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org/JPCC Article

Selective Hydrogenation of CO2 to Ethanol over Sodium-Modified

Rhodium Nanoparticles Embedded in Zeolite Silicalite‑1
Published as part of The Journal of Physical Chemistry virtual special issue “Energy and Catalysis in China”.
Fuyong Zhang,† Wei Zhou,† Xuewei Xiong, Yuhao Wang, Kang Cheng, Jincan Kang,* Qinghong Zhang,
and Ye Wang*
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sı Supporting Information

ABSTRACT: Catalytic transformation of CO2 into chemicals in large

demand such as ethanol has attracted much research attention under the
background of establishing carbon-neutral societies. Supported Rh
catalysts are promising candidates for the hydrogenation of CO2 to
ethanol but suffer from low ethanol productivity and poor catalyst stability.
Here, we report that zeolite silicalite-1 embedded Na-promoted Rh
nanoparticles (Na-Rh@S-1) demonstrate high productivity and stability
for CO2 hydrogenation to ethanol. The ethanol selectivity of 24% was
attained at a CO2 conversion of 10%, and the space-time yield of ethanol
reached 72 mmol gRh−1 h−1, which outperformed most of the Rh-based
catalysts reported to date. While a reference catalyst prepared by
impregnation underwent deactivation, the Na-Rh@S-1 catalyst was stable
for at least for 100 h owing to the confinement effect. The Na+ modifier played crucial roles in enhancing the CO2 conversion and
ethanol selectivity by suppressing methane formation. The characterizations suggest that the presence of Na+ enables the coexistence
of Rh0 and Rh+ and enhances CO2 adsorption, thus boosting ethanol formation. A comparative study between CO and CO2
hydrogenation reveals that the Na-Rh@S-1 catalyst is significantly more active and selective toward CO2 hydrogenation to ethanol.

1. INTRODUCTION ethanol has attracted much research attention, but the

The capture and recycling of CO2 released during industrial
processes to chemical and energy feedstocks in great demand
would contribute to establishing carbon-neutral societies, and
thus have become a hot research area.1,2 The hydrogenation of
CO2 by “green” H2, which can be produced by electrolysis of
H2O using renewable electricity,3 into high-value chemicals is
one of the most promising routes for the utilization of CO2.4−6
Methanol has long been an important target product for CO2
hydrogenation,7,8 but the direct transformation of CO2
selectively into a more value-added multicarbon (C2+)
compound is also very attractive and is more challenging
because the control of C−C coupling is a big challenge in C1
chemistry.6,9 Significant progress has been achieved for the
hydrogenation of CO2 into C2+ hydrocarbons, including lower
olefins,10,11 aromatics,11,12 and liquid hydrocarbon fuels,13 by
developing new strategies such as tandem or relay catalysis.
However, the selective synthesis of C2+ oxygenates by CO2
hydrogenation still remains a big challenge.
As one of the most demanded C2+ oxygenates, ethanol is
considered as an ideal fuel additive, alternative fuel, attractive
hydrogen carrier, and versatile building-block chemical for the
synthesis of value-added chemicals, advanced fuels, and
polymers.14,15 Recently, the hydrogenation of CO2 into
productivity of ethanol remains low.16−19 This is not only
because CO2 is a thermodynamically stable and kinetically
inert molecule but also because the formation of C2H5OH is
generally believed to involve the C−C coupling between
different species (e.g., CHx and CHxO (x = 0−3)), which is
difficult to control.16,19 Among the reported catalysts for CO2
hydrogenation to C2+ oxygenates, mainly including Rh-,20−24
Cu-,25,26 Co-,27,28 and Mo-based catalysts,29 the Rh-based
catalysts show promising performance. It is well-known that
Rh-based catalysts are also among the most efficient catalysts
for the conversion of syngas (CO + H2) to ethanol owing to
the unique abilities of Rh in C−O bond activation and CO
insertion for C−C coupling.30,31 As compared to Rh-catalyzed
CO hydrogenation, the studies on CO2 hydrogenation over
Rh-based catalysts are still limited. Similar to CO hydro-
genation, the CH4 or CO dominated the product in CO2
Received: September 5, 2021
Revised: October 10, 2021
Published: October 24, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acs.jpcc.1c07862

24429 J. Phys. Chem. C 2021, 125, 24429−24439
The Journal of Physical Chemistry C
hydrogenation over unmodified Rh catalysts. Promoters, such
as the alkali metal ions (e.g., Li+, Na+, and K+) and transition
metal oxides (e.g., FeOx, MnOx, and VOx), and supports
played key roles in tuning the electronic state of Rh species and
the metal−support interactions to boost the formation of
ethanol.16,19−24 However, the state-of-the-art ethanol produc-
tivity for CO2 hydrogenation is still far from satisfactory.
Moreover, the supported Rh catalysts usually display poor
stability due to the sintering of nanoparticle during CO2
hydrogenation.16 Therefore, new strategies should be devel-
oped to increase both the productivity and stability of Rh-
based catalysts for CO2 hydrogenation to ethanol. Further-
more, it is of fundamental interest to understand the
similarities and differences between Rh-catalyzed CO2 and
CO hydrogenation reactions, but such comparative studies are
very rare.32
Zeolites, which possess well-defined crystalline microporous
structures and high thermal/hydrothermal stability, have
received renewed interests in catalysis because of recent
successful synthesis and the unique catalytic behaviors of
metal@zeolite materials.33−36 The active metal species (either
single-atom and few-atom clusters smaller than the micropores
or nanoparticles larger than the micropores) in the metal@
zeolite materials are needlessly located inside zeolite micro-
pores but can be embedded in situ in the interrupted zeolite
frameworks during their formation and are fixed by the zeolite
frameworks. This offers more opportunities for designing
different types of metal@zeolite hybrid catalysts with unique
catalytic behaviors such as shape selectivity and high
stability.33−36 For example, a ligand-protected hydrothermal
crystallization was developed to synthesize subnanometer Pt−
Zn clusters confined in silicalite-1 (S-1), a pure silicious zeolite
with MFI structure, and the Pt−Zn@S-1 displayed high
activity and stability for the dehydrogenation of propane to
propylene at 823 K.37 A Pd@S-1 catalyst with an average Pd
particle size of 2.3 nm synthesized by the same ligand-
protected hydrothermal method showed high activity and
stability in methane combustion reaction.38 Rh−Mn nano-
particles were confined within S-1 by a metal-containing seed-
directed crystallization, and the RhMn@S-1 catalyst showed
high activity and stability in the conversion of syngas to C2+
oxygenates.39 Despite being applied successfully in several
types of reactions, the studies on the application of metal@
zeolite catalysts for CO2 hydrogenation to C2+ oxygenates are
rare.33−36
Here, we report our recent studies on the application of Na-
modified Rh nanoparticles embedded in S-1 (denoted as Na-
Rh@S-1) synthesized by the ligand-protected hydrothermal
crystallization in CO2 hydrogenation to ethanol. We have also
carried out a comparative study between hydrogenation of CO
and CO2 over the S-1 confined Rh catalyst. The role of Na+ in
the catalyst and the effect of confinement on catalytic
performances including the stability have also been inves-
tigated to gain insights into nature of active sites for selective
formation of ethanol and the advantage of the metal@zeolite
catalytic materials.
