p–d Orbital Hybridization Induced by a Monodispersed Ga Site on a Pt3Mn Nanocatalyst Boosts Ethanol Electrooxidation

Abstract Constructing monodispersed metal sites in heterocatalysis is an efficient strategy to boost their catalytic performance. Herein, a new strategy using monodispersed metal sites to tailor Pt‐based nanocatalysts is addressed by engineering unconventional p–d orbital hybridization. Thus, monodispersed Ga on Pt 3 Mn nanocrystals (Ga‐O‐Pt 3 Mn) with high‐indexed facets was constructed for the first time to drive ethanol electrooxidation reaction (EOR). Strikingly, the Ga‐O‐Pt 3 Mn nanocatalyst shows an enhanced EOR performance with achieving 8.41 times of specific activity than that of Pt/C. The electrochemical in situ Fourier transform infrared spectroscopy results and theoretical calculations disclose that the Ga‐O‐Pt 3 Mn nanocatalyst featuring an unconventional p–d orbital hybridization not only promote the C−C bond‐breaking and rapid oxidation of ‐OH of ethanol, but also inhibit the generation of poisonous CO intermediate species. This work discloses a promising strategy to construct a novel nanocatalysts tailored by monodispersed metal site as efficient fuel cell catalysts.