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org/JACS Communication

Highly Selective Hydrogenation of CO2 to Ethanol via Designed

Bifunctional Ir1−In2O3 Single-Atom Catalyst
Xue Ye, Chongya Yang, Xiaoli Pan, Junguo Ma,* Yaru Zhang, Yujing Ren, Xiaoyan Liu, Lin Li,
and Yanqiang Huang*
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ABSTRACT: Recently, CO2 hydrogenation for the controlled growth of the carbon chain to produce high-value C2 or C2+ products
has attracted great interest, where achieving high selectivity for a specific product remains a challenge, especially for ethanol. Herein,
we have designed a bifunctional Ir1−In2O3 single-atom catalyst, integrating two active catalytic centers by anchoring the monatomic
Ir onto the In2O3 carrier. This Ir1−In2O3 single-atom catalyst is efficient for the hydrogenation of CO2 in liquid, yielding a high
selectivity for ethanol (>99%) with an excellent initial turnover frequency (481 h−1). Characterization shows that the isolated Ir
atom couples with the adjacent oxygen vacancy forming a Lewis acid−base pair, which activates the CO2 and forms the intermediate
species of carbonyl (CO*) adsorbed on the Ir atom. Coupling this CO* with the methoxide adsorbed on the In2O3 forms a C−C
bond. The strategy of this effective bifunctional single-atom catalyst by synergistically utilizing the distinct catalytic roles of the
single-atom site and the substrates provides a new avenue in catalyst design for complex catalysis.

I t is paramount to reduce the dependence on fossil energy

and to control CO2 emissions by developing renewable
energies.1,2 One of the most attractive strategies is to close the
Here, we designed a bifunctional SAC based on the synergy
of atomic Ir with In2O3 for converting of CO2 to ethanol.
In2O3 is an effective catalyst for hydrogenation of CO2 to
carbon cycle by producing “liquid sunlight” by transforming produce methanol,21 while the Ir-based mononuclear complex
CO2 into liquid fuel.3 Thus, much attention is paid to the can catalyze methanol carbonylation.22,23 We achieved
hydrogenation of CO2 into safe and transportable liquid excellent ethanol selectivity of 99.7% with the highest initial
hydrocarbons, including alcohols and gasoline.4,5 Among them, turnover frequency (TOF) of 481 h−1, outperforming the
ethanol is one of the most desirable products due to its precious metal catalysts. Theoretical calculation and infrared
impressive energy density and existing engine technology.6 spectra revealed that a Lewis acid−base pair was formed
However, the direct synthesis of ethanol from CO2 is still between the monatomic Ir and the adjacent oxygen vacancy
challenging due to the high energy barrier of C−C coupling.7,8 (Ov) on In2O3 forming two distinct catalytic centers, which
The synthesis of ethanol from CO2 has been realized using reduces CO2 to active intermediates and then facilitates the
Rh-, Fe-, or Co-based catalysts via an indirect Fischer− C−C coupling to form ethanol.
Tropsch synthesis (FTS). Although C−C coupling can be The Ir1−In2O3 SAC was synthesized through a modified
greatly promoted in FTS, the degree of C−C coupling is wet-chemical method. In2O3 was partially reduced with
difficult to control. The produced alcohols follow the hydrogen to generate Ov before Ir impregnation.21 Ov served
Anderson−Schulz−Flory (ASF) distribution with a typical as the anchoring site for single atoms and trapped IrCl62− with
ethanol fraction of ∼35%.9−12 great affinity(Figure 1a).24 The Ir loading in the Ir1−In2O3
In an effort to improve ethanol selectivity, recent research SAC was characterized by inductively coupled plasma optical
has focused on the design and modification of novel catalysts emission spectrometry (ICP-OES, Table S1). High angle dark-
for CO2 hydrogenation. Regulating active sites was the most field scanning transmission electron microscope images
effective method to govern the carbon chain growth with confirmed the isolated single-atom structure of Ir (HAADF-
controlled alcohol distribution. For example, by modifying Cu- STEM, Figures 1b and S1), where no nanoparticles were
or Co-based catalysts with ordered and isolated active sites, the observed (Figure S2). Furthermore, the extended X-ray
ethanol selectivity was improved.13−17 For this catalyst, the absorption fine structure (EXAFS) of the Ir LIII-edge of the
separation of the catalytic site was essential for attaining k2 χ(k) data showed the Ir−O coordination number to be 4.8
control over the carbon chain growth. Here, we propose a new
catalyst design strategy based on a single-atom catalyst (SAC)
with uniformly distributed atomic active sites18 to maximize Received: August 11, 2020
the ethanol selectivity. More importantly, SAC also serves as a Published: October 27, 2020
bridge between homogeneous and heterogeneous catalysis.
Our previous research suggests that the catalytic process that
normally occurs with the homogeneous catalyst can be well
realized using supported SACs.19,20