2. METHODS
2.1. Materials and Catalyst Synthesis. All the reagents
were purchased and used without further purification.
Tetraethyl orthosilicate (TEOS), tetrapropylammonium hy-
droxide aqueous solution (TPAOH, 25 wt %), ethylenedi-
amine (EDA), ethylenediaminetetraacetic acid disodium salt
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(EDTA-2Na), and sodium nitrate (NaNO3, 99%) were
purchased from Sinopharm Chemical Reagent Co. Rhodium
chloride hydrate (RhCl3·xH2O, Rh content, 38.5−42.5%) was
purchased from Aladdin.
The nanosized S-1 zeolite was synthesized by a hydro-
thermal method. The molar ratio of the components in the
synthesis gel was 1 SiO2: 0.4 TPAOH: 35 H2O. For typically
procedures, 13.0 g of TPAOH was first dissolved in 15.42 g of
deionized water under vigorous stirring, and then 8.32 g of
TEOS was added dropwise into the above solution. After the
TEOS was hydrolyzed completely, the mixed gel was
transferred into a 100 mL Teflon-lined autoclave for
hydrothermal crystallization. The hydrothermal synthesis was
carried out at 443 K for 96 h. The resultant solid was collected
by centrifugation, thoroughly washed with water 5 times, and
subsequently washed with ethanol. The solid product was
dried at 353 K overnight and calcined in air at 823 K for 8 h.
The Rh@S-1 catalyst, which contained Rh nanoparticles
fixed in nanosized S-1 zeolite, was synthesized by a modified
method reported previously.37 EDA was employed as the
protect ligand. The procedures were similar to those adopted
for the synthesis of S-1 except for the addition of an aqueous
solution of [Rh(NH2CH2CH2NH2)3]Cl3, which was prelimi-
narily prepared by dissolving 0.063 g of RhCl3·3H2O and 0.8
mL of EDA in 5 mL of deionized H2O, into the synthesis gel.
The Na-Rh@S-1 catalyst (i.e., the Na-modified Rh nano-
particles fixed in nanosized S-1) was also synthesized by similar
procedures to those of S-1 or Rh@S-1. EDTA was chosen as
the ligand of Rh in the presence of Na ions. A mixed solution
containing Rh-EDTA complex and NaCl was preliminarily
prepared by dissolving 0.063 g of RhCl3·3H2O and 0.10 g of
EDTA-2Na into 5 mL of deionized H2O, and this solution was
added into the synthesis gel. The content of Na in the final
catalyst was tuned by changing the repeated time used for
water-washing step. The samples with different contents of Na
were denoted as xNa-Rh@S-1, where x was the weight content
of Na.
A reference catalyst (i.e., the S-1-supported catalyst
(denoted as Na-Rh/S-1)) was prepared by the conventional
incipient wetness impregnation method. Typically, 0.004 g of
NaNO3 and 0.012 g of RhCl3·3H2O were dissolved in 3.0 g of
deionized water under vigorous stirring for 30 min to form a
clear solution, and then 0.60 g of S-1 was slowly added into the
mixed aqueous solution under stirring for 10 min. The
obtained slurry was further dried at 353 K for 10 h, followed by
calcination in air at 773 K for 5 h to obtain the catalyst
denoted as 0.17Na-Rh/S-1.
2.2. Catalyst Characterization. X-ray diffraction (XRD)
patterns were recorded on a Rigaku Ultima IV diffractometer
(Rigaku, Japan) using Cu Kα radiation (40 kV and 30 mA) as
the X-ray source. N2 physisorption measurements were carried
out on a Micromeritics ASAP 2460 and the sample was
pretreated under vacuum at 473 K for 2 h prior to each
measurement. The contents of Rh and Na in the catalyst were
measured by inductively coupled plasma-optical emission
spectrometer (ICP-OES). X-ray photoelectron spectroscopy
(XPS) measurements were carried out in an UHV chamber
equipped with an Omicron XPS (base pressure 5 × 10−10
Torr). A monochromatized Al Kα X-ray source and a Sphere 2
analyzer were used. After pretreatment in H2 (5 vol %)/Ar flow
at 673 K for 30 min in a pretreatment chamber directly
connected to the detecting chamber, the sample was
transferred into the UHV detecting chamber for XPS
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Figure 1. Schematic diagram for the formation of Na-Rh@S-1 catalyst.
measurements. To obtain the surface information of the Rh- or
Na-promoted Rh nanoparticles embedded in zeolite, the Ne
ions were used to sputter the sample with a kinetic energy of 5
keV, an ion flux of 1600 pA·m−2, and a spot size of 2 mm × 2
mm, which could strip off the zeolite shell. Then, the sputtered
sample was transferred into the analysis chamber for XPS
measurements to obtain the surface information on the
embedded nanoparticles.
Scanning electron microscopy (SEM) measurements were
carried out with a Hitachi S-4800 operated at 15 kV.
