Relationships between the Surface Hydrophilicity of a Bismuth Electrode and the Product Selectivity of Electrocatalytic CO₂ Reduction

Two types of bismuth films (micro-Bi and nano-Bi) were prepared, and their electrocatalytic behavior was studied in terms of reduction current and product selectivity in a potential range of −0.776 to −1.376 V vs RHE. CO₂ and H₂O molecules competed with each other for reduction on the surfaces of both types of films, and formate and H₂ were the respective major products of reductive reactions. Under the same conditions, nano-Bi exhibited lower selectivity for formate and higher selectivity for H₂ compared to the respective micro-Bi cases with bismuth films of similar thickness. This can be attributed to the higher hydrophilicity of bismuth film surfaces of nano-Bi due to surface nanoscale roughness and lower surface-carbon content compared with those of micro-Bi. Our results suggest a new strategy for controlling the selectivity of electrocatalytic CO₂ reduction under aqueous electrolytes through the use of surface engineering.