Synergistic function of Bi and B in interstitial ternary Pd–Bi–B alloy nanocrystals for highly active and durable electrochemical ethanol oxidation

Abstract

Engineering interstitial alloys by integrating non-metallic atoms into bimetallic frameworks is a promising strategy for optimizing performance in various potential applications. Herein, we introduce a novel synthesis of Pd₄Bi–B ternary alloy nanocrystals for highly efficient ethanol oxidation catalysts. The Bi enhances the electrochemical oxidation of ethanol through C1-pathways by facilitating C–C bond breaking and reducing poisoning intermediates. Concurrently, the interstitial B mitigates the d-band center upshift observed in Pd₄Bi alloys, leading to a lower d-band center in Pd₄Bi–B nanocrystals than in Pd nanocrystals. This further increases the ethanol oxidation rate by facilitating the desorption of intermediates. The synergistic function of Bi and B in the Pd₄Bi–B nanocrystals results in superior EOR activity and durability compared to both Pd₄Bi and Pd/C. Our findings provide valuable insights into the design of metal–nonmetallic alloy catalysts and emphasize the critical role of compositional control in enhancing catalytic efficacy.