Catalysis Communications 11 (2009) 210–213

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Selective ethanol formation from photocatalytic reduction of carbon dioxide

in water with BiVO4 photocatalyst
Yuanyuan Liu a, Baibiao Huang a,*, Ying Dai b, Xiaoyang Zhang a, Xiaoyan Qin a, Minhua Jiang a,
Myung-Hwan Whangbo c
a
State Key Lab of Crystal Materials, Shandong University, Jinan 250100, China
b
School of Physics, Shandong University, Jinan 250100, China
c
Department of Chemistry, North Carolina State University Raleigh, NC 27695-8204, USA

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

Article history: The visible-light responsive photocatalyst BiVO4 was synthesized, and its photocatalytic reduction of CO2
Received 8 August 2009 in water was examined. Our study shows the selective formation of ethanol under the condition of high
Received in revised form 8 September 2009 intensity visible-light irradiation, and suggests that intense irradiation generates a large number of C1
Accepted 5 October 2009
intermediate species anchored on the surface of BiVO4, which dimerize to form ethanol. For the photo-
Available online 12 October 2009
catalytic reduction of CO2 into ethanol, monoclinic BiVO4 is more efficient than tetragonal BiVO4.
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
CO2 reduction
Photocatalyst
Photoreduction
BiVO4

1. Introduction
Carbon dioxide, CO2, has been receiving much attention as a
greenhouse gas, but it is also an inexpensive, non-flammable and
non-toxic C1 source. It is highly desirable to be able to convert
CO2 into useful carbon products [1–3]. Since the first report of
the photocatalytic reduction of CO2 in water over various semicon-
ductor photocatalysts [4], this photoreduction has been explored in
a number of studies [5–9]. However, it still remains a challenge to
find how this reaction can be efficiently carried out using the vis-
ible-light. So far, a few examples have been reported to be visi-
ble-light active for the photoreduction of CO2. Pan and Chen
synthesized NiO/InTaO4 and found that this catalyst is able to re-
duce CO2 into methanol under visible-light irradiation [10]. Dye-
sensitized CO2 reduction over semiconductors and some supramo-
lecular photocatalysts were also reported to be efficient in reduc-
ing CO2 under visible-light irradiation [11–15]. However, the
photocatalytic reduction of CO2 into ethanol as a major product
has rarely been reported in the literature.
Monoclinic bismuth vanadate, BiVO4, is a photocatalyst for O2
production from water that can be driven by the visible-light
[16]. This reaction suggests that the photogenerated holes of BiVO4
are consumed by water to produce O2, namely,
2H2O + 4h+ ? O2 + 4H+. The byproducts of this photocatalytic reac-
* Corresponding author. Tel./fax: +86 531 8836 5969.
E-mail address: bbhuang@sdu.edu.cn (B. Huang).
tion are photogenerated electrons e and protons H+. Since it is dif-
ficult for the photogenerated electrons to capture the protons in
water to form H2 [17,18], one might consider the possibility of con-
verting CO2 to organic compounds by using the photogenerated
electrons e and protons H+. With this in mind, we tested the fea-
sibility of the photocatalytic reduction of CO2 in water with dis-
persed BiVO4 powder. This photoreduction leads selectively to
ethanol, C2H5OH, under the condition of high intensity visible-light
irradiation.
2. Experimental
2.1. Catalysts preparation and characterization
BiVO4 was prepared by using the microwave assisted hydro-
thermal method [19,20]. Stoichiometric amounts of Bi(NO3)3
5H2O
and NH4VO3 were dissolved into dilute HNO3 and NaOH aqueous
solution, respectively. Then surfactant CTAB (cetyl trimethyl
ammonium bromide) or PEG (polyethylene glycol) was added to
both solutions. After stirring for 0.5 h, the two solutions were
mixed. This precursor solution was poured into a Teflon-lined
stainless steel autoclave, and then heated at 200 °C for 30 min un-
der microwave irradiation. After the autoclave was cooled to room
temperature, the yellow precipitate was separated by filtration,
washed with distilled water several times to totally remove the
surfactant, and then dried at 100 °C for 4 h. X-ray diffraction

1566-7367/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2009.10.010
 Y. Liu et al. / Catalysis Communications 11 (2009) 210–213 211

a 80 b
tetragonal BiVO4 1.2
monoclinic BiVO 4
40
1.0
tetragonal BiVO 4

intensity [a.u.]

abs. [a.u.]
0.8
0
2.2
0.6 2.0
1.8 tetragonal BiVO 4
1.6

absorption
80 1.4
monoclinic BiVO 4 0.4 1.2
1.0
0.8
0.6
40 0.2 0.4
0.2
monoclinic BiVO 4

0.0
2.0 2.2 2.4 2.6 2.8 3.0 3.2

0 0.0 hυ(eV)

10 20 30 40 50 60 70 80 200 300 400 500 600

2 theta (degree) wave length (nm)

Fig. 1. (a) XRD patterns and (b) diffuse reflectance spectra of monoclinic fergusonite and tetragonal zircon-type BiVO4.

