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Plasmon-assisted photocatalytic CO2 reduction on
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Cite this: Dalton Trans., 2021, 50,
Au decorated ZrO2 catalysts†
6076
Meng Gu, ‡ Dong Liu,‡ Tao Ding,
Received 3rd February 2021,
Accepted 7th April 2021 Tao Yao *
DOI: 10.1039/d1dt00385b
rsc.li/dalton
ZrO2 is one of the most stable metal oxides which is applicable to
various chemical reactions in harsh environments. However, the
photocatalytic performance of ZrO2 is relatively poor due to the
negligible use of the solar spectrum caused by the wide bandgap
(Eg = 5.3 eV). Here, we report plasmon enhanced Au nanoparticles
decorated onto ZrO2 through a facile tannic acid-reduction
method. The Au/ZrO2 heterojunctions exhibited efficient and
stable photocatalytic activity of reducing CO2 into main CO and
CH4, at the rates of 25.6 μmol g−1 h−1 and 5.1 μmol g−1 h−1 at
most, respectively, approximately 6-fold enhanced compared to
the pristine ZrO2, under simulated solar light. The reduction rates
could also be improved over 10-fold under visible light when Au
nanoparticles were loaded onto ZrO2. UV-Vis diffuse reflectance
spectra confirmed the enhanced visible-light absorption of Au/
ZrO2 caused by localized surface plasmon resonance (LSPR).
Electrochemical impedance spectra (EIS) and photocurrent tests
proved the more efficient charge transport and electron–hole sep-
aration of Au/ZrO2 heterojunctions. This study demonstrates an
effective strategy of LSPR effects to improve the photocatalytic
performances of semiconductors.
Currently, the greenhouse effect caused by excessive usage of
fossil fuels and emission of carbon dioxide (CO2) has become
one of the most serious environmental problems.1,2
Photocatalytic reduction of CO2 has been receiving consider-
able attention for its potential to convert abundant greenhouse
gases to useful hydrocarbon fuels consuming sunlight as the
primary energy source. The dissociation energy of the CvO
bond in CO2 is approximately 750 kJ mol−1, manifesting the
high thermodynamic stability of CO2 molecules.3 It is essential
to design high performance photocatalysts to achieve practical
applications. A wide variety of semiconductors with abundant
National Synchrotron Radiation Laboratory, University of Science and Technology of
China, Hefei 230029, P. R. China. E-mail: yaot@ustc.edu.cn
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
d1dt00385b
‡ These authors contributed equally to this work.
6076 | Dalton Trans., 2021, 50, 6076–6082
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Xiaokang Liu, Tao Chen, Xinyi Shen and
storage, low cost, low toxicity and high stability have been
extensively studied as CO2 photoreduction catalysts since the
first report on photoelectrocatalytic reduction of aqueous CO2
more than three decades ago.4 Currently, there are many
reports on the photocatalytic reduction properties of metal
oxides such as TiO2, CeO2, WO3, Bi2WO6 and so on.5–9
However, the photocatalytic performance of CO2 in sunlight is
still far from satisfaction. Generally, the poor photocatalytic
performance of semiconductors is ascribed to the wide band-
gaps resulting in weak absorption in the visible light region,
slow charge separation and rapid recombination of photo-
induced electrons and holes.10–12
Plasmonic metal nanostructures can harvest visible light
due to localized surface plasmon resonance (LSPR).13,14 There
have been many reports on the utilization of metal nano-
particles including Au, Ag, and Cu to boost photocatalytic reac-
tions under visible light irradiation.15–17 Besides, some metal
oxides also show LSPR effects for photocatalytic reactions.18–20
Incorporating plasmonic nanostructures onto semiconductors
to construct heterojunctions has been proved to be a practical
approach to boost the photocatalytic CO2 reduction. The het-
erojunctions can not only improve the light-harvesting ability,
but also accelerate the separation of electrons and holes and
slow down their recombination. Au is chemically quite stable
and not easily oxidized. A large number of metal–semi-
conductor heterojunctions including Au/TiO2, Au/CeO2 have
not only shown the obvious enhancement of the photocatalytic
performance compared with pure semiconductors but also can
retain their catalytic properties for a long time.21–23 The
thermal and chemical stability of ZrO2 suggests the potential
of catalysts which can withstand harsh chemical environments
for a long time. There have been many catalytic studies, such
as hydrogenation on ZrO2 and ZrO2-based materials.24,25
However, the bandgap of ZrO2 is quite wide (Eg = 5.3 eV),26
implying the rather poor photocatalytic performance.
