Carbon monoxide dehydrogenase (CODH) enzymes are active for the reversible CO oxidation-CO reduction reaction and are of interest in the context of CO abatement and carbon-neutral solar fuels. Bioinspired by the active-site composition of the CODHs, polyoxometalates triply substituted with first-row transition metals were modularly synthesized. The polyanions, in short, {SiM W } and {SiM' M''W }, M, M', M''=Cu , Ni , Fe are shown to be electrocatalysts for reversible CO oxidation-CO reduction. A catalytic Tafel plot showed that {SiCu W } was the most reactive for CO reduction, and electrolysis reactions yielded significant amounts of CO with 98 % faradaic efficiency. In contrast, Fe-Ni compounds such as {SiFeNi W } preferably catalyzed the oxidation of CO to CO similar to what is observed for the [NiFe]-CODH enzyme. Compositional control of the heterometal complexes, now and in the future, leads to control of reactivity and selectivity for CO electrocatalytic reduction.
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