Recent Advances in the Catalyst Design and Mass Transport Control for the Electrochemical Reduction of Carbon Dioxide to Formate.

Closing the carbon cycle by the electrochemical reduction of CO₂ to formic acid and other high-value chemicals is a promising strategy to mitigate rapid climate change. The main barriers to commercializing a CO₂ reduction reaction (CO₂RR) system for formate production are the chemical inertness, low aqueous solubility, and slow mass transport characteristics of CO₂, along with the low selectivity and high overpotential observed in formate production via CO₂ reduction. To address those problems, we first explain the possible reaction mechanisms of CO₂RRs to formate, and then we present and discuss several strategies to overcome the barriers to commercialization. The electronic structure of the catalyst can be tuned to favor a specific intermediate by adjusting the catalyst composition and tailoring the facets, edges, and corners of the catalyst to better expose the active sites, which has primarily led to increased catalytic activity and selectivity. Controlling the local pH, employing a high-pressure reactor, and using systems with three-phase boundaries can tune the mass transport properties of reactants at the catalyst surface. The reported electrocatalytic performances are summarized afterward to provide insight into which strategies have critical effects on the production of formate. [ABSTRACT FROM AUTHOR]