pubs.acs.

org/JACS Communication

“Ship-in-a-Bottle” Integration of Ditin(IV) Sites into a Metal−Organic

Framework for Boosting Electroreduction of CO2 in Acidic
Electrolyte
Huan Xue, Zhen-Hua Zhao, Pei-Qin Liao,* and Xiao-Ming Chen
Cite This: https://doi.org/10.1021/jacs.3c05023 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
Downloaded via UNIV OF TECHNOLOGY SYDNEY on August 7, 2023 at 08:59:17 (UTC).

ABSTRACT: The electrochemical CO2 reduction reaction (eCO2RR) under acidic conditions has become a promising way to
achieve high CO2 utilization because of the inhibition of undesirable carbonate formation that typically occurs under neutral and
alkaline conditions. Herein, unprecedented and highly active ditin(IV) sites were integrated into the nanopores of a metal−organic
framework, namely NU-1000-Sn, by a “ship-in-a-bottle” strategy. NU-1000-Sn delivers nearly 100% formic acid Faradaic efficiency
at an industry current density of 260 mA cm−2 with a high single-pass CO2 utilization of 95% in an acidic solution (pH = 1.67). No
obvious degradation was observed over 15 hours of continuous operation at the current density of 260 mA cm−2, representing the
remarkable eCO2RR performance in acidic electrolyte to date. The mechanism study shows that both oxygen atoms of the key
intermediate *HCOO can coordinate to the two adjacent Sn atoms in a ditin(IV) site simultaneously. Such bridging coordination is
conducive to the hydrogenation of CO2, thus leading to high performance.

C onverting CO2 into value-added chemicals and fuels

through intermittent renewable electricity is an attractive
and promising way to accelerate the carbon cycle.1,2 However,
If a pair of adjacent tin ions can be isolated as an active site for
the eCO2RR, it will be beneficial to further understand the
catalytic mechanism of tin oxides and improve the perform-
due to the extreme stability of CO2 molecules, the electro- ance, but such a ditin active site for eCO2RR has not yet been
chemical CO2 reduction reaction (eCO2RR) requires a high achieved.
activation energy, leading to large overpotential and a Because they possess ultrahigh surface areas and tailorable
competitive hydrogen evolution reaction (HER).3 To meet structures, metal−organic frameworks (MOFs) have been
the industrial requirements, extensive efforts have been extensively used for heterogeneous catalysis, including the
devoted to the development of new and efficient catalysts, eCO2RR. Like traditional heterogeneous catalysts, eCO2RR
leading to great progress. Previous eCO2RR processes were performances of most MOFs have usually been studied under
usually carried out under neutral and alkaline conditions,4−6 in alkaline or neutral conditions. Postsynthetic modification
which, however, the CO2 utilization is low. This phenomenon (PSM) is a useful approach widely used in modifying MOFs
is due to the fact that the CO2 molecules can react with bulk/ to achieve specific functions.17−19 For example, Yaghi et al.
local hydroxides to generate carbonate precipitation, resulting reported that the dicopper sites can be introduced into the
in the consumption of CO2 feedstock.7,8 Under low-pH pores of MOF-808 by PSM, achieving a high selectivity for
conditions, the formation of bicarbonate can be fully inhibited. methane oxidation to methanol.17 [Zr6(μ3-
Therefore, the eCO2RR process conducted in acidic electro- OH)8(OH)8(TBAPY)2] (NU-1000, H4TBAPY = 1,3,6,8−
lytes can solve the above problem and improve CO2 utilization. tetrakis(p-carboxyphenyl)pyrene) is a very stable zirconium-
Unfortunately, HER is generally predominant under acidic based MOF possessing two apertures of different sizes (1.2 and
conditions, and the Faradaic efficiency (FE) of the eCO2RR is 3.0 nm) (Figure 1a).20 In the smaller pore, two zirconium
decreased under acidic conditions; thus, it is challenging to atoms of two adjacent hydroxide nodes, separated at a distance
satisfy industrial requirements.9−11 of ∼0.85 nm on its pore surface,21,22 may be suitable to fix a
ditin site (Figure 1a). Herein, for the first time, we report that
Tin-based catalysts, especially tin oxides, typically exhibit
ditin sites can be integrated in the pores of NU-1000 through a
high performance of the eCO2RR to produce formate/formic
“ship-in-a-bottle” strategy, showing exceptional eCO2RR
acid.12−15 For example, Wang et al. reported that a Bi2S3-
performance under acidic conditions.
derived catalyst achieves a FE(formate) of nearly 100% and an
ampere-level current density for the eCO2RR to formate under
strongly alkaline conditions.6 However, under acidic con- Received: May 15, 2023
ditions, the current best performance is a FE(formic acid)
value of less than 90%, and the current density is only 200 mA
cm−2.16 Previous mechanism studies showed that the high
electrocatalytic performance of tin oxides was ascribed to the
synergistic effect between two adjacent tin ions on its surface.

© XXXX American Chemical Society https://doi.org/10.1021/jacs.3c05023

A J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
Journal of the American Chemical Society pubs.acs.org/JACS Communication

Figure 1. (a) Illustration of the synthesis of NU-1000 and NU-1000-Sn. Color codes: Sn, purple; Zr, light blue; O, red; C, gray. Note: the
hydrogen atoms are omitted for clarity. (b) SEM and EDS mapping of NU-1000-Sn. (c) Sn K-edge XANES spectra of NU-1000-Sn, Sn foil, and
SnO2. (d) The EXAFS fitting curve of the ditin sites in NU-1000-Sn.

NU-1000 was prepared according to the literature,20,38 and S9). To further elucidate the coordination configuration of tin
its purity was confirmed by the powder X-ray diffraction ions, X-ray absorption spectroscopy (XAS) of NU-1000-Sn
(PXRD) patterns (Figure S1), scanning electron microscopy was performed. The K-edge X-ray absorption near-edge
(SEM) images (Figure S2), thermogravimetric (TG) curves structure (XANES) spectra indicated the absence of metallic
(Figure S3), and nitrogen gas sorption isotherms measured at tin and the +4 valence state of tin ions (Figure 1c), which is
77 K (Figure S4). Immersing NU-1000 in an N,N- consistent with the XPS result. The extended X-ray absorption
dimethylformamide (DMF) solution of SnCl2 at 75 °C for fine structure (EXAFS) curve showed that the coordination
24 h to gave NU-1000-Sn (Figure 1a). PXRD patterns environment of NU-1000-Sn is similar to that of tin oxide,
demonstrated that the framework remained intact after PSM with a main signal at 1.66 Å corresponding to Sn−O
treatment (Figure S1). As the crystals are easily cracked into a coordination, while there was no signal at 1.68 Å for the
microcrystalline powder in the PSM process, we determined Sn−Cl coordination bond (Figure S10b). Also, compared with
the crystal structure of NU-1000-Sn by Rietveld refinement of that of a single tin site, the EXAFS fitting result of a ditin site
the PXRD pattern (Figure S5 and Table S1), which exhibits a higher degree of fitting accuracy, implying that it was
preliminarily suggested the existence of ditin(IV) sites in a ditin site rather than a single tin site (Figure 1d, Figure S11,
NU-1000-Sn. Energy-dispersive spectroscopy (EDS) mapping and Tables S3 and S4). Moreover, the EXAFS fitting
suggested that the elements of C, O, Zr, and Sn are uniformly demonstrated that the coordination number is 6, revealing
distributed in NU-1000-Sn (Figure 1b). The content of Sn in that the Sn atom is octahedrally surrounded by six O atoms
NU-1000-Sn was determined to be 9 wt %, and the Sn/Zr (Figure 1d and Table S3). In addition, the signal at 3.72 Å can
ratio was measured to be 1/3 by inductively coupled plasma be assigned to the short distance and weak interaction between
atomic emission spectrometry (ICP-AES) (Table S2), which is two Sn ions (Sn···Sn) (Figure 1d), confirming the presence of
the same as that calculated from the simulated crystal structure. ditin(IV) sites fixed in the pore of NU-1000-Sn. To further
Furthermore, the Cl− content in NU-1000-Sn was measured substantiate the proposed ditin(IV) structure, a reported
by potentiometric titration. As shown in Figure S6, the ditin(IV) structure analogue, namely [Sn(O-i-Pr)4(HO-i-
mutation was reached at the beginning, indicating no residual Pr)]2,39 was used as a benchmark for comparison of EXAFS
chloride ion in NU-1000-Sn. As shown in the X-ray spectroscopy with NU-1000-Sn. As shown in Figure S10c, they
photoelectron spectroscopy (XPS) spectra (Figure S7), the have almost identical EXAFS spectra, indicating that the
binding energies at 495.59 and 487.15 eV were assigned to Sn coordination surrounding the Sn atom of NU-1000-Sn is the
3d3/2 and Sn 3d5/2, respectively, indicating the +4 valence state same as that of [Sn(O-i-Pr)4(HO-i-Pr)]2.
of tin ions. Nitrogen gas sorption isotherms measured at 77 K The eCO2RR measurements of NU-1000-Sn as a catalyst
showed a decrease in the adsorption amount for NU-1000-Sn, coated on carbon paper were carried out in a flow cell
which is attributed to the tin oxide being loaded into the containing an acidic electrolyte composed of 0.005 M H2SO4
framework (Figure S4). The morphology of NU-1000-Sn and 3 M KCl aqueous solution (pH = 1.67) (Figure S12).
observed by SEM and TEM is almost the same as that before Gaseous products CO and H2 were identified by gas
PSM, and no large nanoparticles were observed, implying that chromatography (GC) (Figure S13), and the liquid product
tin oxide might be present in the pores (Figures S2, S8, and formic acid was analyzed through proton nuclear magnetic
B https://doi.org/10.1021/jacs.3c05023
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
Journal of the American Chemical Society pubs.acs.org/JACS Communication

