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Accepted Article

Title: Plasmonic Hot Electrons from Oxygen Vacancies for Infrared

Light-Driven Catalytic CO2 Reduction on Bi2O3-x

Authors: Yingxuan Li, Miaomiao Wen, Ying Wang, Guang Tian,

Chuanyi Wang, and Jincai Zhao

This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.

To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202010156

Link to VoR: https://doi.org/10.1002/anie.202010156

Angewandte Chemie International Edition
RESEARCH ARTICLE
Plasmonic Hot Electrons from Oxygen Vacancies for Infrared
Light-Driven Catalytic CO2 Reduction on Bi2O3-x
Yingxuan Li,*[a] Miaomiao Wen,[a] Ying Wang,[b] Guang Tian,[a] Chuanyi Wang,[a] and Jincai Zhao[c]
Dedication ((optional))
[a] Prof. Y. Li, M. Wen, G. Tian, Prof. C. Wang
School of Environmental Science and Engineering, Shaanxi University of Science and Technology, Xi’an 710021, China
E-mail: liyingxuan@sust.edu.cn
[b] Prof. Y. Wang
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022,
China
[c] Prof. J. Zhao
Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of
Sciences, Beijing 100190, P. R. China
Supporting information for this article is given via a link at the end of the document.
Abstract: Current plasmonic photocatalysts are mainly based on
noble metal nanoparticles and rarely work in the infrared (IR) light
range. Here, cost-effective Bi2O3-x with oxygen vacancies was formed
in situ on commercial bismuth powder by calcination at 453.15 K in
atmosphere. Interestingly, defects introduced into Bi2O3-x
simultaneously induced a localized surface plasmon resonance
(LSPR) in the wavelength range of 600-1400 nm and enhanced the
adsorption for CO2 molecules, which enabled efficient photocatalysis
of CO2-to-CO (~100% selectivity) even under low-intensity near-IR
light irradiation. Significantly, the apparent quantum yield for CO
evolution at 940 nm reached 0.113%, which is approximately 4.0
times that found at 450 nm. We also showed that the unique LSPR
allows for the realization of a nearly linear dependence of
photocatalytic CO production rate on light intensity and operating
temperature. Finally, based on an IR spectroscopy study, an oxygen-
vacancy induced Mars−van Krevlen mechanism was proposed to
understand the CO2 reduction reactions.
Introduction
Solar-driven carbon dioxide (CO2) reduction by photocatalysis
is a promising strategy for producing chemical fuels and reducing
greenhouse gases, which requires the development of efficient
photocatalysts promoted by a wide range of solar light
wavelengths.[1] In early research, photocatalysts that can only
respond to ultraviolet (UV) light (~4% of solar light), such as TiO2,
BaZrO3, Zn2GeO4, and NaTaO3, have been extensively studied
for CO2 reduction.[2-6] To use the broad spectrum of solar light,
different strategies involving the exploration of novel
semiconductors with narrow band gaps, and activating a UV-light
response photocatalysts (through substitutional doping,
combining, etc.) have been studied.[7] Among these methods,
coupling plasmonic metals with semiconductor photocatalysts
has gained heightened interest due to the unique optical
properties generated by localized surface plasmon resonance
(LSPR) features.[7] In these hybrid systems, the plasmonic metals
function as either light antennas or sensitizers. Unfortunately, the
applications of these systems are significantly hindered by the low
hot charge transfer efficiency from metal to catalytically active
1
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10.1002/anie.202010156
Accepted Manuscript
sites on the semiconductor, which is attributed to the built-in
Schottky barrier at the semiconductor-metal interface.[8]
In addition to the indirect use of hot charges in plasmonic
metal/semiconductor heterostructures, theoretical and
experimental evidence has recently shown that the charges
excited by LSPR can be directly transferred from plasmonic
nanoparticles into adsorbed molecules to catalyze chemical
reactions,[8-9] which has been termed as plasmonic
photocatalysis.[10] Unlike semiconductors for which the majority of
surface electronic states are focused in the bulk, the LSPR effect
is confined to the surface of nanostructures. This characteristic
offers a few critical advantages for plasmonic photocatalysis. For
example, a linear dependence of reaction rate on light intensity
has been observed for plasmonic metal-based
photocatalysts.[5,6,11] In sharp contrast, the reaction rates on
semiconductor photocatalysts typically vary as the square root of
the intensity of incident light.[12-15] However, most current
plasmonic photocatalysts are based on noble metal nanoparticles,
and the majority of these photocatalysts can only drive
photocatalytic reactions under UV-visible (UV-Vis) light irradiation.
