p-d Orbital Hybridization Induced by a Monodispersed Ga Site on a Pt₃ Mn Nanocatalyst Boosts Ethanol Electrooxidation

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 Pt₃ Mn nanocrystals (Ga-O-Pt₃ Mn) with high-indexed facets was constructed for the first time to drive ethanol electrooxidation reaction (EOR). Strikingly, the Ga-O-Pt₃ 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-Pt₃ 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.