Low temperature ionic conductor: ionic liquid incorporated within a metal–organic framework

Fujie, Kazuyuki; Otsubo, Kenji; Ikeda, Ryuichi; Yamada, Teppei; Kitagawa, Hiroshi

doi:10.1039/c5sc01398d

Cited by 205 publications

(165 citation statements)

References 46 publications

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“…Partial incorporation of ionic liquids with inorganic fluorinated anions into MOFs/PCPs is also effective for creating a fluorine-modified pore surface. 42 Finally, we anticipate that this review will attract much attention among not only MOF/PCP scientists but also many researchers involved in other scientific fields and provide opportunities to investigate new and/or reported fluorine-functionalized MOFs/PCPs towards future applications.…”

Section: Discussionmentioning

confidence: 99%

“…However, their Fluorine-functionalized MOFs/PCPs S Noro and T Nakamura ionic conductivity dramatically decreases below their freezing points. Kitagawa and colleagues 42 reported a low-temperature ionic conductor obtained by the incorporation of the ionic liquid, EMI-TSFA (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide) within the three-dimensional MOF, [Zn(MeIM) 2 ] (ZIF-8, HMeIM = 2-methylimidazole). The ionic conductivity of EMI-TSFA@ZIF-8 was higher than that of bulk EMI-TFSA below 250 K because there is no freezing transition of the nanosized ionic liquid formed in the restricted pore space.…”

Section: Fluorine-functionalized Mofs/pcpsmentioning

confidence: 99%

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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: Discussionmentioning

confidence: 99%

Section: Fluorine-functionalized Mofs/pcpsmentioning

confidence: 99%

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

2017

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“…EMI-TFSA (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide) IL was incorporated within the micropores of ZIF-8 (composed of Zn(MeIM) 2 ; H(MeIM) = 2-methylimidazole). Basically, a mixture of ZIF-8 powder and EMI-TFSA was heated and stored to enhance the diffusion of EMI-TFSA into ZIF-8 micropores through capillary action [137,138]. The advantage of the capillary action strategy is that it can be applied to various types of ILs and MOFs which don't have CUSs [29].…”

Section: Post Synthesis Methodsmentioning

confidence: 99%

“…In the third strategy, ILs are introduced into the pores of MOFs through capillary action [136][137][138]. EMI-TFSA (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide) IL was incorporated within the micropores of ZIF-8 (composed of Zn(MeIM) 2 ; H(MeIM) = 2-methylimidazole).…”

Section: Post Synthesis Methodsmentioning

confidence: 99%

Recent advances in the synthesis and applications of metal organic frameworks doped with ionic liquids for CO 2 adsorption

Cota

Martínez

2017

Coordination Chemistry Reviews

125

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“…Hybrid materials,i nw hich (EMI)[N-(CN) 2 ]w ith an adequate volumetric filling level (f) [31] at an interval of 12.5 %( f = 12.5, 25, 37.5, 50, 62.5, 75, 87.5, and 100 %) is impregnated into PCN-777, were prepared by grinding together in am ortar and annealed for capillary action [32,33] (see Experimental Details in Supporting Information).…”

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confidence: 99%

Superionic Conduction over a Wide Temperature Range in a Metal–Organic Framework Impregnated with Ionic Liquids

et al. 2019

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Most molecules in confined spaces showm arkedly different behaviors from those in the bulk. Large pores are composed of two regions:aninterface region in whichliquids interact with the pore surface,a nd ac ore region in which liquids behave as bulk. The realization of ahighly mobile ionic liquid (IL) in amesoporous metal-organic framework (MOF) is nowr eported. The hybrid shows ah igh room-temperature conductivity (4.4 10 À3 Scm À1 )a nd lowa ctivation energy (0.20 eV);b oth not only are among the best values reported for IL-incorporated MOFs but also are classified as as uperionic conductor.T he conductivity reaches over 10 À2 Scm À1 above3 43 Ka nd follows the Vogel-Fulcher-Tammann equation up to ca. 400 K. In particular,the hybrid is advantageous at low temperatures (< 263 K), where the ionic conduction is superior to that of bulk IL, making it useful as solid-state electrolytes for electrochemical devices operating over aw ide temperature range.

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Low temperature ionic conductor: ionic liquid incorporated within a metal–organic framework

Abstract: An ionic liquid incorporated into micropores of a metal–organic framework showed higher ionic conductivity than bulk ionic liquid at low temperature because of the absence of marked freezing transition.

Cited by 205 publications

References 46 publications

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

Recent advances in the synthesis and applications of metal organic frameworks doped with ionic liquids for CO 2 adsorption

Superionic Conduction over a Wide Temperature Range in a Metal–Organic Framework Impregnated with Ionic Liquids

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