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 pd orbital hybridization not only promote the CÀ C bondbreaking 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.

d–sp orbital hybridization: a strategy for activity improvement of transition metal catalysts

“…105–107 Wang et al reported a new strategy using monodispersed p-block metal sites to tailor Pt-based nanocatalysts. 108 The pDOS analysis shows that the band energy of the Pt 5d-orbital matched well with the Ga 3p-orbital and O 2p-orbital, resulting in an unconventional p–d orbital hybridization given the unfilled p-orbital of Ga. Therefore, the monodispersed Ga on Pt 3 Mn nanocrystals (Ga–O–Pt 3 Mn) with high-indexed facets showed an enhanced ethanol electrooxidation performance, achieving 8.4 times the specific activity of Pt/C.…”

Synthetic strategies for MOF-based single-atom catalysts for photo- and electro-catalytic CO2 reduction

“…In addition to the corresponding MOFs derivatives generated by the pyrolysis of MOFs, a series of composite materials could be obtained by compounding MOFs with other functional materials. Currently, several materials are frequently used as candidates for composite materials, including the semiconductor, metal nanoparticles, and polymer materials (Chen et al, 2021b;Sun et al, 2021;Wang et al, 2022). They introduce different functionalities to MOF-based catalysts and provide new approaches for the synthesis of MOF-based catalysts.…”

Recent Progress in Thermal Conversion of CO2 via Single‐Atom Site Catalysis

“…Even small fraction of doping atoms in alloy could significantly change its property. [ 87 ] SAA is an expanded concept of SAC and also has potential application in CO 2 activation ( Table 5 ), as revealed by theoretical researches [ 88–90 ] and experiment from Sasmz's group. They reported Pt–Ni SAA and CeO 2 cores confined in nanotubular SiO 2 structure for DRM.…”