Therefore, loading plasmonic metal nanoparticles onto ZrO2
might be an effective way to construct photocatalysts with high
performance.
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In this work, we synthesized Au/ZrO2 heterojunctions via a
simple tannic acid-reduction method at room temperature
without an ultraviolet light resource.27 Under simulated solar
illumination, the Au/ZrO2 heterojunctions show CO and CH4
formation rates of 25.6 μmol g−1 h−1 and 5.1 μmol g−1 h−1
which are both approximately 5-fold larger than that of pris-
tine ZrO2 which are 4.0 μmol g−1 h−1 and 0.8 μmol g−1 h−1,
respectively. The improved photocatalytic performance can be
explained as the plasmonic absorption of Au nanoparticles
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and more efficient separated electron–hole pairs. This work
offers a new synthetic strategy for the construction of plasmon
enhanced heterojunction photocatalysts which might achieve
efficient solar-to-fuel conversion.
The photocatalytic reduction of CO2 of catalysts was carried
out in water with a 20% volume fraction of triethanolamine
(more details in the ESI†).28 We synthesized Au/ZrO2 hetero-
junctions with different loading amounts. The loading
amounts of Au nanoparticles were measured with an induc-
tively coupled plasma–atomic emission spectrometer
(ICP-AES). The main products of ZrO2 and Au/ZrO2 are both
CO and CH4. The photocatalytic yields of CO and CH4 under
simulated solar illumination conditions are shown in Fig. 1a
and b. The amounts of products were measured with a gas
chromatograph. As for pure ZrO2, the rates of CO and CH4 are
4.0 μmol g−1 h−1 and 0.8 μmol g−1 h−1, respectively. The CO
formation rates of 2.7 wt% Au/ZrO2, 4.4 wt% Au/ZrO2 and
Fig. 1 (a) Amounts of CO production of ZrO2 and Au/ZrO2 over time (λ > 300 nm). (b) Amounts of CH4 production of ZrO2 and Au/ZrO2 over time (λ
> 300 nm). (c) Amounts of CO production of ZrO2 and Au/ZrO2 over time (λ > 420 nm). (d) Amounts of CH4 production of ZrO2 and Au/ZrO2 over
time (λ > 420 nm).
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6.3 wt% Au/ZrO2 are 12.6 μmol g−1 h−1, 25.6 μmol g−1 h−1 and
19.8 μmol g−1 h−1 respectively. The formation rates of CH4 are
2.9 μmol g−1 h−1, 5.1 μmol g−1 h−1 and 4.3 μmol g−1 h−1,
respectively. Moreover, the rates of CO and CH4 of pure ZrO2
under visible light decrease dramatically to 0.6 μmol g−1 h−1
and 0.2 μmol g−1 h−1. The CO formation rates of 2.7 wt% Au/
ZrO2, 4.4 wt% Au/ZrO2 and 6.3 wt% Au/ZrO2 are 5.7 μmol g−1
h−1, 12.9 μmol g−1 h−1 and 10.1 μmol g−1 h−1, respectively, and
the CH4 formation rates of 2.7 wt% Au/ZrO2, 4.4 wt% Au/ZrO2,
and 6.3 wt% Au/ZrO2 are 1.2 μmol g−1 h−1, 2.6 μmol g−1 h−1
and 2.3 μmol g−1 h−1, respectively (Fig. 1c and d). 4.4 wt% Au/
ZrO2 shows the best catalytic performance. The formation
rates of CO and CH4 can be improved at most 6-fold under
simulation solar radiation, while the formation rates of CO
and CH4 can be improved 19-fold and 12-fold at most under
visible light radiation.
