Revisiting the behaviour of BiVO4 as a carbon dioxide reduction photo-catalyst

Article abstract of DOI:10.1039/c7dt00414a

Bismuth vanadate is a widely known photocatalyst for the hydro-reduction of CO₂. In spite of the great appeal of such a catalytic system, problems arise due to deactivation of the catalyst with consequent low reaction yield. We have investigated the catalyst behavior during methanol production and have found that the catalyst irreversibly loses vanadium from the structure whilst depositing bismuth oxides on the surface of the catalyst. While catalyst activity can be restored upon heating, leaching of vanadium, leading in long term to catalyst decomposition, is unavoidable and irreversible.

Full text of DOI:10.1039/c7dt00414a

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DOI: 10.1039/C7DT00414A
Journal Name
ARTICLE
Revisiting the Behaviour of BiVO as a Carbon Dioxide Reduction
4
Photo-Catalyst.
Received 00th January 20xx,
Accepted 00th January 20xx
Jacob M. Sommers, Nicholas P. Alderman, Camilo J. Viasus, Sandro Gambarotta*
DOI: 10.1039/x0xx00000x
Bismuth vanadate is a widely known photocatalyst for the hydro-reduction of CO2. In spite of the great appeal of such a
catalytic system, problems arise due to deactivation of the catalyst with consequent low reaction yield. We have investigated
the catalyst behavior during methanol production and have found that the catalyst irreversibly loses vanadium from the
structure whilst depositing bismuth oxides on the surface of the catalyst. While catalyst activity can be restored upon
heating, leaching of vanadium, leading in long term to catalyst decomposition, is unavoidable and irreversible.
www.rsc.org/
Furthermore, BiVO
4
has also been demonstrated versatile
into methanol
. The authors of these remarkable findings have
reported promising hydrocarbon yields along with the
possibility of regenerating BiVO upon heating. The ability of
regenerating BiVO is a critical point for the performance of this
photosemiconductor and which remains otherwise regrettably
limited. In addition, BiVO has been deposited over anodes to
prepare photo-electroanodes of improved catalytic
photosemiconductor for the reduction of CO
and ethanol
2
Introduction
The idea of using water as a hydrogenating agent for organic
products, and for CO in particular, is fascinating and potentially
2
22,23
4
ground breaking. In 1978, Halmann M. was the first to report
the photoelectrochemical reduction of CO2 in water using p-
4
1
GaP , and ever since, a wide spectrum of semiconductors
4
capable of both oxidizing water and reducing CO
2
is being
actively pursued.2 The work of Bocarsly has marked a
milestone in the production of light organic fuels from CO /H
–5
28
behaviour. A recent study, however, has clearly demonstrated
the corrosion of the BiVO film of the photo-anode in alkali
medium thus reiterating the previously suspected ability of this
2
2
O
4
mixtures, a process now referred to as “reverse combustion”.
To overcome the unfavourable thermodynamics of this highly
desirable transformation energy has been provided with
29
binary oxide to irreversibly leach vanadium in alkali solution .
electro-,6 photo-
,7
8,9
or photo-electrochemical devices.
10,11
This led us now to reconsider the activation/deactivation paths
However, the possibility of using purely photochemical devices
remains the ultimate requisite for a completely sustainable and
scalable reverse combustion.
of BiVO
electrochemical input which might otherwise decrease the
stability of BiVO by accelerating the loss of vanadium.