Transmission electron microscopy (TEM), dark-field TEM,
energy dispersive spectroscopy (EDS) mapping, and line-scan
elemental analysis measurements were carried out on a Phillips
Analytical FEI Tecnai 20 electron microscope operated at an
acceleration voltage of 200 kV. The ultramicrotomy of the
resin-embedded catalyst was carried out to expose cross
sections of the catalyst with metal nanoparticles confined or
fixed in S-1. For this purpose, the sample was first embedded in
epoxy resin, and then cut into 60 nm sections using a diamond
knife. Slices of the sample were deposited on carbon-coated
copper grids (200 meshes) for TEM measurements.40,41
Hydrogen temperature-programmed reduction (H2-TPR)
measurements were carried out on a Micromeritics AutoChem
II 2920 instrument. Prior to each measurement, 0.10 g of
sample was pretreated in a He flow at 673 K for 1 h. Then, the
sample was cooled down to 323 K, followed by switching to H2
(5 vol %)/Ar gas flow. Subsequently, the temperature was
increased to 773 K at a ramping rate of 10 K min−1, and the H2
consumption was detected by a thermal conductivity detector
(TCD). The chemisorption of CO2 was measured volumetri-
cally on a Micromeritics 3flex instrument. Prior to each
measurement, the 0.10 g sample was pretreated in a H2 (5%)/
N2 flow at 673 K for 30 min, followed by degassing in vacuum
at 423 K for 2 h. The chemisorption of CO2 was detected at
298 K by a Rubotherm Isosorp-Htgra magnetic suspension
balance.
CO-adsorbed Fourier-transform infrared (CO-FTIR) meas-
urements were carried out on a Nicolet 6700 instrument
equipped with a MCT detector. The spectra were recorded
from 4000 to 600 cm−1 at a resolution of 2 cm−1. The sample
was pressed into a self-supported wafer and was set in an in situ
IR cell. For a typical measurement, after the sample was
pretreated in a H2 (5 vol %)/Ar flow at 673 K for 30 min, the
sample was cooled down to room temperature, and then the
adsorption of CO was conducted for 30 min by introduction of
a CO (10 vol %)/Ar flow to the cell. The CO-FTIR spectrum
was collected after the removal of gaseous CO molecules by
evacuation.
In situ high-pressure diffuse reflectance infrared Fourier-
transform spectroscopy (DRIFTS) measurements were carried
out on the same instrument equipped with a high-pressure
Harrick Scientific DRIFTS cell of ZnSe windows. Prior to each
measurement, the sample was pretreated in H2 (5 vol %)/Ar
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gas flow (30 mL min−1) at 673 K for 30 min in the DRIFTS
cell. Then, the sample was cooled to 523 K, followed by
purging with He. After recording the background spectrum, a
CO2/H2 (24 vol % CO2/72 vol % H2/4 vol % Ar) gas at 2.5
MPa was switched into the in situ DRIFTS cell at 523 K, and
the evolution of IR spectra was recorded. The in situ DRIFTS
measurements were carried out on a Bruker Vertex 70
instrument equipped with a high-pressure Harrick Scientific
DRIFTS cell. After pretreatment with H2 at 673 K followed by
He purging and cooling to 523 K, high-pressure CO2 (2.5
MPa) was first introduced to the cell, and then the gas feed was
switched to high-pressure H2 (2.5 MPa). The evolution of IR
spectra was recorded at different times after switching the gas
feed to H2.
2.3. Catalytic Reaction. The CO2 and CO hydrogenation
reactions were both carried out on a high-pressure, fixed-bed
titanium reactor with an inner diameter of 10 mm designed by
Xiamen HanDe Engineering Co., Ltd. Typically, a catalyst
(0.15 g) with grain sizes of 30−60 mesh was loaded in the
titanium reactor. Prior to each reaction, the catalyst was
pretreated in H2(5 vol %)/Ar (25 mL min−1) at 673 K for 30
min. Then the reactant gases (24%CO2/72%H2/4%Ar) were
introduced into the titanium reactor with 15 mL min−1 at 523
K and 5.0 MPa. Products were analyzed by an on-line gas
chromatograph (Ruimin GC 2060, Shanghai) equipped with a
thermal conductivity detector (TCD) and a flame ionization
detector (FID). A TDX-01-packed column was connected to
the TCD for the separation and analyses of Ar, CO, CH4, and
CO2. A RT-Q-BOND-PLOT capillary column was connected
to the FID for the separation and analyses of organic
oxygenated compounds (including dimethyl ether, methanol,
ethanol, and propanol) and C1−C10 hydrocarbons. The
product selectivity was calculated on a molar carbon basis.
The selectivity of CO formed via the reverse water−gas shift
(RWGS) reaction was calculated separately from the hydro-
genated products. Carbon balances were all in the range of
95−99%.
3. RESULTS AND DISCUSSION
3.1. Morphology and Structure of Catalysts. Figure 1
illustrates the overall process for the formation of Na-modified
Rh nanoparticles confined within S-1 zeolite. In brief, the
ligand EDTA forms a complex with Rh in the presence of Na+
and can avoid the precipitation of Rh species under strong
alkaline conditions for hydrothermal crystallization of S-1.
Furthermore, the Rh complex does not affect the strong
alkaline environment for the synthesis of S-1 in the presence of
TPAOH (the template), and thus would not affect the
crystallization process of S-1. After hydrothermal synthesis and
the removal of organic template by calcination, the Rh species
and Na+ ions would be fixed by the framework of S-1, thus
forming the Na+-modified Rh nanoparticles embedded within
S-1 zeolite. The Na content in catalysts was regulated by
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changing the time for washing. By using this procedure, we EDA or EDTA, used for protecting Rh species during
obtained Na-Rh@S-1 catalysts with Rh contents in a range of hydrothermal synthesis could not affect the size of Rh
0.73−0.77 wt % and Na contents in a range of 0.13−0.26 wt % particles. It is noteworthy that the average micropore size of
(Table 1). S-1 zeolite with the MFI structure is 0.55 nm, significantly
smaller than the size of Rh nanoparticles. Therefore, the Rh
Table 1. Some Physicochemical Properties and nanoparticles in the Rh@S-1 and Na-Rh@S-1 catalysts are not
Compositions of Synthesized Catalysts encapsulated in the micropores of S-1 but are tightly
surrounded and fixed by the framework of S-1.33−36 The
content mean size of Rh particles in the reference sample (i.e., the
(wt %)a
0.17Na-Rh/S-1 prepared by the impregnation) was 4.2 nm
surface pore CO2
area volume chemisorption (Figure S4), larger than those in the Na-Rh@S-1 catalysts.
sample (m2 g−1) (cm3 g−1) Na Rh (μmol g−1)b XPS measurements were carried out to gain insights into the
S-1 360 0.27 state of surface Rh species. It is of interest that the XPS signal
Rh@S-1 326 0.23 0.77 21.9 of Rh 3d could not be discerned for the 0.19Na-Rh@S-1
0.13Na-Rh@S-1 302 0.21 0.13 0.76 23.7 catalyst, whereas the corresponding signal could be clearly
0.19Na-Rh@S-1 304 0.22 0.19 0.73 32.3 observed for the reference 0.17Na-Rh/S-1 sample (Figure S5).