© 2020 American Chemical Society https://dx.doi.org/10.1021/jacs.0c08607

19001 J. Am. Chem. Soc. 2020, 142, 19001−19005
Journal of the American Chemical Society pubs.acs.org/JACS Communication

Figure 2. (a) Selectivity of ROHs (methanol and ethanol) and

achieved the yield of ethanol and (b) comparisons of the TOFIr values
over different Ir loadings on In2O3 during CO2 hydrogenation at 200
°C for 5 h. ROH yields and ethanol selectivity over Ir1−In2O3: effect
of temperature (c) and reaction time (d) in 3.0 mL of H2O, initial
pressure 6.0 MPa (H2 /CO2 = 5:1), catalyst 20 mg.

supports claimed that the selection of components (Ir−In2O3)

in the polar solvent was crucial (Tables S4 and S5).
The excellent catalytic performance of Ir1−In2O3 SAC was
Figure 1. (a) Schematic illustration of the fabrication procedures of closely related to its structure. Electrostatic potentials of In2O3
Ir1−In2O3. (b) HAADF-STEM image of Ir1−In2O3. Inset scale bar, 5 and Ir1−In2O3 were calculated to investigate the catalytic
nm. (c) Ir LIII-edge EXAFS spectra in r-space with different Ir mechanism (Figure 3a and b). The presence of monatomic Ir
loadings (without phase correction). (d) Wavelet transform of the k2-
weighted EXAFS spectrum of the Ir1−In2O3. (e) The fitted XPS
spectra of Ir 4f with diverse Ir loadings.

(Table S2) without Ir−Ir contribution25 (Figure 1c). The

wavelet transformed plot of Ir1−In2O3 (Figure 1d) demon-
strates the existence of Ir single atoms. X-ray photoelectron
spectroscopy (XPS) (Figure 1e) revealed the binding energies
(BE) of 65.2 and 62.1 eV for Ir f5/2 and f 7/2, corresponding to
the higher oxidation state of Irδ+.26
The Ir1−In2O3 SAC was then used for CO2 hydrogenation
reactions in aqueous solution. Both gaseous and liquid
products were analyzed after the reaction, where only Figure 3. Electrostatic potential figures of In2O3 (a) and Ir1−In2O3
methanol and ethanol were detected. Where pure In2O3 only catalyst surface (b). Free energy diagram for CO2 dissociation over
produced methanol, the Ir1−In2O3 SAC preferentially yielded the In2O3 and Ir1−In2O3 catalyst (c).
ethanol with a selectivity of 99.7% and a TOFIr value up to 481
h−1 (Figures 2a and b). This TOF was comparable with the created a negative potential, while the oxygen vacancy (Ov)
best literature results reported under similar conditions (Table remained positively charged on the defective In2O3 basal
S3). Since the catalytic kinetics are dependent on the reaction surface. As such, a local Lewis acid−base pair was formed
temperature, the dependency of ethanol production on time between the monatomic Ir and the adjacent Ov. DFT
and temperature was also investigated. As the temperature calculations demonstrated that CO2 was more favorably
increased from 180 to 240 °C, the yields of both ethanol and adsorbed onto Ir1−In2O3 than onto In2O3 (Figure 3c).
methanol increased monotonically (Figure 2c). However, the Chemisorbed CO2 formed CO2* (asterisk (*) represents the
methanol yield increased at a higher rate, such that the surface-adsorbed species), where the C atom was directly
selectivity of ethanol decreased to 92.2% at 240 °C. Hence, a bound to the Ir atom and one of the O atoms was bound to the
lower temperature is more favorable to ethanol production. As adjacent Ov. This indicated a synergistic effect toward CO2
for reaction time, we found that the initial ethanol yield was activation. The distinct adsorption geometry presented by the
relatively low (0.016 mmol g−1 h−1) but increased to 0.99 Ir1−In2O3 catalyst enabled a decrease in the energy barrier for
mmol g−1 h−1 after 5 h (Figure 2d). Meanwhile, the methanol CO2* dissociation to CO* from 0.77 eV on pure In2O3 to 0.48
yield remained constant at 0.012 mmol g−1 h−1, resulting in an eV. The resulting Irδ+−CO* intermediate was thought to play
increase of ethanol selectivity from 51.6% to 99.7%. The results a critical role in ethanol production.27
suggested that the ethanol selectivity depended on the relative The CO2 transformation was also verified by the in situ
production of methanol, which in turn indicated indirectly that diffuse reflectance infrared Fourier transform spectroscopy
methanol could be an important intermediate for ethanol (DRIFTS, Figures 4a,b and S3). A key intermediate of CO
synthesis. The research of different solvents, metals, and (2076 cm−1) appeared on Ir1−In2O3 after exposing CO2 at 200
19002 https://dx.doi.org/10.1021/jacs.0c08607
J. Am. Chem. Soc. 2020, 142, 19001−19005
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Figure 4. DRIFTS spectra of pure In2O3 (a) and Ir1−In2O3 catalyst (b) after exposure to CO2 at 200 °C. In situ FTIR spectra (c) of CO2
hydrogenation with Ir1−In2O3 catalyst bubbled in aqueous solution. Ir−In2O3 samples with different Ir loadings (d) after exposure to CO2 at 200
°C.