4
in purely photochemical processes and not involving
29
4
Currently, titanium dioxide and BiVO
photo-catalysts for this purpose. These materials have been
4
are the most popular
Eo
/ V vs SHE
redox
-0.50
modified to control size, conductivity and sensitivity to visible
light 3
,12–16
. A plethora of other photo-semiconductors that can
to light organic
fuels, especially methanol and methane, has also been
efficiently absorb visible light and convert CO
2
HCOOH/CO2
HCHO/CO
V)
TiO2
(-0.17
V)
BiVO4
H
2/
2H+
V)
0
2
(-0.04
(0.00
discovered 1 . The unique popularity of BiVO
7–23
is justified by
CH OH/CO2
V)
(+0.04
4
3
its demonstrated versatility as a water oxidation catalyst for
selective alcohol production from CO
2
and also
+
1.00
photodegradation of organic waste24–27. Monoclinic BiVO
~2.4 eV
4
has
H O/O2
V)
~3.2 eV
2
(+1.23
conduction and valence bands which are well suited for water
oxidation coupled with CO reduction and hydrogen evolution
Figure 1). Its usage is in principle advantageous over other
common water oxidation catalysts, including TiO , due to its
2
+
2.00
(
2
narrow band gap of ~2.4 eV, which allows ready absorption of
visible light.
+3.00
Figure 1. Band structure of monoclinic BiVO4 and anatase TiO2 demonstrating filled
valence bands on the bottom (more positive) and empty conduction bands at the top
(
Department of Chemistry and Biomolecular Sciences, University of Ottawa, ON,
Canada, K1N 6N5
more negative) 30,31
.
*
sandro.gambarotta@uottawa.ca
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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Similarly, it has previously been shown that the BiVO can be
4
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o
DOI: 10.1039/C7DT00414A
Experimental
Synthesis of Semiconductors
reactivated simply by heating the catalyst to 80 C, with little loss
of activity 23. In all of our experiments, we saw both a decrease
in methanol concentration after 200 minutes of catalytic testing
and a permanent deactivation of the catalyst after reactivation
by heating. This is in contrast to other published work,23 where
a linear production of methanol was observed with little loss of
activity after regeneration. In an attempt to understand these
discrepancies, further investigation of the intermediate
products and catalyst composition were performed with
pristine and reactivated BiVO4.
Synthesis of m-BiVO
BiVO was prepared by a CTAB-assisted hydrothermal method
as reported by Liu et al.
4
hyperbranched crystals: Monoclinic
4
22
Synthesis of m-BiVO
NH VO and Na SO were added to water in a molar ratio
:1:1.1, respectively. The mixture was stirred in a glass vessel
4 3 3 2
polyhedral crystals: Bi(NO ) .5H O,
4
3
2
4
1
o
pressure vessel forming a yellow solid and heated to 180 C for
4h. The solid was filtered and washed with three portions of
2
o
cold water. The solid was dried at 140 C for 12h. The resulting
solid was analysed by powder X-ray diffraction (XRD) and was in
agreement with published monoclinic bismuth vanadate.
A
Catalytic Testing
In a typical reaction, 0.4 g of catalyst and 200 mL of a 1.0 M
NaOH solution were place in a quartz flat bottom flask adjacent
to a 300 W Xe arc-lamp. Prior to light irradiation, the reaction
mixture was thoroughly degassed and allowed to equilibrate
2
under a CO atmosphere for 30 minutes. Methanol was
detected with an Agilent 7820A GC with a flame ionization
detector (FID), using a Restek Rt-U-Bond column and helium
51
carrier gas. V NMR spectra were recorded on a Bruker Avance
II 300 MHz spectrometer using neat VOCl as a standard.
Chemical shifts are reported in p.p.m. Spectra were recorded at
98 K. Powder XRD diffractograms were obtained on a Rigaku
3
B
2
Ultima IV diffractometer. X-ray Fluorescence (XRF)
measurements were performed on a Rigaku Supermini-200.
UV-Vis spectra were obtained on a Specmate UV-1100
spectrometer. Scanning electron microscopy and energy
dispersive X-ray analysis was performed with a JSM-7500F SEM
instrument by JEOL, Inc. The concentration of formaldehyde
3
2
was determined by a colorimetric procedure by Nash .
