Engineering Metal Organic Frameworks for Heterogeneous Catalysis

Abstract

4636 2.4.1. MOFs as Host Matrices to Incorporate Metal Nanoparticles 4636 2.4.2. Incorporation of Metal Oxide Nanoparticles in MOFs 4642 2.4.3. MOFs as Host Matrices to Incorporate Catalytically Active Guests 4644 2.4.4. MOFs as Nanometric Reaction Cavities 4647 3. Conclusions and Future Possibilities 4651 4. List of Acronyms and Abbreviations Used 4651 5. Acknowledgments 4652 6. References 4652

Metal–Organic Framework Nodes as Nearly Ideal Supports for Molecular Catalysts: NU-1000- and UiO-66-Supported Iridium Complexes

“…A sample consisting of 97 mg of ZrOCl 2 ·8H 2 O (0.30 mmol) and 2700 mg (22 mmol) of benzoic acid was mixed in 8 mL of DMF (in a 6 dram vial) and ultrasonically dissolved. The clear solution was incubated in an oven at 353 K for 1 h. After cooling to room temperature, 40 mg (0.06 mmol) of H 4 TBAPy was added to this solution, and the mixture was sonicated for 20 min. The yellow suspension was held in an oven at 353 K for 24 h. After cooling to room temperature, yellow polycrystalline material was isolated by filtration (35 mg of activated material, 54% yield) and washed with DMF and subsequently activated with HCl.…”

“…16,18 UiO-66 is composed of [Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 ] 12+ nodes, each linked to 12 carboxylates of terephthalate ligands to form tetrahedral and octahedral cages; however, there are many defects from missing linkers in this MOF, with the resulting otherwise open metal sites occupied by hydroxo ligands. 18−20 The node topology of NU-1000 has been determined to be [Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (OH) 4 (OH 2 ) 4 ] 8+ , 21 and it is coordinated to eight tetratopic linkers of 1,3,6,8-tetrakis(p-benzoic-acid)pyrene (H 4 TBAPy) to form triangular and hexagonal pores. We used Ir(CO) 2 (acac) (acac = acetylacetonate) and Ir(C 2 H 4 ) 2 (acac) as precursors to react with functional groups such as OH on the nodes of NU-1000 and UiO-66, accompanied by removal of the acac ligands.…”

Zirconium-containing metal organic frameworks as solid acid catalysts for the esterification of free fatty acids: Synthesis of biodiesel and other compounds of interest

“…In recent years, Metal-Organic Frameworks (MOFs) have attracted much interest for their potential as heterogeneous catalysts [5][6][7][8][9]. MOFs are crystalline porous solids formed by the linkage of metal ions or metal-oxo clusters and polydentate organic linkers, forming three dimensional networks defining strictly regular nanometric pore channels and cavities similar to those found in zeolites.…”

Conversion of levulinic acid into chemicals: Synthesis of biomass derived levulinate esters over Zr-containing MOFs

“…In recent years, Metal-Organic Frameworks (MOFs) have attracted much interest due to their potential as heterogeneous catalysts (Corma et al, 2010a;Farrusseng et al, 2009;Garcia-Garcia et al, 2014;Gascon et al, 2014;Lee et al, 2009;Llabrés i Xamena and Gascon, 2013). MOFs are crystalline porous solids formed by the linkage of metal ions or metal-oxo clusters and polydentate organic linkers, forming three dimensional networks defining regular nanometric pore channels and cavities similar to those found in zeolites.…”