The exploration of plasmonic photocatalysts that can work under
infrared (IR) light (accounting for ~50% of the solar energy)
irradiation is still a big challenge.
Unlike widely studied noble metals, the LSPR achieved in
vacancy-doped semiconductors, such as Cu2-xS, WO2.72, and
MoO3-x, can generally induce intense absorption in the IR light
region.[16-19] This phenomenon creates opportunities for
developing IR light-driven photocatalysts based on plasmonic
semiconductors. However, the number of these types of
photocatalysts is still very limited, and they are rarely able to
reduce CO2 under IR light irradiation.[18,19] Here, Bi2O3-x with
oxygen defects was discovered as a new plasmonic photocatalyst
for efficient CO production by CO2 reduction with H2. Similar to
noble metals, nearly linear dependences for the reaction rates on
the light intensity or reaction temperature were observed on Bi2O3-
x. Especially, the LSPR excitation enables Bi 2O3-x to perform
photocatalytic CO2 reduction under low-intensity light-emitting
diode (LED) light with a wavelength of up to 940 nm. Our findings
create an opportunity for developing broad-light-responsive
photocatalysts for solar energy conversion.
Angewandte Chemie International Edition
RESEARCH ARTICLE
Results and Discussion
Bi2O3-x was synthetized by oxidizing commercial Bi powder in
air at 453.15 K for 8 h. Prior to calcination, the commercial Bi
powder was treated in 0.1 mol/L nitric acid for 2 min to remove the
oxide layer. Without additional illustrations, the Bi powder referred
in the following is the product obtained after acid treatment of the
commercial Bi. The crystal structures for the powders before and
after calcination were determined from powder X-ray diffraction
(XRD). As shown in Figure 1a, the main diffraction peaks for both
samples can be indexed as rhombohedral phase Bi (PDF No. 44-
1246). However, as shown by the blue line in Figure 1a, additional
peaks appear after calcination that correspond to the planes of
Bi2O3 (PDF No. 65-1209). The XRD result shows that Bi oxide
was formed in the calcination process, which results in the
coexistence of elemental Bi and Bi oxide in the sample.
Figure 1. Characterizations for Bi and Bi2O3-x: a) XRD patterns, b) UV-Vis-IR
absorption spectra, c) EPR patterns, d) O 1s XPS spectra, e) Mott-Schottky
plots. f) Schematic illustration of LSPR excitation on Bi2O3-x.
The optical properties of the as-synthesized samples were
measured by UV-Vis-IR absorption spectra (Figure 1b). As shown
in Figure 1b, the sample after calcination shows a strong
absorption peak ranging from 600 nm to 1400 nm, which is
associated with the LSPR of the sample.[18] In contrast, the light
absorption for the Bi powder occurs only in the ultraviolet and
visible light regions with an absorption edge at ~700 nm. The
plasmonic resonance in Figure 1b can be attributed to the
oxidation of Bi by calcination, which originates from the free
electrons and/or deficient oxygen-induced small polarons.[20-22]
Consequently, we can speculate that oxygen vacancies are
formed due to the incomplete oxidation of Bi. Similar LSPR
induced by oxygen vacancies has been observed on W18O49,
2
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10.1002/anie.202010156
WO3-x, MoO2, and In2O3-x.[19,23-25] The Bi powder after calcination
is denoted as Bi2O3-x in this text.