Fig. 2. SEM images of (a) tetragonal zircon-type and (b) monoclinic fergusonite BiVO4.

(XRD) results show that the use of CTAB leads to the monoclinic
scheelite BiVO4, but that of PEG to the tetragonal zircon BiVO4.
XRD patterns of the samples were recorded on an X-ray diffrac-
tometer (Bruker AXS D8). The morphology and microstructure
were determined by scanning electron microscopy SEM (Hitachi
S-4800 microscope), and its diffuse reflectance by UV/visible spec-
troscopy (UV-2550, Shimadzu). FT-IR spectra were recorded by
Nicolet Nexus 670.
tion was determined by using the data obtained for the irradiation
time of 80 min. Blank runs performed with N2 instead of CO2 re-
sulted in no ethanol, as expected.
The evolved O2 and CO2 were measured by Varian GC3800 (TCD
detector, molecular sieve 5A column and Propark Q column, N2
carrier).
3. Results and discussion

2.2. Photocatalytic reaction testing

3.1. Catalyst characterization

For our photoreduction experiment, 0.2 g of BiVO4 powder was

The XRD patterns of the as-prepared BiVO4, shown in Fig. 1a, are
dispersed in 100 ml water and magnetically stirred, and CO2 was
in good agreement with the JCPDS (Joint Committee on Powder
continuously bubbled through the solution at the rate of 0.4 L/
Diffraction Standards) No. 14-0688 (for monoclinic BiVO4) and
min. 300 W Xe arc lamp (PLS-SXE300, Beijing Trusttech Co., Ltd.)
with and without UV cutoff filter (providing visible-light with
k P 400 nm) were used for the irradiation. The temperature of 20
the reaction chamber was kept at 0 °C to increase the solubility
of CO2 in water (334.6 mg/100 g water at 1 atm and 0 °C) and also 10
keep the product ethanol in solution.
tetragonal BiVO4
The repeated experiments were conducted as follows: at the
intensity (a.u.)

0
end of each cycle of photoreduction, the suspension was centri-
fuged and the supernatant was discarded. The recovered catalyst
was dried in air at 80 °C for the next cycle of photoreduction. -10
The product in the liquid solution was first qualitatively identi-
fied by Varian GC3800 (FID detector, VF-5ms capillary columns) by
-20 monoclinic BiVO4
observing the chromatographic peaks related to the elution of eth-
anol and then comparing them with those for an authentic ethanol
standard. This identification was further confirmed by GC/MS- -30
QP2010 (Shimadzu, DB-1 capillary columns), which showed that
the major peak (>90%) has a molecular weight of 46, i.e., ethanol. 500 1000 1500 2000 2500 3000 3500 4000
Varian GC3800 was used to determine the amount of the prod- wavenumber (cm )
-1

