40-Fold Enhanced Intrinsic Proton Conductivity in Coordination Polymers with the Same Proton-Conducting Pathway by Tuning Metal Cation Nodes

Su, Xuelian; Yao, Zizhu; Ye, Yingxiang; Zeng, Heng; Xu, Gang; Wu, Ling; Ma, Xiang; Chen, Qian-huo; Wang, Lihua; Zhang, Zhang-Jin; Xiang, Shengchang

doi:10.1021/acs.inorgchem.5b02686

Cited by 63 publications

(32 citation statements)

References 63 publications

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“…By contrast, the pellet sample showed a much better performance by at least one or two order of magnitude in conductivity. Compared to reported intrinsic proton conduction,[8g], [8t], [8u], these results clearly indicate the dominant extrinsic contribution to the overall proton conduction observed for the pellet sample. Similar results have been obtained in other MOFs …”

Section: Resultssupporting

confidence: 45%

Proton Transportation Behavior in Lanthanide Tartrate Metal‐Organic Frameworks

et al. 2019

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A series of lanthanide tartrate metal-organic frameworks (MOFs) were synthesized and structurally characterized. These include the three-dimensional (3D) frameworks {[Ln-(C 4 H 4 O 6 )(H 2 O) 3 ]Cl·2H 2 O} n (C 4 H 4 O 6 ), tartrate; Ln = La (1), Nd (2), and Pr (3) and the 2D framework {[Ce 2 (C 4 H 4 O 6 ) 3 (H 2 O) 5 ]·2.5H 2 O} n (4). Using compounds 3 and 4 as representatives, proton con- IntroductionMetal-organic frameworks (MOFs), a class of polymeric complexes built by metal ion/cluster nodes and organic linkers, have unique features such as long-range structural order, high crystallinity, and large surface area from the highly regular porous structures. MOF materials have attracted much interest due to their diverse and useful applications including for selective gas adsorption and separation, heterogeneous catalysis, sensory devices, electrical conductivity, magnetism, and drug delivery. [1][2][3][4][5][6] In the past decade, MOFs have also been studied for ion conduction, especially as proton conductors for potential applications in fuel cell technologies. [7][8][9][10][11] In this capacity, MOFs possess clear advantages over conventional proton conductors, such as organic polymers and inorganic solids. Specifically, organic polymer based proton conductors (e.g. Nafion) are always amorphous which suggest the low regularity in the polymeric structure. [12] As a result, determination of the pathway for proton conduction is difficult. Establishing the structure-property relationship, critical for the improvement of materials performance through informed synthesis, is thus a challenge. On the other hand, proton-conducting inorganic solids, such as metal oxides and perovskites, require high working temperature in the range of 400-1000°C despite their welldefined and long-range ordered structures. [10] Furthermore, the limited choices of metal ions and matching anions make tuning the structure and proton-conducting ability of the purely inor- [a]

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Section: Resultssupporting

confidence: 45%

Proton Transportation Behavior in Lanthanide Tartrate Metal‐Organic Frameworks

et al. 2019

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“…In these two complexes, proton conduction probably takes place via extensive hydrogen bonding (Grotthuss mechanism) and intergrain‐transport of surface adsorbed water molecules. Small differences in proton conductivity between the complexes 1 and 2 may be attributed to the different ionic radius of Zn II (74 pm) and Ni II (70 pm), and small differences in hydrogen bonding distances among the components of the complexes. The Nyquist plot at 80 °C and 98 % RH fitted with equivalent circuit model (Figure S11) indicates single phase of the materials.…”

Section: Resultsmentioning

confidence: 99%

“…Generally,m echanism of protonc onductioni sd educed from the activation energy but proton conductioni sac omplex phenomenon and so, in-depth analysis and other experimental evidences are required to establish the mechanism.I nt hese two complexes, protonc onduction probablyt akes place via extensive hydrogen bonding (Grotthuss mechanism) [11] and intergrain-transport of surfacea dsorbed water molecules. Small differences in protonc onductivity between the complexes 1 and 2 may be attributed to the different ionic radius of Zn II (74 pm) and Ni II (70 pm), [49] and small differences in hydrogen bondingd istances among the components of the complexes.T he Nyquist plot at 80 8Ca nd 98 %R Hf itted with equivalent circuit model ( Figure S11) indicates single phase of the materials. Purity of the complexes after the proton conductivity measurement has been verifiedb yt he PXRD analysis( Figure S7 and S8).…”

Section: Resultsmentioning

confidence: 99%

Proton‐Conducting Hydrogen‐Bonded 3D Frameworks of Imidazo‐Pyridine‐Based Coordination Complexes Containing Naphthalene Disulfonates in Rhomboid Channels

Garai

Kumar

Banerjee

et al. 2019

Chemistry An Asian Journal

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Coordination complexes of an olefinic molecule (PIP) containing pyridine and imidazopyridine moieties with ZnII/NiII metal salts were shown to exhibit appreciable proton conductivity. These complexes form 3D‐hydrogen bonded frameworks containing rhomboidal channels that are occupied by uncoordinated 1,5‐naphthalenedisulfonate (NDS). The extensive hydrogen bonding between the frameworks and NDS resulted in thermally stable and water‐insoluble materials. Irrespective of the metal atom present, both complexes exhibited moderate to high proton conduction in the range of 10−5 to 0.5×10−3 S cm−1 depending on the temperature and humidity levels.

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“…Until now, generally including four types (types I to IV) of strategies have been proposed to regulate the proton conductivity of crystalline porous materials. [ 34,35 ] As shown in Scheme 1, the simplest one (type I) is to generate proton carriers as counter ions, such as NH 4 + , H 3 O + , and Me 2 NH 2 + , into the pores of MOFs. [ 36–38 ] In type II, incorporating acidic functional groups (e.g., −SO 3 H, −PO 3 H 2 , −COOH, and −OH moieties) into the host framework to improve the proton concentration and mobility within the pore.…”

Section: Introductionmentioning

confidence: 99%

Metal–Organic Frameworks as a Versatile Platform for Proton Conductors

et al. 2020

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Metal–organic frameworks (MOFs) are an intriguing type of crystalline porous materials that can be readily built from metal ions or clusters and organic linkers. Recently, MOF materials, featuring high surface areas, rich structural tunability, and functional pore surfaces, which can accommodate a variety of guest molecules as proton carriers and to systemically regulate the proton concentration and mobility within the available space, have attracted tremendous attention for their roles as solid electrolytes in fuel cells. Recent advances in MOFs as a versatile platform for proton conduction in the field of humidity condition proton‐conduction, anhydrous atmosphere proton‐conduction, single‐crystal proton‐conduction, and including MOF‐based membranes for fuel cells, are summarized and highlighted. Furthermore, the challenges, future trends, and prospects of MOF materials for solid electrolytes are also discussed.

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40-Fold Enhanced Intrinsic Proton Conductivity in Coordination Polymers with the Same Proton-Conducting Pathway by Tuning Metal Cation Nodes

Cited by 63 publications

References 63 publications

Proton Transportation Behavior in Lanthanide Tartrate Metal‐Organic Frameworks

Proton Transportation Behavior in Lanthanide Tartrate Metal‐Organic Frameworks

Proton‐Conducting Hydrogen‐Bonded 3D Frameworks of Imidazo‐Pyridine‐Based Coordination Complexes Containing Naphthalene Disulfonates in Rhomboid Channels

Metal–Organic Frameworks as a Versatile Platform for Proton Conductors

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