LAUSR

The electrocatalytic properties of metal nanoparticles (NPs) exhibit strong dependence on their compositions and structures. Rational design of alloys and/or heterostructures provides us additional approaches to modifying their surface geometric and electronic structures for optimized electrocatalytic performance. Here we report a solution synthesis of freestanding intermetallic Au 2 Bi NPs, the heterostructures of Au 2 Bi/Bi hetero-NPs, and their promoted electrocatalytic CO 2 reduction reaction (CO 2 RR) performances. We revealed that the formation and in situ conversion of heterogeneous seeds (e.g. Au) were of vital importance for the formation of intermetallic Au 2 Bi and Au 2 Bi/Bi hetero-NPs. We 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 Au 2 Bi/Bi interfaces would create more surface active sites with modulated electronic structures and stronger adsorption strengths for key intermediates, promoting the CO 2 -to-HCOOH conversion with high activity and selectivity. Our 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.