The current status of hydrogen storage in metal–organic frameworks—updated

Sculley, Julian P.; Yuan, Daqiang; Zhou, Hong‐Cai

doi:10.1039/c1ee01240a

Cited by 450 publications

(265 citation statements)

References 171 publications

(153 reference statements)

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“…Recently, a MOF denoted as either PCN-69 27 or NOTT-119 28 with the rht topology was synthesized by both the Zhou and Schroder groups. PCN-69/ NOTT-119 has a Brunauer−Emmett−Teller (BET) surface area of ∼4000 m 2 /g and is made from the phenyl-based strut LH 6 (1) (Scheme 1). Even though LH 6 (1) is longer than LH 6 (2), the strut used to make NOTT-112 26 (3800 m 2 /g), the surface area of PCN-69/NOTT-119 did not increase significantly.…”

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confidence: 99%

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Designing Higher Surface Area Metal–Organic Frameworks: Are Triple Bonds Better Than Phenyls?

et al. 2012

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ABSTRACT:We have synthesized, characterized, and computationally validated the high Brunauer−Emmett− Teller surface area and hydrogen uptake of a new, noncatenating metal−organic framework (MOF) material, NU-111. Our results imply that replacing the phenyl spacers of organic linkers with triple-bond spacers is an effective strategy for boosting molecule-accessible gravimetric surface areas of MOFs and related high-porosity materials.T he chemical and structural diversity of metal−organic frameworks (MOFs) is one of the most notable characteristics of these materials. MOFs are hybrid materials composed of inorganic nodes and organic struts. 1−3 The most intriguing examples exhibit large internal surface areas; ultralow densities; uniform channels, cavities, and voids; and permanent porosity. Because of these exceptional properties, MOFs are being investigated for many potential applications, including gas storage, 4−8 gas and chemical separations, 9−12 chemical catalysis, 13,14 sensing, 15 ion exchange, 16 drug delivery, 17 and light harvesting. 18,19 Furthermore, the availability of singlecrystal structures of MOFs allows the use of computational modeling to calculate guest adsorption capabilities and other properties, which can help in screening MOFs for particular applications and improving our understanding of their performance. 20 The fact that these computational methods can be usefully applied gives MOFs a significant advantage over their amorphous counterparts.Rising concerns about climate change have intensified the search for environmentally friendly and renewable fuels such as water-derived H 2 , cellulosic ethanol, and photo-or electrochemically generated methane. Although molecular hydrogen is a compelling alternative to gasoline in many respects, highdensity storage is a significant challenge for the viability of hydrogen-powered vehicles. In order to drive 300 miles, 5 to 13 kg of H 2 are needed. Therefore, technologies that can efficiently concentrate gases at lower pressures, such as adsorption on porous materials, are desirable. The U.S. Department of Energy (DOE) has set targets for on-board H 2 storage systems for the year 2017: 5.5 wt % in gravimetric capacity and 40 g/L of volumetric capacity at an operating temperature in the range −40 to 60°C under a maximum delivery pressure of 100 atm. 21 Recently, automobile manufacturer Mercedes-Benz has announced its intention to use MOFs for mobile hydrogen storage at cryogenic temperatures. 22 Required are materials with surface areas of ∼24 million square feet of surface area per pound (4900 m 2 /g) and the ability to store substantial hydrogen at 435 psi (30 bar). MOFs are powerful contenders relative to other porous materials in meeting these conditions.We set out to make a MOF that satisfies both of the aforementioned requirements (∼4900 m 2 /g and high hydrogen uptake at 30 bar). We turned our attention to (3,24)-paddlewheel-connected MOF networks (rht topology), 23 for which catenation (interpenetration or interweaving of multiple frameworks)...