Au/ZrO2 shows the best catalytic performance when the
weight loading is 4.4%. So, we chose pristine ZrO2 and
4.4 wt% Au/ZrO2 to study the structures of Au/ZrO2. The main
outcomes of characterization are shown in Fig. 2. The X-ray
diffraction (XRD) patterns of the 4.4 wt% Au/ZrO2 heterojunc-
tion and pure ZrO2 are shown in Fig. 2a. All the peaks of
4.4 wt% Au/ZrO2 could be indexed to pure ZrO2 (JCPDS no. 37-
1484) and pure Au (JCPDS no. 04-4784). Compared with pure
ZrO2, 4.4 wt% Au/ZrO2 shows a relatively higher and broader
peak at 2 theta ≈37° which corresponds to the (111) plane of
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Fig. 2 Structural characterization of 4.4 wt% Au/ZrO2 composites. (a) XRD patterns of 4.4 wt% Au/ZrO2, ZrO2 and the corresponding standard
JCPDS cards. (b) Elemental mapping of 4.4 wt% Au/ZrO2 (Zr, O and Au elements). (c) HRTEM image of the Au nanoparticles. (d) XPS spectrum of Au
4f for 4.4 wt% Au/ZrO2. (e) XPS spectrum of Zr 3d for 4.4 wt% Au/ZrO2. (f ) Au L3-edge XANES spectra for 4.4 wt% Au/ZrO2 and Au foil.
pure Au.29 The XRD results prove that Au nanoparticles were
successfully loaded to the surface of ZrO2. To further demon-
strate the elemental distribution in the Au/ZrO2 heterojunc-
tion, the high-angle annular dark-field scanning transmission
electron microscopy (HAADF-STEM) image and the corres-
ponding elemental mapping images are shown in Fig. 2b and
the size distribution is also listed in Fig. S4.† The average dia-
meter of the Au nanoparticles is approximately 22.5 nm.
Surfaces of the Au nanoparticles can be observed in the high-
resolution transmission electron microscopy (HRTEM) image
in Fig. 2c. The d-spacing of 0.24 nm belongs to the (111) plane
of Au.30 X-ray photoelectron spectroscopy (XPS) was used to
obtain detailed information on the chemical states of atoms in
the interface between Au nanoparticles and ZrO2. Gaussian
curves were used to fit the XPS spectra. Fig. 2d and e list the
best fitting profiles of Au 4f and Zr 3d, respectively. Both of the
fitting profiles demonstrate two pairs of spin–orbit doublets.
In Fig. 2d, the energy peaks of 84.0 and 87.6 eV corresponding
to Au 4f7/2 and Au 4f5/2, respectively, indicate the presence of
Au0 associated with Au–Au bonding. The splitting of 3.6 eV fits
well with a previous report.27 The energy peaks of 85.0 and
88.5 eV demonstrate the presence of Auδ+. The positive shifts
of Au have also been detected in other similar metal–semi-
conductor heterojunctions.31 Furthermore, the energy peaks of
184.4 and 185.7 eV are assigned to Zr4+ oxidation (Zr–O–Zr
bonding) shown in Fig. 2e. The splitting of 2.3 eV also fits well
with a previous report.32 The other pair of energy peaks show
small negative shifts compared with Zr4+ oxidation, corres-
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ponding to Zrq+(q < 4).33 The appearance of Auδ+ and Zrq+ in
this specimen implies that Au–O–Zr bonds are formed
between the Au nanoparticles and ZrO2. This phenomenon is
easy to understand. As the high surface energy of small sized
metal nanoparticles and metal nanoparticles tend to be
adsorbed to decrease the surface areas; therefore strong chemi-
cal bonds between metal ions with positive charges and
oxygen ions with negative charges are formed.27 X-ray absorp-
tion near edge spectroscopy (XANES) and extended X-ray fine
structure (EXAFS) spectroscopy were carried out to study the
localized structures of Au atoms. As shown in Fig. 2f, the
spectra of Au foil and Au/ZrO2 are similar to each other,
showing that most of the Au atoms still retain their character-
istic localized structures. k2-Weighted FT spectra and k2χ(k)
oscillations at the Au L3-edge for Au foil and Au/ZrO2 are
shown in Fig. S1 and S2.† XANES and EXAFS demonstrate that
the coordination structures of the majority of Au atoms do not
change when Au nanoparticles load on the surface of ZrO2,
which means that all effects of Au nanoparticles, including
LSPR, are still applicable to Au/ZrO2 heterojunctions.