To characterize the oxygen deficiency, electron paramagnetic
resonance (EPR) and X-ray photoelectron spectroscopy (XPS)
were carried out. As shown in Figure 1c, the sample after
calcination showed a clear EPR signal at g = 2.001, which is
closely related to the electrons trapped on oxygen vacancies. [26-
27]
Comparatively, no EPR signal was observed for the Bi powder.
The EPR data indicate the existence of oxygen defects in the
sample after calcination, which is consistent with the absorption
spectra shown in Figure 1b. XPS analysis was conducted to
further identify the oxygen vacancy level. O 1s core level spectra
for the samples before and after calcination are shown in Figure
Accepted Manuscript
1d. For both samples, three distinct peaks are observed. The
peaks at 529.9 eV and 532.4 eV are attributed to lattice oxygen
and bridging hydroxyls, respectively.[28] For the Bi powder, the
presence of lattice oxygen is due to the oxidation of the Bi surface,
which can easily occur in air.[29] The Bi 4f XPS spectra (Figure S1)
also show that both surfaces of the two samples are mainly
composed of oxidation state of Bi, which is consistent with the
XPS observations of O 1s in Figure 1d.[30] The peak at 531.2 eV
can be assigned to oxygen defects.[31] Clearly, the area of the
peak at 531.2 eV for the calcinated sample is much larger than
that for the Bi powder, indicating the oxygen vacancies are mainly
obtained by heat treatment. Combined with all the above results,
it can be concluded that distinct oxygen vacancies are indeed
produced in the sample after calcination, which provides an
opportunity to investigate the effect of oxygen vacancies on the
photocatalytic properties.
To study the electronic band structures, Mott-Schottky plots for
Bi and Bi2O3-x were tested (Figure 1e) between at −0.42 V and
1.58 V versus the reversible hydrogen electrode (vs. RHE). The
plots for the two samples display a positive slope, which is a
typical characteristic of n-type semiconductors.[32] Based on the
above XPS analysis and TEM observation in Figure 2a, it can be
concluded that Bi2O3 semiconductor layer was inevitably formed
on the surface of Bi nanosheets due to the air exposure at
ambient temperature. Therefore, it is reasonable that both the Bi
powers before and after calcination exhibit semiconductor
properties as shown in Figure 1e.
The carrier density (Nc) for the sample can be calculated from
equation (1)[33]
1 1 1
Nc  2e0 ε 1ε0 d (C 2 )/dV (1)
where e0 represents the electron charge, ε0 is the vacuum
permittivity, and ε is the dielectric constant. As shown in Figure
1e, Bi2O3-x has a much lower slope compared to Bi, which results
an increase in the value of Nc compared with Bi according to
equation (1). As shown by the electrochemical impedance
spectroscopy measurements carried out in the dark (Figure S2),
the semicircle diameter for Bi2O3-x is less than that for Bi,
indicating a decrease in the charge transfer resistance due to the
introduction of oxygen defects, which is also helpful for enhancing
the Nc value for Bi2O3-x by increasing ε−1 in equation (1). Therefore,
we can conclude that the presence of oxygen defects results in
an enhanced number of excess free electrons in Bi 2O3-x, which
leads to the LSPR for the sample. Based on the above results, a
possible formation mechanism for the hot carriers is proposed in
Figure 1f.
Morphologies for the samples were characterized by scanning
electron microscopy (SEM). SEM images of the commercial Bi
powder are shown in Figure S3. It was found that the sample is
Angewandte Chemie International Edition
RESEARCH ARTICLE
comprised of microspheres with diameters ranging between 20
μm to 80 μm. Furthermore, the spheres have a rough surface that
is assembled by many tiny particles (Figure S3). After calcination,
the original morphology of the Bi powder is retained (Figure S3).
The rugged surface of the sphere provides an ideal structure for
increasing the light scattering, which is beneficial for increasing
the surface area of the as-obtained samples and the contact of
the reactant with the catalyst surface.
Figure 2. The TEM images of a) Bi and b) Bi2O3-x. The HRTEM images of c) Bi
and d) Bi2O3-x. e) Schematic illustration for the formation of Bi2O3-x layer with
oxygen vacancies.
