Tuning Crystal Phase of Palladium–Selenium Nanowires for Enhanced Ethylene Glycol Electrocatalytic Oxidation

Abstract Alcohol electrooxidation is pivotal for a sustainable energy economy. However, designing efficient electrocatalysts for this process is still a formidable challenge. Herein, palladium–selenium nanowires featuring distinct crystal phases: monoclinic Pd ₇ Se ₂ and tetragonal Pd _4.5 Se for ethylene glycol electrooxidation reaction (EGOR) are synthesized. Notably, the supported monoclinic Pd ₇ Se ₂ nanowires ( m ‐Pd ₇ Se ₂ NWs/C) exhibit superior EGOR activity, achieving a mass activity (MA) and specific activity (SA) of 10.4 A mg _Pd ⁻¹ (18.7 mA cm ⁻² ), which are 8.0 (6.7) and 10.4 (8.2) times versus the tetragonal Pd _4.5 Se and commercial Pd/C and surpass those reported in the literature. Furthermore, m ‐Pd ₇ Se ₂ NWs/C displays robust catalytic activity for other alcohol electrooxidation. Comprehensive characterization and density functional theory (DFT) calculations reveal that the enhanced electrocatalytic performance is attributed to the increased formation of Pd ⁰ on the high‐index facets of the m ‐Pd ₇ Se ₂ NWs, which lowers the energy barriers for the C─C bond dissociation in CHOHCHOH* and the CO* oxidation to CO ₂ *. This study provides palladium‐based alloy electrocatalysts exhibiting the highest mass activity reported to date for the electrooxidation of ethylene glycol, achieved through the crystalline phase engineering strategy.