Hierarchically 3D Porous Ag Nanostructures Derived from Silver Benzenethiolate Nanoboxes: Enabling CO₂ Reduction with a Near-Unity Selectivity and Mass-Specific Current Density over 500 A/g

Silver nanostructures with hierarchical porosities of multiple length scales have been synthesized through electrochemical reduction of silver benzenethiolate nanoboxes. The porous Ag nanostructures exhibit superior catalytic performance toward electrochemical reduction of CO₂. The Faradaic efficiency of reducing CO₂ to CO can be close to 100% at high cathodic potentials, benefiting from the readsorbed benzenethiolate ions on the Ag surface that can suppress the hydrogen evolution reaction (HER). Density functional theory calculations using the SCAN functional reveal that the disfavored H binding on the benzenethiolate-modified Ag surface is responsible for inhibiting the HER. The mass-specific activity of CO₂ reduction can be over 500 A/g because the multiple-scale porosities maximize the diffusion of reactive species to and away from the Ag surface. The unique multiscale porosities and surface modification of the as-synthesized Ag nanostructures make them a class of promising catalysts for electrochemical reduction of CO₂ in protic electrolytes to achieve maximum activity and selectivity.