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 °C, 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.

中文翻译：

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有序大孔磷酸硼晶体作为丙烷氧化脱氢的无金属催化剂

摘要 具有快速传质和增强活性位点可及性的有序大孔材料对于提高催化活性至关重要。在这项研究中，制备了具有三维互连有序大孔结构和坚固框架的磷酸硼晶体，并将其用作丙烷氧化脱氢 (ODH) 中的稳定和选择性催化剂。由于有序大孔结构中质量扩散的改善和更多暴露的活性位点，催化剂表现出显着的烯烃生产率~16 g烯烃 gcat-1 h-1，比 ODH 高 2-100 倍迄今为止报道的催化剂。在 515 °C 下，烯烃的选择性为 91.5%（丙烯：82.5%，乙烯：9.0%），丙烷转化率为 14.3%。同时，对不需要的深度氧化 CO2 产物的选择性保持在 1.0% 以下。三配位的表面硼物种被确定为丙烷 ODH 的活性催化位点。该研究为制备结构稳定、催化活性显着的新型无金属催化剂提供了一条途径，有望成为推动ODH工艺产业化的潜在候选者。