title: Toward "metalloMOFzymes": Metal-Organic Frameworks with Single-Site Metal Catalysts for Small-Molecule Transformations.
abstract: Metal-organic frameworks (MOFs) are being increasingly studied as scaffolds and supports for catalysis. The solid-state structures of MOFs, combined with their high porosity, suggest that MOFs may possess advantages shared by both heterogeneous and homogeneous catalysts, with few of the shortcomings of either. Herein, efforts to create single-site catalytic metal centers appended to the organic ligand struts of MOFs will be discussed. Reactions important for advanced energy applications, such as H2 production and CO2 reduction, will be highlighted. Examining how these active sites can be introduced, their performance, and their existing limitations should provide direction for design of the next generation of MOF-based catalysts for energy-relevant, small-molecule transformations. Finally, the introduction of second-sphere interactions (e.g., hydrogen bonding via squaramide groups) as a possible route to enhancing the activity of these metal centers is reported.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego , La Jolla, California 92093, United States.
authors.forename: Seth M
authors.initials: SM
authors.lastname: Cohen
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego , La Jolla, California 92093, United States.
authors.forename: Zhenjie
authors.initials: Z
authors.lastname: Zhang
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego , La Jolla, California 92093, United States.
authors.forename: Jake A
authors.initials: JA
authors.lastname: Boissonnault
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry* / Q000378:metabolism; D002384:Catalysis; D020134:Catalytic Domain; D006859:Hydrogen / Q000737:chemistry / Q000378:metabolism; D000073396:Metal-Organic Frameworks / Q000737:chemistry* / Q000378:metabolism*; D010084:Oxidation-Reduction
chemical_list: D000073396:Metal-Organic Frameworks; D002245:Carbon Dioxide; D006859:Hydrogen