Abstract

Main observation and conclusionOxidative 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 (BPO4/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 BPO4/BN catalyst. The tetra‐coordinated boron (BO4) species of BPO4 was speculated to be responsible for the ODH of ethylbenzene, and a synergistic effect between BPO4 and BN can remarkably improve the catalytic performance of the BPO4/BN catalyst. The optimized BPO4/BN catalyst showed a higher styrene formation rate of 4.0 mmol gcat−1·h−1, compared individually to BPO4 (2.8 mmol·gcat–1·h–1) and BN (0.5 mmol·gcat–1·h–1).

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