A Highly Selective Metal‐Free Boron‐Based Catalyst for Oxidative Dehydrogenation of Ethylbenzene

Main observation and conclusion Oxidative dehydrogenation of ethylbenzene is considered as an alternative route to styrene because of its exothermic and irreversible reaction nature, but encounters low styrene selectivity due to the deep‐oxidation over metal oxide‐based catalysts. Herein, we reported that a metal‐free boron‐based catalyst consisting of boron phosphate and boron nitride (BPO 4 /BN) exhibited high activity and selectivity in oxidative dehydrogenation of ethylbenzene to styrene. High selectivity of styrene (95.1%) was achieved at 27.7% ethylbenzene conversion level over the optimized BPO 4 /BN catalyst. The tetra‐coordinated boron (BO 4 ) species of BPO 4 was speculated to be responsible for the ODH of ethylbenzene, and a synergistic effect between BPO 4 and BN can remarkably improve the catalytic performance of the BPO 4 /BN catalyst. The optimized BPO 4 /BN catalyst showed a higher styrene formation rate of 4.0 mmol g cat −1 ·h −1 , compared individually to BPO 4 (2.8 mmol·g cat –1 ·h –1 ) and BN (0.5 mmol·g cat –1 ·h –1 ).