Atomically Dispersed Pt-Doped Co3 O4 Spinel Nanoparticles Embedded in Polyhedron Frames for Robust Propane Oxidation at Low Temperature.

Abstract

This study adopts a facile and effective in situ encapsulation-oxidation strategy for constructing a coupling catalyst composed of atomically dispersed Pt-doped Co3 O4 spinel nanoparticles (NPs) embedded in polyhedron frames (PFs) for robust propane total oxidation. Benefiting from the abundant oxygen vacancies and more highly valent active Co3+ species caused by the doping of Pt atoms as well as the confinement effect, the optimized 0.2Pt-Co3 O4 NPs/PFs catalyst exhibits excellent propane catalytic activity with low T90 (184 °C), superior apparent reaction rate (21.62×108 (mol gcat -1 s-1 )), low apparent activation energy (Ea = 17.89kJ mol-1 ), high turnover frequency( 811×107 (mol gcat -1 s-1 )) as well as good stability. In situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory calculations indicate that the doping of Pt atoms enhances the oxygen activation ability, and decreases the energy barrier required for CH bond breaking, thus improving the deep oxidation process of the intermediate species. This study opens up new ideas for constructing coupling catalysts from atomic scale with low cost to enhance the activation of oxygen molecules and the deep oxidation of linear short chain alkanes at low temperature.