Metal Nitride-Terminated Metal Oxides Efficiently Catalyzing CO ₂ Oxidative Dehydrogenation of Propane

CO 2 oxidative dehydrogenation of propane (CO 2 -ODHP) is a promising industrial technology for propylene supply and CO 2 utilization. However, the simultaneous activation of propane and CO 2 remains a major challenge. Ga-based catalysts, especially GaN-based catalysts, have shown high propane conversion activity but low Ga utilization and low CO 2 conversion rates. These issues significantly hinder their further industrial applications in CO 2 -ODHP. Herein, we introduce a catalyst named GaN–Ga 2 O 3 /ZSM-5 for the reaction, where GaN was in situ-grown on ≡Si–O–Ga 2 O 3 terminations using N 2 plasma-enhanced chemical vapor deposition. The catalyst exhibits a CO 2 -ODHP activity of 2.53 mol C 3 H 6 g Ga –1 h –1 and a CO 2 conversion above 16%. Compared to Ga 2 O 3 /ZSM-5 without GaN termination, the in situ-grown GaN shows nearly twice the activity. Importantly, it outperforms previously reported GaN- and Ga 2 O 3 -based catalysts by an order of magnitude under similar reaction conditions. Mechanistic studies reveal that strong electron transfer and dual active sites enhance propane and CO 2 adsorption activation, thereby promoting propane dehydrogenation (DHP) and reverse water gas shift (RWGS) reaction performance over those of the GaN–Ga 2 O 3 /ZSM-5 catalysts. The present work provides an efficient strategy for constructing dual functional active sites, especially comprised of metal nitrides and oxides, typically for the dehydrogenation of propane and the RWGS reactions.