The quantum efficiency (QE) was calculated according to
the following equation:34
X n  moles of reduction products
QE ¼  100% ð1Þ
moles of photon flux input
n is the number moles of transferred electrons to produce one
mole of product. Based on the products CO and CH4, the
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“carbene pathway” is used to explain the formation of CO and
CH4. The carbene pathway is listed in Fig. S5.† In the carbene
pathway, one CO molecule requires 2 electrons to be formed,
while one CH4 molecule require 8. So, n equals 2 for CO, while
it is 8 for CH4.35 The quantum efficiency and ultraviolet-visible
(UV/Vis) diffuse reflectance spectra are shown in Fig. 3a and b,
respectively. The QE of both pristine ZrO2 and Au/ZrO2 follows
their corresponding UV/Vis absorbance closely, revealing that
the reduction of CO2 is driven by the light absorbed by cata-
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lysts. Specifically, the QE of Au/ZrO2 at 520 nm and 550 nm
varies when the loading amount of the Au nanoparticles
changes. The QE at 520 nm reaches its maximum which is
approximately 0.75% when the loading is 4.4%, while the QE
at 550 nm reaches its maximum, 0.18%, when the loading is
6.3%. No product was detected in the photocatalytic
reductions of CO2 of pure ZrO2 under the light with wave-
lengths equaling 520 nm and 550 nm. On the other hand, the
UV/Vis diffuse reflectance spectra of Au/ZrO2 show a wide peak
at 530 nm caused by the LSPR, whereas no absorption peak is
detected in the UV/Vis diffuse reflectance spectrum of pure
ZrO2. Both the QE and UV/Vis results prove the plasmonic
enhancement of the photocatalytic activity of the Au nano-
particles in visible light. It is worth noting that the peak of
6.3 wt% Au/ZrO2 is weaker but wider than the peak of 4.4 wt%
Au/ZrO2. To study the difference, elemental mapping and TEM
of 6.3 wt% Au/ZrO2 were carried out. In Fig. S6,† the average
size of Au nanoparticles is around 50 nm, which is obviously
Fig. 3 (a) Quantum efficiencies of ZrO2 and Au/ZrO2. (b) UV/Vis diffuse reflectance spectra of ZrO2 and Au/ZrO2. (c) Electrochemical impedance
spectroscopy of ZrO2 and Au/ZrO2. (d) Photocurrent responses of ZrO2 and Au/ZrO2.
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larger than the size of the Au nanoparticles in 4.4 wt% Au/
ZrO2. The change of Au/ZrO2 based on the loading amount of
Au can be explained as follows: when the loading amount is
small, only a few Au nanoparticles can harvest the visible light.
The photocatalytic performance becomes better as the loading
amount increases. However, as the loading amount and photo-
catalytic performance increase, the particle’s size also
becomes larger. Only atoms on the surface can participate in
the reaction. On the other hand, the intensity of the electro-
magnetic wave decays exponentially when it penetrates into
the metal. Most of the inner Au atoms are wasted in the photo-
catalytic reaction. Therefore, the catalytic performance fails to
increase as the loading amount increases. The best loading
amount of Au nanoparticles is observed in Au/ZrO2
heterojunctions.
In order to measure the charge separation performance,
electrochemical impedance spectroscopy (EIS) and photo-
current tests were carried out which are listed in Fig. 3c and d,
respectively. Obviously, the arc radius of Au/ZrO2 is much
smaller compared with that of pristine ZrO2, indicating that
the photoexcited charge separated more effectively and recom-
bined more slowly. Besides, the difference of the photocurrent
and dark current markedly increased when Au nanoparticles
were loaded onto ZrO2, which also implies the higher
efficiency of the carrier.36 As the light source of the photo-
current contained only visible light irradiation (λ > 420 nm)
which cannot excite electrons from the valence band to the
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conduction band of ZrO2 (Eg = 5.3 eV), the separation of elec-
tron–hole pairs ought to occur in Au nanoparticles. The above
discussion showed that the loaded Au nanoparticles improved
the efficiency of separation of photo-generated electrons and
holes.
Finally, we chose the sample 4.4 wt% Au/ZrO2 which
showed the best catalytic performance to study the stability of
Au/ZrO2 by recycling the catalytic reaction for 4 times under
simulated solar illumination.37 The consequences of re-
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cycling tests are shown in Fig. 4a and b. Both yield rates of
CO and CH4 did not show obvious decay after 4 cycling
experiments. Furthermore, the XRD patterns and UV-Vis
diffuse reflectance spectra of 4.4 wt% Au/ZrO2 before and
after the catalytic reaction are also shown in Fig. 4c and d.