0.26Na-Rh@S-1 303 0.21 0.26 0.74 24.1 This phenomenon is consistent with our expectation that the
0.17Na-Rh/S-1 295 0.22 0.17 0.75 26.6 Rh nanoparticles in the 0.19Na-Rh@S-1 catalyst are embedded
a
Determined by ICP-OES measurement. bMeasured by a magnetic in S-1 zeolite. To provide further evidence about the location
suspension balance at 298 K. of Rh species, we conducted the tomographic TEM character-
izations of the 0.19Na-Rh@S-1 and Rh@S-1 catalysts. The
The XRD measurements showed that the synthesized resin-embedded catalyst was cut into 60 nm slices by using a
samples had the typical diffraction patterns of the well- diamond knife to expose the internal view. By this technique,
crystallized MFI structure of S-1 zeolite (Figure S1), suggesting we confirmed that almost all of the Rh nanoparticles were
that our method of introducing Rh complex prior to uniformly embedded within S-1 (Figures 2c and S6a),
hydrothermal synthesis did not obstruct the crystallization of consistent with our previous result for the Pd@S-1 catalyst
S-1. No diffraction peaks belonging Rh2O3 could be observed synthesized by the same method.38 In contrast, in the 0.17Na-
in our catalysts probably because of the low Rh content or the Rh/S-1 sample, the Rh nanoparticles were mainly located on
small size of Rh species. The N2 physisorption showed that the the outer surface of S-1 (Figures S4 and S5). The dark-field
surface areas and pore volumes of our catalysts were 290−330 STEM and EDS mapping results for the 0.19Na-Rh@S-1 and
m2 g−1 and 0.21−0.27 cm3 g−1, respectively (Table 1 and Rh@S-1 catalysts provided evidence for the uniform dispersion
Figure S2). The surface area and pore volume for the catalysts of Rh throughout the S-1 crystals (Figures 2d−h and S6b−e).
were somewhat lower than those of the pristine S-1. Furthermore, the dark-field TEM, EDS mapping, and line-scan
The SEM micrographs showed that the catalysts were in elemental analysis results showed that Rh and Na were almost
hexagonal morphology and the average sizes of crystals were at identical locations over the 0.19Na-Rh@S-1 catalyst
230−260 nm (Figures 2a and S3). From the TEM micro- (Figures 2g−h and S7), suggesting that Na+ was in close
graphs, it is clear that the Rh particles were uniformly dispersed contact with Rh nanoparticles.
throughout the S-1 crystals (Figures 2b and S4). The mean 3.2. Catalytic Behaviors for Hydrogenation of CO2
sizes of Rh particles in the Rh@S-1 and Na-Rh@S-1 catalysts and CO. We investigated the catalytic behaviors of the Rh@S-
with different Na contents were close to each other and were 1 and Na-Rh@S-1 catalysts for CO2 hydrogenation. The Rh@
in the range of 2.4−2.6 nm, suggesting that the ligand, either S-1 catalyst showed a CO2 conversion of 2.9% and CH4 was

Figure 2. Electron microscopy results of the 0.19Na-Rh@S-1 catalyst. (a) SEM images and size distributions. (b) TEM image and size distributions
of Rh nanoparticles. (c) Tomographic TEM image. (d−h) Dark-field STEM image and the corresponding elemental mappings for Si, O, Rh, and
Na elements.

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Figure 3. Catalytic behaviors of Rh-based catalysts for CO2 hydrogenation. (a) CO2 conversion and product selectivity. (b) STY of C2H5OH and
the fraction of C2H5OH in C2+ oxygenates. Reaction conditions: catalyst loading = 0.15 g; H2/CO2 = 3; P = 5 MPa; T = 523 K; F = 15 mL min−1,
time on stream = 20 h. C2+OH: C2+ oxygenates.
formed as the major product with a small amount of CH3OH
(Figure 3a). No ethanol or other C2+ oxygenates was detected
over this catalyst without Na+ modifier. The Na-Rh@S-1
catalysts with Na + promoters showed enhanced CO 2
conversions and product distributions different from those
for the Rh@S-1 catalyst. The selectivity of CH4 decreased and
those of CH3OH and C2H5OH increased significantly. The
formation of CO via the RWGS reaction also occurred in the
presence of Na (Table S1). There is an optimum Na content,
and the 0.19Na-Rh@S-1 catalyst with a Na content of 0.19 wt
% or a Na/Rh molar ratio close to 1 demonstrated the best
performance for the formation of C2H5OH. Thus, the
modification of Rh sites by excessive Na+ is unbeneficial to
the CO2 hydrogenation.22 The CO2 conversion and C2H5OH
selectivity reached 10 and 24%, respectively, over the 0.19Na-
Rh@S-1 catalyst, both of which were the highest among the
Na-Rh@S-1 catalysts synthesized in this work. The space-time
yield (STY) of C2H5OH reached 72 mmol gRh−1 h−1 over the
0.19Na-Rh@S-1 catalyst (Figure 3b), which outperformed not
only other catalysts synthesized in the present work but also
the Rh-based catalysts reported previously (Table S2).
In addition to CH3OH and C2H5OH, C3−C5 alcohols
(denoted as C3+OH) were also formed (Figure S8a), but their
selectivity was quite low (<5%). The selectivity of C2+
hydrocarbons was also very low (≤1.5%) over that of the
Na-Rh@S-1 catalysts (Table S1). The fraction of C2H5OH in
C2+ oxygenates was around 90% over the Na-Rh@S-1 catalysts
(Figure 3b). The high fraction of C2H5OH in the C2+
oxygenates would simply the product separation in the future
practical application. Furthermore, as compared to 0.19Na-
Rh@S-1, the reference 0.17Na-Rh/S-1 catalyst showed lower
CO2 conversion and lower C2H5OH selectivity as well as
higher CH4 selectivity (Figure 3a). The STY of C2H5OH was
about 28 mmol gRh−1 h−1 (Figure 3b), 2.5 times lower as
compared to that of the 0.19Na-Rh@S-1 catalyst. Therefore,
both the Na+ modification and the confinement effect play
crucial roles in the hydrogenation of CO2 to ethanol.
