Designing Metal-Organic Frameworks for Catalytic Applications

Chapter
First Online:
Part of the Topics in Current Chemistry book series (TOPCURRCHEM, volume 293)

Abstract

Metal-organic frameworks (MOFs) are constructed by linking organic bridging ligands with metal-connecting points to form infinite network structures. Fine tuning the porosities of and functionalities within MOFs through judicious choices of bridging ligands and metal centers has allowed their use as efficient heterogeneous catalysts. This chapter reviews recent developments in designing porous MOFs for a variety of catalytic reactions. Following a brief introduction to MOFs and a comparison between porous MOFs and zeolites, we categorize catalytically active achiral MOFs based on the types of catalytic sites and organic transformations. The unsaturated metal-connecting points in MOFs can act as catalytic sites, so can the functional groups that are built into the framework of a porous MOF. Noble metal nanoparticles can also be entrapped inside porous MOFs for catalytic reactions. Furthermore, the channels of porous MOFs have been used as reaction hosts for photochemical and polymerization reactions. We also summarize the latest results of heterogeneous asymmetric catalysis using homochiral MOFs. Three distinct strategies have been utilized to develop homochiral MOFs for catalyzing enantioselective reactions, namely the synthesis of homochiral MOFs from achiral building blocks by seeding or by statistically manipulating the crystal growth, directing achiral ligands to form homochiral MOFs in chiral environments, and incorporating chiral linker ligands with functionalized groups. The applications of homochiral MOFs in several heterogeneous asymmetric catalytic reactions are also discussed. The ability to synthesize value-added chiral molecules using homochiral MOF catalysts differentiates them from traditional zeolite catalysis, and we believe that in the future many more homochiral MOFs will be designed for catalyzing numerous asymmetric organic transformations.

Keywords

Chiral Enantioselectivity Heterogeneous·catalysis Metal-organic frameworks Porous Size selectivity 

Abbreviations

BDC

1,4-Benzenedicarboxylate acid

BET

Brunauer-Emmett-Teller

BINOL

1,1′-binaphthalene-2,2′-diol

BPDC

Biphenyl-4,4′-dicarboxylic acid

BTC

Benzene-1,3,5-tricarboxylate

MOFs

Metal-organic frameworks

SBU

Secondary building unit

TOF

Turn over frequency

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Notes

Acknowledgments

We would like to acknowledge National Science Foundation for financial support. We also thank former coworkers Drs. Aiguo Hu, Chuan-De Wu, and Helen L. Ngo for their invaluable contributions to the research program in the Lin group.

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Copyright information

© Springer 2009

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of North CarolinaChapel HillUSA

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