Cooperative Crystallization of Heterometallic Indium–Chromium Metal–Organic Polyhedra and Their Fast Proton Conductivity

Zhai, Quan‐Guo; Mao, Chengyu; Zhao, Xiang; Lin, Qipu; Bu, Fei; Chen, Xitong; Bu, Xianhui; Feng, Pingyun

doi:10.1002/anie.201503095

Cited by 147 publications

(70 citation statements)

References 65 publications

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“…This could be attributed to the threshold kinetic energy required for rapid release of the protons from the proton carriers. However, this is not a new phenomenon for MOF‐based materials exhibiting anhydrous proton conductivity in a wide range of temperatures starting from low temperature …”

Section: Resultsmentioning

confidence: 91%

Achieving Amphibious Superprotonic Conductivity in a Cu^I Metal–Organic Framework by Strategic Pyrazinium Salt Impregnation

Khatua

Bar

Sheikh

et al. 2017

Chemistry A European J

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Treatment of a pyrazine (pz)-impregnated Cu metal-organic framework (MOF) ([1⊃pz]) with HCl vapor renders an interstitial pyrazinium chloride salt-hybridized MOF ([1⊃pz⋅6 HCl]) that exhibits proton conductivity over 10 S cm both in anhydrous and under humid conditions. Framework [1⊃pz⋅6 HCl] features the highest anhydrous proton conductivity among the lesser-known examples of MOF-based materials exhibiting proton conductivity under both anhydrous and humid conditions. Moreover, [1⊃pz] and corresponding pyrazinium sulfate- and pyrazinium phosphate-hybridized MOFs also exhibit superprotonic conductivity over 10 S cm under humid conditions. The impregnated pyrazinium ions play a crucial role in protonic conductivity, which occurs through a Grotthuss mechanism.

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Section: Resultsmentioning

confidence: 91%

Achieving Amphibious Superprotonic Conductivity in a Cu^I Metal–Organic Framework by Strategic Pyrazinium Salt Impregnation

Khatua

Bar

Sheikh

et al. 2017

Chemistry A European J

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“…Aesthetic appeal, structural modularity and robustness pertaining to the MOCs showed great promise for diverse applications 31 . MOCs are neutral ( x = 0) or anionic ( x = n-, a -MOC) depending upon the charge balance between M n+ and L 32 .…”

Section: Introductionmentioning

confidence: 99%

Binder driven self-assembly of metal-organic cubes towards functional hydrogels

et al. 2018

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The process of assembling astutely designed, well-defined metal-organic cube (MOC) into hydrogel by using a suitable molecular binder is a promising method for preparing processable functional soft materials. Here, we demonstrate charge-assisted H-bonding driven hydrogel formation from Ga3+-based anionic MOC ((Ga8(ImDC)12)12−) and molecular binders, like, ammonium ion (NH4+), N-(2-aminoethyl)-1,3-propanediamine, guanidine hydrochloride and β-alanine. The morphology of the resulting hydrogel depends upon the size, shape and geometry of the molecular binder. Hydrogel with NH4+ shows nanotubular morphology with negative surface charge and is used for gel-chromatographic separation of cationic species from anionic counterparts. Furthermore, a photo-responsive luminescent hydrogel is prepared using a cationic tetraphenylethene-based molecular binder (DATPE), which is employed as a light harvesting antenna for tuning emission colour including pure white light. This photo-responsive hydrogel is utilized for writing and preparing flexible light-emitting display.

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“…State-of-the-art cells use Nafion-type membranes. [20][21][22][23][24][25] The proton conductivity of MOFs arises from guest molecules (acids, water molecules or clusters) 26,27 counterions (e.g. 5 Second, they are expensive, preventing large-scale commercial applications.…”

Section: Introductionmentioning

confidence: 99%

High proton conductivity in cyanide-bridged metal–organic frameworks: understanding the role of water

et al. 2015

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Supplementary Information (ESI) available: IR, PXRD, TGA and proton conductivity analysis for the as-synthesized NdMo−MOF and its activated forms at 80 °C, 130 °C and 150 °C, respectively. SeeWe investigate and discuss the proton conductivity properties of the cyanide-bridged metal-organic framework (MOF) [Nd(mpca)2Nd(H2O)6Mo(CN)8]·nH2O (where mpca is 5−methyl−2−pyrazinecarboxylate). This MOF is one of an exciting class of cyanide-bridged materials that can combine porosity with magnetism, luminescene, and proton conductivity. Specifically, we show that this material features highly hydrophilic open channels filled with water molecules. They enable a high proton conductivity, as much as 10 -3 S cm -1 . A rich hydrogen-bonding network, formed by the ligands' carboxylate groups with both coordinated and lattice water molecules, facilitates this high proton conductivity. Combined thermogravimetric studies, FTIR spectroscopy and PXRD analysis show that upon heating at 80 °C, the lattice water molecules are removed without any change in the framework. Further heating at 130 °C results in a partial removal of the coordinated water molecules, while still retaining the original framework. These activated MOFs shows an increasing conductivity from ~10 -9 S cm -1 to ~10 -3 S cm -1 when the relative humidity increases from 0% to 98%. Our studies show that the increase in proton conductivity is correlated with the re-hydration of the framework with lattice water molecules. The Arrhenius activation energy for the proton conductivity process is low (Ea = 37 kJ·mol -1 ), indicating that the protons "hop" through the channels following the Grotthuss mechanism. The fact that this MOF is remarkably stable both under high humidity conditions and at relatively high temperatures (up to 130 °C) makes it a good candidate for real-life applications.

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Cooperative Crystallization of Heterometallic Indium–Chromium Metal–Organic Polyhedra and Their Fast Proton Conductivity

Cited by 147 publications

References 65 publications

Achieving Amphibious Superprotonic Conductivity in a Cu^I Metal–Organic Framework by Strategic Pyrazinium Salt Impregnation

Achieving Amphibious Superprotonic Conductivity in a Cu^I Metal–Organic Framework by Strategic Pyrazinium Salt Impregnation

Binder driven self-assembly of metal-organic cubes towards functional hydrogels

High proton conductivity in cyanide-bridged metal–organic frameworks: understanding the role of water

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Cooperative Crystallization of Heterometallic Indium–Chromium Metal–Organic Polyhedra and Their Fast Proton Conductivity

Cited by 147 publications

References 65 publications

Achieving Amphibious Superprotonic Conductivity in a CuI Metal–Organic Framework by Strategic Pyrazinium Salt Impregnation

Achieving Amphibious Superprotonic Conductivity in a CuI Metal–Organic Framework by Strategic Pyrazinium Salt Impregnation

Binder driven self-assembly of metal-organic cubes towards functional hydrogels

High proton conductivity in cyanide-bridged metal–organic frameworks: understanding the role of water

Contact Info

Product

Resources

About

Achieving Amphibious Superprotonic Conductivity in a Cu^I Metal–Organic Framework by Strategic Pyrazinium Salt Impregnation

Achieving Amphibious Superprotonic Conductivity in a Cu^I Metal–Organic Framework by Strategic Pyrazinium Salt Impregnation