To study the microstructure, the Bi microspheres were broken
into primary particles by gentle sonication, and then TEM test was
performed on an individual particle. The TEM images in Figure 2a
and b demonstrate that the Bi spheres are composed of sheet-
like structures. As shown in Figure 2c, no obvious lattice fringes
were observed in a high-resolution TEM (HRTEM) image of the
Bi nanosheets, which indicates that the automatically formed
Bi2O3 layer on the surface of Bi powder at ambient temperature
contains an amorphous structure. This result is also proved by the
Fast-Fourier-transform (FFT) pattern shown in the insert in Figure
2c. In contrast, the HRTEM image of the Bi after calcination shows
clear lattice fringes with spacings of 0.274 nm and 0.281 nm,
which can be ascribed to the (220) and (002) facets of the Bi2O3
phase, respectively.[34] The HRTEM image and the insert FFT
pattern in Figure 2d indicate that highly crystallized Bi2O3-x was
formed after calcination treatment. The HRTEM image
corresponding to a much larger area of the nanosheet in Figure
2d is shown in Figure S4, confirming that the whole surface of the
sample after calcination was covered by a crystallized Bi2O3-x
layer. Moreover, the energy-dispersive spectroscopy (EDS)
mapping images (Figure S5) show that the Bi and O are evenly
This article is protected by copyright. All rights reserved.
10.1002/anie.202010156
distributed on the surface of Bi2O3-x, further demonstrating Bi-
oxide coverage over the surface of elemental Bi.
On the basis of the HRTEM observations, a possible pathway
to form Bi2O3-x with oxygen vacancies is proposed. As shown in
Figure 2e, the outer surface of the Bi powder can be natively
oxidized into an amorphous Bi2O3 layer with poor oxygen
vacancies due to the full contact with oxygen in the air. As a result,
the probability for the Bi in a deep layer coming into contact with
oxygen is sharply reduced, which prevents the further oxidation of
Bi. The amount of Bi3+ in the Bi powders was analyzed by
inductively coupled plasma (ICP) after the sample was treated in
nitric acid. The contents of Bi2O3 at different oxidation times (3-48
h) of the fresh Bi powders were calculated based on the ICP
Accepted Manuscript
measurements (Figure S6). The result indicates that the weight
percentage ratio of Bi2O3 reaches to a maximum value of 0.07%
at 12 h, which shows no obvious change when the exposed time
is further increased. A similar phenomenon was also found in
previous reports.[30]
Under the calcination condition at 453.15 K, the diffusion and
reaction between the Bi in a deep layer and the outer Bi2O3 was
increased. When Bi and Bi2O3 were mixed together, Bi2O3-x was
produced by the synproportionation between metallic Bi and
Bi2O3. Similarly, production of low-valence bismuth species by
Bi3+ and Bi0 synproportionation has been previously reported in
borate and phosphate glasses.[35] In this process, the oxidation of
Bi may also take place at the same time. However, the concerted
action of the reduction and oxidation reactions results in the
formation of Bi2O3-x. Furthermore, the heat treatment also
contributes to the crystallization of the formed Bi2O3-x, as
observed in Figure 2d. Furthermore, the weight percentage
ratio of Bi2O3 in the Bi powders after heat treatment was
determined to be 0.13%, which is much higher than that in the Bi
powders.
Next, the photocatalytic reactivity of the as-prepared catalyst
was measured by gas-phase reduction of CO2 with H2 under
irradiation by LED light at 473.15 K. The catalyst with the
microsphere morphology as shown in Figure S2c was used for
the photocatalytic reaction. Figure 3a shows the photocatalytic
activities measured for Bi and Bi2O3-x under irradiation from 420
nm LED light with an intensity of 121 mW•cm−2. As shown in
Figure 3a, the amount of CO evolution increased linearly with time.
