Hydrogen Storage in Microporous Metal-Organic Frameworks

Rosi, Nathaniel L.; Eckert, Juergen; Eddaoudi, Mohamed; Vodak, David T.; Kim, Jaheon; O’Keeffe, Michael; Yaghi, Omar M.

doi:10.1126/science.1083440

Cited by 4,592 publications

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“…The porosity, structure and functionality of the MOF can be tuned by varying the linkers (bridging ligands) and/or the metal centers. MOFs are promising materials for applications in gas adsorption 3,4 , separation 5 and catalysis 6,7,8 . By introducing catalytically active metal-connecting points or functional groups into the highly porous MOF structure, MOFs exhibit clear advantages in heterogeneous catalysis.…”

Section: Introductionmentioning

confidence: 99%

The coordinatively saturated vanadium MIL-47 as a low leaching heterogeneous catalyst in the oxidation of cyclohexene

Leus

Vandichel

Liu

et al. 2012

Journal of Catalysis

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A Metal Organic Framework, containing coordinatively saturated V +IV sites linked together by terephthalic linkers (V-MIL-47) is evaluated as a catalyst in the epoxidation of cyclohexene. Different solvents and conditions are tested and compared. If the oxidant TBHP is dissolved in water, a significant leaching of V-species into the solution is observed and also radical pathways are 2 prominently operative leading to the formation of an adduct between the peroxide and cyclohexene. If however the oxidant is dissolved in decane, leaching is negligible and the structural integrity of the V-MIL-47 is maintained during successive runs. The selectivity towards the epoxide is very high in these circumstances. Extensive computational modelling is performed to show that several reaction cycles are possible. EPR and NMR measurements confirm that at least two parallel catalytic cycles are co-existing: one with V +IV sites and one with pre-oxidized V +V sites, and this in complete agreement with the theoretical predictions.

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Section: Introductionmentioning

confidence: 99%

The coordinatively saturated vanadium MIL-47 as a low leaching heterogeneous catalyst in the oxidation of cyclohexene

Leus

Vandichel

Liu

et al. 2012

Journal of Catalysis

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“…Th ough the electrode materials typically used in modern batteries, such as the lithium-ion and metal hydride / nickel systems, are carbon, metal oxides, oxyfl uorides, or alloys, metal -organic-framework (MOF) structures are attractive candidates because they are host structures with tunable, open channels that allow rapid insertion of species such as hydrogen 7,8 . Recently, some MOFs such as [Fe III (OH) 0.8 F 0.2 (O 2 CC 6 H 4 CO 2 )] · H 2 O have been shown to undergo reversible electrochemical reactions with lithium ions, but only at low rates for a small number of cycles 9 .…”

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confidence: 99%

Copper hexacyanoferrate battery electrodes with long cycle life and high power

2011

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Short-term transients, including those related to wind and solar sources, present challenges to the electrical grid. Stationary energy storage systems that can operate for many cycles, at high power, with high round-trip energy effi ciency, and at low cost are required. Existing energy storage technologies cannot satisfy these requirements. Here we show that crystalline nanoparticles of copper hexacyanoferrate, which has an ultra-low strain open framework structure, can be operated as a battery electrode in inexpensive aqueous electrolytes. After 40,000 deep discharge cycles at a 17 C rate, 83 % of the original capacity of copper hexacyanoferrate is retained. Even at a very high cycling rate of 83 C, two thirds of its maximum discharge capacity is observed. At modest current densities, round-trip energy effi ciencies of 99 % can be achieved. The low-cost, scalable, room-temperature co-precipitation synthesis and excellent electrode performance of copper hexacyanoferrate make it attractive for largescale energy storage systems.

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“…1,2 Recently, the catalytic applications of MOFs have been reviewed by Hupp et al and Farrusseng et al 3,4 However, catalytic reaction mechanisms in metal organic frameworks and in particular at saturated coordinated centres are still poorly understood.…”

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confidence: 99%

The remarkable catalytic activity of the saturated metal organic framework V-MIL-47 in the cyclohexene oxidation

et al. 2010

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The remarkable catalytic activity of the saturated metal organic framework MIL-47 in the epoxidation of cyclohexene is elucidated by means of both experimental results and theoretical calculations.Metal organic frameworks (MOFs) are crystalline porous solids composed of a three-dimensional network of metal ions held in place by multidentate organic molecules. 1,2 Recently, the catalytic applications of MOFs have been reviewed by Hupp et al. and Farrusseng et al. 3,4 However, catalytic reaction mechanisms in metal organic frameworks and in particular at saturated coordinated centres are still poorly understood.In this study, we describe the high catalytic activity of a coordinative saturated V-MOF in the liquid phase oxidation of cyclohexene. The metal organic framework MIL-47 consists of a porous terephthalate framework built from infinite chains of V 4+ O 6 octahedra and has a three-dimensional orthorhombic structure that exhibits large pores. 5 Every structure unit in MIL-47 contains an O-V +IV -O bridge. The linkage of the V +IV to dicarboxylate groups of the terephthalate linkers results in an octahedral structure unit. Hence each vanadium(+IV) centre is saturated.The selective oxidation of cyclohexene is particularly interesting as it can yield, depending on the catalyst and the reaction conditions, several products as shown in Scheme 1. In this study, the reaction was carried out with tert-butyl hydroperoxide (70 wt% TBHP in water) as oxidant and chloroform as solvent. The internal standard used was 1,2,4-trichlorobenzene. The molar ratios were chloroform : cyclohexene : TBHP : 1,2,4-trichlorobenzene = 462 : 1 : 2 : 1. The reaction temperature was kept constant at 323 K. Samples were taken out from the reaction mixture at certain times and analyzed by gas chromatography. Next, MIL-47 was compared with a homogeneous vanadium catalyst vanadyl acetylacetonate VO(acac) 2 . Prior to the reaction, all the catalysts were dried under vacuum. Blank tests were performed without catalyst and no cyclohexene conversion was observed. Fig. 1 depicts the cyclohexene conversion and the detailed product distributions for MIL-47 and the homogeneous VO(acac) 2 catalyst. In both reactions, we used an identical amount of V-sites (0.4 mmol, 0.095 g MIL-47 and 0.106 g VO(acac) 2 ). The four main reaction products formed are cyclohexene oxide 2, cyclohexane-1,2-diol 3, tert-butyl-2-cyclohexenyl-1-peroxide 4 and 2-cyclohexen-1-one 5. From these figures it can be seen that the homogeneous catalyst VO(acac) 2 and the MIL-47 show high reaction rates for the conversion of cyclohexene. The initial turnover frequencies considered at the first 20 min are 57 h À1 and 43 h À1 for the VO(acac) 2 and the MIL-47 respectively. Both catalysts showed an almost linear conversion rate during the first 2 h of reaction and finally topped out at 60% conversion. The turnover numbers calculated at the end of the reaction were 62 and 68 for VO(acac) 2 and MIL-47 respectively. Moreover, considering the product distributions, truly interesting similaritie...

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Hydrogen Storage in Microporous Metal-Organic Frameworks

Cited by 4,592 publications

References 19 publications

The coordinatively saturated vanadium MIL-47 as a low leaching heterogeneous catalyst in the oxidation of cyclohexene

The coordinatively saturated vanadium MIL-47 as a low leaching heterogeneous catalyst in the oxidation of cyclohexene

Copper hexacyanoferrate battery electrodes with long cycle life and high power

The remarkable catalytic activity of the saturated metal organic framework V-MIL-47 in the cyclohexene oxidation

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