Concentration of dissolved formate was determined by a
colorimetric procedure by Sleat and Mah.33
C
Results and Discussion
CO
In this study, we focused on using hyperbranched structures
hyp-BiVO ) for CO reduction due to high activity, and for
decomposition studies both polyhedral crystals (poly-BiVO
and hyperbranched structures (hyp-BiVO ) (Figure 2).
Both hyp-BiVO and poly-BiVO are capable of reducing carbon
dioxide into methanol. Literature data indicate that the
2
reduction
(
4
2
4
)
4
4
4
methanol production reaches
decomposition .
a
maximum with no
14
Figure 3. Concentration of a) methanol, b) formaldehyde and c) formate during catalysis.
A
B
Figure 2. a) Polyhedral crystals of monoclinic BiVO4 and b) hyperbranched crystals of
monoclinic BiVO4.
2
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Table 1. Quantitative analysis of oxidation and reduction of intermediates and products
with BiVO4 after 24 hr.
View Article Online
DOI: 10.1039/C7DT00414A
Starting
Material
Methanol
MeOH
(µmol)
CH
(μmol)
28
2
O
HCOO-
(μmol)
13
H
2
(μmol)
3.6
Formaldehyde 460
71
25
Sodium
formate
300
n.d.
n.d.
While we did not observe the formation of EtOH as reported in
the literature,22 both formate anion and formaldehyde, along
with methylformate were generated during the catalytic runs.
Formate concentration appears to stabilize after 3 hours
without loss of activity. Formaldehyde and methanol
production decreases after recovery of the BiVO
4
catalyst, Figure 5. Comparison of powder XRD patterns of A) inactive hyp-BiVO4 from reaction
with formaldehyde B) inactive hyp-BiVO4 from CO2 photoreduction and C) literature
although the activity in formate formation does not appear to
be affected by catalyst recovery. In all cases, no methane was
detected confirming that the methanol loss after initial
formation (Figure 3a) is not due to further reduction. We
2
spectrum of Bi O4-x. SEM micrograph of hyp-BiVO4 from formaldehyde-spiked conditions
is inset
attribute the loss of methanol to the re-oxidation into lower This effect is also seen during methanol production but to a
value organics, including formaldehyde and formate by either lesser extent. The heavy coating of the active surface of BiVO4,
BiVO
4
or the quartz reactor. The oxidation of several alcohols, which is present only in inactive samples, suggests that this
including methanol into formaldehyde, has been shown to coating is at least partially responsible for the deactivation of
34
occur in glass and quartz reaction vessels upon irradiation . No the catalyst. This likely occurs due to blocking of the active
other small organic molecules were detected. This perhaps surface by the coating of bismuth oxide, which can be partially
could be taken as evidence for CO
2
photoreduction to initiate removed by regenerating the catalyst during heating.
via monodentate binding, with stepwise proton-coupled From the experiments of BiVO with formaldehyde, we observe
4
electron transfers producing methanol as a final product.
that the deposition of Bi2O4-x is caused at the surface of the
Potential oxidation products of methanol, formaldehyde, and catalyst by a reaction with formaldehyde, one of the key
sodium formate (Table 1) in a 1M solution of NaOH were intermediates in the reduction to methanol. In turn, this
studied to help decipher the pathway for methanol reoxidation. indicated irreversible loss of vanadium from the original BiVO4
In all cases methane, carbon monoxide or other organic structure.
products were not observed.
Several unsuccessful attempts were performed to try to reinsert
To observe the effect of formaldehyde on BiVO
4
, an experiment the vanadium back into the etched BiVO4 structures by
was performed with formaldehyde as the starting organic illuminating with various vanadium sources in water (NH VO or
4
3
material. Interestingly, when this BiVO
4
catalyst was analysed etched vanadium solution).
by XRD and SEM, large amounts of Bi2O4-x nanoparticles were
detected over the starting BiVO
4
(Figure 5).
A
B
C
hv
NaOH
150oC
CO
2
D
E
F
Figure 4. SEM images of (a) pristine, (b) inactive, and c) reactivated poly-BiVO4, and (d)
pristine, (e) inactive and (f) reactivated hyp-BiVO4.
