General synthesis and atomic arrangement identification of ordered Bi-Pd intermetallics with tunable electrocatalytic CO2 reduction selectivity.

Abstract

Intermetallic compounds (IMCs) with fixed chemical composition and ordered crystallographic arrangement are highly desirable platforms for elucidating the precise correlation between structures and performances in catalysis. However, diffusing a metal atom into a lattice of another metal to form a controllably regular metal occupancy remains a huge challenge. Herein, we develop a general and tractable solvothermal method to synthesize the Bi-Pd IMCs family, including Bi2Pd, BiPd, Bi3Pd5, Bi2Pd5, Bi3Pd8 and BiPd3. By employing electrocatalytic CO2 reduction as a model reaction, we deeply elucidated the interplay between Bi-Pd IMCs and key intermediates. Specific surface atomic arrangements endow Bi-Pd IMCs different relative surface binding affinities and adsorption configuration for *OCHO, *COOH and *H intermediate, thus exhibiting substantially selective generation of formate (Bi2Pd), CO (BiPd3) and H2 (Bi2Pd5). This work provides a comprehensive understanding of the specific structure-performance correlation of IMCs, which serves as a valuable paradigm for precisely modulating catalyst material structures.