No other product was detected, and ~100% selectivity for CO
production from photoreduction of CO2 was obtained on Bi and
Bi2O3-x. The CO evolution rate on the Bi2O3-x photocatalyst
reaches 16.15 μmol•g−1•h−1, which is approximately 3 times
higher than that for the Bi powder. This result indicates that the
Bi2O3-x catalyst with oxygen defects is more active for the
conversion of CO2 than the Bi powder. Furthermore, during three
cycles, the activity did not show any loss after 24 h photoreaction,
indicating that the stability of the Bi2O3-x catalyst is pretty good.
Control experiments carried out in the absence of catalyst or
CO2 were performed, and negligible CO gas was detected,
indicating that the formed CO in Figure 3a originates from the
catalytic reduction of CO2, but not contamination. To further prove
that the CO2 was a reactant, an isotope experiment using 13CO2
was performed over Bi2O3-x (Figure S7). Importantly, the main
product in the mass spectrum was found to be 13CO at m/z = 29,
which unequivocally demonstrates that the used CO 2 is the
carbon source for the photoproduced CO on Bi 2O3-x. This
observation is also consistent with the nearly 100% selectivity
found for CO production on Bi2O3-x.
Angewandte Chemie International Edition
RESEARCH ARTICLE
To explore the reason for the better performance of the Bi2O3-x
catalyst, CO2 temperature-programmed desorption (CO2-TPD)
profiles for the Bi and Bi2O3-x were investigated (Figure 3b). Only
a slight peak at ~623.15 K in the chemical desorption is observed
on the CO2-TPD curve for the Bi powders. In addition to the weak
peak at ~623.15 K, Bi2O3-x exhibits an extra strong peak at
~673.15 K, which is probably due to the desorption of CO 2 from
new sites of oxygen vacancies. Moreover, the peak area for the
Bi2O3-x sample is much larger than that for the Bi powder,
confirming an enhanced amount of CO2 adsorption. This result
confirmed that the oxygen vacancies can work as new trapping
sites for CO2 adsorption, which can significantly enhance the
bonding between CO2 and the Bi2O3-x layer. This might be
responsible for the improved photocatalytic performance for CO2
reduction on Bi2O3-x shown in Figure 3a.
Figure 3. a) The cycling test for photocatalytic CO production over Bi2O3-x. b)
CO2-TPD of the Bi and Bi2O3-x. Wavelength dependence of the apparent
quantum yields for photocatalytic CO production on the c) Bi2O3-x and d) Bi
samples. e) The effect of reaction temperature on the CO formation rates under
940 nm LED light irradiation at a constant light intensity. f) The correlation of CO
formation rates with the intensity of 940 nm LED light of Bi2O3-x.
Furthermore, the CO2 adsorption curves for Bi and Bi2O3-x
samples were tested (Figure S8). An almost linear dependence
for CO2 adsorption capacity on relative pressure is observed on
Bi, indicating physical adsorption of CO2 by the sample. For Bi2O3-
x, the amount of CO2 adsorption significantly increases in the high
pressure region (p/p0 > 0.8), suggesting the chemisorption of CO2
on Bi2O3-x.[36] More importantly, the Bi2O3-x catalyst exhibits a
much higher CO2 adsorption capability (~70% enhancement)
than Bi under ambient pressure. The specific surface area of the
sample was estimated by the Brunauer-Emmett-Teller (BET)
method based on the nitrogen adsorption isotherm at 77 K (Figure
S9). The BET surface area of the calcined Bi2O3-x (0.3947 m2•g−1)
4
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10.1002/anie.202010156
is a little lower than that of Bi (0.4312 m2•g−1). Therefore, the
improved CO2 adsorption capability on Bi2O3-x can be ascribed to
the presence of oxygen defects. This result further demonstrates
that introducing oxygen vacancies plays a significant role in
enhancing CO2 adsorption capacity on Bi2O3-x, which is consistent
with the TPD result shown in Figure 3b.
