Hybrid Nafion Membranes of Ionic Hydrogen-Bonded Organic Framework Materials for Proton Conduction and PEMFC Applications

Xu, Xiaoqian; Cao, Li‐Hui; Yang, Yan; Fang, Zhao; Bai, Xiang-Tian; Zang, Shuang‐Quan

doi:10.1021/acsami.1c15748

Cited by 51 publications

(47 citation statements)

References 50 publications

(62 reference statements)

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“…For example, tecton pairs based on charge-assisted mixed ligands mainly include ammonium-carboxylate ( Amm-C ), ,, ammonium-sulfonate ( Amm-S ), ,− amidinium-carboxylate ( Ami-C ), ,− amidinium-sulfonate ( Ami-S ), imidazolium-carboxylate ( I-C ), ,− imidazolium-sulfonate ( I-S ), pyridinium-carboxylate ( Py-C ), − pyridinium-sulfonate ( Py-S ), , guanidium-sulfonate ( G-S ), − or diaminotriazinium/sulfonate ( D-S ) pairs (Figure ). HOFs assembled with these charge-assisted H-bonding interactions typically show improved thermal and chemical stabilities (Table ).…”

Section: Design Rules Of Stable Hofsmentioning

confidence: 99%

Design Rules of Hydrogen-Bonded Organic Frameworks with High Chemical and Thermal Stabilities

et al. 2022

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Hydrogen-bonded organic frameworks (HOFs), self-assembled from strategically pre-designed molecular tectons with complementary hydrogen-bonding patterns, are rapidly evolving into a novel and important class of porous materials. In addition to their common features shared with other functionalized porous materials constructed from modular building blocks, the intrinsically flexible and reversible H-bonding connections endow HOFs with straightforward purification procedures, high crystallinity, solution processability, and recyclability. These unique advantages of HOFs have attracted considerable attention across a broad range of fields, including gas adsorption and separation, catalysis, chemical sensing, and electrical and optical materials. However, the relatively weak H-bonding interactions within HOFs can potentially limit their stability and potential use in further applications. To that end, this Perspective highlights recent advances in the development of chemically and thermally robust HOF materials and systematically discusses relevant design rules and synthesis strategies to access highly stable HOFs.

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Section: Design Rules Of Stable Hofsmentioning

confidence: 99%

Design Rules of Hydrogen-Bonded Organic Frameworks with High Chemical and Thermal Stabilities

et al. 2022

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“…Metal–organic frameworks (MOFs) have attracted much attention because of their extensive applications. − Especially, more and more researchers are interested in MOFs as proton conductors in recent years. − In order to enhance the σ H+ of MOFs, researchers usually fill MOF pores with proton carriers, such as NH 4 + or H 2 O, as guest molecules, expecting to form rich hydrogen bond networks between guest molecules and host framework, providing pathways for proton conduction. The second strategy commonly used to improve MOF proton conductivities is to use substituents, such as −SO 3 H and −COOH, to modify rigid ligands, expecting to form hydrophilic channels and facilitate proton transfer . Up to now, although many obtained MOFs exhibited high σ H+ , their realistic applications in PEMs have been hampered because of their brittleness, low processability, and large grain boundary resistance.…”

Section: Introductionmentioning

confidence: 99%

“…The second strategy commonly used to improve MOF proton conductivities is to use substituents, such as −SO 3 H and −COOH, to modify rigid ligands, expecting to form hydrophilic channels and facilitate proton transfer. 22 to now, although many obtained MOFs exhibited high σ H+ , their realistic applications in PEMs have been hampered because of their brittleness, low processability, and large grain boundary resistance.…”

Section: Introductionmentioning

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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“…Nowadays, HOFs have several applications: for example, in gas separation and storage [43,44,[56][57][58][59][60][61][62][63][64], heterogeneous catalysis [65][66][67], biomedicine [68,69], and proton conduction [70][71][72][73][74]. In addition, they have been proposed for photonic applications [54] such as sensing [75][76][77][78][79][80][81][82][83], photocatalysis [84,85], biomedicine [86], and optoelectronics [87].…”

Section: Introductionmentioning

confidence: 99%

HOFs Built from Hexatopic Carboxylic Acids: Structure, Porosity, Stability, and Photophysics

Nunzio

Suzuki

Hisaki

et al. 2022

IJMS

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Hydrogen-bonded organic frameworks (HOFs) have attracted renewed attention as another type of promising candidates for functional porous materials. In most cases of HOF preparation, the applied molecular design principle is based on molecules with rigid π-conjugated skeleton together with more than three H-bonding groups to achieve 2D- or 3D-networked structures. However, the design principle does not always work, but results in formation of unexpected structures, where subtle structural factors of which we are not aware dictate the entire structure of HOFs. In this contribution, we assess recent advances in HOFs, focusing on those composed of hexatopic building block molecules, which can provide robust frameworks with a wide range of topologies and properties. The HOFs described in this work are classified into three types, depending on their H-bonded structural motifs. Here in, we focus on: (1) the chemical aspects that govern their unique fundamental chemistry and structures; and (2) their photophysics at the ensemble and single-crystal levels. The work addresses and discusses how these aspects affect and orient their photonic applicability. We trust that this contribution will provide a deep awareness and will help scientists to build up a systematic series of porous materials with the aim to control both their structural and photodynamical assets.

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Hybrid Nafion Membranes of Ionic Hydrogen-Bonded Organic Framework Materials for Proton Conduction and PEMFC Applications

Cited by 51 publications

References 50 publications

Design Rules of Hydrogen-Bonded Organic Frameworks with High Chemical and Thermal Stabilities

Design Rules of Hydrogen-Bonded Organic Frameworks with High Chemical and Thermal Stabilities

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

HOFs Built from Hexatopic Carboxylic Acids: Structure, Porosity, Stability, and Photophysics

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