Three representative catalysts (i.e., Rh@S-1, 0.19Na-Rh@S-
1, and 0.17Na-Rh/S-1) were chosen for the CO hydrogenation
study to gain insights into the similarities and differences in
Rh-catalyzed CO and CO2 hydrogenation reactions. The Rh@
S-1 catalyst showed a CO conversion of 4.1% and CH4
selectivity of 46% (Figure 4a). Different from CO2 hydro-
genation, the CO hydrogenation over the Rh@S-1 catalyst
provided C2+ oxygenates with a considerable selectivity (27%),
and C2+ hydrocarbons were also formed with a selectivity of
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Figure 4. Catalytic behaviors of Rh-based catalysts for CO
hydrogenation. The insets represent the distributions of C2+
oxygenates. (a) Rh@S-1. (b) 0.19Na-Rh@S-1. (c) 0.17Na-Rh/S-1.
Reaction conditions: catalyst loading = 0.15 g; H2/CO = 2; P = 5
MPa; T = 523 K; F = 15 mL min−1, time on stream = 20 h. C2+oxy:
C2+ oxygenates. C2+HC: C2+ hydrocarbons. MA: methyl acetate. EA:
ethyl acetate.
18%. It is noteworthy that the selectivity of C2H5OH was very
low, and instead, acetaldehyde, acetic acid, methyl acetate, and
ethyl acetate dominated the C2+ oxygenates (Figure S8b).
Thus, the Rh@S-1 catalyst without Na+ modifier could already
catalyze the C−C coupling or the chain growth to form C2+
oxygenates and hydrocarbons in the CO hydrogenation.
Unexpectedly, different from the CO2 hydrogenation, where
CO2 conversion increased by Na modification, for the CO
hydrogenation, the CO conversion rather decreased markedly
from 4.1 to 1.0% after the modification of Rh@S-1 by Na
(Figure 4b). At the same time, the selectivity of CH4 decreased
and that of CH3OH increased significantly. The shift of
methanation to methanol formation by Na+ modification is
similar to that for CO2 hydrogenation. However, the
selectivities of ethanol and C2+ oxygenates were not
significantly enhanced, and that of C2+ hydrocarbons was
decreased by Na+ modification. These observations indicate
that the Na modification also enhances CH3OH formation by
suppressing CH4 formation but does not accelerate C−C
coupling in CO hydrogenation. Therefore, the 0.19Na-Rh@S-
1 catalyst becomes a methanol-synthesis catalyst in CO
hydrogenation despite the low CO conversion activity.
Another difference from CO2 hydrogenation is that the
reference catalyst (i.e., 0.17Na-Rh/S-1 prepared by impregna-
tion) showed higher activity and selectivity of C2+ oxygenates
in CO hydrogenation than the 0.19Na-Rh@S-1 catalyst
(Figure 4c). The selectivity of methanol was lower over the
0.17Na-Rh/S-1. We further carried out CO hydrogenation
over 0.19Na-Rh@S-1 and 0.17Na-Rh/S-1 catalysts at higher
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reaction temperatures. Although CO conversions increased
with an increase in temperature from 523 to 573 K, the change
in product selectivity is insignificant (Table S3). The 0.19Na-
Rh@S-1 catalyst was selective for CH3OH formation, whereas
the 0.17Na-Rh/S-1 catalyst showed higher selectivity of C2+
oxygenates. The selectivity of C2+ oxygenates was 58% at a CO
conversion of 4.8% at 573 K. However, unlike in the
hydrogenation of CO2, the C2+ oxygenates in CO hydro-
genation over the 0.17Na-Rh/S-1 catalyst were broadly
distributed, including ethanol, acetaldehyde, acetic acid, methyl
acetate, and ethyl acetate, and the selectivity of C2H5OH was
only 4.8% (Table S3).
3.3. Stability of Na-Modified Rh Catalyst for CO2
Hydrogenation and the Confinement Effect. The catalyst
deactivation is a critical issue for Rh-catalyzed CO2 hydro-
genation because of the irreversible sintering of nano-
particles.16 We have examined the long-term stability of the
0.19Na-Rh@S-1 and 0.17Na-Rh/S-1 catalysts in CO2 hydro-
genation. As displayed in Figure 5, the 0.19Na-Rh@S-1 catalyst
Figure 5. Stability of the 0.19Na-Rh@S-1 and 0.17Na-Rh/S-1
catalysts for CO2 hydrogenation. Reaction conditions: catalyst loading
= 0.15 g; H2/CO2 = 3; P = 5 MPa; T = 523 K; F = 15 mL min−1.
was stable in 100 h of reaction; both the CO2 conversion
(∼10%) and STY of ethanol (∼72 mmol gRh−1 h−1) remained
unchanged with time on stream. However, the 0.17Na-Rh/S-1
catalyst underwent deactivation in 50 h of reaction under the
same conditions.
We carried out characterizations of the 0.19Na-Rh@S-1 and
0.17Na-Rh/S-1 catalysts after reactions. The XRD and N2
physisorption results clarified that the crystallinity and porous
structure of S-1 in the catalyst did not undergo any changes
after 100 h of reaction (Figures S9 and 10 and Table S4),
confirming the good stability of S-1 zeolite under our reaction
conditions. The contents of Rh and Na in the 0.19Na-Rh@S-1
and 0.17Na-Rh/S-1 catalysts did not change significantly after
reactions (Table S5), revealing that the leakage of Rh or Na
Figure 6. Characterizations of Rh@S-1 and Na-Rh@S-1 catalysts. (a) H2-TPR profiles. (b) CO-adsorbed FT-IR spectra. (c) Rh 3d XPS spectra
after Ne ion sputtering.