Considering the absorption property of Bi2O3-x in Figure 1b, it is
reasonable to expect that the sample may show activities under
near-infrared (NIR) light irradiation. To verify the light-responsive
activity, the apparent quantum yields (AQYs) for the Bi2O3-x
photocatalyst under different wavelength conditions were tested
in the wavelength range of 365-940 nm according to equation (2)
in the Experimental section of Supporting Information. Due to
Accepted Manuscript
instrument limitations, the AQYs at wavelengths over 940 nm
were not tested. The intensities of the incident photons from
different LEDs are shown in Table S1. For measuring the AQYs,
the CO production reaction was tested for 3 hours and the
temperature of the reaction system was maintained at 473.15 K.
The action spectrum of Bi2O3-x is closely related to the wavelength
of the incident light and is similar to the light-absorption spectrum
of the catalyst (Figure 3c), indicating that the photocatalytic CO
production can be ascribed to the hot electrons generated by the
LSPR absorption of Bi2O3-x. Particularly, as shown in Figure 3c,
the Bi2O3-x catalyst can reduce CO2 under LED light at
wavelengths up to 940 nm and reaches an AQY of approximately
0.113%, which is approximately 4.0 times that found at 450 nm.
This observation further confirms that Bi2O3-x is a suitable
photocatalyst for IR light-driven CO2 reduction. For comparison,
the action spectrum of Bi was also tested (Figure 3d), indicating
that the Bi catalyst can only work under light illumination below a
wavelength of 660 nm. Furthermore, the Bi2O3-x catalyst shows
stable performance for 10 h of continuous photocatalytic reaction
under 940 nm LED light irradiation (Figure S10). As shown in
Figure S10, a catalytic activity as high as 4.6 μmol•g−1•h−1 is
achieved.
For further comparison, crystallized Bi2O3 without oxygen
defects was synthetized by heating the Bi power in air at an
elevated temperature of 473.15 K for 8 h. The XRD pattern shows
that a pure phase of Bi2O3 was crystallized on Bi (Figure S11a),
which is similar with the Bi2O3-x obtained at 453.15 K. However,
the EPR spectrum shown in Figure S11b displays that no signal
at g = 2.001 is observed, demonstrating that the amount of oxygen
vacancies in the obtained Bi2O3 sample is greatly reduced. In
addition, UV-Vis-IR absorption spectrum of Bi2O3 (Figure S11c)
shows that the LSPR peak observed in Figure 1b disappears with
the absence of oxygen vacancies, further confirming that the
plasmonic resonance of Bi2O3-x is caused by the presence of
oxygen defects. The photocatalytic CO production rate on the
formed Bi2O3 at 420 nm is 3.12 μmol•g−1•h−1 (Figure S12a), which
is only about 19.3% of that on Bi2O3-x (16.15 μmol•g−1•h−1).
Furthermore, the wavelength-dependent AQYs of Bi2O3 (Figure
S12b) shows that photocatalytic CO2 reduction can only occur
below 660 nm light irradiation. The enhanced CO reduction
activity and light absorption ability of Bi2O3-x indicate that creating
surface oxygen vacancies on oxides is a simple but effective
approach for designing plasmonic photocatalysts for CO2
reduction.
To further prove that charge carriers can indeed be generated
and transferred under NIR light irradiation, transient photocurrent
density analysis was performed for the two samples. Under light
irradiation at 940 nm, the Bi2O3-x sample shows a strong
Angewandte Chemie International Edition
RESEARCH ARTICLE
photocurrent response whereas no photocurrent signal was
observed for the Bi powder (Figure S13), which provides clear
evidence for hot-electron transfer on Bi2O3-x under NIR light
excitation.
For plasmonic photocatalysts based on noble metals, a linear
dependence of reaction rate on light intensity or reaction
temperature has been generally observed. [12,15] Therefore, the
effect of reaction temperature on the photocatalytic CO2 reduction
activities was investigated under 940 nm LED light irradiation at
constant light intensity. As shown in Figure 3e, the photocatalytic
reduction is found to hardly occur at 413.15 K with light
illumination, with the CO rate observed to increase linearly with
increasing temperature. This result proves that the reaction
temperature plays a crucial role in the CO2 reduction process
under light irradiation.
The negligible activity under low reaction temperature (Figure
3e) suggests that the induced electrons do not have enough
energy to drive the photocatalytic CO2 reduction at this condition.
