Abstract
Facile conversion of CO(2) to commercially viable carbon feedstocks offer a unique way to adopt a net-zero carbon scenario. Synthetic CO(2)-reducing catalysts have rarely exhibited energy-efficient and selective CO(2) conversion. Here, the carbon monoxide dehydrogenase (CODH) enzyme blueprint is imitated by a molecular copper complex coordinated by redox-active ligands. This strategy has unveiled one of the rarest examples of synthetic molecular complex-driven reversible CO(2) reduction/CO oxidation catalysis under regulated conditions, a hallmark of natural enzymes. The inclusion of a proton-exchanging amine groups in the periphery of the copper complex provides the leeway to modulate the biases of catalysts toward CO(2) reduction and CO oxidation in organic and aqueous media. The detailed spectroelectrochemical analysis confirms the synchronous participation of copper and redox-active ligands along with the peripheral amines during this energy-efficient CO(2) reduction/CO oxidation. This finding can be vital in abating the carbon footprint-free in multiple industrial processes.