resonance (1H NMR) (Figure S14). As shown in Figure 2a, ditin(IV) sites. There is no signal at 1.53 Å for Sn−N in the
the onset potential of the linear sweep voltammetry (LSV) EXAFS spectrum, indicating no single-atom tin site within the
porphyrin macrocycle. The electrocatalytic performance of
PCN-222-Sn was tested under the same conditions. As shown
in Figure S21, FEHCOOH of PCN-222-Sn was 92% at −1.6 V vs
RHE. Its stability was also confirmed by PXRD and SEM
(Figures S22 and S23). In contrast, without the presence of
ditin sites, the catalytic performances of NU-1000 and PCN-
222 showed that the products were mostly H2 with FEHCOOH
values <5%, further indicating that the ditin sites in both NU-
1000-Sn and PCN-222-Sn indeed acted as the catalytic sites
(Figure S24).
To reveal the mechanism of eCO2RR, we carried out
operando attenuated total reflectance Fourier transform
infrared spectroscopy (ATR-FTIR) measurements (Figure
S25). As shown in Figure 3a, the peak at 1540 cm−1 belongs

Figure 2. Electrocatalytic performance of NU-1000-Sn. (a) LSV

curves of NU-1000-Sn in Ar or CO2-saturated acidic electrolyte
composed of 0.005 M H2SO4 and 3 M KCl (pH = 1.67) aqueous
solution. (b) FEs of all products with NU-1000-Sn as the
electrocatalyst at various potentials. (c) Durability test. (d)
Comparison of FEHCOOH and current density for NU-1000-Sn and
reported electrocatalysts under acidic (green),16,23,24 neutral (or-
ange),25−31 and alkaline conditions (blue).32−37

curve under a CO2 atmosphere is lower than that under Ar,

implying the occurrence of the eCO2RR. As depicted in Figure
2b, NU-1000-Sn exhibited a high FE (>90%) for formic acid Figure 3. (a) Operando ATR-FTIR spectra of NU-1000-Sn collected
production over a wide potential range from −1.5 to −1.8 V at −1.7 V vs RHE in CO2-saturated 0.005 M H2SO4 catholyte with 3
(vs RHE, RHE = reversible hydrogen electrode). After M KCl. (b) Free energy diagram of CO2 to HCOOH. (c) Proposed
adjusting the feeding ratio of NU-1000 and SnCl2 in the reaction pathway of NU-1000-Sn for the eCO2RR to produce
catalyst preparation, we observed that the ratio of 1/5 (i.e., the HCOOH.
ratio of Sn/Zr was 1/3) exhibited an optimal performance
(Figure S15). Notably, at −1.8 V vs RHE, the FEHCOOH of NU- to the CO2− intermediate,40 and that at 1390 cm−1 can be
1000-Sn reached 95% with a current density of 260 mA cm−2. assigned to *HCOO,41 which is recognized as the key
No obvious degradation was observed over 15 h of continuous intermediate to generate formic acid. Based on the IR result,
operation at a current density of 260 mA cm−2; FEHCOOH also we further carried out periodic density functional theory
remained ∼95% after long-term electrolysis (Figure 2c). Thus, (PDFT) calculations to understand the transition of CO2 to
NU-1000-Sn exhibited a superior eCO2RR performance to HCOOH. Interestingly, both oxygen atoms of *HCOO can
yield formic acid under acidic conditions compared to most of simultaneously coordinate to two adjacent Sn atoms (μ-O,O′-
the reported catalysts working under acidic, neutral, and bridging mode) (Figure 3c). The adsorption energy of the
alkaline conditions (Figure 2d). The 13C isotope labeling *HCOO intermediate in the bridging coordination mode
experiment verified that the carbon source of formic acid did (0.014 eV) was found to be lower than that of the unidentate
come from CO2 (Figure S16). The PXRD patterns, XAS, XPS mode (0.029 eV), indicating the thermodynamic dominance of
spectra, and SEM and TEM images of NU-1000-Sn remained the bridging mode. Compared with the unidentate mode (3.05
constant before and after electrocatalysis, confirming its eV), such a bridging mode of *HCOO gave a lower Gibbs
stability during electrocatalysis (Figures S9, S10, and S17− energy value of 1.19 eV for the hydrogenation of CO2 to the
S19). After the reaction, the contents of Sn and Zr in the *HCOO intermediate (Figure 3b). Therefore, the bridging
electrolyte were detected by ICP-AES analysis to be below the mode is conducive to the hydrogenation of CO2 into the key
detection limit, suggesting that no metal ions were leached into intermediate HCOO*, thus achieving a high performance in
the electrolyte during the eCO2RR process. Considering that formic acid production.
PCN-222 and NU-1000 have the same topology and similar In summary, we described a “ship-in-a-bottle” strategy of
pore environments, to validate the applicability of this “ship-in- integrating isolated ditin(IV) sites into the pore of NU-1000
a-bottle” strategy, PCN-222-Sn was also synthesized using the by PSM, for the first time. The resulting NU-1000-Sn shows
same method, and its purity was confirmed by PXRD, TG, and an outstanding performance of the eCO2RR to produce formic
ICP-AES results (Figure S20 and Table S2). The XAS acid under acidic conditions. Our experimental and theoretical
spectrum of PCN-222-Sn was also measured. As shown in calculation results revealed that the synergistic effect between
Figure S10b,d, PCN-222-Sn has an EXAFS spectrum similar the pair of tin atoms in a ditin(IV) site might be the key to
to that of NU-1000-Sn, suggesting that they have the same enhance the eCO2RR performance under acidic conditions.
C https://doi.org/10.1021/jacs.3c05023
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
Journal of the American Chemical Society pubs.acs.org/JACS Communication

Using the same strategy, PCN-222-Sn possessing ditin(IV)