The chemical transformations on plasmonic Bi 2O3-x should be
similar with that on metal photocatalysts because both are mainly
driven by free electrons. Therefore, raising the temperature may
have two positive effects on the photocatalytic reactions on Bi2O3-
x according to the literature. First, it is beneficial to activate the
adsorbed CO2 and H2 molecules into excited states according to
the Bose-Einstein distribution,[37] and excite other thermal reaction
steps that occur on the catalyst surface, such as the adsorption-
desorption equilibrium of reactants and products, and the
diffusion of adsorbed species.[38] Second, by gaining energy from
heating, the energy levels for the hot-electrons excited by the
LSPR of Bi2O3-x can be raised further; thus, these electrons are
more active than those only excited by light irradiation. [37] Thus,
the coupling effects of light illumination and heating enable
plasmonic Bi2O3-x to overcome the activation energy barrier and
transfer electrons to the lowest unoccupied molecular orbital of
the adsorbed molecules. As a result, photocatalytic CO 2 reaction
on Bi2O3-x is facilitated.
Based on the previous report,[39] the photothermal effect of the
incident light may play a role in the CO2 reduction process.
However, as we know that the photothermal mechanism on
plasmonic photocatalysts works only when the intensity of the
incident light is significant large (orders of magnitude higher than
solar intensity).[9] As shown in Table S1, the light intensities used
in the present study are 11-136 mW•cm−2 (around or much lower
than solar intensity), which suggests that the light-induced
thermal effect on the photocatalytic process of Bi2O3-x can be
neglected. Furthermore, the photothermal effect was
experimentally studied by in situ monitoring the temperature of
Bi2O3-x catalyst induced by photons from different LEDs. The
ambient temperature during these tests was about 299.15 K. After
5 min irradiation, the temperatures reached to maximum values
between 299.57 and 309.13 K depending on the used LEDs
(Table S2). To exclude the effect of photothermal heating on
catalytic CO2 reduction, the thermocatalytic activity of Bi2O3-x prior
to illumination was examined, showing that almost no CO was
produced even at 473.15 K (Figure S14). This result
demonstrates that the CO2 reduction on Bi2O3-x hardly occurs with
only heat input. Therefore, we can confirm that the photoinduced
heating of Bi2O3-x under LED light illumination plays a negligible
effect on the photocatalytic CO2 conversion.
To further support the existence of photocatalytic CO2 reduction,
the effect of irradiation intensity on the photocatalytic performance
This article is protected by copyright. All rights reserved.
10.1002/anie.202010156
of Bi2O3-x was examined (other experimental conditions remained
unchanged) at 473.15 K. Figure 3f displays the correlation of the
CO formation rates with 940 nm LED light intensity, indicating that
a nearly linear dependence between the activity and light intensity
is found for the catalyst. This behavior is a characteristic of the
photocatalytic process found for noble metal-based plasmonic
catalysts because the photogenerated charges on the metal
surface are proportional to the light intensity. The strong
dependence of the evolution rate of CO on the light intensity
suggests that the photogeneration of charges is the primary factor
responsible for CO2 reduction.[37,40] Based on the experimental
results shown in Figure 3e and f, we can confirm that Bi2O3-x has
noble-metal like properties from the aspect of the photocatalytic
Accepted Manuscript
reduction of CO2 and that catalytic performance originates from
the synergetic effect between light irradiation and heating.
Photocatalysis on semiconductor photocatalysts has been well
studied and provides an attractive approach for room temperature
reactions,[41-42] but a negative dependence of photocatalytic rates
on operating temperature is commonly observed in
semiconductor-based photocatalysis because of the relatively low
Debye temperatures of the semiconductors involved and
significant recombination of photogenerated electron-hole pairs
even at moderately elevated temperatures. [43] Furthermore,
previous reports have also indicated that the reaction rates for
semiconductor photocatalysts depend on the square root of the
light intensity.[15] Therefore, in practical applications, if we want to
increase the yield of products, the efficiencies for general
photocatalysts can be significantly reduced by increasing the light
intensity, which might be a potential factor that can hinder use of
semiconductor photocatalysts because high-intensity light,
especially IR light, will inevitably increase the temperature of the
gas-solid reaction system.
