Mechanisms of hydrogen diffusion and conduction in DUO 2 AsO 4 ·4D 2 O as inferred from neutron diffraction evidence

Bernard, L.; Fitch, Andrew N.; Wright, A. F.; Fender, B. E. F.; Howe, Arthur T.

doi:10.1016/0167-2738(81)90292-7

Cited by 45 publications

(14 citation statements)

References 6 publications

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“…The activation energy ( E a ) of BIL25–BIL100, calculated by the Arrhenius equation, are 0.60, 0.76, and 0.76 eV, respectively. These values are higher than those of the typical hydrated proton conductors with H + transfer through a Grotthuss mechanism, such as Nafion ( E a =0.22 eV) and HUO 2 AsO 4 ⋅4 H 2 O ( E a =0.32 eV), but are comparable to that of the anhydrous proton conductors, such as 0.66 eV for [Zn(H 2 PO 4 ) 2 (HPO 4 )]⋅(H 2 dmbim) 2 , and 0.90 eV for Im@{Al( μ 2 ‐OH)(1,4‐bdc)} n (dmbim=5,6‐dimethylbenzimidazole; 1,4‐bdc=1,4‐benzenedicarboxylate) . The rate‐limiting step of the Grotthuss mechanism is the structural reorientation of the proton carrier after H + transfer, and thus the E a would automatically be higher for a larger molecule.…”

Section: Methodsmentioning

confidence: 76%

A Metal–Organic Framework Impregnated with a Binary Ionic Liquid for Safe Proton Conduction above 100 °C

Sun

Wen

Chen

et al. 2016

Chemistry A European J

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To develop proton-conducting materials under low-humidity conditions and at moderate working temperature still remains challenging for fuel-cell technology. Here, a new type of proton-conducting material, EIMS-HTFSA@MIL, which was prepared by impregnating the binary ionic liquid, EIMS-HTFSA (EIMS=1-(1-ethyl-3-imidazolium)propane-3-sulfonate; HTFSA=N,N-bis(trifluoromethanesulfonyl)amide), into a mesoporous metal-organic framework, MIL-101 ([Cr F(H O) O(BDC) ⋅n H O] (n≈0.25, BDC=1,4-benzenedicarboxylate)) is reported. By taking advantage of the ionic-liquid properties, such as high thermal stability, non-volatility, non-flammability, and low corrosivity, EIMS-HTFSA@MIL shows potential application as a safe electrolyte in proton conduction above 100 °C.

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Section: Methodsmentioning

confidence: 76%

A Metal–Organic Framework Impregnated with a Binary Ionic Liquid for Safe Proton Conduction above 100 °C

Sun

Wen

Chen

et al. 2016

Chemistry A European J

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“…Thet emperature dependence of the proton conductivity was measured at 93 %R Hu sing as ample (pelletized at 50 MPa) of CPM-103a to further probe the mechanism of proton conduction (Supporting Information, Figure S14). Figure 2c shows the Arrhenius plot of the proton conductivity.The activation energy (E a )was found to be 0.66 eV,which indicates that the mechanism of proton conduction is expected to be similar to that of the Grotthus mechanism, that is,p roton transport from Himdc 2À by re-forming hydrogen bonds between Himdc 2À and H 2 Og uest molecules.T he E a value is higher than some well-known hydrated proton conductors,s uch as PCMOF-5 (0.32 eV) [16] ,H UO 2 PO 4 ·H 2 O (0.32 eV) [17] and Nafion (0.22 eV); [18] but comparable to inorganic-organic hybrid highly proton-conductive materials,s uch as (NH 4 ) 2 (adipic acid)[Zn 2 (oxalate) 3 ]·3 H 2 O . .…”

