Controlled Synthesis of Intermetallic Au2Bi Nanocrystals and Au2Bi/Bi Hetero-Nanocrystals with Promoted Electrocatalytic CO2 Reduction Properties

The electrocatalytic properties of metal nanoparticles (NPs) strongly depend on their compositions and structures. Rational design of alloys and/or heterostructures provides additional approaches to modifying their surface geometric and electronic structures for optimized electrocatalytic performance. Here, a solution synthesis of freestanding intermetallic Au2Bi NPs, the heterostructures of Au2Bi/Bi hetero-NPs, and their promoted electrocatalytic CO2 reduction reaction (CO2RR) performances were reported. It was revealed that the formation and in-situ conversion of heterogeneous seeds (e. g., Au) were of vital importance for the formation of intermetallic Au2Bi and Au2Bi/Bi hetero-NPs. It was also found that the Au components would act as the structure promoter moderating the binding strength for key intermediates on Bi surfaces. The alloying of Bi with Au and the formation of heterogeneous Au2Bi/Bi interfaces would create more surface active sites with modulated electronic structures and stronger adsorption strengths for key intermediates, promoting the CO2-to-HCOOH conversion with high activity and selectivity. This work presents a novel route for preparing intermetallic nanomaterials with modulated surface geometric/electric structures and promoting their electrocatalytic activities with alloying effects and interfacial effects. Such strategy may find wide application in catalyst design and synthesis for more electrocatalytic reactions.