°C, confirmed the Irδ+−CO* formation.28−30 The peak above structural features were also supported by X-ray
intensities attributed to carbonate (1309, 1365, and 1496 diffraction (XRD) patterns (Figure S10). The Ir LIII edge
cm−1) and bicarbonate (1450 and 1630 cm−1) moieties31,32 EXAFS spectra revealed the presence of Ir−Ir metallic bond
were notably higher on Ir1−In2O3 than those on pure In2O3, with increasing intensity as the Ir loading augmented (Figures
implying that the effect of the Lewis acid−base pair on CO2 1c and S11a; and Table S2). XPS spectra (Ir 4f, Figure 1e)
activation was promoted. The adsorption of CO* was deemed showed that the peak intensities associated with metallic Ir0
strong since no significant reduction of CO peak intensity in enhanced with increasing Ir loading,36 accompanied by the
Ar flush experiments (Figure S4). Meanwhile, the formation of redshift in In 3d BE (Figure S11b and Table S6). The soft X-
another important intermediate CH3O* (2856, 2960, and ray absorption spectra (XAS) showed a decrease in peak
2994 cm−1)33,34 was observed during hydrogenation with in intensity at the In M-edge and O K-edge as the Ir loading
situ Fourier transform infrared spectroscopy (FTIR, Figure augmented (Figure S12).37 Therefore, the increase of Ir also
4c). These peaks have rarely been observed using pure In2O3 caused a reduction of In2O3. The excessive reduction of In2O3
based methanol catalysts, suggesting that the Ir single atoms at higher Ir contents was also confirmed in the temperature-
also help to stabilize the methoxide on the Ov of Ir1−In2O3. programmed reduction (H2-TPR, Figure S13 and Table S7).
Combined with the 13CH3OH isotope experiment (Figure S5), With the increase of Ir0, the In2O3 reduction peak shifted from
we concluded that the stable intermediates of Irδ+−CO* and 242 (In2O3) to 170 °C (1.0 wt % Ir−In2O3). The reduced
CH3O*−Ov were the pivotal species for C−C coupling.35 The In2O3 became less active21,38 toward the formation of
proposed reaction path is shown in Scheme S1. methoxide with decreased ethanol selectivity. Besides, Ir1−
The excellent catalytic performance of the Ir1−In2O3 SAC In2O3 showed a gradual decrease of TOF to a value of 186 h−1
was the colocalization of atomically dispersed Ir and Ov in the after the fourth catalytic cycle (Table S8), also due to the
carrier phase. The importance of the atomic dispersion of Ir reduction of In2O3 (Figure S14).
was examined by preparing Ir−In2O3 catalysts with increased CO2 activation was also affected by the increase in non-
Ir loading and then testing them under identical conditions. monoatomic Ir loading. CO2 DRIFTS showed that the amount
The ethanol selectivity was suppressed significantly from 85.3% of adsorbed CO2 species significantly decreased as the Ir
to 5.7%, as the Ir content increased from 0.2 wt % to 1.0 wt % content increased (Figures 4d and S15). The formation of Ir0−
(Figure 2a). The TOF also decreased accordingly (Figure 2b). CO was evidenced with a peak at a lower wavenumber of 2040
TEM and scanning electron microscopy energy-dispersive cm−1 compared to Irδ+−CO.30 Hence, the C−O bond strength
X-ray spectroscopy (SEM-EDS) images revealed the growth of was weaker on Ir0 than on Irδ+ due to more electron transfer
Ir from small clusters (0.5 wt %, Figures S6−S8) to aggregated from Ir0 to CO 2π antibonding orbital,39 while the Ir0−C bond
nanoparticles of 1−2 nm in size (1.0 wt %, Figure S9). The became stronger. This meant that the alkylation activity was
19003 https://dx.doi.org/10.1021/jacs.0c08607
J. Am. Chem. Soc. 2020, 142, 19001−19005
Journal of the American Chemical Society pubs.acs.org/JACS Communication

