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Why Is C–C Coupling in CO2 Reduction Still Difficult on Dual-Atom Electrocatalysts?

  • Weijie Yang
    Weijie Yang
    Department of Power Engineering, School of Energy, Power and Mechanical Engineering, North China Electric Power University, Baoding 071003, China
    More by Weijie Yang
  • Zhenhe Jia
    Zhenhe Jia
    Department of Power Engineering, School of Energy, Power and Mechanical Engineering, North China Electric Power University, Baoding 071003, China
    More by Zhenhe Jia
  • Binghui Zhou
    Binghui Zhou
    Department of Power Engineering, School of Energy, Power and Mechanical Engineering, North China Electric Power University, Baoding 071003, China
    More by Binghui Zhou
  • Liugang Chen
    Liugang Chen
    Department of Power Engineering, School of Energy, Power and Mechanical Engineering, North China Electric Power University, Baoding 071003, China
    More by Liugang Chen
  • Xunlei Ding
    Xunlei Ding
    Institute of Clusters and Low Dimensional Nanomaterials, School of Mathematics and Physics, North China Electric Power University, Beinong Road 2, Changping, Beijing 102206, China
    Hebei Key Laboratory of Physics and Energy Technology, North China Electric Power University, Baoding 071000, China
    More by Xunlei Ding
  • Long Jiao
    Long Jiao
    Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China
    More by Long Jiao
  • Huiling Zheng
    Huiling Zheng
    State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China
  • Zhengyang Gao*
    Zhengyang Gao
    Department of Power Engineering, School of Energy, Power and Mechanical Engineering, North China Electric Power University, Baoding 071003, China
    *E-mail: [email protected]
  • Qiang Wang*
    Qiang Wang
    State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, China
    *E-mail: [email protected]
    More by Qiang Wang
  • , and 
  • Hao Li*
    Hao Li
    Advanced Institute for Materials Research (WPI−AIMR), Tohoku University, Sendai 980−8577, Japan
    *E-mail: [email protected]
    More by Hao Li
Cite this: ACS Catal. 2023, 13, 14, 9695–9705
Publication Date (Web):July 10, 2023
https://doi.org/10.1021/acscatal.3c01768
Copyright © 2023 American Chemical Society

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    Abstract

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    The emerging metal–nitrogen–carbon (M–N–C) dual–atom catalysts (DACs) have been expected to generate multicarbon products in the CO2 reduction reaction (CO2RR) due to the presence of multimetal sites of DACs. Unfortunately, numerous recent experiments suggested that almost no DAC could effectively produce a high quantity of multicarbon products. To uncover the reason for this phenomenon, we probed the surface states of typical homonuclear and heteronuclear DACs and explored the reaction mechanisms in the CO2RR by spin-polarized density functional theory calculations with van der Waals interactions. Contrary to the conventional hypothesis that C–C coupling can occur through the metal-top sites, surface Pourbaix analyses indicate that CO preferentially occupies the bridge sites between two metals, which would hinder the subsequent C–C coupling. Moreover, according to the energy variation, the C–C coupling occurring on the surface of a DAC is not feasible in both thermodynamics and kinetics. Based on the derived microkinetic models of DACs in the CO2RR, CO formation is more favorable than other reduction products, which is consistent with current experimental results. Furthermore, we found that double-side occupancy is also favorable if the molecules can penetrate the carbon layer through a large defect, which would lead to a more favorable HCOOH formation in the CO2RR. By developing an analytical framework combining surface state analysis, activity modeling, and electronic structure analysis, this work reveals why C–C coupling in the CO2RR remains difficult on DACs and provides insights into regulating the adsorption strength of *CO on the bridge site to enhance the selectivity and activity of the CO2RR at DACs.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.3c01768.

    • Additional computation and modeling methods, contributions to the free energy, construction strategy of DACs, adsorption configurations, a flowchart of developing a surface Pourbaix diagram, adsorption sites, and reaction paths for CO2RR (PDF)

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    Cited By

    This article is cited by 9 publications.

    1. Tianyang Liu, Yu Jing, Yafei Li. First-Principles Insights into the Selectivity of CO2 Electroreduction over Heterogeneous Single-Atom Catalysts. The Journal of Physical Chemistry Letters 2024, 15 (23) , 6216-6221. https://doi.org/10.1021/acs.jpclett.4c01096
    2. Juan Zhang, Yu Wang, Yafei Li. Not One, Not Two, But at Least Three: Activity Origin of Copper Single-Atom Catalysts toward CO2/CO Electroreduction to C2+ Products. Journal of the American Chemical Society 2024, 146 (22) , 14954-14958. https://doi.org/10.1021/jacs.4c05669
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