High-performance and long-lived Cu/SiO2 nanocatalyst for CO2 hydrogenation

Article abstract of DOI:10.1021/acscatal.5b00682

Cu-based nanocatalysts have been widely used for CO₂ hydrogenation, but their poor stability is the bottleneck for further industrial applications. A high-performance and long-lived Cu/SiO₂ nanocatalyst was synthesized by an ammonia-evaporation method for CO₂ hydrogenation. The conversion of CO₂ reaches up to 28%, which is close to the equilibrium conversion of CO₂ (30%), and the selectivity to methanol is 21.3%, which is much higher than the equilibrium selectivity (6.6%) at 320 °C and 3.0 MPa. Furthermore, after 120 h of evaluation, the conversion can be still maintained at a high value (27%), which is much better than a Cu/SiO₂ catalyst prepared by traditional impregnation. The Cu⁺ species has been demonstrated to be the active component for the activation and conversion of CO₂. The higher ratio of Cu⁺/(Cu⁰ + Cu⁺) and interaction between the metal and support deriving from copper phyllosilicate are mainly responsible for the high catalytic activity and excellent stability, respectively.

Full text of DOI:10.1021/acscatal.5b00682

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Letter
A High-Performance and Long-Lived Cu/
SiO2 Nanocatalyst for CO2 Hydrogenation
Zhi-Qiao Wang, Zhong-Ning Xu, Si-Yan Peng, Ming-Jian Zhang,
Gang Lu, Qing-Song Chen, Yumin Chen, and Guo-Cong Guo
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.5b00682 • Publication Date (Web): 08 Jun 2015
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ACS Catalysis
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A High-Performance and Long-Lived Cu/SiO2 Nanocatalyst for
CO2 Hydrogenation
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Zhi-Qiao Wang,†,‡ Zhong-Ning Xu,*,†,‡ Si-Yan Peng,† Ming-Jian Zhang,† Gang Lu,† Qing-Song
Chen,† Yumin Chen,† and Guo-Cong Guo*,†
†State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese
Academy of Sciences, Fuzhou, Fujian 350002, P. R. China
‡Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Chinese Academy of Sciences, Fuzhou, Fu-
jian 350002, P. R. China
Abstract: Cu-based nanocatalysts have been widely used for CO2 hydrogenation, but the poor stability is the bottleneck
for further industrial application.
evaporation method for CO2 hydrogenation. The conversion of CO2 reaches up to 28%
A
high-performance and long-lived Cu/SiO2 nanocatalyst was synthesized b
,
y ammonia-
which is close to the equilibrium
conversion of CO2 (30%), and the selectivity to methanol is 21.3%, which is much higher than the equilibrium selectivity
(6.9%) at 320 °C and 3.0 MPa. Furthermore, after 120 h evaluation the conversion can still maintain at a high value (27%),
which is much better than Cu/SiO2 catalyst prepared by traditional impregnation. The Cu+ species has been demonstrated
to be the active component for the activation and conversion of CO2. The higher ratio of Cu+/(Cu0 + Cu+) and interaction
between metal and support deriving from copper phyllosilicate are mainly responsible for the high catalytic activity and
excellent stability, respectively.
Keywords: ammonia-evaporation method, Cu/SiO2 nanocatalyst, CO2 hydrogenation, copper phyllosilicate, Cu+ spe-
cies
CO2 is a main kind of “greenhouse gas”, which is pro-
duced by the utilization of carbon-rich fossil fuels (e.g.,
coal, oil and natural gas).1,2 In recent decades, the rapidly
raising concentration of CO2 in the atmosphere results in
a series of environment problems, such as global warm-
ing, ocean acidification, climate change and so on.3-5
Though the natural photosynthesis can convert CO2 to
organic carbon, it is far from enough to consume so much
CO2 in a short period with its increasing concentration.6
Recently, much attention has been attracted to the cata-
lytic conversion of CO2 because it can not only close the
anthropogenic carbon cycle but also provide useful chem-
icals such as epoxides, methanol, formic acid and so on.7-13
However, few industrial processes have utilized CO2 as a
raw material to produce high-value chemicals.14 The big-
gest challenge is that CO2 activating requires a large
number of energy due to its high oxidation state and
thermodynamic stability under lacking of effective cata-
lysts.15,16 Hence, it is quite essential to develop high-
performance catalysts to activate and convert CO2 under
mild conditions.17,18
the preparation and using processes.29 Notably, the
growth of metal NPs, which can result in losing of active
surface area, is the main reason for deactivation of many
supported nanocatalysts.29 The poor stability of Cu NPs is
the bottleneck for industrial application.30, 31 Introducing
structure promoters has been used to mitigate the growth
Cu NPs32, 33, but sometimes it just does not work because
it would restrict the chemical composition and function-
ality of Cu-based nanocatalysts.29, 34, 35 Hence, developing a
new strategy to prepare high-performance and long-lived
supported Cu-based nanocatalysts without any promoter
has important significance for activation and conversion
of CO2.
