Steering the Selective Production of Glycolic Acid by Electrocatalytic Oxidation of Ethylene Glycol with Nanoengineered PdBi‐Based Heterodimers

Abstract Heterodimers of metal nanocrystals (NCs) with tailored elemental distribution have emerged as promising candidates in the field of electrocatalysis, owing to their unique structures featuring heterogeneous interfaces with distinct components. Despite this, the rational synthesis of heterodimer NCs with similar elemental composition remains a formidable challenge, and their impact on electrocatalysis has remained largely elusive. In this study, Pd@Bi‐PdBi heterodimer NCs are synthesized through an underpotential deposition (UPD)‐directed growth pathway. In this pathway, the UPD of Bi promotes a Volmer‐Weber growth mode, allowing for judicious modulation of core‐satellite to heterodimer structures through careful control of supersaturation and growth kinetics. Significantly, the heterodimer NCs are employed in the electrocatalytic process of ethylene glycol (EG) with high activity and selectivity. Compared with pristine Pd octahedra and common PdBi alloy NC, the unique heterodimer structure of the Pd@Bi‐PdBi heterodimer NCs endows them with the highest electrocatalytic performance of EG and the best selectivity (≈93%) in oxidizing EG to glycolic acid (GA). Taken together, this work not only heralds a new strategy for UPD‐directed synthesis of bimetallic NCs, but also provides a new design paradigm for steering the selectivity of electrocatalysts.