Atomically Dispersed Dual-Metal Site Catalysts for Enhanced CO2 Reduction: Mechanistic Insight into Active Site Structures

Yi Li; Weitao Shan; Michael J Zachman; Maoyu Wang; Sooyeon Hwang; Hassina Tabassum; Juan Yang; Xiaoxuan Yang; Stavros Karakalos; Zhenxing Feng; Guofeng Wang; Gang Wu

doi:10.1002/anie.202205632

Atomically Dispersed Dual-Metal Site Catalysts for Enhanced CO₂ Reduction: Mechanistic Insight into Active Site Structures

Angew Chem Int Ed Engl. 2022 Jul 11;61(28):e202205632. doi: 10.1002/anie.202205632. Epub 2022 May 9.

Authors

Yi Li^{1

2}, Weitao Shan³, Michael J Zachman⁴, Maoyu Wang⁵, Sooyeon Hwang⁶, Hassina Tabassum², Juan Yang¹, Xiaoxuan Yang², Stavros Karakalos⁷, Zhenxing Feng⁵, Guofeng Wang³, Gang Wu²

Affiliations

¹ School of Materials Science and Engineering, Jiangsu University, Zhenjiang, 212013, China.
² Department of Chemical and Biological Engineering, University at Buffalo, The State University of New York, Buffalo, NY 14260, USA.
³ Department of Mechanical Engineering and Materials Science, University of Pittsburgh, Pittsburgh, PA 15261, USA.
⁴ Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA.
⁵ School of Chemical Biological and Environmental Engineering, Oregon State University, Corvallis, OR 97331, USA.
⁶ Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY 11973, USA.
⁷ Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, USA.

PMID: 35470950
DOI: 10.1002/anie.202205632

Abstract

Carbon-supported nitrogen-coordinated single-metal site catalysts (i.e., M-N-C, M: Fe, Co, or Ni) are active for the electrochemical CO₂ reduction reaction (CO₂ RR) to CO. Further improving their intrinsic activity and selectivity by tuning their N-M bond structures and coordination is limited. Herein, we expand the coordination environments of M-N-C catalysts by designing dual-metal active sites. The Ni-Fe catalyst exhibited the most efficient CO2RR activity and promising stability compared to other combinations. Advanced structural characterization and theoretical prediction suggest that the most active N-coordinated dual-metal site configurations are 2N-bridged (Fe-Ni)N₆ , in which FeN₄ and NiN₄ moieties are shared with two N atoms. Two metals (i.e., Fe and Ni) in the dual-metal site likely generate a synergy to enable more optimal *COOH adsorption and *CO desorption than single-metal sites (FeN₄ or NiN₄ ) with improved intrinsic catalytic activity and selectivity.

Keywords: CO2 Reduction; Dual Metal-Nitrogen Sites; Electrocatalysis; M−N−C Catalysts.

Abstract

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