectroscopy. J.
Lu, G. Q.; Wang, L. N-doped CsTaWO6 as a new photocatalyst for Am. Chem. Soc. 2010, 132, 13692.
hydrogen production from water splitting under solar irradiation. Adv. (34) McAlpin, J. G.; Surendranath, Y.; Dincã, M.; Stich, T. A.; Stoian,
Funct. Mater. 2011, 21, 126. S. A.; Casey, W. H.; Nocera, D. G.; Britt, R. D. EPR evidence for
(16) Yan, H. J.; Yang, J. H.; Ma, G. J.; Wu, G. P.; Zong, X.; Lei, Z. B.; Co(IV) species produced during water oxidation at neutral pH. J. Am.
Chem. Soc. 2010, 132, 6882.
Shi, J. Y.; Li, C. Visible-light-driven hydrogen production with
(35) Seabold, J. A.; Choi, K. S. Effect of a cobalt-based oxygen
extremely high quantum efficiency on Pt-PdS/CdS photocatalyst. J.
evolution catalyst on the stability and the selectivity of photo-oxidation
Catal. 2009, 266, 165. reactions of a WO3 photoanode. Chem. Mater. 2011, 23, 1105.
(17) Zhang, W.; Wang, Y.; Wang, Z.; Zhong, Z.; Xu, R. Highly (36) McDonald, K. J.; Choi, K. S. Photodeposition of co-based
efficient and noble metal-free NiS/CdS photocatalysts for H2 oxygen evolution catalysts on α-Fe2O3 photoanodes. Chem. Mater.
evolution from lactic acid sacrificial solution under visible light. 2011, 23, 1686.
Chem. Commun. 2010, 46, 7631. (37) Zhong, D. K.; Sun, J.; Inumaru, H.; Gamelin, D. R. Solar water
(18) Zhang, W.; Zhong, Z.; Wang, Y.; Xu, R. Doped solid solution: oxidation by composite catalyst/α-Fe2O3 photoanodes. J. Am. Chem.
(Zn0.95Cu0.05)1‑xCdxS nanocrystals with high activity for H2 evolution Soc. 2009, 131, 6086.
from aqueous solutions under visible light. J. Phys. Chem. C 2008, 112, (38) Zhong, D. K.; Cornuz, M.; Sivula, K.; Grätzel, M.; Gamelin, D.
17635. R. Photo-assisted electrodeposition of cobalt-phosphate (Co−Pi)
(19) Wang, Y.; Wu, J.; Zheng, J.; Xu, R. Highly active ZnxCd1‑xS catalyst on hematite photoanodes for solar water oxidation. Energy
photocatalysts containing earth abundant elements only for H2 Environ. Sci. 2011, 4, 1759.
production from water under visible light. Catal. Sci. Technol. 2011, (39) Barroso, M.; Cowan, A. J.; Pendlebury, S. R.; Grätzel, M.; Klug,
1, 940. D. R.; Durrant, J. R. The role of cobalt phosphate in enhancing the
(20) Li, Y. X.; Chen, G.; Zhou, C.; Sun, J. X. A simple template-free photocatalytic activity of α-Fe2O3 toward water oxidation. J. Am. Chem.
synthesis of nanoporous ZnS−In2S3−Ag2S solid solutions for highly Soc. 2011, 133, 14868.
efficient photocatalytic H2 evolution under visible light. Chem. (40) Surendranath, Y.; Kanan, M. W.; Nocera, D. G. Mechanistic
Commun. 2009, 2020. studies of the oxygen evolution reaction by a cobalt−phosphate
(21) Xin, G.; Guo, W.; Ma, T. Effect of annealing temperature on the catalyst at neutral pH. J. Am. Chem. Soc. 2010, 132, 16501.
photocatalytic activity of WO3 for O2 evolution. Appl. Surf. Sci. 2009, (41) Maensiri, S.; Laokul, P.; Promarak, V. Synthesis and optical
256, 165. properties of nanocrystalline ZnO powders by a simple method using
(22) Kominami, H.; Yabutani, K. I.; Yamamoto, T.; Kera, Y.; Ohtani, zinc acetate dihydrate and poly(vinyl pyrrolidone). J. Cryst. Growth
B. Synthesis of highly active tungsten(VI) oxide photocatalysts for 2006, 289, 102.
oxygen evolution by hydrothermal treatment of aqueous tungstic acid (42) Srikant, V.; Clarke, D. R. On the optical band gap of zinc oxide.
J. Appl. Phys. 1998, 83, 5447.
solutions. J. Mater. Chem. 2001, 11, 3222.
(43) Spathis, P.; Poulios, I. The corrosion and photocorrosion of zinc
(23) Wang, Z.; Luo, W.; Yan, S.; Feng, J.; Zhao, Z.; Zhu, Y.; Li, Z.;
and zinc oxide coatings. Corros. Sci. 1995, 37, 673.
Zou, Z. BiVO4 nano-leaves: Mild synthesis and improved photo-
(44) Fu, H.; Xu, T.; Zhu, S.; Zhu, Y. Photocorrosion inhibition and
catalytic activity for O2 production under visible light irradiation. enhancement of photocatalytic activity for ZnO via hybridization with
CrystEngComm 2011, 13, 2500. C60. Environ. Sci. Technol. 2008, 42, 8064.
(24) Liu, H.; Nakamura, R.; Nakato, Y. Bismuth−copper vanadate
BiCu2VO6 as a novel photocatalyst for efficient visible-light-driven
oxygen evolution. ChemPhysChem 2005, 6, 2499.
(25) Liu, H.; Nakamura, R.; Nakato, Y. A visible-light responsive
photocatalyst, BiZn2VO6, for efficient oxygen photoevolution from
aqueous particulate suspensions. Electrochem. Solid-State Lett. 2006, 9,
G187.
(26) Maeda, K.; Lee, B.; Lu, D.; Domen, K. Physicochemical effects
on photocatalytic water oxidation by titanium fluorooxynitride powder
under visible light. Chem. Mater. 2009, 21, 2286.
(27) Zong, X.; Sun, C.; Chen, Z.; Mukherji, A.; Wu, H.; Zou, J.;
Smith, S. C.; Lu, G. Q.; Wang, L. Nitrogen doping in ion-exchangeable
layered tantalate towards visible-light induced water oxidation. Chem.
Commun. 2011, 47, 6293.
(28) Silva, C. G.; Bouizi, Y.; Fornés, V.; García, H. Layered double
hydroxides as highly efficient photocatalysts for visible light oxygen
generation from water. J. Am. Chem. Soc. 2009, 131, 13833.
(29) Yi, Z.; Ye, J.; Kikugawa, N.; Kako, T.; Ouyang, S.; Stuart-
Williams, H.; Yang, H.; Cao, J.; Luo, W.; Li, Z.; Liu, Y.; Withers, R. L.
An orthophosphate semiconductor with photooxidation properties
under visible-light irradiation. Nat. Mater. 2010, 9, 559.
(30) Steinmiller, E. M. P.; Choi, K. S. Photochemical deposition of
cobalt-based oxygen evolving catalyst on a semiconductor photoanode
for solar oxygen production. Proc. Natl. Acad. Sci. U.S.A. 2009, 106,
20633.

G dx.doi.org/10.1021/ie2027469 | Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX