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Atomically Dispersed Dual‐Metal Site Catalysts for Enhanced CO<sub>2</sub> Reduction: Mechanistic Insight into Active Site Structures

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

2022Angewandte Chemie International Edition179 citationsDOIOpen Access PDF

Abstract

Abstract Carbon‐supported nitrogen‐coordinated single‐metal site catalysts (i.e., M−N−C, M: Fe, Co, or Ni) are active for the electrochemical CO 2 reduction reaction (CO 2 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)N 6 , in which FeN 4 and NiN 4 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 (FeN 4 or NiN 4 ) with improved intrinsic catalytic activity and selectivity.

Topics & Concepts

CatalysisActive siteSelectivityMetalElectrochemistryAdsorptionChemistryInorganic chemistryMaterials sciencePhysical chemistryElectrodeOrganic chemistryCO2 Reduction Techniques and CatalystsCarbon dioxide utilization in catalysisIonic liquids properties and applications