High‐Performance All‐Solid‐State Proton Rectifier Using a Heterogeneous Membrane Composed of Coordination Polymer and Layered Double Hydroxide

Lu, Jiangfeng; Yoshida, Yukihiro; Maesato, Mitsuhiko; Kitagawa, Hiroshi

doi:10.1002/anie.202213077

Cited by 4 publications

(2 citation statements)

References 53 publications

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“…Namely, the occurrence of the double-semicircle-inducing proton-bias phenomenon at low DC bias voltages indicates that the protons reached the electrode rapidly, corresponding with higher proton conductivity in that direction than in the opposite direction. Notably, the previous approaches for fabricating ICR materials and devices − comprised designing macroscopic asymmetric structures with different window sizes at the entrance and exit of the channels. Conversely, 1·H 2 O achieved such an atomic-level structural feature by the 1D anisotropic assembly of the umbrella-shaped [MnN(CN) 4 ] 2– units, imparting the strong polarity–proton transport coupling for the directional conductivity changes (Figure b).…”

Section: Resultsmentioning

confidence: 99%

Strongly Enhanced Polarization in a Ferroelectric Crystal by Conduction-Proton Flow

Yanagisawa,

Aoyama,

Fujii

et al. 2024

J. Am. Chem. Soc.

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Ion conductors comprising noncentrosymmetric frameworks have emerged as new functional materials. However, strongly correlated polarity functionality and ion transport have not been achieved. Herein, we report a ferroelectric proton conductor, K 2 MnN(CN) 4 •H 2 O (1•H 2 O), exhibiting the strong correlation between its polar skeleton and conductive ions that generate anomalous ferroelectricity via the proton-bias phenomenon. The application of an electric field of ±1 kV/cm (0.1 Hz) on 1•H 2 O at 298 K produced the ferroelectricity (polarization = 1.5 × 10 4 μC/cm 2 ), which was enhanced by the ferroelectric-skeletontrapped conductive protons. Furthermore, the strong polarity− proton transport coupling of 1•H 2 O induced a proton-rectificationlike directional ion-conductive behavior that could be adjusted by the magnitude and direction of DC electric fields. Moreover, 1•H 2 O exhibited reversible polarity switching between the polar 1•H 2 O and its dehydrated form, 1, with a centrosymmetric structure comprising an order−disorder-type transition of the nitrido-bridged chains.

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Section: Resultsmentioning

confidence: 99%

Strongly Enhanced Polarization in a Ferroelectric Crystal by Conduction-Proton Flow

Yanagisawa,

Aoyama,

Fujii

et al. 2024

J. Am. Chem. Soc.

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“…For instance, two isoreticular zirconium phenolate porphyrin networks are described by Chen et al [ 45 ] as having “exceptional conductivity” with values of 8.0 × 10 −3 and 4.2 × 10 −3 S·cm −1 , respectively (pelleted sample, under 98% relative humidity at 25 °C). Another example is Cu 2 (CuTCPP) (where H 4 (H 2 TCPP) is 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin), exhibiting a “high in-plane proton conductivity” of 3.9 × 10 −3 S·cm −1 at 25 °C under 98 % relative humidity [ 46 ]. Therefore, porphyrin-based MOFs and SMOFs can be a good compromise for bio-inspired solid-state materials.…”

Section: Introductionmentioning

confidence: 99%

Superprotonic Conductivity in a Metalloporphyrin-Based SMOF (Supramolecular Metal–Organic Framework)

Fidalgo-Marijuan,

Ruiz de Larramendi,

Barandika

2024

Nanomaterials

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Metal–organic frameworks and supramolecular metal–organic frameworks (SMOFs) exhibit great potential for a broad range of applications taking advantage of the high surface area and pore sizes and tunable chemistry. In particular, metalloporphyrin-based MOFs and SMOFs are becoming of great importance in many fields due to the bioessential functions of these macrocycles that are being mimicked. On the other hand, during the last years, proton-conducting materials have aroused much interest, and those presenting high conductivity values are potential candidates to play a key role in some solid-state electrochemical devices such as batteries and fuel cells. In this way, using metalloporphyrins as building units we have obtained a new crystalline material with formula [H(bipy)]2[(MnTPPS)(H2O)2]·2bipy·14H2O, where bipy is 4,4′-bipyidine and TPPS4− is the meso-tetra(4-sulfonatephenyl) porphyrin. The crystal structure shows a zig-zag water chain along the [100] direction located between the sulfonate groups of the porphyrin. Taking into account those structural features, the compound was tested for proton conduction by complex electrochemical impedance spectroscopy (EIS). The as-obtained conductivity is 1 × 10−2 S·cm−1 at 40 °C and 98% relative humidity, which is a remarkably high value.

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Robust Proton Conduction against Mechanical Stress in Flexible Free‐Standing Membrane Composed of Two‐Dimensional Coordination Polymer

Yoshida

Kanamori

et al. 2023

Angewandte Chemie

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Introduction of mechanical flexibility into proton‐conducting coordination polymers (CPs) is in high demand for future protonic applications such as fuel cells and hydrogen sensors. Although such mechanical properties have been primarily investigated in one‐dimensional (1D) CPs, in this study, we successfully fabricated highly flexible free‐standing CP membranes with a high surface‐to‐volume ratio, which is beneficial for enhanced performance in the aforementioned applications. We fabricated a layered CP, Cu2(NiTCPP) (H4(H2TCPP); 5,10,15,20‐tetrakis(4‐carboxyphenyl) porphyrin), in which a two‐dimensional (2D) square grid sheet composed of tetradentate nickel porphyrins and paddlewheel‐type copper dimers was connected to each other by weak van der Waals forces. The mechanical flexibility was evaluated by bending and tensile tests. The flexural and Young's moduli of the membrane were significantly higher than those of conventional Nafion membranes. Electrochemical impedance spectroscopy analysis revealed that the in‐plane proton conductivity of the membrane was maintained even under applied bending stress. Because the X‐ray diffraction analysis indicates that the proton‐conducting pathway through the hydrogen bonding network remains intact during the bending operation, our present study provides a promising strategy for the fabrication of new and advanced 2D CPs without using substrates or additional polymers for protonic devices.

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High‐Performance All‐Solid‐State Proton Rectifier Using a Heterogeneous Membrane Composed of Coordination Polymer and Layered Double Hydroxide

Cited by 4 publications

References 53 publications

Strongly Enhanced Polarization in a Ferroelectric Crystal by Conduction-Proton Flow

Strongly Enhanced Polarization in a Ferroelectric Crystal by Conduction-Proton Flow

Superprotonic Conductivity in a Metalloporphyrin-Based SMOF (Supramolecular Metal–Organic Framework)

Robust Proton Conduction against Mechanical Stress in Flexible Free‐Standing Membrane Composed of Two‐Dimensional Coordination Polymer

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