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High current density microkinetic and electronic structure analysis of CO2reduction using Co and Fe complexes on gas diffusion electrode

Authors :
Lu, Xiaofei
Dereli, Busra
Shinagawa, Tatsuya
Eddaoudi, Mohamed
Cavallo, Luigi
Takanabe, Kazuhiro
Source :
Chem Catalysis; May 2022, Vol. 2 Issue: 5 p1143-1162, 20p
Publication Year :
2022

Abstract

Reaction mechanisms of electrocatalytic CO2reduction into CO over Co or Fe complexes were examined using gas diffusion electrodes to meet the requirement of high current densities for industrial deployment. Our experimental and theoretical calculation results consistently revealed that the Fe-based molecular catalysts exhibited more positive redox potentials relevant to CO2electrocatalysis but disfavored the desorption of generated CO, especially at high overpotentials, failing to achieve appreciable reaction rates. Distinctively, the heterogenized Co-based molecular complexes were found to be tolerant to the high coverage of CO at steady state on the active site and achieved rates exceeding 100 mA cm−2toward exclusive CO evolution. Density-functional theory calculations not only disclosed the redox non-innocent tetraphenylporphyrins and phthalocyanines during electrocatalytic CO2reduction but also corroborated the energetics, especially for CO2and CO adsorption, accounting for distinctive reaction pathways between Co and Fe complexes.

Details

Language :
English
ISSN :
26671093
Volume :
2
Issue :
5
Database :
Supplemental Index
Journal :
Chem Catalysis
Publication Type :
Periodical
Accession number :
ejs59688574
Full Text :
https://doi.org/10.1016/j.checat.2022.03.010