摘要
Climate change caused by the increasing emission of CO_(2)to the atmosphere has become a global concern.To ameliorate this issue,converting CO_(2)into valuable chemicals is highly desirable,enabling a sustainable low-carbon future.To this end,developing efficient catalytic systems for CO_(2)conversion has sparked intense interests from both academia and industry.Taking advantage of their highly porous structures and unique properties,metal−organic frameworks(MOFs)have shown great potential as heterogeneous catalysts for CO_(2)conversion.Various transformations involving CO_(2)have been accomplished over MOFs-based materials.Here we provide a comprehensive and up-to-date review on recent advances of heterogeneous CO_(2)thermocatalysis using MOFs,highlighting relationships between structures and properties.Special attention is given to the design strategies for improving the catalytic performance of MOFs.Avenues available to enrich the catalytic active sites in MOF structures are stressed and their respective impacts on CO_(2)conversion efficiency are presented.The synergistic effects between each active site within the structure of MOFs and derivatives are discussed.In the end,future perspectives and challenges in CO_(2)conversion by heterogeneous catalysis with MOFs are described.
近年来,大气中CO_(2)的浓度不断增加,带来全球变暖等一系列严重后果,成为国际社会共同关注的环境问题.将CO_(2)催化转化为高附加值化学品可有效降低其向大气中的排放,同时可实现其资源化利用,符合低碳社会的发展目标.目前,已有多种催化体系实现了CO_(2)向不同化学品的转化.然而,由于CO_(2)自身的热力学稳定性和动力学惰性,这些转化通常需要在苛刻的反应条件和较高能耗下进行.设计开发高效催化体系、实现温和条件下CO_(2)的转化利用引起了工业界和学术界的广泛兴趣.金属有机骨架材料(MOFs)是一类由有机配体和金属中心通过配位键组装而成的有机-无机杂化材料,在很多方面展现出良好的应用性能.由于其结构的多样性、可设计性、高比表面积和多孔性等独特性质,MOFs在催化领域吸引了很多研究者的关注.其中,MOFs作为非均相催化剂在CO_(2)热催化转化中表现出良好的应用前景,已实现多种CO_(2)向高值化学品的转化路径.但这些催化体系也存在一些缺点,如有些MOFs材料在催化反应中稳定性差以及其微孔性对反应中的传质造成限制等.因此,设计稳定的MOFs和MOF-基材料并对其结构进行优化改性,从而在温和条件下实现高效的CO_(2)转化具有重要意义.本文综述了提高MOFs在CO_(2)热催化转化反应中性能的几种策略:(1)对MOFs结构中的配体进行设计,包括具有活性官能团的配体、活性配合物作为配体和引入混合配体设计多元MOF;(2)调节MOFs结构中的金属中心,设计混合金属中心和包含活性金属团簇的金属中心;(3)构筑多级孔MOFs;(4)设计MOF-基的复合材料,包括MOFs作为载体与金属纳米颗粒、活性配合物和聚合物构建复合材料;(5)利用MOFs作为前驱体制备MOF-基衍生物材料,重点阐述了如何增加MOFs作为非均相催化剂的催化活性位点以及在CO_(2)转化反应中各位点之间的协同作用.此
基金
国家自然科学基金(21972010,21972056)
北京市自然科学基金面上项目(2192039)
有机-无机复合材料国家重点实验室基金(oic-201901001).
