Metal@MOF: Loading of Highly Porous Coordination Polymers Host Lattices by Metal Organic Chemical Vapor Deposition

Abstract

Standing out from the vast majority of metal organic coordination polymers is the class of highly porous basic zinc carboxylates developed by Yaghi and co-workers.[1] Its prototype is MOF-5 (MOF = metal organic framework), in which {Zn 4 O} building blocks are linked together by terephthalate bridges to form a zeolite-like, cubic framework.[2] The extremely high specific surface area [2] of up to 4500 m 2 g À1 and a pore volume of 0.69 cm 3 cm À3 (for MOF-177), which has not been surpassed by any other crystalline substance, and thermal stability (up to 350 8C) opens up fascinating perspectives for the supramolecular host-guest chemistry.[3] Applications for these materials in miniaturized fuel cells and convenient gas-storage devices (for H 2 , CH 4 ), as gas sensors and for gas separation, as catalyst materials, and also for molecular electronics are emerging. [4] A report on the quantitative inclusion of C 60 and large polycyclic dye molecules (e.g. Astrazon Orange R) into the cavities of MOF-177 single crystals attracted our attention. [5] Could these MOF host lattices also be suitable to efficiently and selectively absorb typical metal organic chemical vapor deposition (CVD) precursors, provided these were volatile (gas absorption) or very soluble in nonpolar hydrocarbons and had matching size and shape to fit into the cavity? The release of the metal atoms of the precursors imbedded in the

Estudos espectroscópicos e estruturais dos polímeros de coordenação 2D, ∞[Tb(DPA)(HDPA)] e ∞[Gd(DPA)(HDPA)]

“…A maioria dos trabalhos recém publicados é referente ao emprego de metais de transição na construção de redes de coordenação, [10][11][12] enquanto os sistemas com lantanídeos são muito menos estudados. [12][13][14] Os lantanídeos possuem propriedades espectroscópicas peculiares, como tempo de vida longo e bandas de emissão finas e bem definidas.…”

Recent advances on simulation and theory of hydrogen storage in metal–organic frameworks and covalent organic frameworks

“…157 The clustering of transition metals in MOFs was also experimentally proven. 161,162 This clustering of exposed metal atoms could be prevented by using another organic linker such as [(Bipydc)M(CO) 4 ] 2À (Bipydc = 2,2 0 -bipyridine-5,5 0 -dicarboxylate) which is shown in Fig. 9(a).…”

One-potN-alkylation of primary amines to secondary amines by gold clusters supported on porous coordination polymers

“…It is worth noting that Au clusters supported on Al-MIL53 could promote the one-pot N-alkylation of 4 with 5 under inert atmosphere without O 2 and H 2 to produce 7 in the co-presence of base (entry 5), whereas Au NPs on CPL-2 and on MOF-5 could not (entry 7,8). It can be assumed that hydrogen atoms generated by the dehydrogenation of 4 are used for the hydrogenation of 6 to give 7.…”

“…Porous coordination polymers (PCPs) with highly ordered nanometer-sized porous structures have been attracting growing interests as supports for metal clusters smaller than 2 nm in diameter (7)(8)(9)(10)(11). It has been reported that Pd (7,8), Cu (7), Ru (9) clusters in the range of 1-3 nm could be deposited on or in PCPs by chemical vapor deposition (CVD) whereas Au clusters with diameters of smaller than 2 nm had been hardly obtained by CVD because of the weak interactions of Au with PCP frameworks (7).…”

“…It has been reported that Pd (7,8), Cu (7), Ru (9) clusters in the range of 1-3 nm could be deposited on or in PCPs by chemical vapor deposition (CVD) whereas Au clusters with diameters of smaller than 2 nm had been hardly obtained by CVD because of the weak interactions of Au with PCP frameworks (7). Recently, we have developed a new deposition technique that enables the deposition of Au as clusters on PCPs and have found that the supported Au clusters and Au NPs smaller than 5 nm are catalytically active for the aerobic oxidation of alcohols (10).…”