In this work,
a high-performance and long-lived
Cu/SiO2 nanocatalyst (denoted as Cu/SiO2-AE, see the
preparation process details in ESI) has been synthesized
by ammonia-evaporation (AE) method.36 CO2 hydrogena-
tion to methanol was chosen as a probe reaction to evalu-
ate the Cu/SiO2-AE nanocatalyst.
Figure 1 presents the performances of Cu/SiO2-AE
nanocatalyst for CO2 hydrogenation to methanol. The
products of Cu/SiO2-AE nanocatalyst for CO2 hydrogena-
tion are methanol, CO and a small amount of methane.
Cu-based nanocatalysts have been widely used in the
field of CO2 hydrogenation because of their high activity
for activation and conversion of CO2.19-27 The catalytic
activity of Cu-based nanocatalyst would dramatically im-
prove with decreasing of the Cu particle size.28 However,
Cu-based nanocatalysts are not stable because Cu nano-
particles (NPs) would easily aggregate and sinter during
With the reaction temperature increasing from 260 to
380 °C, the conversion of CO2 increases from 8.2 to 35.0%
and the selectivity to methanol decreases from 40.2% to
5.9%, implying low temperature is suitable for the synthe-
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sis of methanol but not for the CO2 catalytic conversion37
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(Figure 1a). The conversion of CO2 at 320 °C is close to the
equilibrium conversion (30%, Table S1), suggesting the as-
synthesized Cu/SiO2-AE nanocatalyst is of high activity
for CO2 hydrogenation. Interestingly, the selectivity to
methanol at 320 °C is 21.3%, which is much higher than
that (6.9%) of equilibrium selectivity to methanol (Figure
S1). The main product CO can further hydrogenated to
methanol over Cu/SiO2-AE nanocatlayst (Figure S2). The
influence of WHSV has been presented in Figure S3. The
weight time yield (WTY) of methanol presents the volcan-
ic type trend and reaches the maximum of 0.26 g·gcat.-1·h-1
at 320 °C according to the conversion and selectivity (Fig-
ure 1b). Most importantly, the conversion of CO2 over
Cu/SiO2-AE nanocatalyst can still maintain at a high value
(27%) after 120 h evaluation (Figure 2), which indicates
that the as-synthesized Cu/SiO2-AE nanocatalyst is quite
stable and has promising industrial application value. In
order to highlight the advantage of ammonia-evaporation
method, a Cu/SiO2 nanocatalyst had been synthesized by
traditional impregnation method for comparison (denot-
ed as Cu/SiO2-TI, see the preparation process details in
ESI). The catalytic activity of Cu/SiO2-TI nanocatalyst is
just 5% at 320 °C, which is much less than that of
Cu/SiO2-AE nanocatalyst (Figure S4) under the same re-
action conditions. Furthermore, the stability of Cu/SiO2-
TI nanocatalyst is quite poor since the catalytic activity is
almost completely lost after 25 h (Figure 2). Moreover, the
turnover frequency (TOF) values (details shown in ESI) of
Cu/SiO2-AE and Cu/SiO2-TI nanocatalysts are 79.85 and
10.44 h-1, respectively. The intrinsic TOF value of Cu/SiO2-
AE nanocatalyst is 7.7 times as much as that of Cu/SiO2-
TI nanocatalyst, indicating that the Cu/SiO2-AE nanocata-
lyst is a high-performance catalyst for CO2 hydrogenation.
