Constructing Asymmetric Double-atomic Sites for Synergistic Catalysis of Electrochemical CO Reduction

Overview

Journal Nat Commun

Specialty Biology

Date 2023 Oct 3

PMID 37789007

Authors

Jiqing Jiao

Qing Yuan

Meijie Tan

Xiaoqian Han

Mingbin Gao

Chao Zhang

Xuan Yang

Zhaolin Shi

Yanbin Ma

Hai Xiao

Jiangwei Zhang

Tongbu Lu

Affiliations

Soon will be listed here.

Abstract

Elucidating the synergistic catalytic mechanism between multiple active centers is of great significance for heterogeneous catalysis; however, finding the corresponding experimental evidence remains challenging owing to the complexity of catalyst structures and interface environment. Here we construct an asymmetric TeN-CuN double-atomic site catalyst, which is analyzed via full-range synchrotron pair distribution function. In electrochemical CO reduction, the catalyst features a synergistic mechanism with the double-atomic site activating two key molecules: operando spectroscopy confirms that the Te center activates CO, and the Cu center helps to dissociate HO. The experimental and theoretical results reveal that the TeN-CuN could cooperatively lower the energy barriers for the rate-determining step, promoting proton transfer kinetics. Therefore, the TeN-CuN displays a broad potential range with high CO selectivity, improved kinetics and good stability. This work presents synthesis and characterization strategies for double-atomic site catalysts, and experimentally unveils the underpinning mechanism of synergistic catalysis.

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References

Xie W, Li H, Cui G, Li J, Song Y, Li S . NiSn Atomic Pair on an Integrated Electrode for Synergistic Electrocatalytic CO Reduction. Angew Chem Int Ed Engl. 2020; 60(13):7382-7388. DOI: 10.1002/anie.202014655. View

Zhu W, Zhang L, Liu S, Li A, Yuan X, Hu C . Enhanced CO Electroreduction on Neighboring Zn/Co Monomers by Electronic Effect. Angew Chem Int Ed Engl. 2020; 59(31):12664-12668. DOI: 10.1002/anie.201916218. View

Wang X, Wang Y, Sang X, Zheng W, Zhang S, Shuai L . Dynamic Activation of Adsorbed Intermediates via Axial Traction for the Promoted Electrochemical CO Reduction. Angew Chem Int Ed Engl. 2020; 60(8):4192-4198. DOI: 10.1002/anie.202013427. View

Feng J, Gao H, Zheng L, Chen Z, Zeng S, Jiang C . A Mn-N single-atom catalyst embedded in graphitic carbon nitride for efficient CO electroreduction. Nat Commun. 2020; 11(1):4341. PMC: 7455739. DOI: 10.1038/s41467-020-18143-y. View

Yang F, Ma X, Cai W, Song P, Xu W . Nature of Oxygen-Containing Groups on Carbon for High-Efficiency Electrocatalytic CO Reduction Reaction. J Am Chem Soc. 2019; 141(51):20451-20459. DOI: 10.1021/jacs.9b11123. View

Zhang S, Fan Q, Xia R, Meyer T . CO Reduction: From Homogeneous to Heterogeneous Electrocatalysis. Acc Chem Res. 2020; 53(1):255-264. DOI: 10.1021/acs.accounts.9b00496. View

Gao D, Zhang Y, Zhou Z, Cai F, Zhao X, Huang W . Enhancing CO Electroreduction with the Metal-Oxide Interface. J Am Chem Soc. 2017; 139(16):5652-5655. DOI: 10.1021/jacs.7b00102. View

Li J, Zeng H, Dong X, Ding Y, Hu S, Zhang R . Selective CO electrolysis to CO using isolated antimony alloyed copper. Nat Commun. 2023; 14(1):340. PMC: 9860050. DOI: 10.1038/s41467-023-35960-z. View

Yan Y, Li Q, Huo S, Ma M, Cai W, Osawa M . Ubiquitous strategy for probing ATR surface-enhanced infrared absorption at platinum group metal-electrolyte interfaces. J Phys Chem B. 2006; 109(16):7900-6. DOI: 10.1021/jp044085s. View

10.

Hulva J, Meier M, Bliem R, Jakub Z, Kraushofer F, Schmid M . Unraveling CO adsorption on model single-atom catalysts. Science. 2021; 371(6527):375-379. DOI: 10.1126/science.abe5757. View

11.

Li Y, Wei B, Zhu M, Chen J, Jiang Q, Yang B . Synergistic Effect of Atomically Dispersed Ni-Zn Pair Sites for Enhanced CO Electroreduction. Adv Mater. 2021; 33(41):e2102212. DOI: 10.1002/adma.202102212. View

12.

Gong Y, Jiao L, Qian Y, Pan C, Zheng L, Cai X . Regulating the Coordination Environment of MOF-Templated Single-Atom Nickel Electrocatalysts for Boosting CO Reduction. Angew Chem Int Ed Engl. 2019; 59(7):2705-2709. DOI: 10.1002/anie.201914977. View

13.

Franco F, Rettenmaier C, Jeon H, Cuenya B . Transition metal-based catalysts for the electrochemical CO reduction: from atoms and molecules to nanostructured materials. Chem Soc Rev. 2020; 49(19):6884-6946. DOI: 10.1039/d0cs00835d. View

14.

Li S, Zhao S, Lu X, Ceccato M, Hu X, Roldan A . Low-Valence Zn (0<δ<2) Single-Atom Material as Highly Efficient Electrocatalyst for CO Reduction. Angew Chem Int Ed Engl. 2021; 60(42):22826-22832. DOI: 10.1002/anie.202107550. View

15.

Yin J, Jin J, Yin Z, Zhu L, Du X, Peng Y . The built-in electric field across FeN/FeN interface for efficient electrochemical reduction of CO to CO. Nat Commun. 2023; 14(1):1724. PMC: 10050184. DOI: 10.1038/s41467-023-37360-9. View

16.

Ren W, Tan X, Yang W, Jia C, Xu S, Wang K . Isolated Diatomic Ni-Fe Metal-Nitrogen Sites for Synergistic Electroreduction of CO. Angew Chem Int Ed Engl. 2019; 58(21):6972-6976. DOI: 10.1002/anie.201901575. View

17.

Wu Z, Zhang X, Niu Z, Gao F, Yang P, Chi L . Identification of Cu(100)/Cu(111) Interfaces as Superior Active Sites for CO Dimerization During CO Electroreduction. J Am Chem Soc. 2021; 144(1):259-269. DOI: 10.1021/jacs.1c09508. View

18.

Koshy D, Chen S, Lee D, Stevens M, Abdellah A, Dull S . Understanding the Origin of Highly Selective CO Electroreduction to CO on Ni,N-doped Carbon Catalysts. Angew Chem Int Ed Engl. 2020; 59(10):4043-4050. DOI: 10.1002/anie.201912857. View

19.

Jiao J, Lin R, Liu S, Cheong W, Zhang C, Chen Z . Copper atom-pair catalyst anchored on alloy nanowires for selective and efficient electrochemical reduction of CO. Nat Chem. 2019; 11(3):222-228. DOI: 10.1038/s41557-018-0201-x. View

20.

Creissen C, Fontecave M . Keeping sight of copper in single-atom catalysts for electrochemical carbon dioxide reduction. Nat Commun. 2022; 13(1):2280. PMC: 9046394. DOI: 10.1038/s41467-022-30027-x. View