Flowing-Air-Induced Transformation to Promote the Dispersion of the CrO_x Catalyst for Propane Dehydrogenation

Highly dispersed chromium (Cr)-based catalysts are promising candidates for the catalytic dehydrogenation of propane (DHP). However, the easier aggregation of Cr species into crystalline Cr₂O₃ at the high-temperature calcination and reaction process is a big challenge, which severely restricts the improvement of activity and stability of the DHP reaction. Herein, a flowing-air-induced transformation method was first proposed, and the catalytic performance of the prepared Cr/MCM-41 catalysts was found to be significantly improved compared to that of the Cr-based catalyst prepared by the traditional calcination method, even better than that of most of the reported Cr-based catalysts and some noble metal-based catalysts. X-ray absorption spectroscopy and in situ Raman spectroscopy as well as other characterization techniques demonstrated that the in situ calcination in flowing air could not only effectively restrain the conversion of Cr(VI) into Cr(III) but also largely improve the dispersion of Cr species. Furthermore, DHP activity is found to have a positive correlation with the amount of monomeric Cr(VI) species, which is proved to be the precursor of active coordinatively unsaturated Cr sites. Our proposed flowing-air-induced transformation method provides a general strategy for preparing the highly dispersed Cr-based catalysts and other metal oxide materials with varied valence and exhibits potential application prospects in industry.