In contrast, the results shown in Figure 3 imply that the quantum
efficiency of Bi2O3-x for photocatalytic CO2 reduction cannot be
reduced by increasing light intensity and temperature, indicating
that the photocatalytic behavior on plasmonic Bi2O3-x is
fundamentally different from that on semiconductor
photocatalysts. Previously, such a phenomenon has been mainly
observed on noble metal-based plasmonic photocatalysts.[44]
However, theses noble metal nanoparticles required either high-
intensity light from laser pulses (~kW•cm−2) to drive the chemical
transformations or only worked under visible light irradiation. [45-51]
Specifically, the photocatalysis of CO2-to-CO on Bi2O3-x can be
realized under low-intensity light illumination (11 mW•cm−2) at 940
nm. To the best of our knowledge, this is the first report showing
that low-cost Bi2O3-x can be used as a plasmonic semiconductor
photocatalyst to drive photocatalytic CO2 reactions under NIR
light illumination, which offers an opportunity to expand the
photoresponse of current plasmonic photocatalysts for solar
energy conversion.
To understand the reaction mechanism in the CO2-to-CO
conversion process, surface adsorbed intermediates on Bi2O3-x
were probed using Fourier-transform infrared (FTIR)
spectroscopy. As shown in Figure 4a, the strong peaks in the
wavenumber region of 2200-2400 cm−1 arise from the CO2
adsorbed onto Bi2O3-x.[52] The peaks observed at 1392 and 1644
cm−1 can be assigned to the symmetrical and antisymmetric
stretching vibrations of the COO− group, respectively.[53-54]
Furthermore, the synchronous increase in the intensities of the
two peaks is consistent with the result that the two different peaks
are attributed to the stretching vibrations of the same COO − group.
Angewandte Chemie International Edition 10.1002/anie.202010156

RESEARCH ARTICLE
Based on the FTIR observations, a possible Mars-van Krevlen
pathway for the light-assisted reduction of CO2 on Bi2O3-x is
proposed,[55] as described in Figure 4b. First, the CO2 molecules
are preferentially adsorbed onto the oxygen vacancies (step 1) to
form the surface CO2 species. Under the reaction conditions, the
adsorbed CO2 can react with the oxygen vacancy to induce the
formation of the free COO− group (step 2) by capturing the O atom
of the CO2 into the vacancy. In the meantime, H2 is dissociated
into protons by the photogenerated holes on Bi2O3-x (step 3).
Subsequently, fast conversion of COO− into CO and H2O
proceeds under the assistance of protons and photoinduced
electrons (step 4 and 5). In this step, the consumed oxygen
vacancy on Bi2O3-x can be regenerated to complete the catalytic
temperature, respectively, which might be beneficial for its
practical applications. The low-cost, broad light absorption, and
durability of the present Bi2O3-x catalyst represent a significant
step in producing chemical fuel by a CO2 reduction technique
using solar energy.
Acknowledgements
The authors thank the final supports by National Natural Science
Foundation of China (Grant Nos. 21972082 and 21673220).
Keywords: Bi2O3-x • infrared light driven CO2 reduction • localized

Accepted Manuscript
cycle. The presence of an oxygen vacancy is helpful in triggering
surface plasmon resonance • oxygen vacancies • photocatalysis
and stabilizing the free COO− intermediate, which may lower the
energy barrier for CO2 reduction, thus improving the production of
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Entry for the Table of Contents

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Accepted Manuscript
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Bifunctional oxygen defects were created on cost-effective Bi2O3-x, which enables noble-metal like localized surface plasmon resonance
and enhanced CO2 adsorption properties of the sample. As a result, photocatalytic CO2-to-CO conversion with ∼100% selectivity was
successfully realized even under low-intensity light at 940 nm, showing a quantum efficiency of 0.113% that is 4.0 times of that at 450
nm.

8
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