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did not occur during the reaction. The TEM studies revealed
that the mean size of Rh nanoparticles in the 0.19Na-Rh@S-1
catalyst changed insignificantly after the reaction (Figure
S11a). However, the mean size of Rh nanoparticles over the
0.17Na-Rh/S-1 catalyst increased significantly from 4.2 to 7.8
nm after the reaction (Figure S11b). These results
demonstrate that the rigid framework of S-1 zeolite is able to
stabilize the embedded Rh nanoparticles and prevent their
aggregation under the reaction conditions, whereas the Rh
particles without the confinement effect would suffer from
sintering, leading to catalyst deactivation of the impregnated
catalyst. Therefore, the confinement of the active Na-modified
Rh nanoparticles by the framework of zeolite is a useful
strategy to enhance the catalyst stability. The present work also
offers a new example of application of the metal@zeolite type
catalysts for stable catalysis.
3.4. Functions of the Na+ Modifier. Our present work
has demonstrated that the Na modifier plays crucial roles in
determining the catalytic behaviors of Rh catalysts for the
hydrogenation of CO2 and CO. We studied in more depth the
roles of Na modifier in affecting the chemical state of Rh
species to gain insights into the structure−performance
relationship. The H2-TPR result showed that the reduction
of Rh species in the Rh@S-1 catalyst occurred at temperatures
below 423 K (Figure 6a). Upon the introduction of Na+ to
Rh@S-1, the reduction peak shifted to higher temperatures
and became broader or was even split into two peaks, which
might be attributed to the stepwise reduction of Rh3+ to Rh+
and then Rh+ to Rh0 or the reduction of Rh species of different
states.42,43 Therefore, the Na+ modifier suppressed the
reduction of Rh species.
In situ CO-adsorbed FT-IR was employed to study the
chemical state of Rh species over our catalysts. Prior to each
measurement, the catalyst was pretreated by a procedure
similar to that adopted for catalytic reactions (i.e., with a H2 (5
vol %)/Ar flow at 673 K for 30 min). Then, the sample was
cooled to room temperature in H2, followed by CO adsorption
at room temperature and then evacuation to remove gaseous
CO. The IR bands at ∼2045 and ∼1860 cm−1 were observed
for the Rh@S-1 catalyst (Figure 6b), which could be assigned
to the linear CO and bridged CO adsorption on the Rh0 sites,
respectively.44,45 This observation indicates that Rh0 dominates
the Rh@S-1 catalyst after the reduction treatment. Additional
bands at ∼2080 and ∼2010 cm−1 appeared for the Na-Rh@S-1
catalyst (Figure 6b), and these two bands were attributable to
the symmetric and asymmetric stretching of CO adsorbed on
Rh+ sites in the form of germinal dicarbonyl (i.e., Rh-
(CO)2).46,47 Therefore, the CO-adsorbed FT-IR results
provide further evidence that surface of the Rh@S-1 catalyst
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is dominated by Rh0 species, and the presence of Na+ modifier
induces the generation of Rh+ together with Rh0 species. It is
noteworthy that the intensity of adsorbed CO bands decreased
for the 0.26Na-Rh@S-1 catalyst with a Na/Rh molar ratio of
∼1.6, suggesting that some surface Rh sites were covered by
Na+ at a higher Na content.
Because Rh species were embedded in the zeolite matrix, the
conventional XPS measurement was not useful (Figure S5).
Thus, we carried out the sputtering of the surface of Rh-
embedded catalysts by Ne ions with repeated sputtering−
annealing cycles to gain information about the chemical state
of the Rh species. The sample was pretreated under H2
atmosphere at 673 K prior to sputtering and XPS measure-
ments. After sputtering treatment for 25 times, the Rh signals
could be detected and the binding energy of Rh 3d5/2 for the
Rh@S-1 catalyst was observed at 307.1 eV (Figure 6c), which
corresponded to metallic Rh species.42,43 In contrast, the Rh
3d spectrum of the 0.19Na-Rh@S-1 catalyst contained both
metallic Rh0 (307.1 eV) and oxidic Rh+ (308.2 eV)
components. Therefore, the XPS results obtained for the
samples after Ne ions sputtering offer further evidence that the
presence of Na+ retards the reduction of Rh species and both
Rh0 and Rh+ coexist on the surface of Na-promoted Rh
nanoparticles embedded with S-1 zeolite.
The experimental results described above all point out that
Rh0 is the predominant species over the Rh@S-1 catalyst and
that a fraction of oxidic Rh+ species coexist on the Na-modified
Rh@S-1 catalyst due to role of Na+. We further measured the
amount of CO2 chemisorption, and the result revealed that the
presence of Na+ promoted the chemisorption of CO2 (Table
1). The enhanced CO2 adsorption and the presence of Rh+
species after Na+ modification may also decrease the H2
adsorption and dissociation ability,20,22 thus inhibiting the
formation of hydrocarbons, in particular CH4, and promoting
the C−O bond activation and CO insertion for C−C coupling
over Rh sites. Therefore, the increased amount of CO2
chemisorption and the coexistence of Rh0 and Rh+ species in
the presence of Na+ may mainly account for the higher CO2
conversion and the larger ethanol selectivity for CO 2
hydrogenation.
3.5. Possible Reaction Mechanism. We carried out in
situ DRIFTS studies over the Rh@S-1 catalyst at 2.5 MPa and
523 K to gain insights into the adsorbed species and possible
reaction intermediates. Under (H2 + CO2) atmosphere, IR
bands at 1300, 1260, and 1200 cm−1 were observed over the
Rh@S-1 catalyst, and these bands could be assigned to the
adsorbed bidentate carbonate (CO3*) species (Figure 7a).48,49
At the same time, the IR bands at 2052 and 1850 cm−1, which
were attributable to the linear- and bridge-adsorbed CO
species,44 and the bands at 2923 and 2852 cm−1 assignable to
stretching vibrations of CHx species50,51 were observed over
the Rh@S-1 catalyst. The IR band at 3016 cm−1 belonging to
gaseous CH4 also appeared. The intensities of IR bands
attributable to CH4 and adsorbed CHx species increased with
time on stream. These observations are consistent with our
catalytic result that the CO2 hydrogenation over Rh@S-1
mainly offers CH4 product and further suggest that the
formation of CH4 proceeds through CO intermediate.
