Mechanistic Study of CO₂ Reduction in a Metal Nanoparticle/Ligand-Based Nanoconfined Pocket

Achieving this requires electrocatalysts with high selectivity and energy efficiency. Nanopocket engineering enhances catalytic activity by modulating interfacial reactivity and stabilizing key intermediates, especially those involved in the rate-determining step.

Here, we use density functional theory to systematically evaluate the CO₂ reduction reaction (CO₂RR) and the competing hydrogen evolution reaction (HER) on three systems: Ag surface without confinement, double Ag confinement, and Ag surface confined by a ligand in the absence and presence of interfacial water. We find that decreasing the confinement distance from 7 to 4 Å stabilizes CO₂RR intermediates over HER in the double Ag and Ag/ligand systems, due to additional secondary interactions, such as hydrogen bonding, in the latter.