No 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.

Metalloenzymes are remarkable for facilitating challenging redox transformations with high efficiency and selectivity. In the area of alternative energy, scientists aim to capture these properties in bioinspired and engineered biomolecular catalysts for the efficient and fast production of fuels from low‐energy feedstocks such as water and carbon dioxide. In this short review, efforts to mimic biological catalysts for proton reduction and carbon dioxide reduction are highlighted. Two important recurring themes are the importance of the microenvironment of the catalyst active site and the key role of proton delivery to the active site in achieving desired reactivity. Perspectives on ongoing and future challenges are also provided.