A semisynthetic electrocatalyst for carbon dioxide reduction to carbon monoxide in water is reported. Cobalt microperoxidase-11 (CoMP11-Ac) is shown to reduce CO to CO with a turnover number of up to 32,000 and a selectivity of up to 88:5 CO:H. Higher selectivity for CO production is favored by a less cathodic applied potential and use of a higher p 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 CO reduction for a biocatalyst previously developed for H production.
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| http://dx.doi.org/10.1021/acscatal.2c03297 | DOI Listing |
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