Enhanced H2 adsorption enthalpy in the low-surface area, partially fluorinated coordination polymer Zn5(triazole)6(tetrafluoroterephthalate)2(H2O)2·4H2O

Hulvey, Zeric; Falcão, Eduardo H.L.; Eckert, Juergen; Cheetham, Anthony K.

doi:10.1039/b900879a

Cited by 81 publications

(64 citation statements)

References 32 publications

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“…48 The polar C-F bond may be useful for a preferable gas adsorption site. Cheetham and colleagues 9 Fluorine-functionalized MOFs/PCPs S Noro and T Nakamura (Figure 3a). This MOF had a small pore and fluorine atoms exposed on the pore surface (Figure 4a), which was expected to cause high enthalpy of H 2 adsorption (-8 kJ mol − 1 at low coverage, Figure 4b), comparable to MOFs with coordinatively unsaturated metal centers that considerably increase this value.…”

Section: Mofs Containing Fluorine-and Trifluoromethyl-substituted Orgmentioning

confidence: 99%

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

2017

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Fluorine, the element with the highest electronegativity and low electric polarizability, can produce a variety of characteristics, including specific adsorption sites for molecules as well as flexibility to the host materials. In this review, we will introduce fluorine-functionalized metal-organic frameworks/porous coordination polymers that show unique and unprecedented structures, structural transformations, and gas and vapor adsorption/separation properties derived from the fluorine characteristics. NPG Asia Materials (2017) 9, e433; doi:10.1038/am.2017.165; published online 29 September 2017 INTRODUCTIONDuring the last two decades, metal-organic frameworks (MOFs)/ porous coordination polymers (PCPs) composed of metal ions and organic bridging ligands as main building units and, in some cases, inorganic ligands, have been investigated extensively because of their versatile structural diversity, high structural controllability (pore size, shape, dimension, flexibility and surface environment), high crystallinity, and their potential porous properties/functionalities in a variety of research fields such as storage and separation, catalysis, drug delivery and sensing ability. 1-3 The porous properties of MOFs/PCPs can be finely tailored by not only chemical modification of organic ligands and judicious choice of components but also a variety of techniques such as solid solution formation, defect engineering, core-shell structure, crystal morphology and size control, and so on. For example, the appropriate combination of organic bridging ligands provided the Zn(II) MOF, [Zn 4 O(bte) 4/3 (bpdc)] (bte = 4,4′,4′′-[benzene-1,3,5-triyl-tris (ethyne-2,1-diyl)]tribenzoate, bpdc = biphenyl-4,4′-dicarboxylate), with ultra-high Brunauer-Emmett-Teller and Langmuir specific surface areas close to 6000 and 10 000 m 2 g − 1 , respectively. 4 Unlike porous inorganic zeolites and porous carbon materials, MOFs often give flexible structures. As coordination bonds, hydrogen bonds and van der Waals interactions that are used to assemble each component are weaker (bonding energies are 10~200 kJ mol − 1 ) than covalent and ionic bonds (200~1000 kJ mol − 1 ), reversible rotation, bending and breaking of these weaker bonds easily occurs, resulting in structural changes. One representative of flexible MOFs is [Cr(OH)(1,4-bdc)] (MIL-53(Cr), 1,4-bdc = 1,4-benzenedicarboxylate), in which local reorientation of the coordination bond triggered by guest adsorption/ desorption induced the structural transformation between narrow pore and large pore forms. 5 In addition, many MOFs show high crystallinity as with porous inorganic zeolites, which is advantageous for understanding deeply the structure-property relationship using single-crystal and powder X-ray diffraction techniques. For example, the unprecedented highly selective CO sorption from a CO/N 2 mixture, which is

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Section: Mofs Containing Fluorine-and Trifluoromethyl-substituted Orgmentioning

confidence: 99%

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

2017

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“…Structures containing many types of coordinating organic molecules have been synthesized [6], but the use of perfluorinated molecules or even partially-fluorinated molecules as ligands has been largely ignored to date. Recently, reports by ourselves and Omary have indicated that porous materials containing exposed fluorine atoms display interesting hydrogen storage properties [7][8][9]. There have also been examples of interesting luminescence and catalytic properties in lanthanide materials containing large trifluoromethyl-substituted ligands [10][11][12][13].…”

Section: Introductionmentioning

confidence: 99%

Structural Trends in Coordination Polymers Containing Perfluorinated Dicarboxylates and 4,4′‐Bipyridine

Hulvey

Ayala

Cheetham

2009

Zeitschrift anorg allge chemie

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A new family of coordination polymers has been synthesized using cobalt or zinc, 4,4′‐bipyridine (4,4′‐bpy), and the perfluorinated dicarboxylates tetrafluoroterephthalate (tftpa), tetrafluorophthalate (tfpha), tetrafluoroisophthalate (tfipa), and tetrafluorosuccinate (tfsuc). These materials form under similar conditions and all display similar octahedral metal coordination environments despite significant differences in their structures. The compounds M(4,4′‐bpy)(tftpa)(H2O)2 (M = Co, Zn) (1) and M(4,4′‐bpy)(tfpha)(H2O)2 (M = Co, Zn) (2) are two‐dimensional layered structures, whereas Co(4,4′‐bpy)(tfsuc)(H2O)2 (3) and M(4,4′‐bpy)(tfipa)(H2O)2 (M = Co, Zn) (4) display three‐dimensional connectivity built up from two types of interconnected chains.

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“…3a), was found to be porous with a rather modest surface area of 150 m 2 /g. The isosteric heat of adsorption 3 for hydrogen in this material was found to be as high as 8 kJ/mol over a considerable range of loadings, which is more than 50 % higher than that in a typical MOF (without F substitution). This result was convincingly supported by our inelastic neutron scattering data on this system obtained on the TOFTOF Spectrometer of the FRM-II reactor at the Technical University of Munich, Germany ( This line of investigation was logically continued to include the larger bipyridine-based ligands in combination with perfluorinated dicarboxylates in order to achieve significant porosity in these materials, and we were able to synthesize several phases incorporating the ligands 1,2-bis(4-pyridyl)ethane (bpa) and 1,3-bis(4-pyridyl)propane, the most interesting of which is a structure containing zinc 4 , 1,2-bis(4-pyridyl)ethane and tetrafluoroterephthalate (tftpa) (Fig.…”

Section: Summary Of Project Activitiesmentioning

confidence: 69%

“…We were successful in synthesizing a very large number of novel, previously unknown hybrid materials which incorporate fluorinated links. Only one of these compounds 3 (Fig. 3a), was found to be porous with a rather modest surface area of 150 m 2 /g.…”

Section: Summary Of Project Activitiesmentioning

confidence: 99%

Final Report

Eckert¹,

Cheetham²

2011

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Enhanced H2 adsorption enthalpy in the low-surface area, partially fluorinated coordination polymer Zn5(triazole)6(tetrafluoroterephthalate)2(H2O)2·4H2O

Abstract: A porous coordination polymer containing zinc, 1,2,4-triazolate, and tetrafluoroterephthalate displays a high physisorptive hydrogen adsorption enthalpy of 8 kJ/mol, as a result of fluorine atoms exposed to the pore surface and the structure's small pore size.

Cited by 81 publications

References 32 publications

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

Structural Trends in Coordination Polymers Containing Perfluorinated Dicarboxylates and 4,4′‐Bipyridine

Final Report

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