sites can also be obtained by replacing the host framework of
■ REFERENCES
(1) Qiu, X.-F.; Zhu, H.-L.; Huang, J.-R.; Liao, P.-Q.; Chen, X.-M.
NU-1000 to PCN-222. We suppose that other metal Highly Selective CO2 Electroreduction to C2H4 Using a Metal-
hydroxides/oxide clusters could possibly also be integrated Organic Framework with Dual Active Sites. J. Am. Chem. Soc. 2021,
into the host frameworks. Therefore, the “ship-in-a-bottle” 143, 7242−7246.
strategy would have a potential universality for the rational (2) Zhu, H.-L.; Huang, J.-R.; Zhang, X.-W.; Wang, C.; Huang, N.-Y.;
design of porous materials with highly efficient active sites for Liao, P.-Q.; Chen, X.-M. Highly Efficient Electroconversion of CO2
electroreduction of CO2 to valuable products, especially under into CH4 by a Metal-Organic Framework with Trigonal Pyramidal
acidic conditions. Cu(I)N3 Active Sites. ACS Catal. 2021, 11, 11786−11792.
(3) Wang, Y.-R.; Liu, M.; Gao, G.-K.; Yang, Y.-L.; Yang, R.-X.; Ding,
■ ASSOCIATED CONTENT
* Supporting Information
sı
H.-M.; Chen, Y.; Li, S.-L.; Lan, Y.-Q. Implanting Numerous
Hydrogen-Bonding Networks in a Cu-Porphyrin-Based Nanosheet
to Boost CH4 Selectivity in Neutral-Media CO2 Electroreduction.
The Supporting Information is available free of charge at Angew. Chem., Int. Ed. 2021, 60, 21952−21958.
https://pubs.acs.org/doi/10.1021/jacs.3c05023. (4) Yao, D.; Tang, C.; Vasileff, A.; Zhi, X.; Jiao, Y.; Qiao, S.-Z. The
Detailed information on synthetic methods, character- Controllable Reconstruction of Bi-MOFs for Electrochemical CO2
Reduction through Electrolyte and Potential Mediation. Angew.
ization analyses, electrochemical measurements, and
Chem., Int. Ed. 2021, 60, 18178−18184.
PDFT calculations (PDF) (5) Zhu, Z.-H.; Zhao, B.-H.; Hou, S.-L.; Jiang, X.-L.; Liang, Z.-L.;
Accession Codes Zhang, B.; Zhao, B. A Facile Strategy for Constructing a Carbon-
CCDC 2277185 contains the supplementary crystallographic Particle-Modified Metal-Organic Framework for Enhancing the
Efficiency of CO2 Electroreduction into Formate. Angew. Chem., Int.
data for this paper. These data can be obtained free of charge
Ed. 2021, 60, 23394−23402.
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing (6) Lin, L.; He, X.; Zhang, X.-G.; Ma, W.; Zhang, B.; Wei, D.; Xie,
[email protected], or by contacting The Cam- S.; Zhang, Q.; Yi, X.; Wang, Y. A Nanocomposite of Bismuth Clusters
bridge Crystallographic Data Centre, 12 Union Road, and Bi2O2CO3 Sheets for Highly Efficient Electrocatalytic Reduction
Cambridge CB2 1EZ, UK; fax: +44 1223 336033. of CO2 to Formate. Angew. Chem., Int. Ed. 2023, 62, No. e202214959.

■ AUTHOR INFORMATION
Corresponding Author
(7) Huang, J. E.; Li, F.; Ozden, A.; Rasouli, A. S.; Arquer, F. P. G. d.;
Liu, S.; Zhang, S.; Luo, M.; Wang, X.; Lum, Y.; Xu, Y.; Bertens, K.;
Miao, R. K.; Dinh, C.-T.; Sinton, D.; Sargent, E. H. CO2 electrolysis
Pei-Qin Liao − MOE Key Laboratory of Bioinorganic and to multicarbon products in strong acid. Science 2021, 372, 1074−
1078.
Synthetic Chemistry, School of Chemistry, Sun Yat−Sen (8) Chen, C.; Li, Y.; Yang, P. Address the “alkalinity problem” in
University, Guangzhou 510275, People’s Republic of China; CO2 electrolysis with catalyst design and translation. Joule 2021, 5,
orcid.org/0000-0001-5888-1283; Email: liaopq3@ 737−742.
mail.sysu.edu.cn (9) Monteiro, M. C. O.; Dattila, F.; López, N. r.; Koper, M. T. M.
The Role of Cation Acidity on the Competition between Hydrogen
Authors Evolution and CO2 Reduction on Gold Electrodes. J. Am. Chem. Soc.
Huan Xue − MOE Key Laboratory of Bioinorganic and 2022, 144, 1589−1602.
Synthetic Chemistry, School of Chemistry, Sun Yat−Sen (10) Monteiro, M. C. O.; Dattila, F.; Hagedoorn, B.; García-Muelas,
University, Guangzhou 510275, People’s Republic of China R.; López, N.; Koper, M. T. M. Absence of CO2 electroreduction on
Zhen-Hua Zhao − MOE Key Laboratory of Bioinorganic and copper, gold and silver electrodes without metal cations in solution.
Synthetic Chemistry, School of Chemistry, Sun Yat−Sen Nat. Catal. 2021, 4, 654−662.
University, Guangzhou 510275, People’s Republic of China (11) Bondue, C. J.; Graf, M.; Goyal, A.; Koper, M. T. M.
Xiao-Ming Chen − MOE Key Laboratory of Bioinorganic and Suppression of Hydrogen Evolution in Acidic Electrolytes by
Electrochemical CO2 Reduction. J. Am. Chem. Soc. 2021, 143, 279−
Synthetic Chemistry, School of Chemistry, Sun Yat−Sen
285.
University, Guangzhou 510275, People’s Republic of China; (12) Jeong, S.; Ohto, T.; Nishiuchi, T.; Nagata, Y.; Fujita, J.-i.; Ito, Y.
Chemistry and Chemical Engineering Guangdong Polyethylene Glycol Covered Sn Catalysts Accelerate the Formation
Laboratory, Shantou 515031, People’s Republic of China; Rate of Formate by Carbon Dioxide Reduction. ACS Catal. 2021, 11,
orcid.org/0000-0002-3353-7918 9962−9969.
Complete contact information is available at: (13) Wang, T.; Chen, J.; Ren, X.; Zhang, J.; Ding, J.; Liu, Y.; Lim, K.
H.; Wang, J.; Li, X.; Yang, H.; Huang, Y.; Kawi, S.; Liu, B. Halogen-
https://pubs.acs.org/10.1021/jacs.3c05023
Incorporated Sn Catalysts for Selective Electrochemical CO 2
Reduction to Formate. Angew. Chem., Int. Ed. 2022, 62,
Notes No. e202211174.
The authors declare no competing financial interest. (14) Zhang, Y.; Jang, H.; Ge, X.; Zhang, W.; Li, Z.; Hou, L.; Zhai, L.;

