Electrocatalytic Conversion of CO to Formic Acid: A Journey from 3d-Transition Metal-Based Molecular Catalyst Design to Electrolyzer Assembly.

ConspectusElectrochemical CO reduction to obtain formate or formic acid is receiving significant attention as a method to combat the global warming crisis. Significant efforts have been devoted to the advancement of CO reduction techniques over the past few decades. This Account provides a unified discussion on various electrochemical methodologies for CO to formate conversion, with a particular focus on recent advancements in utilizing 3d-transition-metal-based molecular catalysts.

Expedited Proton Relay in Enzyme-Inspired Cobaloximes Facilitate Organic Transformations.

Developing a water-soluble, oxygen-tolerant, and acid-stable synthetic H production catalyst is vital for renewable energy infrastructure. To access such an effective catalyst, we strategically incorporated enzyme-inspired, multicomponent outer coordination sphere elements around the cobaloxime (Cl-Co-X) core with suitable axial coordination (X). Our cobaloximes with axial imidazole or L-histidine coordination in photocatalytic HAT including the construction of anilines via a non-canonical cross-coupling approach is found superior compared to commonly used cobaloxime catalysts.

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

Facile conversion of CO to commercially viable carbon feedstocks offer a unique way to adopt a net-zero carbon scenario. Synthetic CO-reducing catalysts have rarely exhibited energy-efficient and selective CO conversion. Here, the carbon monoxide dehydrogenase (CODH) enzyme blueprint is imitated by a molecular copper complex coordinated by redox-active ligands.

Electrochemical water splitting by a bidirectional electrocatalyst.

The presence of efficient energy storage and conversion technologies is essential for the future energy infrastructure. Here, we describe crafting a heterostructure composed of a suitably interlinked CeO and polycrystalline BiO dopant prepared on a reduced graphene oxide (Ce_BiO@rGO) surface. This material exhibits exceptional electrocatalytic hydrogen and oxygen evolution reaction in alkaline water (pH∼14.

Improving the synthetic H production catalyst design strategy with the neurotransmitter dopamine.

The strategic incorporation of the neurotransmitter dopamine around a cobaloxime core resulted in excellent electrocatalytic (rate 8400 s) and photocatalytic H production under neutral aqueous conditions. The influence of the synthetic outer coordination sphere features continues even with a phenylene-diimino-dioxime motif-coordinated cobalt core.