Chinese Journal of Catalysis ›› 2020, Vol. 41 ›› Issue (12): 1837-1845.DOI: 10.1016/S1872-2067(20)63654-3

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Ordered macroporous boron phosphate crystals as metal-free catalysts for the oxidative dehydrogenation of propane

Wen-Duo Lua, Xin-Qian Gaoa, Quan-Gao Wanga, Wen-Cui Lia, Zhen-Chao Zhaoa, Dong-Qi Wangb, An-Hui Lua   

  1. a State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory for Catalytic Conversion Carbon Resources, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China;
    b Multi-Disciplinary Research Division, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
  • Received:2020-04-18 Revised:2020-04-27 Online:2020-12-18 Published:2020-08-14
  • Supported by:
    This work was supported by the State Key Program of the National Natural Science Foundation of China (21733002), and the Cheung Kong Scholars Program of China (T2015036).

Abstract: Ordered macroporous materials with rapid mass transport and enhanced active site accessibility are essential for achieving improved catalytic activity. In this study, boron phosphate crystals with a three-dimensionally interconnected ordered macroporous structure and a robust framework were fabricated and used as stable and selective catalysts in the oxidative dehydrogenation (ODH) of propane. Due to the improved mass diffusion and higher number of exposed active sites in the ordered macroporous structure, the catalyst exhibited a remarkable olefin productivity of ~16 golefin gcat-1 h-1, which is up to 2-100 times higher than that of ODH catalysts reported to date. The selectivity for olefins was 91.5% (propene: 82.5%, ethene:9.0%) at 515 ℃, with a propane conversion of 14.3%. At the same time, the selectivity for the unwanted deep-oxidized CO2 product remained less than 1.0%. The tri-coordinated surface boron species were identified as the active catalytic sites for the ODH of propane. This study provides a route for preparing a new type of metal-free catalyst with stable structure against oxidation and remarkable catalytic activity, which may represent a potential candidate to promote the industrialization of the ODH process.

Key words: Ordered macroporous material, Metal-free catalyst, Boron phosphate, Oxidative dehydrogenation, Propane