Transforming Boron Carbon Nitride: A Carbon-to-Oxygen Switch to Boost Propane Oxidative Dehydrogenation

Hexagonal boron nitride (h-BN) catalysts exhibit high alkene selectivity in the oxidative dehydrogenation of propane (ODHP). Nevertheless, the conversion-selectivity trade-off persisted primarily due to the low density of oxygen-containing boron active species, while simple and controllable modification strategies for h-BN still face challenges. Herein, we developed an in situ carbon-to-oxygen switch strategy within a tailored boron carbon nitride (BCN) framework, in which uniformly embedded B–C₃ were transformed into B–O₃ via oxidative treatment (denoted as BNO_x). The structural evolution from B–C₃ to B–O₃ was well characterized by spectroscopy and soft X-ray absorption techniques. The resulting BNO_x catalysts, enriched with B–O₃ units, demonstrated performance in ODHP, achieving a propane conversion of 50.4% with 32.7% olefin yield at 500 °C. Density functional theory (DFT) calculations confirmed that B–O₃ species preferentially lower activation barriers, rendering the process thermodynamically more favorable. This work introduced an in situ reconstruction method for atomic-level heteroatom-engineered h-BN catalysts, opening an avenue for advanced catalyst design across energy conversion systems.