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Electrocatalytic CO 2 Reduction with a Half‐Sandwich Cobalt Catalyst: Selectivity towards CO
Author(s) -
Kumar Pandey Indresh,
Kumar Abhishek,
Choudhury Joyanta
Publication year - 2020
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201901805
Subject(s) - overpotential , catalysis , benzimidazole , cobalt , chemistry , faraday efficiency , ligand (biochemistry) , electrolysis , selectivity , electrocatalyst , aqueous solution , denticity , inorganic chemistry , acetonitrile , electrophile , electrochemistry , organic chemistry , biochemistry , receptor , electrode , electrolyte , crystal structure
We present herein a Cp*Co(III)‐half‐sandwich catalyst system for electrocatalytic CO 2 reduction in aqueous acetonitrile solution. In addition to an electron‐donating Cp* ligand (Cp*=pentamethylcyclopentadienyl), the catalyst featured a proton‐responsive pyridyl‐benzimidazole‐based N,N‐bidentate ligand. Owing to the presence of a relatively electron‐rich Co center, the reduced Co(I)‐state was made prone to activate the electrophilic carbon center of CO 2 . At the same time, the proton‐responsive benzimidazole scaffold was susceptible to facilitate proton‐transfer during the subsequent reduction of CO 2 . The above factors rendered the present catalyst active toward producing CO as the major product over the other potential 2e/2H + reduced product HCOOH, in contrast to the only known similar half‐sandwich CpCo(III)‐based CO 2 ‐reduction catalysts which produced HCOOH selectively. The system exhibited a Faradaic efficiency (FE) of about 70% while the overpotential for CO production was found to be 0.78 V, as determined by controlled‐potential electrolysis.

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