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

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

Materials MicroAnalysis

Research output: Contribution to journal › Article › peer-review

154 Scopus citations

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 (CO₂RR) 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.

Original language	English
Article number	e202205632
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	28
DOIs	https://doi.org/10.1002/anie.202205632
State	Published - Jul 11 2022

Funding

G. Wu and G. F. Wang acknowledge the support from the U.S. National Science Foundation (CBET-1804326 and 1804534). Electron microscopy research was conducted at Brookhaven National Laboratory (S. Hwang, under contract No. DE-SC0012704), which is the DOE Office of Science User Facilities. XAS measurements were performed at beamline 9-BM-C at Argonne National Laboratory. Aberration-corrected STEM imaging, EELS point spectra, and EDS quantification were conducted at the Center for Nanophase Materials Sciences, which is a U.S. DOE Office of Science User Facility. The authors also thank Dr. Shengwen Liu for the SEM and BET analysis. Y. Li, a visiting Ph.D. student at the University at Buffalo, acknowledges the support from the China Scholarship Council (201808320253) and the Natural Science Foundation of Jiangsu Province (BK20210769). Y. Li's advisor at the Jiangsu University (J. Yang) thanks to the support from the National Natural Science Foundation of China (Grant No. 51972150). G. Wu and G. F. Wang acknowledge the support from the U.S. National Science Foundation (CBET‐1804326 and 1804534). Electron microscopy research was conducted at Brookhaven National Laboratory (S. Hwang, under contract No. DE‐SC0012704), which is the DOE Office of Science User Facilities. XAS measurements were performed at beamline 9‐BM‐C at Argonne National Laboratory. Aberration‐corrected STEM imaging, EELS point spectra, and EDS quantification were conducted at the Center for Nanophase Materials Sciences, which is a U.S. DOE Office of Science User Facility. The authors also thank Dr. Shengwen Liu for the SEM and BET analysis. Y. Li, a visiting Ph.D. student at the University at Buffalo, acknowledges the support from the China Scholarship Council (201808320253) and the Natural Science Foundation of Jiangsu Province (BK20210769). Y. Li's advisor at the Jiangsu University (J. Yang) thanks to the support from the National Natural Science Foundation of China (Grant No. 51972150).

Funders	Funder number
National Science Foundation	DE‐SC0012704, 1804534, CBET‐1804326
Office of Science
Argonne National Laboratory
National Natural Science Foundation of China	51972150
Jiangsu University
China Scholarship Council	201808320253
Natural Science Foundation of Jiangsu Province	BK20210769

Keywords

CO Reduction
Dual Metal–Nitrogen Sites
Electrocatalysis
M−N−C Catalysts

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/anie.202205632

Cite this

Li, Y., Shan, W., Zachman, M. J., Wang, M., Hwang, S., Tabassum, H., Yang, J., Yang, X., Karakalos, S., Feng, Z., Wang, G., & Wu, G. (2022). Atomically Dispersed Dual-Metal Site Catalysts for Enhanced CO₂ Reduction: Mechanistic Insight into Active Site Structures. Angewandte Chemie - International Edition, 61(28), Article e202205632. https://doi.org/10.1002/anie.202205632

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