Deng Xiaoyu, Li Zhaohui, García Hermenegildo
Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, 350002, P. R. China.
Instituto de Tecnología Química, CSIV-UPV, Av. Delos Naranjos s/n, 46022, Valencia, Spain.
Chemistry. 2017 Aug 22;23(47):11189-11209. doi: 10.1002/chem.201701460. Epub 2017 Jul 19.
With the aim of developing renewable energy based processes, researchers are paying increasing interest to light induced organic transformations. Metal-organic frameworks (MOFs), a class of micro-/mesoporous hybrid materials, are recently emerging as a new type of photoactive materials for organic syntheses due to their unique structural characteristics. In this Review, we summarized the recent applications of MOFs as photocatalysts for light induced organic transformations, including (1) oxidation of alcohols, amines, alkene, alkanes and sulfides; (2) hydroxylation of aromatic compounds like benzene; (3) activation of the C-H bonds to construct new C-C or C-X bonds; (4) atom-transfer radical polymerization (ATRP). This Review starts with general background information of using MOFs in photocatalysis, followed by a description of light induced organic transformations promoted by photoactive inorganic nodes and photocatalytic active ligands in MOFs, respectively. Thereafter, the use of MOFs as multifunctional catalysts for light induced organic transformations via an efficient merge of the metal/ligand/guest based catalysis where the photocatalytic activity of MOFs plays a key role are discussed. Finally, the limitations, challenges and the future perspective of the application of MOFs for light induced organic transformations were addressed. The objective of this Review is to serve as a starting point for other researchers to get into this largely unexplored field. It is also our goal to stimulate intensive research in this field for rational designing of MOF materials to overcome their current limitations in photocatalysis, which can lead to more creative visible-light-induced organic transformations.
为了开发基于可再生能源的工艺,研究人员对光诱导有机转化越来越感兴趣。金属有机框架(MOFs)是一类微孔/介孔杂化材料,由于其独特的结构特征,最近作为一种新型的有机合成光活性材料而出现。在本综述中,我们总结了MOFs作为光催化剂用于光诱导有机转化的最新应用,包括:(1)醇、胺、烯烃、烷烃和硫化物的氧化;(2)苯等芳香族化合物的羟基化;(3)C-H键的活化以构建新的C-C或C-X键;(4)原子转移自由基聚合(ATRP)。本综述首先介绍了MOFs在光催化中的一般背景信息,随后分别描述了由MOFs中光活性无机节点和光催化活性配体促进的光诱导有机转化。此后,讨论了通过金属/配体/客体基催化的有效合并,将MOFs用作光诱导有机转化的多功能催化剂,其中MOFs的光催化活性起着关键作用。最后,阐述了MOFs在光诱导有机转化应用中的局限性、挑战和未来展望。本综述的目的是为其他研究人员进入这个 largely unexplored field提供一个起点。我们的目标也是激发该领域的深入研究,以便合理设计MOF材料,克服它们目前在光催化方面的局限性,从而实现更具创造性的可见光诱导有机转化。