Single‐Atom In‐Doped Subnanometer Pt Nanowires for Simultaneous Hydrogen Generation and Biomass Upgrading

Abstract Replacing the anodic oxygen evolution reaction (OER) with a thermodynamically favorable ethanol oxidation reaction (EOR) is regarded as a promising approach to simultaneously realize energy‐saving H 2 evolution and high‐value chemical production. Herein, the single‐atom In‐doped subnanometer Pt nanowires (SA In‐Pt NWs) as high‐performance electrocatalysts for both the hydrogen evolution reaction (HER) and EOR under universal pH conditions is designed. The SA In‐Pt NWs/C can be employed to integrate HER with EOR to avoid the large overpotential caused by sluggish OER, which requires a smaller voltage of 0.62 V to reach 10 mA cm –2 compared with that of water splitting (2.07 V). The reaction also exhibits a high faradaic efficiency of over 93% in upgrading ethanol to valuable acetate in the anodic cell. Mechanistic investigations indicate that the combination of the ultrathin 1D morphology and single‐atom In decoration provides the maximum number of active sites and effectively activates Pt atoms for catalysis. Density functional theory calculations further demonstrate that doped In can effectively promote the HER, while also promoting the conversion of ethanol to acetate. Moreover, through the use of SA In‐Pt NWs/C as electrocatalysts, many other alcohols can also be employed as anodic feedstock to achieve coupled electrolysis.