■ ACKNOWLEDGMENTS
This work was supported by the National Key Research and
Wei, X.; Wang, Z.; Kim, M. G.; Liu, S.; Qin, Q.; Liu, X.; Cho, J.
Single-Atom Sn on Tensile-Strained ZnO Nanosheets for Highly
Efficient Conversion of CO2 into Formate. Adv. Energy Mater. 2022,
Development Program of China (2021YFA1500401), the 12, 2202695.
NSFC (21890380 and 21821003), the Local Innovative and (15) Jiang, Y.; Shan, J.; Wang, P.; Huang, L.; Zheng, Y.; Qiao, S.-Z.
Stabilizing Oxidation State of SnO2 for Highly Selective CO2
Research Teams Project of Guangdong Pearl River Talents
Electroreduction to Formate at Large Current Densities. ACS Catal.
Program (2017BT01C161), the Science and Technology Key 2023, 13, 3101−3108.
Project of Guangdong Province, China (2020B010188002), (16) Gu, J.; Liu, S.; Ni, W.; Ren, W.; Haussener, S.; Hu, X.
and the Science and Technology Innovation Special Support Modulating electric field distribution by alkali cations for CO2
Project of Guangdong Province City County, China electroreduction in strongly acidic medium. Nat. Catal. 2022, 5,
(STKJ2023078). 268−276.

D https://doi.org/10.1021/jacs.3c05023
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
Journal of the American Chemical Society pubs.acs.org/JACS Communication

