Conversion of Carbon Dioxide by Methane Reforming under Visible-Light Irradiation: Surface-Plasmon-Mediated Nonpolar Molecule Activation

Article abstract of DOI:10.1002/anie.201504933

A novel CO₂ photoreduction method, CO₂ conversion through methane reforming into syngas (DRM) was adopted as an efficient approach to not only reduce the environmental concentration of the greenhouse gas CO₂ but also realize the net energy storage from solar energy to chemical energy. For the first time it is reported that gold, which was generally regarded to be inactive in improving the performance of a catalyst in DRM under thermal conditions, enhanced the catalytic performance of Rh/SBA-15 in DRM under visible-light irradiation (1.7times, CO₂ conversion increased from 2100 to 3600μmol g^-1 s^-1). UV/Vis spectra and electromagnetic field simulation results revealed that the highly energetic electrons excited by local surface plasmon resonances of Au facilitated the polarization and activation of CO₂ and CH₄ with thermal assistance. This work provides a new route for CO₂ photoreduction and offers a distinctive method to photocatalytically activate nonpolar molecules. Storing solar energy: Gold enhances the catalytic performance of a Rh/SBA-15 catalyst in the dry reforming process of methane under visible-light irradiation (see picture). The highly energetic electrons excited by local surface plasmon resonances of gold facilitated the polarization and activation of carbon dioxide and methane under thermal conditions.

Full text of DOI:10.1002/anie.201504933

Angewandte
Chemie
International Edition: DOI: 10.1002/anie.201504933
German Edition: DOI: 10.1002/ange.201504933
Photocatalysis
Conversion of Carbon Dioxide by Methane Reforming under Visible-
Light Irradiation: Surface-Plasmon-Mediated Nonpolar Molecule
Activation
Huimin Liu, Xianguang Meng, Thang Duy Dao, Huabin Zhang, Peng Li, Kun Chang,
Tao Wang, Mu Li, Tadaaki Nagao, and Jinhua Ye*
Abstract: A novel CO2 photoreduction method, CO2 con-
version through methane reforming into syngas (DRM) was
adopted as an efficient approach to not only reduce the
environmental concentration of the greenhouse gas CO2 but
also realize the net energy storage from solar energy to
chemical energy. For the first time it is reported that gold, which
was generally regarded to be inactive in improving the
performance of a catalyst in DRM under thermal conditions,
enhanced the catalytic performance of Rh/SBA-15 in DRM
under visible-light irradiation (1.7 times, CO2 conversion
increased from 2100 to 3600 mmolgÀ1 sÀ1). UV/Vis spectra
and electromagnetic field simulation results revealed that the
highly energetic electrons excited by local surface plasmon
resonances of Au facilitated the polarization and activation of
CO2 and CH4 with thermal assistance. This work provides
a new route for CO2 photoreduction and offers a distinctive
method to photocatalytically activate nonpolar molecules.
a convenient mode to relieve the energy crisis caused by the
increasing fossil fuels consumption.[2] The ideal vision is to
convert CO2 photocatalytically with H2O, nevertheless, there
is a long way to go because of the sluggish nature of CO2 and
H2O in activation. Current studies were mainly focused on the
photoreduction of CO2 into CO or CH4 by employing H2 as
the reductant,[3] which could reduce the environmental
concentration of CO2 whereas the downhill reactions are
not favorable for energy storage. Dry reforming of methane
(DRM), converting two kinds of greenhouse gases CO2 and
CH4 into syngas (CO and H2), is an uphill reaction and
beneficial for the sustainable development of energy strata-
gem.[4] It has been extensively studied in thermal catalysis,[4,5]
however, there were no reports on the reaction driven by
solar energy up to now.
For DRM reaction, the high reaction barrier associated
with the successive activation of CH4 and CO2, requires it to
be operated at high temperatures (800–10008C).[6] It is known
that, without the help of special apparatus, the temperature
induced by solar light is usually very low, and even on the
group-VIII-metal-based catalysts, the highest temperature
was about 4008C with the irradiation of 300 W Xe arc lamp,[3a]
which is not high enough to initiate the DRM reaction.[6]
Therefore, herein both photon energy (visible light) and
thermal energy were employed as the energy input to meet
the temperature requirement of DRM.
As for CO2, it is difficult to be photocatalytically one-
electron activated because of its À1.9 eV reduction poten-
tial,[7] which is above nearly all the conduction band of the
known semiconductors. Earlier reports disclosed that, com-
pared with the traditional thermal method, CO2 could be
more easily activated by plasma by collision with the highly
energetic plasma electrons.[8] Gold (Au) was reported to have
the property of local surface plasmon resonances (LSPRs) by
irradiation of photon energy, with positive ions and electrons
generated on its local surface, which might offer an analogous
and potential pathway for CO2 activation. However, Au was
inactive in the DRM reaction in thermal catalysis,[9] and
cannot be used as the active component of a catalyst for
DRM. On the contrary, group-VIII metals were effective in
DRM,[10] whereas the effects of photons on the excitation of
molecules cannot be well-distinguished since the photon
energy would be finally transformed into thermal energy
through the decay of hot electrons of the group-VIII
metals.[3a] Herein, Au was selected as the plasmonic promoter
of the desired catalyst to photocatalytically activate CO2, and
Rh and SBA-15 were employed as the active component and
C
onverting CO2 into high-value-added chemicals offers
a promising and challenging route for the environmental
targets on reducing CO2 emission.[1] Simultaneously, storing
the abundant solar energy into renewable fuels provides
[*] Dr. H. Liu, X. Meng, Dr. T. D. Dao, Dr. H. Zhang, Dr. P. Li,
Dr. K. Chang, Dr. T. Wang, M. Li, Dr. T. Nagao, Prof. J. Ye
International Center for Materials Nanoarchitectonics (WPI-MANA)
National Institute for Materials Science (NIMS)
1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)
E-mail: Jinhua.YE@nims.go.jp
Dr. P. Li, Prof. J. Ye
Environmental Remediation Materials Unit
National Institute for Materials Science (NIMS)
1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan)
X. Meng, M. Li, Prof. J. Ye
Graduate School of Chemical Science and Engineering
Hokkaido University, Sapporo 060-0814 (Japan)
Prof. J. Ye
TU-NIMS Joint Research Center
School of Materials Science and Engineering
Tianjin University
92 Weijin Road, Nankai District, Tianjin 300072 (China)
Dr. T. D. Dao, Dr. T. Nagao
CREST (Japan) Science and Technology Agency (JST)
4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan)
Prof. J. Ye
Collaborative Innovation Center of Chemical Science and
Engineering(Tianjin), Tianjin 300072 (China)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201504933.
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those over Rh/SBA-15 and Au/SBA-15 (the dotted lines in
Figure 2). The detailed reasons for the enhanced performance
of Rh-Au/SBA-15 under light illumination will be discussed in
the section of mechanism study. For all cases, the conversions
of CO2 were always higher than those of CH4 owing to the
coexistence of reverse water gas shift-reaction as side
reaction. Meanwhile, the selectivities to CO and H2, and the
mass balances were nearly 100%, and then the yields to CO
and H2 exhibited analogous trends with the conversions of
CO2 and CH4. Under visible-light irradiation the performance
of Rh/SBA-15 remained constant with the variation of light
intensity, owing to the total transformation of photon energy
to thermal energy through Rh hot electrons. The total energy
input ensured the stable reaction temperature (5008C).[3a] For
Au/SBA-15 and Rh-Au/SBA-15 catalysts, enhanced perform-
ances were observed under irradiation of visible light
(Figure 2 and Figure S4), and this phenomenon could also
be obtained over other Rh-Au/SBA-15 catalysts with Au
loadings in the range of 0.47–4.00 wt%. (The successful
synthesis of the catalysts were confirmed by the XRD
patterns in Figure S5, N2 adsorption-desorption isotherms in
Figure S6 and UV/Vis spectra in Figure S7. The actual Au
loadings were analyzed through ICP-OES and shown in
Table S1, and their catalytic performances were displayed in
Figure S8.) Then it could be speculated that except for the
steady reaction temperature (5008C), Au LSPRs induced by
visible light might facilitate the activation of CO2 and CH4.
In order to confirm the activation function of LSPRs, the
influence of the light wavelength on the performance in DRM
reaction was investigated over Rh-Au/SBA-15 catalyst, with
several types of filters employed to obtain the desired
wavelength range (Figure 3a). By irradiating light of a wave-
length in the range of 490–550 nm, a spherical Au LSPR was
Figure 1. XRD patterns of SBA-15 and the supported fresh catalysts.
Table 1: Elemental analysis and specific surface areas of the catalysts.
Samples
Rh [wt%][a]
Au [wt%][a]
SBET [m2 gÀ1 [b]
]
SBA-15
–
1.10
–
–
–
0.80
0.72
815
501
322
375
Rh/SBA-15
Au/SBA-15
Rh-Au/SBA-15
1.50
[a] Analyzed by the ICP-OES method. [b] Obtained by the N2 adsorption–
desorption method through the Brunauer–Emmett–Teller (BET) equa-
tion.
support, respectively, because CO2 activation was the rate-
determining step in DRM over Rh/SiO2.[11]
The crystalline structures of the catalysts were character-
ized by XRD (Figure 1). The broad peak at about 20–308 was
assigned to the amorphous SiO2, and the sharp and strong
peaks centered at 38.08, 43.78, and 64.48 were attributed to the
Au particles of large sizes. No peaks of Rh could be observed
owing to the small sizes and low loadings (the existence of Rh
could be detected through XPS in Figure S1 in
the Supporting Information and ICP-OES in
Table 1; it is about 1.0 wt%). TEM images in
Figure S2 indicated the Au and Rh particles were
located mainly on the outside surface of SBA-15.
The specific surface areas of the catalysts were
obtained by the N2 adsorption–desorption iso-
therm method (Figure S3) and calculated
through Brunauer–Emmett–Teller (BET) equa-
tion, and in the range of 300–500 m2 gÀ1 (Table 1).
The catalytic performances of the catalysts
were evaluated in DRM (Figure 2 and Fig-
ure S4). Clearly, without irradiation of visible
light, the Au/SBA-15 catalyst exhibited almost no
activity in DRM (CH4 conversion 16 mmolgÀ1 sÀ1,
CO2 conversion 25 mmolgÀ1 sÀ1), while Rh/SBA-
15 and Rh-Au/SBA-15 showed high and similar
catalytic activities (CH4 conversion 1600–
1900 mmolgÀ1 sÀ1,
CO2
conversion
2100–
2200 mmolgÀ1 sÀ1). The results were consistent
with the earlier report that Au as promoter was
inactive in improving the catalytic performance
of a catalyst in the reaction of DRM.[9] On the
contrary, it is surprising to discover that, under
visible-light irradiation, the catalytic activity over
Rh-Au/SBA-15 was much higher than the sum of
Figure 2. Effects of visible-light intensities on the performance of the catalysts in
DRM reaction (The dotted lines are the sum performance of Rh/SBA-15 and Au/SBA-
15). a) CH4 conversion, b) CO2 conversion, c) H2 yield, and d) CO yield. Reaction
conditions: 5008C, CH4/CO2 =1, flowrate 20.0 mLminÀ1, 0.0050 g catalyst.
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Figure 3. a) Wavelength range obtained with different filter sets (the wavelength of Y50+B440+HA30 was shown in the inset), b) UV/Vis spectra
of the catalysts (the spectra of 200–800 nm was in the inset), c) CH4 and CO2 conversions, and d) H2 and CO yields without or with light
irradiation of different wavelength ranges. Reaction conditions: 5008C, CH4/CO2 =1, flowrate 20.0 mLminÀ1, 0.0050 g catalyst.
excited (Figure 3b) and an enhanced catalytic activity was
observed (CH4 and CO2 conversions were 1850 and
2350 mmolgÀ1 sÀ1, H2 and CO yields were 3700 and
4050 mmolgÀ1 sÀ1, in Figure 3c,d), while the performances
under light irradiation with wavelengths outside of the Au
LSPR band (<480 nm or > 620 nm) were comparable with
that without light irradiation (CH4 and CO2 conversions were
in the ranges of 1650–1750 and 2150–2200 mmolgÀ1 sÀ1, H2 and
CO yields were in the ranges of 3450–3550 and 3700–
3750 mmolgÀ1 sÀ1, in Figure 3c,d). Additionally, the light
intensity adopted to excite Au LSPRs was quite low
(160 mWcmÀ2, in Figure 3a), about one hundredth of the
other two cases (they were 17300 and 12050 mWcmÀ2,
respectively, in Figure 3a). Then it could be speculated that
it was the Au plasmonic effects that promoted the catalytic
performances of Au-containing catalysts in DRM.