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Figure 1. The performances of Cu/SiO2-AE nanocatalyst for
CO2 hydrogenation[i]: (a) Conversion of CO2, selectivity to
CH3OH and selectivity to CH4 as functions of reaction tem-
perature, (b) WTY[ii] of methanol as functions of reaction
temperature. [i] Reaction conditions: 0.3 g catalyst, 3.0 MPa,
weight hour space velocity (WHSV) = 16 L·gcat-1·h-1, H2 : CO2 =
[ii]
4 : 1.
WTY represents the weight-time yield, grams of
The powder X-ray diffraction (PXRD) patterns of cal-
cined Cu/SiO2-AE samples reveal that the main peaks
centred at 2θ = 30.8, 35.0, 57.5, 62.3 ° (JCPDS No. 027–
0188, Figure 3a), which can be indexed to the phase of
copper phyllosilicate.29 Meanwhile, there is the phase of
CuO (2θ = 32.2, 35.2, 38.4, 48.4, 53.2, 58.0, 61.2, 65.9, 67.7
°) (JCPDS No. 044–0706, Figure 3b) in calcined Cu/SiO2-
TI sample.26 The board peaks at 22 ° belong to the amor-
phous SiO2 support (Figure 3).26 Fourier-transform IR (FT-
IR) spectra were further measured to discriminate Cu
species. There are two shoulder peaks at 1040 and 670 cm-
methanol per gram of catalyst per hour (g·gcat.-1·h-1).
1
in calcined Cu/SiO2-AE sample (Figure S5a), confirming
the existing of copper phyllosilicate.38 There were no cor-
responding shoulder peaks in the FT-IR spectroscopy of
calcined Cu/SiO2-TI sample (Figure S5b), suggesting that
there was no copper phyllosilicate in the Cu/SiO2-TI sam-
ple.38 Cu 2p X-ray photoelectron spectroscopy (XPS) spec-
tra are shown in Figure 4. Cu 2p3/2 peak binding energy of
calcined Cu/SiO2-AE sample is 935.96 eV (Figure 4a),
which is consistent with 936.0 eV of copper phyllosilicate.
Meanwhile, Cu 2p3/2 peak binding energy of calcined
Cu/SiO2-TI sample is 933.75 eV (Figure 4b) corresponding
to the 933.6 eV of CuO.38 Based on the discussion above,
Figure 2. Conversion of CO2 as functions of time on stream
at 320 °C and 3.0 MPa over (a) Cu/SiO2-AE and (b) Cu/SiO2-
TI nanocatalysts.
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Figure 5. TEM images of (a) calcined Cu/SiO2-AE sample
and (b) freshly reduced Cu-SiO2-AE nanocatalyst. The inset
of panel shows the corresponding size distribution diagram.
equation. However, it is worthy to note that there are no
obvious diffraction peaks for freshly reduced Cu/SiO2-AE
nanocatalyst except for the diffraction peak at 22 ° for
SiO2 support39 (Figure S13a), suggesting that the Cu spe-
cies are highly dispersed on the surface of SiO2. In addi-
tion, there are still no obvious diffraction peaks for
Cu/SiO2-AE nanocatalyst after 120 h evaluation (Figure
S13b).
Figure 3. XRD patterns of (a) calcined Cu/SiO2-AE sample,
(b) calcined Cu/SiO2-TI sample, and (c) mSiO2·nH2O.
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Transmission electron microscopy (TEM) image of cal-
cined Cu/SiO2-AE sample (Figure 5a) exhibits that the
copper phyllosilicate presents lamellar structure, which
was formed during the unique ammonia-evaporation pro-
cess.39 Figure 5b shows the TEM image of freshly reduced
Cu/SiO2-AE nanocatalyst. The active Cu NPs are homo-
geneously dispersed on the surface of SiO2 with the aver-
age size of Cu NPs being about 2.1 nm, which is ultra-
small among the reported Cu-based nanocatalysts. The
active Cu NPs are still highly dispersed on the surface of
SiO2 after 120 h evaluation (Figure S14), implying the as-
synthesized Cu/SiO2-AE nanocatalyst is quite stable. On
the other hand, the Cu NPs of freshly reduced Cu/SiO2-TI
nanocatalyst aggregated and the average size is very large
(about 49.5 nm) (Figure S15).
Figure 4. Cu 2p XPS spectra of calcined (a) Cu/SiO2-AE and
(b) Cu/SiO2-TI samples.
we conclude that the main Cu species in calcined
Cu/SiO2-AE and Cu/SiO2-TI samples are copper phyllosil-
icate and CuO, respectively. The Cu 2p3/2 peak binding
energy shifts from 933.75 to 935.96 eV (Figure 4), demon-
strating the existence of interaction between metal and
support in calcined Cu/SiO2-AE sample due to the for-
mation of copper phyllosilicate (Figure S6 and S7).39 The
interaction was further proved by the combination of Si
2p XPS (Figure S8), H2-TPR (Figure S9), PXRD (Figure
S10), H2-TGA (Figure S11) and UV-Vis-NIR diffuse reflec-
tance spectroscopy (Figure S12) characterizations. The ex-
istence interaction can effectively restrain the migration
and aggregation, which mainly accounts for the long life
of Cu/SiO2-AE nanocatalyst without any structure pro-
moters.
The Cu 2p3/2 and Cu 2p1/2 peaks of freshly reduced
Cu/SiO2-AE and Cu/SiO2-TI nanocatalysts both appear at
932.8 and 952.7 eV, respectively (Figure S16a), which sug-
gests that the Cu2+ species in calcined Cu/SiO2-AE and
Cu/SiO2-TI samples can be both reduced to Cu+ and/or
Cu0 species.40 Cu LMM X-ray auger electron spectroscopy
(XAES) spectrum is measured to distinguish Cu+ and Cu0
species.41-42 Interestingly, the kinetic energy of Cu/SiO2-
AE nanocatalyst is 914.9 eV, indicating the Cu species is
Table 1. Physicochemical properties of as-
synthesized nanocatalysts.
[a]
[b]
[c]
Cu
Nanocatalysts loading
(%)
SBET
DCu
SCu
(m2g-1)
The FT-IR in Figure S5b confirm that the disappearing
of copper phyllosilicate in the freshly reduced Cu/SiO2-AE.
The PXRD pattern of freshly reduced Cu/SiO2-TI nano-
catalyst (Figure S13c) shows obvious diffraction peaks at
43.30, 50.44 and 74.10 °, which are assigned to Cu (111),
(200) and (220) planes (JCPDS No. 070–3039), respective-
ly. The average size of Cu NPs for Cu/SiO2-TI nanocata-
lyst is about 46.5 nm, which is calculated by the Scherrer
(m2g-1)
(%)
Cu/SiO2-AE
Cu/SiO2-TI
10.7
10.1
400.7
335.4
5.3
3.1
31.8
20.8
[a]
[b]
SBET: BET surface area of catalysts. DCu: Cu disper-
sion of catalysts. [c] Cu specific surface area.
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which demonstrates that the Cu+ species is the active
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component in Cu/SiO2-AE nanocatalyst for activation and
conversion of CO2 (Figure 6). Considering the reaction
was carried out under reduction atmosphere, we change
the reaction temperature of CO2 hydrogenation to 200 °C
and maintain other conditions unchanged. The reaction
temperature of 200 °C is lower than the reduction tem-
perature (248 °C) obtained from the H2-TPR profile (Fig-
ure S6). It is worth mentioning that the conversion of CO2
increased significantly with the raising of Cu+ ratio (Fig-
ure S27), which is consistent with the result derived from
Figure 6. Therefore, the high ratio of Cu+/(Cu0 + Cu+) is
mainly responsible for the high performance of Cu/SiO2-
AE nanocatalyst for CO2 activation.