(17) Baek, J.; Rungtaweevoranit, B.; Pei, X.; Park, M.; Fakra, S. C.; (33) Li, L.; Ozden, A.; Guo, S.; Arquer, F. P. G. d.; Wan, C.; Zhang,
Liu, Y.-S.; Matheu, R.; Alshmimri, S. A.; Alshehri, S.; Trickett, C. A.; M.; Zhang, J.; Jiang, H.; Wang, W.; Dong, H.; Sinton, D.; Sargent, E.
Somorjai, G. A.; Yaghi, O. M. Bioinspired Metal-Organic Framework H.; Zhong, M. Stable, active CO2 reduction to formate via redox-
Catalysts for Selective Methane Oxidation to Methanol. J. Am. Chem. modulated stabilization of active sites. Nat. Commun. 2021, 12, 5223.
Soc. 2018, 140, 18208−18216. (34) Lu, P.; Tan, X.; Zhao, H.; Xiang, Q.; Liu, K.; Zhao, X.; Yin, X.;
(18) Cohen, S. M. Postsynthetic methods for the functionalization of Li, X.; Hai, X.; Xi, S.; Wee, A. T. S.; Pennycook, S. J.; Yu, X.; Yuan,
metal-organic frameworks. Chem. Rev. 2012, 112, 970−1000. M.; Wu, J.; Zhang, G.; Smith, S. C.; Yin, Z. Atomically Dispersed
(19) Feng, X.; Song, Y.; Chen, J. S.; Xu, Z.; Dunn, S. J.; Lin, W. Indium Sites for Selective CO2 Electroreduction to Formic Acid. ACS
Rational Construction of an Artificial Binuclear Copper Monoox- Nano 2021, 15, 5671−5678.
ygenase in a Metal-Organic Framework. J. Am. Chem. Soc. 2021, 143, (35) Wang, Y.; Li, Y.; Liu, J.; Dong, C.; Xiao, C.; Cheng, L.; Jiang,
1107−1118. H.; Jiang, H.; Li, C. BiPO4-Derived 2D Nanosheets for Efficient
(20) Mondloch, J. E.; Bury, W.; Fairen-Jimenez, D.; Kwon, S.; Electrocatalytic Reduction of CO2 to Liquid Fuel. Angew. Chem., Int.
DeMarco, E. J.; Weston, M. H.; Sarjeant, A. A.; Nguyen, S. T.; Stair, Ed. 2021, 60, 7681−7685.
P. C.; Snurr, R. Q.; Farha, O. K.; Hupp, J. T. Vapor-phase metalation (36) Xie, H.; Zhang, T.; Xie, R.; Hou, Z.; Ji, X.; Pang, Y.; Chen, S.;
by atomic layer deposition in a metal-organic framework. J. Am. Chem. Titirici, M.-M.; Weng, H.; Chai, G. Facet Engineering to Regulate
Soc. 2013, 135, 10294−10297. Surface States of Topological Crystalline Insulator Bismuth Rhombic
(21) Duan, J.; Shabbir, H.; Chen, Z.; Bi, W.; Liu, Q.; Sui, J.; Dodecahedrons for Highly Energy Efficient Electrochemical CO2
Đorđević, L.; Stupp, S. I.; Chapman, K. W.; Martinson, A. B. F.; Li, A.; Reduction. Adv. Mater. 2021, 33, No. 2008373.
Schaller, R. D.; Goswami, S.; Getman, R. B.; Hupp, J. T. Synthetic (37) Zhang, M.; Wei, W.; Zhou, S.; Ma, D.-D.; Cao, A.; Wu, X.-T.;
Zhu, Q.-L. Engineering a conductive network of atomically thin
Access to a Framework-Stabilized and Fully Sulfided Analogue of an
bismuthene with rich defects enables CO2 reduction to formate with
Anderson Polyoxometalate that is Catalytically Competent for
industry-compatible current densities and stability. Energy Environ. Sci.
Reduction Reactions. J. Am. Chem. Soc. 2023, 145, 7268−7277.
2021, 14, 4998−5008.
(22) Vicchio, S. P.; Chen, Z.; Chapman, K. W.; Getman, R. B.
(38) Lu, Z.; Liu, J.; Zhang, X.; Liao, Y.; Wang, R.; Zhang, K.; Lyu, J.;
Computational and Experimental Characterization of the Ligand Farha, O. K.; Hupp, J. T. Node-Accessible Zirconium MOFs. J. Am.
Environment of a Ni-Oxo Catalyst Supported in the Metal-Organic Chem. Soc. 2020, 142, 21110−21121.
Framework NU-1000. J. Am. Chem. Soc. 2023, 145, 2852−2859. (39) Hampden-Smith, M. J.; Wark, T. A.; Rheingold, A.; Huffman, J.