For Au-based catalysts under irradiation of visible light,
Au LSPR could be triggered and positive ions and electrons
could be generated on its local surface,[12] which could be
considered as a kind of plasma. The movement of the
generated positive ions and electrons could induce an
electromagnetic field, with its intensity serving as an indicator
of the density of the energetic electrons. In order to study Au
LSPR, the electromagnetic simulations were performed using
the finite-difference time-domain (FDTD) method (Full-
WAVE. RSoft, and the model used for the simulation was
displayed in Figure S9). Figure 4 reveals the electric field
distribution of the catalyst under visible-light excitation of
530 nm. Obviously, with the irradiation of 530 nm single
2
wavelength light, the field intensity (j E j ) was quite weak on
Rh/SBA-15 (Figure 4a), since the plasmon resonance of Rh
nanoparticles occurred in the UV region,[13] and it was high on
Au/SBA-15 (Figure 4b) due to its plasmon resonance in the
visible-light region (Figure 3b). Because of the near field
coupling between the Rh and Au nanoparticles,[12a] the
magnetic field on Rh-Au/SBA-15 (Figure 4c) was four times
enhanced compared with Rh/SBA-15, and 1.5 times of that on
Au/SBA-15. It should be noted that the field enhancement on
Au/SBA-15 was strongest at the centered gaps between Au
nanoparticles, which was more than 10 nm away from the
SBA-15 surface, while the strongest hot spots on Rh-Au/SBA-
15 were located at the Au-Rh and Rh-Rh gaps. Under
irradiation of visible light at the LSPR band of Au (530 nm),
the hot electrons in Au particles have the tendency to escape
from its Fermi level to the surfaces with an energy of 1.8 eV,
and the free electrons move more randomly and violently due
to thermal excitation and become more energetic at the
elevated temperature (5008C).[14] Considering the properties
of plasma and Au LSPR, it could be speculated that CO2 and
CH4 could be partially polarized by the plasmonic nano-
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Rh-Au/SBA-15 catalysts before and after DRM reaction
evaluation were available in Figure S2.)
As mentioned above, from Figure 2 it could be observed
that the catalytic activity over Rh-Au/SBA-15 was much
higher than the sum of those over Rh/SBA-15 and Au/SBA-15
under visible-light irradiation, which was proposed to be
related with the different reaction mechanisms.
For all the three catalysts except Au/SBA-15, which
exhibited no activity in DRM without light irradiation, the
thermal catalytic mechanism was widely studied[4,5] and CH4
and CO2 were regarded to be activated on the Rh active sites
through the steps (3) and (4) [Eqs. (3) and (4)], with products
H2, CO, and water produced by steps (5)–(9) given in
Equations (5) to (9). * and *ꢀ are used to denote the active
sites on a catalyst for the activation of CH4 and CO2,
respectively.
*
*
*
*
*
CH4þ Ð CH3 þ H Ð CH2 þ 2 H Ð CH þ 3 H Ð C þ 4 H ð3Þ
0
0
*
*
CO2 þ Ð CO þ O
ð4Þ
ð5Þ
ð6Þ
ð7Þ
ð8Þ
ð9Þ
H þ H Ð H2
0
0
*
*
*
*
CHx þ O Ð CO þ 0:5x H2 þ
þ
*
C
*
þ CO2 Ð 2 CO þ
0
0
*
*
*
*
CHx þ O Ð CHxÀ1 þ HO
0
0
*
*
HO þ H Ð H2O þ
Figure 4. Cross-sectional views of the electromagnetic field distribution
and enhancement simulated with FDTD method (The color scale bar
shows the electric field enhancement). a) Rh/SBA-15, b) Au/SBA-15,
and c) Rh-Au/SBA-15.
For the Rh/SBA-15 catalyst, since the LSPR spectrum of
Rh nanoparticles heavily tails from the UV region to the
visible-light region,[13] LSPR of Au nanoparticles and Rh
nanoparticles could couple each other effectively in the
visible-light region. As the Rh LSPR was heavily lossy in the
visible-light region, the plasmonic energy of Rh nanoparticles
would be readily transformed to thermal energy through the
damping process of the electron oscillation.[3a] However, the
thermal energy generated could not significantly influence
the reactor temperature as it was controlled as 5008C.
Therefore, even under irradiation of visible light, the reaction
was proposed to be proceeded by the thermally activated
methods, steps (3) to (9). However, CO2 activation was the
rate-determining step over the Rh/SBA-15 catalyst,[11] which
restricted the reaction rate at a limited level. Addition of Au
promoter did not improve the catalytic performance in DRM
in the thermal catalytic process, whereas the catalytic activity
was much improved under irradiation of visible light
(Figure 2). Considering the fact that CO2 could be activated
by the highly energetic plasmon electrons, then it suggested
that in addition to steps (3)–(9), step (1) also existed over the
Rh-Au/SBA-15 catalyst under light irradiation, which
resulted in promoted CO2 conversions. The promoted CO2
activation further facilitated the Boudouard reaction, which
increased the exposed Rh surface by the removal of deposited
carbon. (Deposited carbon was analyzed by thermogravimet-
ric analysis, TGA, in Table S2 and Raman method in Fig-
ure S10) or active C* species (step 7) and finally provided
more active sites for CH4 activation. CH4 could also be faintly
activated by plasmon electrons via step (2) (Figure S11).
metals[15] and electronically excited by the highly energetic
plasmon-induced hot electrons by collisional processes[16]
[steps (1) and (2), shown below, in Eqs. (1) and (2)].
e ðwith high energyÞ þ CO2 ! CO þ O þ e
ð1Þ
ð2Þ
e ðwith high energyÞ þ CH4 ! CHx þ ð4ÀxÞH þ e
Therefore, the catalytic activities of Au/SBA-15 and Rh-
Au/SBA-15 increased with light intensity in the range of 0–
0.22 WcmÀ2 (Figure 2). However, excessive light irradiation
was not favorable for the reaction and the performance
deteriorated with the light intensity further increased to
0.44 WcmÀ2 (Figure 2). The Tammann temperature of Au
particles is 3958C,[17] namely, at temperatures higher than
3958C, the Au particles begin to melt and aggregate. It was
reported that the local temperature of the Au particle surface
would increase under irradiation of visible light,[18] and the
higher intensity of visible light, the higher temperature of the
Au particles. Therefore, with the further increase of the
visible-light intensity to 0.44 WcmÀ2, the local temperature of
Au particles increased and the mobility of Au particles was
enhanced, which resulted in the transformation of Au
plasmon energy to its melt energy[15a] and ultimately
decreased the catalytic performance. (The TEM images of
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À
bond in CH4.[9] Additionally, both the conversions of CO2 and
CH4 limitedly increased with the increase of light intensity
from 0.0 to 0.22 WcmÀ2. Then it could be predicted that CH4
cleavage was the limiting step for the DRM reaction over the
Au/SBA-15 catalyst. Under light irradiation, CO2 and CH4
were electronically excited by the highly energetic plasmon
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to that the energy required to activate CH4 was quite high and
much higher than that for CO2 activation[16] (The simulated
electromagnetic field in Figure 4b implied that there were
fewer energetic electrons on Au/SBA-15 catalyst).
In summary, visible-light-induced Au local surface plas-
mon resonances were firstly reported to possess the ability to
activate the nonpolar molecules CO2 and CH4, with DRM as
the probe reaction. Under visible-light irradiation, Au as
promoter could effectively enhance the catalytic performance
of Rh/SBA-15 in DRM, since except for the traditional
thermal activation method, CO2 and CH4 could also be
effectively activated by the highly energetic electrons plas-
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nonpolar molecules.
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Acknowledgements
This work received financial support from the World Premier
International Research Center Initiative (WPI Initiative) on
Materials Nano-architectonics (MANA), MEXT (Japan), the
National Basic Research Program of China (973 Program,
grant number 2014CB239301) and the Mitsubishi Foundation.
Keywords: carbon dioxide activation · gold · photocatalysis ·
surface plasmon resonances · sustainable chemistry
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Received: June 1, 2015
Published online: August 13, 2015
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