Electrocatalyst Microenvironment Engineering for Enhanced Product Selectivity in Carbon Dioxide and Nitrogen Reduction Reactions

Carbon and nitrogen fixation strategies are regarded as alternative routes to produce valuable chemicals used as energy carriers and fertilizers that are traditionally obtained from unsustainable and energy-intensive coal gasification (CO and CH4), Fischer–Tropsch (C2H4), and Haber–Bosch (NH3) processes. Recently, the electrocatalytic CO2 reduction reaction (CO2RR) and N2 reduction reaction (NRR) have received tremendous attention, with the merits of being both efficient strategies to store renewable electricity while providing alternative preparation routes to fossil-fuel-driven reactions. To date, the development of the CO2RR and NRR processes is primarily hindered by the competitive hydrogen evolution reaction (HER); however, the corresponding strategies for inhibiting this undesired side reaction are still quite limited. Considering such complex reactions involve three gas–liquid–solid phases and successive proton-coupled electron transfers, it appears meaningful to review the current strategies for improving product selectivity in light of their respective reaction mechanisms, kinetics, and thermodynamics. By examining the developments and understanding in catalyst design, electrolyte engineering, and three-phase interface modulation, we discuss three key strategies for improving product selectivity for the CO2RR and NRR: (i) targeting molecularly defined active sites, (ii) increasing the local reactant concentration at the active sites, and (iii) stabilizing and confining product intermediates.