lowered while the cleavage of the C−O bond became easier. University of Chinese Academy of Science, Beijing 100049,
The larger size of Ir0 particles could also enrich the surface H China
concentration, resulting in a direct reduction of C1 species Yujing Ren − CAS Key Laboratory of Science and Technology
forming methanol, while the C−C coupling activity decreased. on Applied Catalysis, Dalian Institute of Chemical Physics,
Our results confirmed that the over-reduction of In2O3 would Chinese Academy of Sciences, Dalian 116023, China;
alter the coordination of critical intermediate components. University of Chinese Academy of Science, Beijing 100049,
Hence, the SAC design of the monatomic Ir on In2O3 was China
optimized for the selective hydrogenation of CO2 to ethanol. Xiaoyan Liu − CAS Key Laboratory of Science and Technology
In conclusion, an Ir1−In2O3 single-atom catalyst for CO2 on Applied Catalysis, Dalian Institute of Chemical Physics,
hydrogenation to ethanol was presented. Thanks to the Chinese Academy of Sciences, Dalian 116023, China;
bifunctional nature of the Ir1−In2O3, composed of partially orcid.org/0000-0003-2694-2306
reduced In2O3 and a Lewis acid−base pair between the single- Lin Li − CAS Key Laboratory of Science and Technology on
atom Ir and adjacent oxygen vacancy (Ov), it not only Applied Catalysis, Dalian Institute of Chemical Physics, Chinese
promotes the adsorption and activation CO2 into CO* but Academy of Sciences, Dalian 116023, China; orcid.org/
also provides great opportunities for C−C coupling between 0000-0002-3036-0934
CH3O*−Ov and Irδ+−CO*. As a result, CO2 was hydro- Complete contact information is available at:
genated into ethanol with a selectivity up to 99.7% at an initial https://pubs.acs.org/10.1021/jacs.0c08607
TOF up to 481 h−1. Our study presents a new, green, and
promising catalyst for the conversion of CO2 into a versatile Author Contributions
energy source; introduces the rational design of bifunctional All authors have given approval to the final version of the
single-atom catalysts for simplifying complex reaction manuscript.
processes, and expands the applications of single-atom
catalysts. Notes

■
The authors declare no competing financial interest.
ASSOCIATED CONTENT
* Supporting Information
sı
■ ACKNOWLEDGMENTS
This work was supported by the National Key R&D Program
The Supporting Information is available free of charge at of China (2016YFB0600902), the Strategic Priority Research
https://pubs.acs.org/doi/10.1021/jacs.0c08607. Program of the Chinese Academy of Sciences
Experimental procedures, details on the synthesis of Ir/ (XDB36030200), the National Natural Science Foundation
In2O3 catalysts, and additional characterizations of the of China (21925803, U19A2015), Dalian National Laboratory
for Clean Energy (DNL180401).

■
Ir/In2O3 catalysts (PDF)

■ AUTHOR INFORMATION
Corresponding Authors
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