Heterogenization of Homogeneous Catalysts in Metal–Organic Frameworks via Cation Exchange

Abstract

This paper describes the heterogenization of single-site transition-metal catalysts in metal-organic frameworks (MOFs) via cation exchange. A variety of cationic complexes of Pd, Fe, Ir, Rh, and Ru have been incorporated into ZJU-28, and the new materials have been characterized by optical microscopy, inductively coupled plasma optical emission spectroscopy, and powder X-ray diffraction. MOF-supported [Rh(dppe)(COD)]BF4 catalyzes the hydrogenation of 1-octene to n-octane. The activity of this supported catalyst compares favorably to its homogeneous counterpart, and it can be recycled at least four times. Overall, this work provides a new and general approach for supporting transition-metal catalysts in MOFs.

Metal–organic frameworks containing N-heterocyclic carbenes and their precursors

“…Notwithstanding the fact that NHC complexes have efficient and wide catalytic applications, these catalysts are mainly homogeneous in nature. One of the ways of heterogenizing these catalysts is by the use of azolium-based linkers for the synthesis of the frameworks, followed by postsynthetic modification (PSM) by tethering a metal to the carbene carbons [6]. Alternatively, NHC complexes can be used as linkers for the synthesis of MOFs.…”

Facile TEMPO Immobilization onto Poly(acrylic acid)-Modified Magnetic Nanoparticles: Preparation and Property

“…Recently, different types of catalyst support materials such as polymer supports [4][5][6][7][8][9][10], ionic liquid supports [10][11][12], inorganic supports [13][14][15][16][17][18], metal organic frame supports [19], and nanocomposite supports [20][21][22] have been invented for immobilizing catalysts on beads, surfaces, and membranes, and so forth [23]. Of these, magnetic iron oxide nanocomposites have been the most widely used support material [2] because they offer enormous surface area with more binding sites; this reduces the disadvantages of heterogeneous catalysis [24].…”

Oxidative cross-dehydrogenative coupling of amines and α-carbonyl aldehydes over heterogeneous Cu-MOF-74 catalyst: A ligand- and base-free approach

“…Metal-organic frameworks (MOFs), a new class of crystalline porous materials, have recently exhibited potential applications in a variety of areas, including energy technologies, gas storage, gas separation, sensors, optics, biomedicine, and catalysis [13][14][15][16][17]. The combination of organic linkers and metal-connecting points in the framework leads to several interesting properties for MOFs, such as high surface areas, high porosity, well-defined structures, structural diversity, and the ability to tune the pore size as well as the surface hydrophobicity/hydrophilicity [13,14,[18][19][20][21][22][23][24][25].…”