Energy-efficient CO₂/CO interconversion by homogeneous copper-based molecular catalysts

Facile conversion of CO₂ to commercially viable carbon feedstocks offer a unique way to adopt a net-zero carbon scenario. Synthetic CO₂-reducing catalysts have rarely exhibited energy-efficient and selective CO₂ 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 CO₂ 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 CO₂ 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 CO₂ reduction/CO oxidation. This finding can be vital in abating the carbon footprint-free in multiple industrial processes.