Photothermal Propane Dehydrogenation Catalyzed by VO_x‑Doped TiO₂ Nanoparticles

Propane direct dehydrogenation (PDH) has received much attention. How to effectively catalyze inert C–H bond activation is of great significance for industrial development. Pt-based catalysts show excellent activity but are limited by their expensive price. Cr-based catalysts are scarcely applied owing to their high toxicity. V-based catalysts are appropriate candidates for their cheap price and low toxicity, but they suffer from high energy consumption. The photothermal synergy effect induced by nonradiative relaxation is expected to make the C–H bond activation and hydrogen coupling process easier compared to bare thermal catalysis. Herein, a set of V/TiO₂ nanoscale catalysts were synthesized. The optimized 3 wt % V/TiO₂ catalyst (hereafter simplified as 3V) has a particle size of ∼26 nm, achieving a propylene production rate of 342 μmol·g^–1·h^–1 at 500 °C with UV–vis light radiation, which is 9.2% higher compared with bare thermal conditions. In situ radiation X-ray photoelectron spectroscopy (XPS) shows that photon injection leads to more electron-deficient V atoms (V^δ+, 5 > δ > 3). The strengthened Lewis acidity enhances the C₃H₈ activation as revealed by kinetic evidence and in situ C₃H₈-DRIFT measurements. The calculated molecular orbital diagrams show that the V atoms decrease the energy gap between the highest occupied orbital (HOMO) of C₃H₈ and the lowest unoccupied orbital (LUMO) of the model catalyst. This work describes an efficient photothermal synergy approach, specifically the nonthermal effect for promoting propane dehydrogenation.