The recycling tests of the catalysts confirm the relatively high
stability of Au/ZrO2 heterojunctions synthesized via the
tannic acid-reduction method. The peak of the UV-Vis diffuse
reflectance spectrum caused by LSPR after the reaction did
not weaken compared with the spectrum before the reaction,
showing that the LSPR effect can still remain. TEM, HRTEM
and elemental mapping results are shown in Fig. S7.† The
exposed Au (111) plane can still be detected. Besides, the Au
nanoparticles still retained the size and did not fall off after
the photocatalytic reaction. All these experiments prove the
great stability of Au/ZrO2.
Fig. 4 (a) Cycling test of photocatalytic CO2 reduction producing CO of ZrO2 and 4.4 wt% Au/ZrO2 under simulated solar illumination. (b) Cycling
test of photocatalytic CO2 reduction producing CH4 of 4.4 wt% Au/ZrO2 under simulated solar illumination. (c) XRD patterns of 4.4 wt% Au/ZrO2
before and after the reaction. (d) UV-Vis diffuse reflectance spectra of 4.4 wt% Au/ZrO2 before and after the reaction.
6080 | Dalton Trans., 2021, 50, 6076–6082
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Photocatalytic mechanism
Based on the experimental results and previous reports, we
proposed a possible explanation shown in Fig. 5. Because of
the wide bandgap of ZrO2, electrons could hardly be excited to
the conduction band of ZrO2 directly by visible light, which
can rationalize the poor photocatalytic performance of pure
ZrO2. However, Au nanoparticles act as visible light-harvesters
due to their LSPR, as explained by eqn (2). The electrons of the
Au nanoparticles are delocalized and form electron clouds.
These free electrons are driven into oscillation due to their
strong coupling with incident light. Subsequently, these photo-
generated hot electrons are transferred to the conduction
bands of ZrO2; thus the CO2 is reduced on the surface of ZrO2
with the assistance of the transferred hot electrons.38
Triethanolamine was oxidized on the surface of the Au nano-
particles at the same time. Hence, CO2 was reduced into CO
and CH4 through the carbene pathway, which can be summar-
ized as eqn (3) and (4). All the processes can be summarized
as the following chemical equations:
eAu  þ hv ¼ eLSPR  ð2Þ
CO2 þ 2H þ 2e ! CO þ H2 O ð3Þ
CO þ 6H þ 6e ! CH4 þ H2 O ð4Þ
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Fig. 5 The mechanism of the photocatalytic reduction of CO2 induced by LSPR.
Therefore, not only the utilization rate of light is improved,
electrons and holes are also separated to two sections of het-
erojunctions and the recombination slowed down. As a result,
photocatalytic performance increases tremendously.
Conclusion
In summary, Au/ZrO2 was prepared through the tannic acid-
reduction method. The incorporated Au nanoparticles play
important roles in harvesting visible light due to their loca-
lized surface plasmon resonance. Au nanoparticles harvest
visible light and transfer hot electrons to ZrO2, improving the
utilization of light and retarding the recombination of elec-
trons and holes. Au/ZrO2 shows superior catalytic activity
towards the photocatalytic reduction of CO2. The formation
rates of CO and CH4 of Au/ZrO2 are markedly improved under
both simulated solar light and visible light. The best loading
amount of Au nanoparticles, 4.4 wt%, is achieved for the Au/
ZrO2 heterojunctions. However, the rates of CO and CH4 are
still not high enough for practical applications. The correlation
between the loading amount and absorbance curves and
the effect towards the sizes of Au nanoparticles still need more
in-depth investigation. This work exhibits the potential of ZrO2
for photocatalytic reduction of CO2, providing another
member to the Au/semiconductor heterojunction catalysts.
Besides, the work emphasizes the importance of the most suit-
able loading amounts of metal nanoparticles.
Conflicts of interest
The authors declare no conflict of interest.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grants No. 12025505 and 21471143),
Youth Innovation Promotion Association CAS (CX2310007007
and CX2310000091), and Fundamental Research Funds for
Central Universities (KY2310000020).
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