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Potential- and Buffer-Dependent Selectivity for the Conversion of CO2 to CO by a Cobalt Porphyrin-Peptide Electrocatalyst in Water.


ABSTRACT: A semisynthetic electrocatalyst for carbon dioxide reduction to carbon monoxide in water is reported. Cobalt microperoxidase-11 (CoMP11-Ac) is shown to reduce CO2 to CO with a turnover number of up to 32,000 and a selectivity of up to 88:5 CO:H2. Higher selectivity for CO production is favored by a less cathodic applied potential and use of a higher pK a buffer. A mechanistic hypothesis is presented in which avoiding the formation and protonation of a formal Co(I) species favors CO production. These results demonstrate how tuning reaction conditions impact reactivity toward CO2 reduction for a biocatalyst previously developed for H2 production.

SUBMITTER: Alvarez-Hernandez JL 

PROVIDER: S-EPMC9724230 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature

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Potential- and Buffer-Dependent Selectivity for the Conversion of CO<sub>2</sub> to CO by a Cobalt Porphyrin-Peptide Electrocatalyst in Water.

Alvarez-Hernandez Jose L JL   Salamatian Alison A AA   Han Ji Won JW   Bren Kara L KL  

ACS catalysis 20221116 23


A semisynthetic electrocatalyst for carbon dioxide reduction to carbon monoxide in water is reported. Cobalt microperoxidase-11 (CoMP11-Ac) is shown to reduce CO<sub>2</sub> to CO with a turnover number of up to 32,000 and a selectivity of up to 88:5 CO:H<sub>2</sub>. Higher selectivity for CO production is favored by a less cathodic applied potential and use of a higher p<i>K</i> <sub>a</sub> buffer. A mechanistic hypothesis is presented in which avoiding the formation and protonation of a form  ...[more]

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