Atomically Dispersed Pt-Doped Co₃O₄ Spinel Nanoparticles Embedded in Polyhedron Frames for Robust Propane Oxidation at Low Temperature

This study adopts a facile and effective in situ encapsulation-oxidation strategy for constructing a coupling catalyst composed of atomically dispersed Pt-doped Co₃O₄ 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-Co₃O₄ NPs/PFs catalyst exhibits excellent propane catalytic activity with low T₉₀ (184 °C), superior apparent reaction rate (21.62×10⁸ (mol g_cat⁻¹ s⁻¹)), low apparent activation energy (E_a = 17.89 kJ mol⁻¹), high turnover frequency (811×10⁷ (mol g_cat⁻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 CH 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.