Atomically Dispersed Pt‐Doped Co₃O₄ 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 Co 3 O 4 spinel nanoparticles (NPs) embedded in polyhedron frames (PFs) for robust propane total oxidation. Benefiting from the abundant oxygen vacancies and more highly valent active Co 3+ species caused by the doping of Pt atoms as well as the confinement effect, the optimized 0.2Pt-Co 3 O 4 NPs/PFs catalyst exhibits excellent propane catalytic activity with low T 90 (184 °C), superior apparent reaction rate (21.62×10 8 (mol g cat −1 s −1 )), low apparent activation energy (E a = 17.89 kJ mol −1 ), high turnover frequency ( 811×10 7 (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 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.

A Low-Noble-Metal Ru@CoMn2O4 Spinel Catalyst for the Efficient Oxidation of Propane

“…This may be because the in situ doped Ru was not only deposited on the surface of the catalyst but also dispersed inside the spinel, which resulted in higher activity and better stability. In a word, the Ru@CoMn 2 O 4 catalyst displayed excellent catalytic activity, even better than some other noble-metal catalysts reported in recent years [27][28][29][30][31][32][33], indicating that the Ru@CoMn 2 O 4 catalyst has potential for practical industrial applications in alkane removal. The catalyst activities in some of the relevant literature are shown in Table 1.…”

“…It is worth noting that T 90 of the Pt-Co 3 O 4 NPs/PFs catalyst in ref. [30] was only 184 • C. This was due to its low GSHW (30,000 mL g•cat −1 •h −1 ) and high Pt load (0.2 wt %). In addition, as shown in Figure 1b, the T 90 of 0.1% Ru@CoMn 2 O 4 was only 6 • C higher than that of 1% Ru@CoMn 2 O 4 .…”