The same in situ DRIFTS studies for the 0.19Na-Rh@S-1
catalyst under 2.5 MPa (H2 + CO2) and 523 K also showed
the presence of the adsorbed bidentate CO3* species (IR
bands at 1294 and 1204 cm−1) and CO species (IR bands at
1930 and 1874 cm−1, Figure 7b). Moreover, the IR bands at
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Figure 7. In situ DRIFTS spectra of adsorbed species on Rh@S-1 and
0.19Na-Rh@S-1 catalysts. (a) Rh@S-1 under 2.5 MPa (CO2 + H2) at
523 K. (b) 0.19Na-Rh@S-1 under 2.5 MPa (CO2 + H2) at 523 K. (c)
Rh@S-1 after switching CO2 to H2 (2.5 MPa) at 523 K. (d) 0.19Na-
Rh@S-1 after switching CO2 to H2 (2.5 MPa) at 523 K.
2720, 1742, 1605, and 1362 cm−1 attributable to HCOO*
species and those at 2815 and 1042 cm−1 assignable to CH3O*
species were observed.52−54 The HCOO*, CH3O*, and CO*
species might be formed by the hydrogenation of adsorbed
CO3* species.49,55 Moreover, the IR bands at 2962, 2874, and
1092 cm−1, which could be attributed to CH3CH2O*
species,52 were observed. This species is proposed to be the
key adsorbed species for C2H5OH formation.
To further gain information about the evolution of surface
adsorbed species in the reaction course of CO2 hydrogenation,
we carried out in situ DFIFTS studies by first introducing CO2
(2.5 MPa) into the IR cell and then switching the feed from
CO2 to H2 (2.5 MPa) at 523 K. The result for the Rh@S-1
catalyst showed that the decrease in the intensities of the bands
belonging to adsorbed bidentate CO3* species and the increase
in those of the bands belonging to CH4 (3015 cm−1) and
CHx* species (2956, 2926, and 2856 cm−1) (Figure 7c). The
intensity of adsorbed CO* species kept strong at the initial
stage, implying that the reduction of bidentate CO3* species to
CO is more facile than the hydrogenation of CO intermediate.
For the 0.19Na-Rh@S-1 catalyst, the intensity of IR bands of
bidentate CO3* species similarly decreased significantly after
switching to H2. However, the intensities for the IR bands of
HCOO* species (2720, 1605, and 1362 cm−1) and CH3O*
species (2815 cm−1) increased with time. This suggests that
the HCOO* and CH3O* species are generated from the
hydrogenation of bidentate CO3* species.49 The bands at
2962, 2874, and 1090 cm−1 assignable to the CH3CH2O*
species emerged and intensified with time. The adsorbed CO
species (1910 and 1820 cm−1) appeared instantly after the
switching to H2 (Figure 7d), and their intensities decreased to
some extent with time. These observations are consistent with
the mechanism that the CH3CH2O* species is generated by
the insertion of CO.
The reaction mechanisms for CO2 hydrogenation on the
Rh@S-1 and Na-Rh@S-1 catalysts are discussed based on the
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The Journal of Physical Chemistry C
in situ DFIFTS results and the information about the active
site. We first briefly discuss the mechanism for CO 2
hydrogenation over the Rh@S-1 catalyst without Na +
modification. Previous studies on CO hydrogenation suggest
that the Rh0 particles mainly functions for the dissociation of
CO as well as H2, favoring the formation of CH4 as the major
product.56,57 As already mentioned, the Rh@S-1 catalyst
contains mainly Rh0 sites. The in situ DRIFTS studies for
CO2 hydrogenation showed that the adsorbed CO and CHx
species were mainly present on the Rh@S-1 surface. In
agreement with our experimental observation that CH4 is the
predominant product during the CO2 hydrogenation over the
Rh@S-1 catalyst, we propose that CO is the intermediate for
the formation of CH4 from CO2 over this catalyst. That is,
CO2 is first hydrogenated to CO adsorbed on Rh0 surfaces,
which undergoes further dissociation and hydrogenation to
adsorbed CHx species and CH4.
Next, we discuss the CO2-hydrogenation mechanism on the
Na+-modified Rh@S-1 catalyst. It is accepted that the Rh+ site
cannot dissociate CO, favoring the formation of CH3OH as the
major product during CO hydrogenation.56 The Rh0−Rh+ pair
site is believed to be necessary for the formation of ethanol,
which is believed to proceed by the insertion of adsorbed CO
species into Rh−CH3 or the coupling between nondissociative
CO and dissociative species.39,42 Our characterizations have
pointed out that Rh0 and Rh+ coexist on the Na-Rh@S-1
catalyst. The in situ DRIFTS studies revealed that in addition
to the adsorbed CO and bidentate CO3* species, the adsorbed
HCOO*, CH3O*, and CH3CH2O* species also appeared on
the catalyst surface. Therefore, we propose a possible
mechanism for CO2 hydrogenation on the Na-Rh@S-1 catalyst
in Figure 8. In brief, CO2 is first adsorbed on the catalyst
Figure 8. Proposed reaction mechanism for CO2 hydrogenation over
Na-Rh@S-1 catalysts.
surface in the form of *CO3 species, which is hydrogenated by
the adsorbed H (Ha) species to CO* or HCOO*. The
HCOO* species is further hydrogenated to CH3O* and
CH3OH on the Rh+ site. The CO* species undergo
dissociation and hydrogenation to the CHx* species on the
Rh0 site, which may either be converted to CH4 or undergo
coupling with CO* to form the CHxCO*, which is further
hydrogenated into CH3CH2OH via CH3CH2O*. Zeolite is
believed to play the following roles. First, the confinement by
S-1 zeolite offers Rh nanoparticles with smaller sizes,
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contributing to higher CO2 conversion activity. Second, the
zeolite confinement effect can restrict the sintering of Na-
modified Rh nanoparticles, making the Na-Rh@S-1 catalyst
highly stable as compared to the reference Na-Rh/S-1 catalyst.
Furthermore, both Rh0 and Rh+ species coexist over the Na-
Rh@S-1 catalyst with Na+ modification, which play a crucial
role in the coupling between adsorbed CHx and CO species to
form ethanol, and the confinement by zeolite may stabilize the
Rh0−Rh+ pair site during the reaction. Therefore, the synergy
of the confinement effect of S-1 zeolite and the Rh0−Rh+ pair
site boosts the formation of ethanol by CO2 hydrogenation.
