Metal–organic frameworks with catalytic centers: From synthesis to catalytic application

• Published in: Coordination chemistry reviews Vol. 378; pp. 262 - 280
• Main Authors: Kang, Yan-Shang, Lu, Yi, Chen, Kai, Zhao, Yue, Wang, Peng, Sun, Wei-Yin
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.01.2019
• Subjects: Catalytic centers; Efficiency; Porous MOFs; Post-synthetic method; Recyclability; Selectivity; Post-synthetic method; Selectivity; Porous MOFs; Catalytic centers; Efficiency; Recyclability
• ISSN: 0010-8545; 1873-3840
• DOI: 10.1016/j.ccr.2018.02.009

[Display omitted] •In organometallic catalytic chemistry, most catalysts are dissolved in organic solvents to ensure their activity.•The catalysts, however, cannot be recycled from the reaction system after several turnovers, which is a waste of the noble metals.•Metal–organic frameworks (MOFs), with the periodic order and site isolation of the catalytic struts, eliminate the multimolecular catalyst deactivation, thus extending the catalytic centers’ functional lifetime.•Meanwhile, MOFs can facilitate reactions like enzymatic catalysis due to their organization of the reactants in suitable positions and their ability to minimize the entropy loss and to reduce the transition-state energy.•In this review, typical examples of MOF-catalyzed reactions are given to show the increasingly visible advantage of MOFs in catalytic reactions.•Classification of the catalytic centers, how they work for various reactions in porous MOFs, as well as how to control their selectivity and activity will be discussed in detail.•Furthermore, functional groups introduced to MOFs by different post-synthetic catalytic reactions are discussed thoroughly. Metal-organic frameworks (MOFs), as a new stable class of hybrid materials synthesized, regulated and decorated by rational incorporating organic bridging ligands and metal ions with well-defined coordination geometry have become promising candidates for heterogeneous catalysis in industrial applications. Compared with homogeneous catalysts, MOF catalysts can be easily recycled and reused for several times; while compared with traditional heterogeneous catalysts, they possess tunable size and catalytic centers via exchange or modification of their components. This review will sketch typical successful MOF-catalyzed reactions and summarize various catalytic centers, including the open metal sites, bifunctional acid-base sites in MOFs, as well as catalytic centers introduced to MOFs via PSM. The periodic order and site isolation of the catalytic struts in MOFs eliminate the multimolecular catalyst deactivation pathways to extend the catalytic centers’ functional lifetime and facilitate the studies of their activities and reaction mechanisms. Furthermore, detailed discussion on how the catalytic centers play the roles in the catalytic reactions and how to control the activity and selectivity of them will be given via typical reported examples.