Abstract:

The recent discovery of boron-based catalytic system, especially represented by boron nitride catalyst, exhibits high activity and selectivity to olefins with negligible formation of CO₂ in oxidative dehydrogenation of light alkane reactions and has become a new hotspot worldwide. Herein, the recent progress of boron-based materials in oxidative dehydrogenation of light alkanes was summarized. The effects of different boron-based catalysts, such as hexagonal boron nitride, silicon boride, boron carbide, and elemental boron, were clarified. Combining the evidence of spectrum (IR, XPS, NMR, SVUV-PIMS, etc.) and kinetics (partial pressure, kinetic isotope effect, isotope labeling, etc.) and theoretical calculation, the active sites of boron-based catalysts, namely the surface of the tricoordinated boroxol species (B—OH/B—O) and the reaction mechanism containing surface and gas-phase radical reaction were highlighted. The opportunities and the challenges of using boron-based materials in oxidative dehydrogenation of light alkanes were summarized. It indicates that the design of the boron-based materials with highly promoted olefin selectivity is the main topic in further researches. Several suggestions were proposed for the rational design and practical application of boron-based catalytic materials.

Key words: boron-based materials, catalysis, alkanes, oxidative dehydrogenation, olefins

摘要：

以氮化硼为代表的硼基材料在低碳烷烃氧化脱氢反应中显示出高的催化活性和优异的烯烃选择性，已在国际上形成新的研究热点。本文主要综述了近年来硼基材料催化低碳烷烃氧化脱氢的研究进展，阐述了不同硼基催化剂（h-BN、SiB₆、BC₄、硼单质等）对氧化脱氢烯烃选择性的影响，结合多种谱学（IR、XPS、NMR、SVUV-PIMS等）、动力学（分压、同位素效应、同位素标记等）证据和理论计算，探讨了硼基催化剂表面三配位的硼氧物种（B—OH/B—O）是引发烷烃氧化脱氢生成烯烃的活性位，主要遵循表面和气相自由基反应机理。总结了硼基催化材料氧化脱氢中存在的机遇和挑战，提升烯烃选择性是材料设计合成的主要方向，并提出后续硼基催化材料理性设计和实际应用的一些参考建议。

关键词: 硼基材料, 催化, 烷烃, 氧化脱氢, 烯烃