Controllable P Doping of the LaCoO₃ Catalyst for Efficient Propane Oxidation: Optimized Surface Co Distribution and Enhanced Oxygen Vacancies

The properties of LaCoO3 are modified by a controllable P doping strategy via a simple sol–gel route. It is demonstrated that appropriate P doping is beneficial for forming a relatively pure perovskite phase and hinders the growth of perovskite nanoparticles. The combined results of density functional theory (DFT), extended X-ray absorption fine structure (EXAFS), X-ray absorption near-edge structure (XANES), temperature-programmed reduction of hydrogen (H2-TPR), X-ray photoelectron spectroscopy (XPS), and temperature-programmed desorption of ammonia (NH3-TPD) reveal that appropriate P doping gives rise to more oxygen vacancies, optimized distribution of Co ions, and improved surface acidity, which are beneficial for the adsorption of active oxygen species and the activation of propane molecules, resulting in an excellent catalytic oxidation performance. Especially, LaCo0.97P0.03O3 exhibits more surface-active oxygen species, higher bulk Co3+ proportion, increased surface Co2+ species, and increased acidity, resulting in its superior propane oxidation performance, which is dominated by the Langmuir–Hinshelwood mechanism. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) confirms that the presence of P will accelerate oxygen mobility, which in turn promotes the oxidation rate. Moreover, the obtained LaCo0.97P0.03O3 catalyst displays excellent thermal stability during the 60 h durability test at 400 °C and strong resistance against 5 vol % H2O and/or 5 vol % CO2 for prolonged 150 h.