It is well-known that Rh-based catalysts are efficient for the
conversion of syngas to C2+ oxygenates.30,31 It is quite
unexpected that our 0.19Na-Rh@S-1 catalyst, which is active
and selective for the hydrogenation of CO2 to ethanol,
exhibited much lower CO conversion and ethanol selectivity
during CO hydrogenation even at an increased temperature
(Figure 4 and Table S3). We speculate that unlike in CO2
hydrogenation, where the formed CO intermediate is in low
concentration, the high concentration of CO in CO hydro-
genation may poison the Rh0 site,58,59 in particular over our
catalyst with small sizes of confined Rh particles, which only
contain a fraction of Rh0. In fact, the Na-Rh@S-1 catalyst
shows high selectivity of CH3OH during CO hydrogenation
despite the low CO conversion. This also implies that the
major active site over this catalyst is Rh+, which cannot
dissociate CO molecules.
4. CONCLUSIONS
We have successfully synthesized Na-modified Rh nano-
particles embedded in zeolite S-1 (Na-Rh@S-1) by a ligand-
protected crystallization method. The Rh content is around
0.75 wt %, and the Na content can be regulated in a range of
0.13−0.26 wt %. The mean size of the Rh particles in close
contact with Na+ is around 2.5 nm. The 0.19Na-Rh@S-1
catalyst is efficient for CO2 hydrogenation to ethanol, offering
a space−time yield of ethanol as high as 72 mmol gRh−1 h−1,
which outperforms those obtained over Rh-based catalysts
reported to date. The presence of Na+ induces the coexistence
of Rh0 and Rh+ species, dramatically shifting the major product
from methane to oxygenates mainly including methanol and
ethanol. The smaller size of Rh particles and the enhancement
in CO2 adsorption by Na+ contribute to improving the CO2
conversion. The confinement by the rigid framework of S-1
protects the Rh nanoparticles from aggregation, offering
superior stability of the Na-Rh@S-1 catalyst during long-
term CO2 hydrogenation. We further found that compared to
CO2 hydrogenation the 0.19Na-Rh@S-1 catalyst shows
significantly lower activity during the CO hydrogenation and
that the catalyst is more selective toward the formation of
methanol instead of ethanol.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.1c07862.
XRD, N2 adsorption−desorption isotherms, SEM micro-
graphs, TEM micrographs, XPS spectra, ICP-OES, GC
graphs and additional catalytic data (PDF)
https://doi.org/10.1021/acs.jpcc.1c07862
J. Phys. Chem. C 2021, 125, 24429−24439
The Journal of Physical Chemistry C
■
AUTHOR INFORMATION
Corresponding Authors
Jincan Kang − State Key Laboratory of Physical Chemistry of
Solid Surfaces, Innovation Laboratory for Sciences and
Technologies of Energy Materials of Fujian Province,
National Engineering Laboratory for Green Chemical
Productions of Alcohols, Ethers and Esters, College of
Chemistry and Chemical Engineering, Xiamen University,
Xiamen 361005, PR China; Email: kangjc@xmu.edu.cn
Ye Wang − State Key Laboratory of Physical Chemistry of
Solid Surfaces, Innovation Laboratory for Sciences and
Technologies of Energy Materials of Fujian Province,
National Engineering Laboratory for Green Chemical
Productions of Alcohols, Ethers and Esters, College of
Chemistry and Chemical Engineering, Xiamen University,
Xiamen 361005, PR China; orcid.org/0000-0003-0764-
2279; Email: wangye@xmu.edu.cn
Authors
Fuyong Zhang − State Key Laboratory of Physical Chemistry
of Solid Surfaces, Innovation Laboratory for Sciences and
Technologies of Energy Materials of Fujian Province,
National Engineering Laboratory for Green Chemical
Productions of Alcohols, Ethers and Esters, College of
Chemistry and Chemical Engineering, Xiamen University,
Xiamen 361005, PR China
Wei Zhou − State Key Laboratory of Physical Chemistry of
Solid Surfaces, Innovation Laboratory for Sciences and
Technologies of Energy Materials of Fujian Province,
National Engineering Laboratory for Green Chemical
Productions of Alcohols, Ethers and Esters, College of
Chemistry and Chemical Engineering, Xiamen University,
Xiamen 361005, PR China
Xuewei Xiong − State Key Laboratory of Physical Chemistry
of Solid Surfaces, Innovation Laboratory for Sciences and
Technologies of Energy Materials of Fujian Province,
National Engineering Laboratory for Green Chemical
Productions of Alcohols, Ethers and Esters, College of
Chemistry and Chemical Engineering, Xiamen University,
Xiamen 361005, PR China
Yuhao Wang − State Key Laboratory of Physical Chemistry of
Solid Surfaces, Innovation Laboratory for Sciences and
Technologies of Energy Materials of Fujian Province,
National Engineering Laboratory for Green Chemical
Productions of Alcohols, Ethers and Esters, College of
Chemistry and Chemical Engineering, Xiamen University,
Xiamen 361005, PR China
Kang Cheng − State Key Laboratory of Physical Chemistry of
Solid Surfaces, Innovation Laboratory for Sciences and
Technologies of Energy Materials of Fujian Province,
National Engineering Laboratory for Green Chemical
Productions of Alcohols, Ethers and Esters, College of
Chemistry and Chemical Engineering, Xiamen University,
Xiamen 361005, PR China; orcid.org/0000-0002-7112-
4700
Qinghong Zhang − State Key Laboratory of Physical
Chemistry of Solid Surfaces, Innovation Laboratory for
Sciences and Technologies of Energy Materials of Fujian
Province, National Engineering Laboratory for Green
Chemical Productions of Alcohols, Ethers and Esters, College
of Chemistry and Chemical Engineering, Xiamen University,
Xiamen 361005, PR China
Complete contact information is available at:
24437
pubs.acs.org/JPCC Article
https://pubs.acs.org/10.1021/acs.jpcc.1c07862
Author Contributions
†
F.Z. and W.Z. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Key Research and
Development Program of Ministry of Science and Technology
of China (No. 2019YFE0104400), and the National Natural
Science Foundation of China (Nos. 22121001, 91945301,
21872112, 21972116, and 22172123).
■
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