For the CO2RR rate-determining step, the RDF focuses on the interaction between Au(staple) and the hydrogen atoms of water molecules because *CO2 and *COOH adsorption as well as the conversion to *CO occur exclusively at the Au(staple) site. Figure presents the Bader charge analysis of the Au(surface) and Au(staple) sites for both nanoclusters before and after the adsorption of key intermediates (*H, *COOH) in HER and CO2RR. These data reveal distinct differences in how the two systems interact with reactants, helping explain their differing catalytic performances.