Modulating the electrocatalytic CO ₂ reduction performances of bismuth nanoparticles with carbon substrates with controlled degrees of oxidation

The catalytic performances of metal nanoparticles can be widely tuned and promoted by the metal-support interactions. Here, we report that the morphologies and electrocatalytic CO₂ reduction reaction (CO₂RR) properties of bismuth nanoparticles (BiNPs) can be rationally modulated by their interactions with carbon black (CB) supports by controlling the degree of surface oxidation. Appropriately oxidized CB supports can provide sufficient oxygen-containing groups for anchoring BiNPs with tunable sizes and surface areas, desirable key intermediate adsorption abilities, appropriate surface wettability, and adequate electron transfer abilities. As a result, the optimized Bi/CB catalysts exhibited a promoted CO₂RR performance with a Faradaic efficiency of 94% and a current density of 16.7 mA cm^-2 for HCOO^- at -0.9 V versus a reversible hydrogen electrode. Our results demonstrate the significance of regulating the interactions between supports and metal nanoparticles for both synthesis of the catalyst and electrolysis applications, which may find broader applicability in more electrocatalyst designs.