TY - JOUR
T1 - Single transition metal atoms on nitrogen-doped carbon for CO2 electrocatalytic reduction
T2 - CO production or further CO reduction?
AU - Guo, Chen
AU - Zhang, Tian
AU - Liang, Xiongyi
AU - Deng, Xiangxuan
AU - Guo, Wenyue
AU - Wang, Zhaojie
AU - Lu, Xiaoqing
AU - Wu, Chi-Man Lawrence
PY - 2020/12/15
Y1 - 2020/12/15
N2 - Electrochemical CO2 reduction reaction (CO2RR) is an effective strategy for CO2 conversion and clean fuel generation. Diverse nitrogen-doped carbon-supported transition metal (M-N-C) have been proved as favorable catalysis materials for CO2RR, especially for CO production. Herein, density functional theory is performed to investigate the CO2RR mechanisms over M-Nx-C with twelve types of transition metal centers. Fe-, Co-, Ni-, Cu-, Rh-, Pd-, Ir-, and Pt-Nx embedded on graphene with double vacancies are relatively stable structures contributing to electrocatalysis operation. The adsorption energies of COOH and CO, which are the reaction intermediates during CO2RR, are linearly related and can be used as a descriptor for CO production. Moderate adsorption strengths of CO and COOH are favorable for CO generation with low limiting potential. Co-N4, Ni-N1, Pd-N1, Pt-N1, and Rh-N4 are the most active sites for CO2RR by thermodynamics analysis. However, the discussion on competition between CO2RR and hydrogen evolution reaction (HER) indicates that these sites show low selectivity. Considering both CO2RR selectivity and activity, Ni-N4 site is proved to be the most effective site for CO production among all the M-Nx sites. It is also noted that Fe-N4 is more favorable to further reduction towards *CO with the products of CH3OH and CH4.
AB - Electrochemical CO2 reduction reaction (CO2RR) is an effective strategy for CO2 conversion and clean fuel generation. Diverse nitrogen-doped carbon-supported transition metal (M-N-C) have been proved as favorable catalysis materials for CO2RR, especially for CO production. Herein, density functional theory is performed to investigate the CO2RR mechanisms over M-Nx-C with twelve types of transition metal centers. Fe-, Co-, Ni-, Cu-, Rh-, Pd-, Ir-, and Pt-Nx embedded on graphene with double vacancies are relatively stable structures contributing to electrocatalysis operation. The adsorption energies of COOH and CO, which are the reaction intermediates during CO2RR, are linearly related and can be used as a descriptor for CO production. Moderate adsorption strengths of CO and COOH are favorable for CO generation with low limiting potential. Co-N4, Ni-N1, Pd-N1, Pt-N1, and Rh-N4 are the most active sites for CO2RR by thermodynamics analysis. However, the discussion on competition between CO2RR and hydrogen evolution reaction (HER) indicates that these sites show low selectivity. Considering both CO2RR selectivity and activity, Ni-N4 site is proved to be the most effective site for CO production among all the M-Nx sites. It is also noted that Fe-N4 is more favorable to further reduction towards *CO with the products of CH3OH and CH4.
KW - CO production
KW - CO2 electrocatalytic reduction
KW - Density functional theory
KW - Metal-Nx-carbon
KW - CO production
KW - CO2 electrocatalytic reduction
KW - Density functional theory
KW - Metal-Nx-carbon
KW - CO production
KW - CO2 electrocatalytic reduction
KW - Density functional theory
KW - Metal-Nx-carbon
UR - http://www.scopus.com/inward/record.url?scp=85089341968&partnerID=8YFLogxK
UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85089341968&origin=recordpage
U2 - 10.1016/j.apsusc.2020.147466
DO - 10.1016/j.apsusc.2020.147466
M3 - RGC 21 - Publication in refereed journal
SN - 0169-4332
VL - 533
JO - Applied Surface Science
JF - Applied Surface Science
M1 - 147466
ER -