uct. Each measurement was repeated three times, and the average
values were used for our analysis. The rate of the product forma- Fig. 3. FT-IR spectra of the as-prepared BiVO4.
212 Y. Liu et al. / Catalysis Communications 11 (2009) 210–213
a b
30
25
20
monoclinic BiVO4
μmol
μmol
15
10
5 tetragonal BiVO4
0
0 20 40 60 80
time/min
Fig. 4. Photocatalytic ethanol evolution under 300 W Xe-arc lamp irradiation (a) with and (b) without UV cutoff filter (providing visible-light with k P 400 nm).
No. 14-0133 (for tetragonal zircon-type BiVO4). The UV/visible dif-
fuse reflectance spectra of the as-prepared monoclinic and tetrag-
onal BiVO4 are presented in Fig. 1b. The absorption of monoclinic
BiVO4 covers the UV and visible regions. The absorption tail of
tetragonal BiVO4 at k = 450–550 nm may result from crystal de-
fects. The band gaps of the monoclinic and tetragonal forms are
estimated to be 2.24 and 2.56 eV, respectively (the inset of
Fig. 1b). The scanning electron microscopy (SEM) images of BiVO4
(Fig. 2) show that the tetragonal phase forms rod-like structures
with diameter of 1 lm, and the monoclinic phase sheet-like struc-
tures with length of 400 nm–1 lm. FT-IR spectra indicates that no
CTAB or PEG were remained on the as-prepared BiVO4 (Fig. 3).
3.2. Photocatalytic reduction of CO2
Fig. 4 summarizes the production of ethanol over monoclinic
and tetragonal BiVO4 as a function of the irradiation time. For both
tetragonal and monoclinic BiVO4, the ethanol yield increases al-
most linearly with increasing the irradiation time. Monoclinic
BiVO4 exhibits a much higher photocatalytic activity than does
tetragonal BiVO4. When the irradiation light is extended into the
UV region, the rate of the ethanol production increases by a factor
of 17 for monoclinic BiVO4 (Fig. 4 and Table 1). Our further exper-
iments show that the intensity of the light irradiation plays an
important role in the ethanol formation, because both methanol
and ethanol were formed with comparable rates when a 36 W fluo-
rescent lamp is used for the irradiation (Table 1). Blank runs with
N2 instead of CO2 with a pH value of ca. 3 (pH value of the satu-
rated CO2 solution at 0 °C, 1 atm) were performed, which resulted
in no ethanol, as expected. In addition, both commercial P25 and
N-doped P25 were used for the photocatalytic reduction of CO2 un-
der the same condition for a comparative study, and no ethanol or
methanol production was detected in aqueous solution.
The outlet gases were determined to be O2 and CO2. This is in
agreement with the literature that the monoclinic BiVO4 is a pho-
tocatalyst for O2 evolution in water as mention above. The absence
Table 1
Rates of the ethanol and methanol production in lmol/h (reth and rmeth, respectively)
under three different light-irradiation conditions.a,b
BiVO4 Condition 1 Condition 2 Condition 3
Monoclinc reth = 21.6 reth = 406.6 reth = 2.3
rmeth = 0 rmeth = 0 rmeth = 1.8
Tetragonal reth = 1.1 reth = 4.9 reth = 0.6
rmeth = 0 rmeth = 0 rmeth = 0.6
a
The rate was determined on the basis of the average production rate after a
reaction time of 80 min.
b
Condition 1: 300 W Xe-arc lamp with UV cutoff filter; Condition 2: 300 W Xe-
arc lamp without UV cutoff filter; Condition 3: 36 W fluorescent lamp.
600
500
400 monoclinic BiVO4
300
200
100
tetragonal BiVO4
0
0 20 40 60 80
time/min
of H2 in the outlet gases suggests that the proton failed to capture
the photogenerated electrons, which confirmed the previous re-
port that it is difficult for the photogenerated electrons to interact
with the protons in water to form H2 [17,18]. It is known that the
potential is lowered by nearly 0.7 eV when CO2 was changed to
CO23 [10]; so that CO23 is most likely to adopt the photogenerated
electrons and give rise to methanol after protonation. It is reported
that tetraalkylammonium salts can promote the dimerization rad-
ical anion CO2 due to high concentration of both CO2 molecules
and CO2 radical anions adsorbed at the photocatalysis [21].
Accordingly, under intense irradiation, a large number of photo-
generated electrons and protons leading to a large number of C1
intermediate species anchored on the surface of BiVO4, which will
facilitate their dimerization to form ethanol.
The stability of BiVO4 was checked by carrying out the photo-
catalytic reduction experiment repeatedly five times. As shown
in Fig. 5, nearly constant amount of ethanol was obtained for each
cycle. The XRD pattern of BiVO4 at the end of the repeated exper-
iment is almost identical to that of the as-prepared sample.
Monoclinic BiVO4 is efficient for ethanol formation most likely
because CO23 is anchored to the Bi3+ sites on the surface through
a weak Bi. . .O bond so that they can efficiently receive the photo-
generated electrons from the V 3d-block bands of BiVO4. The pro-
posed mechanism explains why monoclinic BiVO4 is more efficient
than tetragonal BiVO4. The local environment around the Bi3+ ion is
more strongly asymmetric in the monoclinic phase than in the
tetragonal phase, so that the Bi3+ ion has a stronger lone pair char-
acter in the monoclinic phase and hence has a stronger tendency to
form a Bi. . .O bond with CO23 [22]. This will lead to a more efficient
600
500
400
300
μmol
200
100
0
0 1 2 3 4 5
number of cycle
Fig. 5. Repeated photoreduction experiments under UV–visible-light, irradiation
time 80 min.
 Y. Liu et al. / Catalysis Communications 11 (2009) 210–213 213

transfer of photogenerated electrons from the V 3d-block bands to References

the anchored CO23 in the case of monoclinic BiVO4.
4. Conclusions
In summary, under UV–visible-light irradiation, the photore-
duction of CO2 in water with BiVO4 leads selectively to ethanol.
This photoreduction is more effective over monoclinic than over
tetragonal BiVO4, and becomes strongly enhanced under UV irradi-
ation. Our finding is promising because this photoreduction can be
driven by visible-light irradiation, removes the greenhouse gas CO2
and forms the useful organic compound ethanol. The optimization
of this reaction condition and the investigation of the reaction
mechanism are under progress.
Acknowledgments
This work was financially supported by the National Basic Re-
search Program of China (973 Program, Grant 2007CB613302),
the National Natural Science Foundation of China under Grant
20973102, 50721002, and 10774091. M.-H.W. is thankful for sup-
port by the Office of Basic Energy Sciences, Division of Materials
Sciences, US Department of Energy, under Grant DE-FG02-
86ER45259. We acknowledge Professor L. M. Mei and Z.G. Zou
for discussions.
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