Section: Methodsmentioning

confidence: 85%

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

et al. 2015

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Metal-organic polyhedra (MOPs) or frameworks (MOFs) based on Cr 3+ are notoriously difficult to synthesize, especially as crystals large enough to be suitable for characterization of the structure or properties.I ti sn ow shown that the co-existence of In 3+ and Cr 3+ induces arapid crystal growth of large single crystals of heterometallic In-Cr-MOPs with the [M 8 L 12 ]( M=In/Cr,L=dinegative 4,5-imidazole-dicarboxylate) cubane-like structure.W ith ah igh concentration of protons from 12 carboxyl groups decorating every edge of the cube and an extensive H-bonded network between cubes and surrounding H 2 Omolecules,the newly synthesized In-CrMOPs exhibit an exceptionally high proton conductivity (up to 5.8 10 À2 Scm À1 at 22.5 8 8Ca nd 98 %r elative humidity,s ingle crystal).Metal-organic frameworks (MOFs) [1] (or more generally coordination polymers,C Ps [2] )a nd hydrogen-bonded frameworks including recently developed hydrogen-bonded organic frameworks (HOFs) [3] have emerged as an ew promising class of materials that are capable of fast ion conductivity.T heir high crystallinity and open framework architecture,t ogether with tunable compositions and structures,m ake it possible to not only better design materials to optimize ion conduction carriers and pathways,but also better understand conducting behaviors and mechanisms. [4,5] Highly proton-conducting materials are essential in many applications,especially hydrogen fuel cells.F or MOF materials,r ecently reported strategies for enhancing the proton conductivity have focused on increasing the concentration of proton carriers by controlling framework or extra-framework compositions as well as on improving proton mobility by constructing materials with desired H-bonded networks.F or example,K itagawa et al. reported highly proton-conductive zinc oxalate MOFs by maximizing the proton carriers with the simultaneous introduction of adipic acid molecules on the framework and the counter cation (NH 4 ) + in the void space.[6]Another example is PCMOF2 1 = 2 reported by Shimizu et al. [7] which combined trisulfonate and triphosphonate groups and had conductivity over 0.01 Scm À1 . Thed esign strategy for the synthesis of MOFs can vary significantly depending on the intended applications.F or developing better proton conductors,t he conventional strategy targeting extended 1D,2D, or 3D frameworks may not always be desirable.T his is because ah igher dimensional structure generally requires ag reater degree of ligand deprotonation, which necessarily reduces the proton concentration. Forthis reason, we expect that discrete metal-organic polyhedra (MOPs) that can be formed through partial deprotonation of ligands might represent ap romising source of materials capable of improved fast proton conductivity. Thef inite polyhedral structures of MOPs provide an opportunity to decorate the entire surface with organic ligands that carry extra functional groups so that ahigher concentration of proton carriers can be achieved. Moreover,t he extensive hydrogen bonding ...

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“…The activation energy ( E a ) was found to be 0.66 eV, which indicates that the mechanism of proton conduction is expected to be similar to that of the Grotthus mechanism, that is, proton transport from Himdc 2− by re‐forming hydrogen bonds between Himdc 2− and H 2 O guest molecules. The E a value is higher than some well‐known hydrated proton conductors, such as PCMOF‐5 (0.32 eV)16, HUO 2 PO 4 ⋅H 2 O (0.32 eV)17 and Nafion (0.22 eV);18 but comparable to inorganic–organic hybrid highly proton‐conductive materials, such as (NH 4 ) 2 (adipic acid)[Zn 2 (oxalate) 3 ]⋅3 H 2 O (0.63 eV),6 In‐IA‐2D‐1(0.61 eV),19 and {[Ca( D ‐Hpmpc)(H 2 O) 2 ]⋅2 HO 0.5 } n /PVP composite (0.65 eV) 20…”

mentioning

confidence: 82%

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

et al. 2015

View full text Add to dashboard Cite

Metal-organic polyhedra (MOPs) or frameworks (MOFs) based on Cr(3+) are notoriously difficult to synthesize, especially as crystals large enough to be suitable for characterization of the structure or properties. It is now shown that the co-existence of In(3+) and Cr(3+) induces a rapid crystal growth of large single crystals of heterometallic In-Cr-MOPs with the [M8L12] (M=In/Cr, L=dinegative 4,5-imidazole-dicarboxylate) cubane-like structure. With a high concentration of protons from 12 carboxyl groups decorating every edge of the cube and an extensive H-bonded network between cubes and surrounding H2O molecules, the newly synthesized In-Cr-MOPs exhibit an exceptionally high proton conductivity (up to 5.8×10(-2) S cm(-1) at 22.5 °C and 98% relative humidity, single crystal).

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Mechanisms of hydrogen diffusion and conduction in DUO 2 AsO 4 ·4D 2 O as inferred from neutron diffraction evidence

Cited by 45 publications

References 6 publications

A Metal–Organic Framework Impregnated with a Binary Ionic Liquid for Safe Proton Conduction above 100 °C

A Metal–Organic Framework Impregnated with a Binary Ionic Liquid for Safe Proton Conduction above 100 °C

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

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

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