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“…Thus, six linked alkynes would replace two linked phenyl groups. Given the synthetic challenge presented by the corresponding trigonal linker, however, we chose instead to start by replacing each phenyl spacer in LH 6 (1) by one carbon−carbon triple bond.…”

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Designing Higher Surface Area Metal–Organic Frameworks: Are Triple Bonds Better Than Phenyls?

et al. 2012

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“…MOFs have been of interest due to their applications in gas storage/separation and catalysis as well as their photoluminescence and magnetic and electrical properties. [20][21][22][23][24][25][26][27][28] Interest in ferroelectric and subsequently multiferroic MOFs stems from work by Okada and Sugie 29 who synthesized Cu(HCOO) 2 .4H 2 O and discovered it to be antiferroelectric, the first instance of such behavior in a MOF. Suzuki and Okada 30 subsequently showed that there may be a temperature range below this transition where the compound becomes ferrielectric.…”

Section: Introductionmentioning

confidence: 99%

Elastic relaxation behavior, magnetoelastic coupling, and order-disorder processes in multiferroic metal-organic frameworks

et al. 2012

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Resonant ultrasound spectroscopy has been used to analyze magnetic and ferroelectric phase transitions in two multiferroic metal-organic frameworks (MOFs) with perovskite-like structures [(CH 3 ) 2 NH 2 ]M(HCOO) 3 (DMA[M]F, M = Co, Mn). Elastic and anelastic anomalies are evident at both the magnetic ordering temperature and above the higher temperature ferroelectric transition. Broadening of peaks above the ferroelectric transition implies the diminishing presence of a dynamic process and is caused by an ordering of the central DMA ([(CH 3 ) 2 NH 2 ] + ) cation which ultimately causes a change in the hydrogen bond conformation and provides the driving mechanism for ferroelectricity. This is unlike traditional mechanisms for ferroelectricity in perovskites which typically involve ionic displacements. A comparison of these mechanisms is made by drawing on examples from the literature. Small elastic stiffening at low temperatures suggests weak magnetoelastic coupling in these materials. This behavior is consistent with other magnetic systems studied, although there is no change in Q −1 associated with magnetic order-disorder, and is the first evidence of magnetoelastic coupling in MOFs. This could help lead to the tailoring of MOFs with a larger coupling leading to magnetoelectric coupling via a common strain mechanism.

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“…In addition, their syntheses can be carried out under mild conditions, allowing for their rational design and facile pre-and post-synthetic modification. 2 While some MOFs display extraordinary high hydrogen uptake at cryogenic temperatures, as a result of the generally low enthalpy of hydrogen adsorption (ca. 2-8 kJ mol -1 ) 2-4 being considerably lower than the ideal adsorption enthalpy allowing for ambient-temperature hydrogen storage, 15-25 kJ mol -1 , 5,6 their hydrogen capacity is practically negligible near ambient conditions; a serious drawback for application.…”

Section: Introductionmentioning

confidence: 99%

Interplay of Linker Functionalization and Hydrogen Adsorption in the Metal–Organic Framework MIL-101

Szilágyi

Weinrauch

et al. 2014

J. Phys. Chem. C

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Functionalization of metal-organic frameworks results in higher hydrogen uptakes owing to stronger hydrogen-host interactions. However, it has not been studied whether a given functional group acts on existing adsorption sites (linker or metal) or introduces new ones. In this work, the effect of two types of functional groups on MIL-101 (Cr) is analyzed. Thermal-desorption spectroscopy reveals that the -Br ligand increases the secondary building unit's hydrogen affinity, while the -NH2 functional group introduces new hydrogen adsorption sites. In addition, a subsequent introduction of -Br and -NH2 ligands on the linker results in the highest hydrogenstore interaction energy on the cationic nodes. The latter is attributed to a push-and-pull effect of the linkers.

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The current status of hydrogen storage in metal–organic frameworks—updated

Cited by 450 publications

References 171 publications

Designing Higher Surface Area Metal–Organic Frameworks: Are Triple Bonds Better Than Phenyls?

Designing Higher Surface Area Metal–Organic Frameworks: Are Triple Bonds Better Than Phenyls?

Elastic relaxation behavior, magnetoelastic coupling, and order-disorder processes in multiferroic metal-organic frameworks

Interplay of Linker Functionalization and Hydrogen Adsorption in the Metal–Organic Framework MIL-101

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