Ligand substitution induced single-crystal-to-single-crystal transformations in two Ni(<scp>ii</scp>) coordination compounds displaying consequential changes in proton conductivity

Li, Rong-Yun; Liu, Hou-Ting; Zhou, Chuan-Cong; Chu, Zhi-Tong; Lü, Jing; Wang, Suna; Jin, Juan; Yan, Wenfu

doi:10.1039/d0qi00088d

Cited by 35 publications

(19 citation statements)

References 62 publications

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“…8 In contrast, improving the proton conductivity of non-porous MOFs can be highly challenging due to limitations in their design to enable flexible chemical modification or doping. 15,16 Phase transition has been reported to be an effective approach to tune the property of flexible MOFs, 17 and this can be triggered by ligand substitution, 18 guest uptake, 19 or by changes in temperature 20 and/or pressure. 21 However, studies on the impact of single-crystal-to-singlecrystal (SCSC) transformations on proton conductivity in MOFs have been reported rarely.…”

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confidence: 99%

Enhanced proton conductivity in a flexible metal–organic framework promoted by single-crystal-to-single-crystal transformation

et al. 2021

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Enhanced proton conductivity in a flexible metal–organic framework promoted by single-crystal-to-single-crystal transformation

et al. 2021

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“…The proton conductivity was calculated using the equation: σ H+ = L /( RS ), where L is the distance between the silver electrodes, S is the surface area (cm 2 ) of the Ag electrode, and R is the resistance (Ω) of sample, which can be obtained from the AC impedance spectrum. The proton conductivity activation energy, E a can be obtained from the Arrhenius relation of σ T = σ 0 exp(− E a /( kT )), where σ 0 is the pre-exponent factor and k is Boltzmann constant …”

Section: Methodsmentioning

confidence: 99%

“…The proton conductivity activation energy, E a can be obtained from the Arrhenius relation of σ T = σ 0 exp(−E a /(kT)), where σ 0 is the pre-exponent factor and k is Boltzmann constant. 37 2.5. Measurement of Water Uptake and Swelling Ratio.…”

Section: Preparation Of Tb-mof/nafion Composite Membranesmentioning

confidence: 99%

Enhancing Proton Conductivity of Nafion Membrane by Incorporating Porous Tb-Metal–Organic Framework Modified with Nitro Groups

et al. 2022

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A rigid carboxylate ligand with a nitro functional group was selected to coordinate with Tb(III) cation, and Tb-MOF ({[Tb 4 (L) 4 (OH) 4 (H 2 O) 3 ]•8H 2 O} n , H 2 L = 2-nitroterephthalic acid) with large porous and excellent hydrophilicity was obtained successfully. The obtained Tb-MOF was filled into the Nafion matrix to improve its proton conduction performance. The Tb-MOF/ Nafion composite membrane was characterized by PXRD, IR, and thermogravimetry (TG) and for water uptake, area swelling, and proton conductivity. The activity energy, E a , value of the composite membrane, which is a very important factor affecting the proton conduction performance of the membrane, was fitted and calculated. It was revealed that Tb-MOF can improve the proton conductivities of composite membranes, and the improvement degree and E a value were both affected by Tb-MOF content. When Tb-MOF content was 5%, the proton conductivity of the composite membrane was 1.53 × 10 −2 S•cm −1 at 100% RH and 80 °C, which is 1.81 times that of the pure Nafion membrane. A MOF containing a nitro functional group was first doped into Nafion in this study and exhibited excellent performance for improving composite membrane proton conductivity. This study will provide a valuable reference for designing different functionalized MOFs to promote the proton conductivities of proton exchange membranes.

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“…The dissociation of the original ligands and the coordination of the new ligands render entry of ligands into the cavity and exit of the ligands from the cavity more frequent. Because the structure of the ligand is larger than the central metal, the skeleton vibrates to a greater extent and the cavity is fully opened, which can cause an accessible environment for proton transport. − …”

Section: Introductionmentioning

confidence: 99%

High Proton Conductivity in Nafion/Ni-MOF Composite Membranes Promoted by Ligand Exchange under Ambient Conditions

et al. 2021

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Metal−organic frameworks (MOFs) have appeared to be promising competitive candidates as crystalline porous materials for proton conduction. Explorations of the method of preparation of proton conductive MOFs and the proton transfer mechanism have enabled them to attract widespread attention, and tremendous efforts have been made to improve the proton conductivity of MOFs. On the basis of our previous work, we explicitly propose that ligand exchange can upgrade the proton conduction performance of MOFs. Using MOF-azo as the precursor, the proton conductivities of exchange products MOF-bpy and MOF-bpe increase by 3.5-and 2.8-fold, respectively. After the MOFs had been doped into the Nafion matrix to prepare composite membranes, the proton conduction performance of composite membranes filled with subproducts (2.6 × 10 −2 and 1.95 × 10 −2 S cm −1 ) is significantly better than that of a composite membrane filled with a parent product (1.12 × 10 −2 S cm −1 ) under ambient conditions (without heating or humidifying). The ligand exchange strategy presented herein demonstrates great promise for the development of high-proton conductivity MOFs and MOF composites with expanded future applications.

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Ligand substitution induced single-crystal-to-single-crystal transformations in two Ni(ii) coordination compounds displaying consequential changes in proton conductivity

Abstract: Two Ni(ii) coordination compounds can reversibly SC–SC transform into each other induced by ligand substitution, causing changes in their proton conductivities.

Cited by 35 publications

References 62 publications

Enhanced proton conductivity in a flexible metal–organic framework promoted by single-crystal-to-single-crystal transformation

Enhanced proton conductivity in a flexible metal–organic framework promoted by single-crystal-to-single-crystal transformation

Enhancing Proton Conductivity of Nafion Membrane by Incorporating Porous Tb-Metal–Organic Framework Modified with Nitro Groups

High Proton Conductivity in Nafion/Ni-MOF Composite Membranes Promoted by Ligand Exchange under Ambient Conditions

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