杂多酸基复合材料的制备及其催化应用研究进展

Research progress in preparation and catalytic performance of heteropolyacid-based composite materials

摘要:

在清洁生物燃料的研究开发中，生物质的催化转化及生物柴油的合成是关键过程，而催化剂的选择对清洁生物燃料的高效制备至关重要。与传统均相催化剂相比，杂多酸具有稳定的结构、兼具强的Br?nsted酸性和氧化还原性，且能在较低的催化剂浓度和温度下高效催化反应，近年来在催化、材料化学、光化学等领域备受关注。本文主要聚焦于近年来杂多酸基复合催化材料在催化酯化、酯交换合成生物燃料方面的应用，综述其最新研究进展，分析了纯杂多酸、掺杂型杂多酸（使用反荷阳离子或离子液体功能化杂多酸）及负载型杂多酸（以硅基材料、金属氧化物、活性炭、金属有机框架等为载体）三类杂多酸基催化材料的制备、物化特性及催化应用；此外，介绍了杂多酸基复合催化材料在光催化、催化脱硫等方面的新型应用；最后，对杂多酸基复合催化材料在催化领域的发展趋势进行展望，并提出两条发展建议，一是大力发展绿色合成工艺，通过跨学科技术对杂多酸基复合催化材料结构进行设计，二是借助量子化学的方法阐释其催化机理与路径，明确制备、结构与催化性能间的关联，以期为工业上设计开发绿色杂多酸基非均相复合催化材料提供参考。

Abstract:

In the research and development of clean biofuels, the catalytic conversion of biomass and the synthesis of biodiesel are key processes, and the selection of catalysts is crucial for the efficient preparation of clean biofuels. Compared with traditional homogeneous catalysts, heteropolyacids have attracted much attention in the fields of catalysis, material chemistry, and photochemistry owing to its stable structures, strong Br?nsted acidity, redox properties, and can efficiently catalyze reactions at lower catalyst concentrations and temperatures. This review focuses on summarizing the recent advances in the development of heteropolyacid-based composite materials in catalyzing esterification and transesterification to synthesize biofuels, and the preparation, physicochemical properties, and the catalytic applications of three types of heteropolyacid-based materials, including pure heteropolyacid, doped heteropolyacid (heteropolyacid functionalized with counter charged cations or ionic liquids), and supported heteropolyacid (silicon-based materials, metal oxides, activated carbon, metal-organic frameworks, etc., are used as supports), are summarized. Meanwhile, new applications of heteropolyacid-based composite materials in photocatalysis and catalytic desulfurization were introduced. Also, the development trend of heteropolyacid-based composite materials in the catalysis field is prospected, and two development suggestions were advised. One was to vigorously develop green synthesis technology and design the structure of heteropolyacid-based composite catalytic materials through interdisciplinary technology; the other was to explain its catalytic mechanism and path by means of quantum chemistry, and to clarify the relationship between preparation, structure and catalytic performance. The study of this article may contribute to the industrial design and development of green heteropolyacid-based heterogeneous composite materials.