High and Highly Anisotropic Proton Conductivity in Organic Molecular Porous Materials

Yoon, Minyoung; Suh, Kyungwon; Kim, Hyunuk; Kim, Yonghwi; Selvapalam, Narayanan; Kim, Kimoon

doi:10.1002/anie.201101777

Cited by 203 publications

(165 citation statements)

References 49 publications

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“…There are also recent studies that demonstrate new possibilities for porous solids (105)(106)(107)(108)(109)(110)(111)(112)(113)(114)(115) where the advantages over materials such zeolites are perhaps more clear-cut. For example, in battery and supercapacitor technologies, new porous solids (114) will be competing instead with materials such as graphite and graphene.…”

Section: Discussionmentioning

confidence: 95%

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Function-led design of new porous materials

Slater

Cooper

2015

Science

1,380

918

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Porous solids are important as membranes, adsorbents, catalysts, and in other chemical applications. But for these materials to find greater use at an industrial scale, it is necessary to optimize multiple functions in addition to pore structure and surface area, such as stability, sorption kinetics, processability, mechanical properties, and thermal properties. Several different classes of porous solids exist, and there is no one-size-fits-all solution; it can therefore be challenging to choose the right type of porous material for a given job. Computational prediction of structure and properties has growing potential to complement experiment to identify the best porous materials for specific applications.

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Section: Discussionmentioning

confidence: 95%

“…Porous frameworks (108)(109)(110), porous molecular solids (111), and zeolites (112) all show promise as proton conductors. Porous COFs (105)(106)(107) and MOFs (113) have potential in organic electronics, and porous conjugated microporous polymers are promising supercapacitors (114).…”

Section: Other Specific Functionsmentioning

confidence: 99%

Function-led design of new porous materials

Slater

Cooper

2015

Science

1,380

918

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“…demonstrated the effectiveness of such materials for gas sorption and separation applications . Very recently, HOF materials have been explored for their potential usage in proton‐conduction applications . The inherent aspect of hydrogen bonding in HOF materials could be utilized to create effective proton‐conduction pathways by suitably designing the material decorated with donor–acceptor Brønsted acid–base pairs.…”

Section: Intoductionmentioning

confidence: 99%

Metal–Organic Frameworks and Other Crystalline Materials for Ultrahigh Superprotonic Conductivities of 10⁻² S cm⁻¹ or Higher

Chand

Elahi

Pal

et al. 2019

Chemistry A European J

124

112

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Proton‐conducting materials in the solid state have received immense attention for their role as electrolytes in proton‐exchange membrane fuel cells. Recently, crystalline materials—metal–organic frameworks (MOFs), hydrogen‐bonded organic frameworks (HOFs), covalent organic frameworks (COFs), polyoxometalates (POMs), and porous organic crystals—have become an exciting research topic in the field of proton‐conducting materials. For a better electrolyte, a high proton conductivity on the order of 10−2 S cm−1 or higher is preferred as efficient proton transport between the electrodes is ultimately necessary. With an emphasis on design principles, this Concept will focus on MOFs and other crystalline solid‐based proton‐conducting platforms that exhibit “ultrahigh superprotonic” conductivities with values in excess of 10−2 S cm−1. While only a handful of MOFs exhibit such an ultrahigh conductivity, this quality in other systems is even rarer. In addition to interpreting the structural–functional correlation by taking advantage of their crystalline nature, we address the challenges and promising directions for future research.

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“…Similar behavior has been observed for solid forms of other calixarenes, 8,26,27,28,29,30,31,32,33,34,35,36 including partially solvated phases. 37 And over the past decade or so, several other classes of cage compounds exhibiting only 0D pores have been found to be dynamically porous toward gases, including hemicarcerands, 38 cucubit[n]urils, [39][40][41][42] organic and metalorganic macrocycles, 43,44 and discrete molecule cages. 45 All of these structures exhibit, from a static point of view, discrete, unconnected microcavities.…”

Section: Introductionmentioning

confidence: 99%

Many Simple Molecular Cavitands Are Intrinsically Porous (Zero-Dimensional Pore) Materials

et al. 2015

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The guest-free crystal forms of eight related small molecule cavitands (Scheme 1; simplified nomenclature: R,R',Y) are investigated as candidate discrete molecule microcavity materials (DMMMs). Due to their rigid bowl-like molecular structures, many cavitands are incapable of efficient crystal packing in pure form, yielding zero-dimensionally porous apohost phases. By molecular modifications that eschew self-inclusion, emphasis is placed on engineering structures that exhibit uniform microcavities that are large enough to accommodate small molecules of interest (e.g., gases or volatile organic compounds). The most thermodynamically stable guest-free crystal forms of several cavitands-namely, H,H,CH 2 , H,Me,CH 2 , α-Me,H,CH 2 , Me,Me,CH 2 , Br,Me,CH 2 , Me,Et,CH 2 , Me,Et,SiMe 2 , and Me,i-Bu,CH 2 -appear to be as-close-packed-as-possible, yet exhibit relatively large microcavities (or, zero-dimensional pores) in the range of 27-115 Å 3 . Where self-inclusion is ineffective, the microcavities predictably assimilate the intrinsic cavitand molecular cavity, yet the ultimate size and shape of cavities are also strongly influenced by crystal packing. It is demonstrated that some cavitand solvates, CH 2 Cl 2 @H,Me,CH 2 , xH 2 O@Me,Et,SiMe 2 , and CH 2 Cl 2 @Me,iBu,CH 2 (84:16 rccc:rcct) maintain host crystal packings that are equivalent to their empty, intrinsically porous phases and it is argued that the intrinsic pores of DMMMs are particularly suited to selective gas enclathration and/or storage. As a proof-ofconcept demonstrations, the porous phase of Me,Et,SiMe 2 is shown to capture and temporarily hold Freon-41 (fluoromethane, bp = -78 °C) at room temperature. A single crystal of empty Me,Et,SiMe 2 is shown to uptake CO 2 gas at room temperature, allowing structure determination of xCO 2 @Me,Et,SiMe 2 , and single-crystal-to-single-crystal dehydration of xH 2 O@Me,Et,SiMe 2 demonstrates its permeability to water.

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High and Highly Anisotropic Proton Conductivity in Organic Molecular Porous Materials

Cited by 203 publications

References 49 publications

Function-led design of new porous materials

Function-led design of new porous materials

Metal–Organic Frameworks and Other Crystalline Materials for Ultrahigh Superprotonic Conductivities of 10⁻² S cm⁻¹ or Higher

Many Simple Molecular Cavitands Are Intrinsically Porous (Zero-Dimensional Pore) Materials

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High and Highly Anisotropic Proton Conductivity in Organic Molecular Porous Materials

Cited by 203 publications

References 49 publications

Function-led design of new porous materials

Function-led design of new porous materials

Metal–Organic Frameworks and Other Crystalline Materials for Ultrahigh Superprotonic Conductivities of 10−2 S cm−1 or Higher

Many Simple Molecular Cavitands Are Intrinsically Porous (Zero-Dimensional Pore) Materials

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Metal–Organic Frameworks and Other Crystalline Materials for Ultrahigh Superprotonic Conductivities of 10⁻² S cm⁻¹ or Higher