Electrocatalytic Conversion of CO₂ to Formic Acid: A Journey from 3d-Transition Metal-Based Molecular Catalyst Design to Electrolyzer Assembly

ConspectusElectrochemical CO₂ 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 CO₂ reduction techniques over the past few decades. This Account provides a unified discussion on various electrochemical methodologies for CO₂ to formate conversion, with a particular focus on recent advancements in utilizing 3d-transition-metal-based molecular catalysts. This Account primarily focuses on understanding molecular functions and mechanisms under homogeneous conditions, which is essential for assessing the optimized reaction conditions for molecular catalysts. The unique architectural features of the formate dehydrogenase (FDH) enzyme provide insight into the key role of the surrounding protein scaffold in modulating the active site dynamics for stabilizing the key metal-bound CO₂ intermediate. Additionally, the protein moiety also triggers a facile proton relay around the active site to drive electrocatalytic CO₂ reduction forward. The fine-tuning of FDH machinery also ensures that the electrocatalytic CO₂ reduction leads to the production of formic acid as the major yield without any other carbonaceous products, while limiting the competitive hydrogen evolution reaction. These lessons from the enzymes are key in designing biomimetic molecular catalysts, primarily based on multidentate ligand scaffolds containing peripheral proton relays. The subtle modifications of the ligand framework ensure the favored production of formic acid following electrocatalytic CO₂ reduction in the solution phase. Next, the molecular catalysts are required to be mounted on robust electroactive surfaces to develop their corresponding heterogeneous versions. The surface-immobilization provides an edge to the molecular electrocatalysts as their reactivity can be scaled up with improved durability for long-term electrocatalysis. Despite challenges in developing high-performance, selective catalysts for the CO₂ to formic acid transformation, significant progress is being made with the tactical use of graphene and carbon nanotube-based materials. To date, the majority of the research activity stops here, as the development of an operational CO₂ to formic acid converting electrolyzer prototype still remains in its infancy. To elaborate on the potential future steps, this Account covers the design, scaling parameters, and existing challenges of assembling large-scale electrolyzers. A short glimpse at the utilization of electrolyzers for industrial-scale CO₂ reduction is also provided here. The proper evaluation of the surface-immobilized electrocatalysts assembled in an electrolyzer is a key step for gauging their potential for practical viability. Here, the key electrochemical parameters and their expected values for industrial-scale electrolyzers have been discussed. Finally, the techno-economic aspects of the electrolyzer setup are summarized, completing the journey from tactical design of molecular catalysts to their appropriate application in a commercially viable electrolyzer setup for CO₂ to formate electroreduction. Thus, this Account portrays the complete story of the evolution of a molecular catalyst to its sustainable application in CO₂ utilization.