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XRD data (Figure 7) reveals the formation of a newVi,ewcrAyrtsictlae lOlinnlinee,
material contaminating the sample of BiVODO
ti
photoreduction necessarily peaks correspond with literature samples of a mixed valence
requires the use of base 22. However we have found that in 1M bismuth oxide, denoted as Bi 4-x36. Attempts to separate this
NaOH aqueous solutions, both with and without 1 atmosphere contaminant from the bulk BiVO have been unsuccessful. We
of CO , BiVO will become etched and Bi 4-x nanoparticles are assign the electron rich surface deposits (Figure 6) to Bi
deposited on the surface of the catalyst (Figure 4 b/e). By using
Catalyst deactivation
4
.
I:
T
1
h
0
e
.10
c
3
o
9
n
/
t
C
a
7
m
DTin00
a
4
14A
o
n
4 2
The activity of BiVO towards CO
2
O
4
2
4
2
O
2 4-x
O .
a backscatter filter to determine surface electron density, The molar percent of oxygen does not change significantly
deposited nanoparticles are revealed to be very dense, between samples (Table 2), although vanadium and bismuth
compared to bulk BiVO
deactivated and shows limited CO
etching has also been shown to occur without illumination . is compared to the inactive ratio of 0.77 and the recovered ratio
The catalyst can be reactivated by heating to 150 C which of 0.83. This confirms that a large amount of surface vanadium
4
. In this state, the catalyst has become percentages are greatly altered in post-reaction. Pristine hyp-
reduction activity. The BiVO has a ratio of 0.99 V/Bi, by surface molar percentage. This
2
4
3
5
o
removes the electron rich deposits from the surface by drawing is irreversibly lost during the reaction, likely caused by leaching
vanadium density from the inner BiVO
can be reactivated, it remains irreversibly etched (Figure 4 c/f). observed from the structure by XRF measurements (see S.I.). To
The reactivated catalyst was tested for CO reduction under the confirm that vanadium was lost to the filtrate, a sample of the
same conditions and was shown to have reduced activity filtrate was dried and EDS measurements of the filtrate taken
compared to pristine BiVO (Figure 3). Composition of the BiVO which shows only vanadium in solution (Figure 6b). This is
surface was analysed during all stages of BiVO
Table 2).
4
. Although the catalyst in the alkaline conditions. Similar losses of vanadium were
2
4
4
regeneration further confirmed by 51V NMR of the filtrate which shows
multiple peaks, characteristic of a mixture of aqueous vanadium
oxides (Figure 4c).
4
(
In addition to visual modifications and vanadium leaching, the
Table 2. Energy dispersive spectroscopy (EDS) derived molar % of bismuth, vanadium and
oxygen on the surface of hyp-BiVO4 averaged over three samples.
bulk inactive catalyst undergoes changes in its crystal structure
Figure 7).
(
Sample
Pristine hyp-
% Bi
15.3
% V
% O
±
±
±
1.4
0.7
0.3
15.2
±
1.5
69.5
±
±
±
±
2.7
1.1
0.4
2.4
BiVO
Inactive hyp-
BiVO
Reactivated
hyp-BiVO
4
17.6
16.7
0.00
13.52
13.92
±
±
0.4
69.4
4
0.02 68.8
4
Dried hyp-BiVO
filtrate
4
19.0
±
2.4
81.0
A
B
C
C
Figure 6. A) SEM image of dried filtrate after etching, B) elemental composition of particle obtained by EDS, and C) 51V NMR of post-reaction filtrate.
4
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1
3
4
recombination rates, etc.) BiVO will rapidly decay with loss of
vanadium and deposition of bismuth oxides and will require
constant recovery by heating. However, vanadium leaching and
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4
, deactivated BiVO
4
and reactivated BiVO
4
20
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The major and minor products formed in this reaction provide
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2
1
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