(23) Qiao, Y.; Lai, W.; Huang, K.; Yu, T.; Wang, Q.; Gao, L.; Yang, C. Solid state and solution structural investigation of homoleptic
Z.; Ma, Z.; Sun, T.; Liu, M.; Lian, C.; Huang, H. Engineering the tin(IV) alkoxide compounds. Part I. Sn(O-t-Bu)4 and [Sn(O-i-Pr)4
Local Microenvironment over Bi Nanosheets for Highly Selective (HO-i-Pr)]2. Can. J. Chem. 1991, 69, 121.
Electrocatalytic Conversion of CO2 to HCOOH in Strong Acid. ACS (40) Yao, K.; Wang, H.; Yang, X.; Huang, Y.; Kou, C.; Jing, T.;
Catal. 2022, 12, 2357−2364. Chen, S.; Wang, Z.; Liu, Y.; Liang, H. Metal-organic framework
(24) Li, Z.; Sun, B.; Xiao, D.; Wang, Z.; Liu, Y.; Zheng, Z.; Wang, P.; derived dual-metal sites for electroreduction of carbon dioxide to
Dai, Y.; Cheng, H.; Huang, B. Electron-Rich Bi Nanosheets Promote HCOOH. Appl. Catal., B 2022, 311, 121377.
CO2·‑‑ Formation for High-Performance and pH-Universal Electro- (41) Wu, Z.; Wu, H.; Cai, W.; Wen, Z.; Jia, B.; Wang, L.; Jin, W.;
catalytic CO2 Reduction. Angew. Chem., Int. Ed. 2023, 62, Ma, T. Engineering Bismuth-Tin Interface in Bimetallic Aerogel with
No. e202217569. a 3D Porous Structure for Highly Selective Electrocatalytic CO2
(25) Li, F.; Chen, L.; Knowles, G. P.; MacFarlane, D. R.; Zhang, J. Reduction to HCOOH. Angew. Chem., Int. Ed. 2021, 60, 12554−
Hierarchical Mesoporous SnO2 Nanosheets on Carbon Cloth: A 12559.
Robust and Flexible Electrocatalyst for CO2 Reduction with High
Efficiency and Selectivity. Angew. Chem., Int. Ed. 2017, 56, 505−509.
(26) Sutherland, B. R. Breaking Compromises in CO2 Reduction.
Joule 2017, 1, 643−645.
(27) Arquer, F. P. G. d.; Bushuyev, O. S.; Phil De Luna, C.-T. D.;
Seifitokaldani, A.; Saidaminov, M. I.; Tan, C.-S.; Li Na Quan, A. P.;
Kibria, M. G.; Kelley, S. O.; Sinton, D.; Sargent, E. H. 2D Metal
Oxyhalide-Derived Catalysts for Efficient CO2 Electroreduction. Adv.
Mater. 2018, 30, No. e1802858.
(28) He, S.; Ni, F.; Ji, Y.; Wang, L.; Wen, Y.; Bai, H.; Liu, G.; Zhang,
Y.; Li, Y.; Zhang, B.; Peng, H. The p-Orbital Delocalization of Main-
Group Metals to Boost CO2 Electroreduction. Angew. Chem., Int. Ed.
2018, 57, 16114−16119.
(29) Wu, H.; Song, J.; Xie, C.; Hu, Y.; Han, B. Highly efficient
electrochemical reduction of CO2 into formic acid over lead dioxide
in an ionic liquid-catholyte mixture. Green Chem. 2018, 20, 1765−
1769.
(30) Zhang, Y.; Zhang, X.; Ling, Y.; Li, F.; Bond, A. M.; Zhang, J.
Controllable Synthesis of Few-Layer BismuthSubcarbonate by
Electrochemical Exfoliation for Enhanced CO2 Reduction Perform-
ance. Angew. Chem., Int. Ed. 2018, 57, 13283−13287.
(31) Gong, Q.; Ding, P.; Xu, M.; Zhu, X.; Wang, M.; Deng, J.; Ma,
Q.; Han, N.; Zhu, Y.; Lu, J.; Feng, Z.; Li, Y.; Zhou, W.; Li, Y.
Structural defects on converted bismuth oxide nanotubes enable
highly active electrocatalysis of carbon dioxide reduction. Nat.
Commun. 2019, 10, 2807.
(32) Ye, K.; Zhou, Z.; Shao, J.; Lin, L.; Gao, D.; Ta, N.; Si, R.; Wang,
G.; Bao, X. In Situ Reconstruction of a Hierarchical Sn-Cu/SnOx
Core/Shell Catalyst for High-Performance CO2 Electroreduction.
Angew. Chem., Int. Ed. 2020, 59, 4814−4821.

E https://doi.org/10.1021/jacs.3c05023
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX