Intermediates‐induced CO2 reduction reaction activity at single‐atom M‐N2 (M = Fe, Co, Ni) sites
-
Published:2023-07-19
Issue:
Volume:
Page:
-
ISSN:1439-4235
-
Container-title:ChemPhysChem
-
language:en
-
Short-container-title:ChemPhysChem
Author:
Liu Kang1,
Ni Ganghai2,
Luo Tao2,
Fu Junwei2,
Li Hongmei2,
Liu Min3,
Lin Zhang4
Affiliation:
1. Central South University School of physics and electronics 932 South Lushan Road 410083 Changsha CHINA
2. Central South University School of Physics and Electronics CHINA
3. Central South University School of Physics and Electronics 932 Lushan Nan Road 410081 Changsha CHINA
4. Central South University School of Metallurgy and Environment CHINA
Abstract
Single‐atom M‐N2 (M = Fe, Co, and Ni) catalysts exhibit high activity for CO2 reduction reaction (CO2RR). However, the CO2RR mechanism and the origin of activity at the single‐atom sites remain unclear, which hinders the development of single‐atom M‐N2 catalysts. Here, we reveal intermediates‐induced CO2RR activity at the single‐atom M‐N2 sites by density functional theory calculations. At the M‐N2 sites, the asymmetric *O*CO configuration tends to split into *CO and *OH intermediates. Intermediates become part of the active moiety to form M‐(CO)N2 or M‐(OH)N2 sites, which can optimize the adsorption of intermediates on the M sites. The limiting potentials along the optimal CO2RR pathway are –0.30, –0.54, and –0.28 V for Fe‐(OH)N2, Co‐(CO)N2, and Ni‐(OH)N2 sites, more positive than those of Fe‐N2 (–1.03 V), Co‐N2 (–1.24 V) and Ni‐N2 (–0.73 V) sites. The intermediate modification can shift the d‐band center of the spin‐up (minority) state downward by regulating the charge distribution at the M sites, leading to less charge accepted by the intermediates from the M sites. This work provides new insights into the understanding of the activity of single‐atom M‐N2 sites.
Funder
National Natural Science Foundation of China
China Postdoctoral Science Foundation
Subject
Physical and Theoretical Chemistry,Atomic and Molecular Physics, and Optics