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In summary, we have successfully synthesized a high-
performance and long-lived Cu/SiO2-AE nanocatalyst for
CO2 hydrogenation by ammonia-evaporation method
without introducing any structure promoters. The Cu+
species has been demonstrated to be the active compo-
nent for the activation and conversion of CO2. The high
value of Cu+/(Cu0 + Cu+) is mainly responsible for the
high performance of Cu/SiO2-AE nanocatalyst in CO2 ac-
tivation. The ultra-small size, relative high dispersion and
specific surface area of Cu+ species are contributed to the
high catalytic activity. The interaction between metal
and support mainly accounts for the excellent thermal
stability. This work will provide an effiective way for syn-
thesizing transition metal based nanocatalysts (such as Fe,
Co, Ni, etc.) with high activity and stability.
Figure 6. Three-dimensional histogram of conversion of
CO2, Cu+/(Cu0 + Cu+) and reaction temperature.
Cu+, while that of Cu/SiO2-TI nanocatalyst is 917.6 eV,
suggesting the Cu species is Cu0 (Figure S16b).43, 44 In Fig-
ure S17, the dominating Cu species after 120 h of time-on-
stream is still Cu+.
The BET surface area (Table S2, Figure S18 and S19) of
Cu/SiO2-AE nanocatalyst is 400.7 m2/g, which is higher
than that (335.4 m2/g) of Cu/SiO2-TI nanocatalyst, sug-
gesting that the AE method is superior to the TI method
for acquiring higher BET surface area. Interestingly, there
are smaller pores (about 2 nm) distribute in Cu/SiO2-AE
nanocatalyst (Figure S20a), while there are no this kind of
pores in Cu/SiO2-TI nanocatalyst (Figure S20b). The larg-
er BET surface area and small pore size may be benefit for
the CO2 hydrogenation. Moreover, the Cu dispersion (DCu)
and Cu specific surface area (SCu) of Cu0 in Cu/SiO2-TI
nanocatalyst were measured by N2O titration, while those
of Cu+ in Cu/SiO2-AE nanocatalyst were measured by ir-
reversible CO adsorption (Table 1 and Figure S21, see
more details in ESI). The DCu of Cu/SiO2-AE nanocatalyst
is 5.3%, which is higher than 3.1% of Cu/SiO2-TI nanocata-
lyst (Table 1). And the SCu of Cu/SiO2-AE nanocatalyst is
31.8 m2/g, which is also bigger than that (20.8 m2/g) of
Cu/SiO2-TI nanocatalyst. High-angle annular dark-field
scanning transmission electron microscopy (HAADF-
STEM) and scanning transmission electron microscopy-
energy dispersive X-ray (STEM-EDX) were used to deter-
mine the surface distribution of Cu+ species in Cu/SiO2-
AE nanocatalyst (Figure S22 and S23). The relative high
DCu and SCu could be contributed to the high performance
of Cu/SiO2-AE nanocatalyst.
ASSOCIATED CONTENT
Supporting Information
Reaction of CO2 hydrogenation to methanol, experimental
details, BET surface areas, N2O titration, irreversible CO ad-
sorption measurement, PXRD patterns, TEM images,
HAADF-STEM image, STEM-EDX, XPS and XAES spectra,
H2-TPR profiles, H2-TGA profile, UV-Vis-NIR diffuse reflec-
tance spectra. This material is available free of charge via the
Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
gcguo@fjirsm.ac.cn (Guo-Cong Guo);
znxu@fjirsm.ac.cn (Zhong-Ning Xu)
Notes
The authors declare no competing financial interest
ACKNOWLEDGMENT.
We gratefully acknowledge financial support from the 973
Program (2011CBA00505, 2013CB933200), the NSF of China
(21403237, 21303202, 21303203), the NSF of Fujian Province
(2014J05025), and Open Project of State Key Laboratory of
Supramolecular Structure and Materials (sklssm201506).
Three Cu/SiO2-AE nanocatalysts (Figure S24, see the
preparation process in ESI) with the different Cu+/(Cu0 +
Cu+) ratios have been synthesized to investigate the influ-
ence of valence state. The Cu+/(Cu0 + Cu+) ratio was de-
termined by Cu LMM XAES spectra (Figure S25 and Fig-
ure S26). Notably, the conversion of CO2 rapidly raises
with increasing of the Cu+/(Cu0 + Cu+) value and reaches
up to the maximum when the Cu+/(Cu0 + Cu+) is 1.00,
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