N-doped CoAl oxides from hydrotalcites with enhanced oxygen vacancies for excellent low-temperature propane oxidation

A series of nitrogen-doped CoAlO (N-CoAlO) were constructed by a hydrothermal route combined with a controllable NH₃ treatment strategy. The effects of NH₃ treatment on the physico-chemical properties and oxidation activities of N-CoAlO catalysts were investigated. In comparison to CoAlO, a smallest content decrease in surface Co³⁺ (serving as active sites) while a largest increased amount of surface Co²⁺ (contributing to oxygen species) are obtained over N-CoAlO/4h among the N-CoAlO catalysts. Meanwhile, a maximum N doping is found over N-CoAlO/4h. As a result, N-CoAlO/4h (under NH₃ treatment at 400°C for 4 hr) with rich oxygen vacancies shows optimal catalytic activity, with a T₉₀ (the temperature required to reach a 90% conversion of propane) at 266°C. The more oxygen vacancies are caused by the co-operative effects of N doping and suitable reduction of Co³⁺ for N-CoAlO/4h, leading to an enhanced oxygen mobility, which in turn promotes C₃H₈ total oxidation activity dominated by Langmuir-Hinshelwood mechanism. Moreover, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) analysis shows that N doping facilities the decomposition of intermediate species (propylene and formate) into CO₂ over the catalyst surface of N-CoAlO/4h more easily. Our reported design in this work will provide a promising way to develop abundant oxygen vacancies of Co-based catalysts derived from hydrotalcites by a simple NH₃ treatment.