OH Regulator of Amorphous CrOx on Defect-Rich Ultrafine Pd Nanowires Boosts Electrocatalytic Ethanol Oxidation

Small. 2024 Oct 20:e2408373. doi: 10.1002/smll.202408373. Online ahead of print.

Abstract

Reasonable construction of high activity and selectivity electrocatalysts is crucial to achieve efficient ethanol oxidation reaction (EOR). However, the oxidation of ethanol tends to produce CO species that poison the active centers of the EOR electrocatalysts. Herein, a unique amorphous CrOx-protected defect-rich ultrafine Pd nanowires (CrOx-Pd NWs) is developed. On the one hand, the CrOx layer can act as a protective layer to maintain the structure of the nanowire. On the other hand, it can play the role of OH regulator to optimize the adsorption energy barrier of intermediate species in Pd nanowire, thereby enhancing the ability of the catalyst to resist CO poisoning. The CrOx-Pd NWs exhibit excellent EOR performance with 3.64 times higher mass activity and 50 mV lower CO electro-oxidation potential than commercial Pd black. The results show that the CrOx layer promotes the dissociation of H2O into OHads, while the CrOx transfers electrons to neighboring Pd atoms optimizing the electronic configuration of Pd, thus selectively oxidizing ethanol to acetate and preventing the formation of toxic *CO. This work provides an effective strategy for the synthesis of nanowire materials with oxide/metal interfaces and offers new ideas for the design of catalysts that can efficiently drive EOR.

Keywords: Pd nanowires; amorphous CrOx; defect; electrocatalysts; ethanol oxidation reaction.