Effect of hydrogen-bonding networks in water on the proton conductivity properties of metal–organic frameworks

Nguyen, My V.; Dong, Hieu C.; Nguyen-Manh, D.; Vu, Nam Hoang; Trinh, Thuat T.; Phan, Thắng Bách

doi:10.1016/j.jsamd.2021.06.005

Cited by 7 publications

(6 citation statements)

References 46 publications

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“…For the excitation spectra, the profiles for MOF-2a to MOF-2e are quite similar with a strong band in 320–410 nm, while for MOF-2f , the intensity in the wavelength range longer than 350 nm decrease obviously. In consideration of the relatively short C–H···O distance between the TPB and NO 3 – in MOF-2 , the redshifted emission might be attributed to the charge transfer-based emissions with the TPB as the donor and NO 3 – as the acceptor. , It could be well supported by the redshifted adsorption and emission band observed (Figure a). In consideration of the similar components and PXRD patterns of the MOF-2 samples with different anthracene feedings, the varied fluorescence emission along with the increased anthracene feeding should be originated from the subtle changes of the interactions between the TPB and NO 3 – . ,− …”

Section: Resultsmentioning

confidence: 68%

Highly Tunable MOF Luminophores Featuring Anthracene Directed Assembly and Fluorescence Regulation

et al. 2023

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Metal−organic frameworks (MOFs) have been recognized as a potential platform for the development of tunable luminophores owing to their highly modulable structures and components. Herein, two MOF luminophores based on Cd(II) ions, 1,3,5-tri(4-pyridinyl)benzene (TPB), and 1,4-dicarboxybenzene (H 2 BDC) were constructed. The directed assembly of the metal ions and organic linkers results in [Cd 2 (BDC) 2 (TPB)(H 2 O)]•x(solvent) (MOF-1) featuring TPB-based blue fluorescence centered at 425 nm. By introducing anthracene as the structure directing agent (SDA) for assembly regulation, [Cd 2 (BDC)-(TPB) 2 (NO 3 ) 2 ]•x(solvent) (MOF-2) was obtained, which reveals anthracene feeding-dependent high tunable emission in the 517−650 nm range. Detailed components, photophysical properties, and structural characteristics investigations of MOF-2 indicate the TPB and NO 3 − interactions as the origin of its redshifted emission compared with that of MOF-1. Furthermore, the fluorescence of MOF-2 was found to be regulatable by the anthracene feeding based on the SDA-determined crystallinity of the crystalline sample. All these results provided a unique example of the structural and fluorescence regulation of MOF luminophores.

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Section: Resultsmentioning

confidence: 68%

Highly Tunable MOF Luminophores Featuring Anthracene Directed Assembly and Fluorescence Regulation

et al. 2023

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“…The adsorption heat ( Q st ) of the water in CuCpz is calculated to be 27.33 kJ mol –1 , well supporting the high water affinity of this MOF towards water. Further, during the moisture decreasing from 100 to 43% RH, the water molecules fully occupy the MOF cavity (Figure g–i) all the time, leading to the integrity of the hydrogen bonding networks (Figure S14) and well explaining the steady and high proton conductivity in such a wide range of RH. , Therefore, the MD simulation strongly proves that the hydrophilic atoms in CuCpz hold the water molecules to form the successive hydrogen bonding networks, especially during the RH decreasing from 100 to 43% RH, eventually leading to high proton conductivity in such a wide range of RH.…”

Section: Resultsmentioning

confidence: 73%

Abundant Hydrophilic Atoms Enhanced the Proton Conductivity of a Stable Metal–Organic Framework in a Wide Relative Humidity Range

Zhang

Han

Zhang

et al. 2022

ACS Sustainable Chem. Eng.

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The low proton conductivity of proton-conducting solids at reduced relative humidity (RH) hinders the performance of fuel cells. Hence, we propose an assumption that a metal− organic framework (MOF) with a large portion of hydrophilic atoms may hold the adsorbed water molecules at reduced RH and thus maintain a high proton conductivity. As a proof, a Cu-based MOF whose ligand contains a large portion of O and N atoms is investigated and verified to be able to sustain the high water uptake capacity from 100 to 43% RH. Benefiting from the high and steady water uptake, the proton conductivity surpasses 10 −3 S cm −1 even at 43% RH, higher than that of most reported proton-conducting MOFs at low RH. Moreover, the conductivity reaches up to 1.80 × 10 −2 S cm −1 at 80 °C and 100% RH and is maintained up to 120 h, not only demonstrating an excellent stability but also reaching the highest proton conductivity benchmark (>10 − 2 S cm −1 ) of MOFs. Also, the synthesis time of this MOF is shortened to 7 h with a high yield of 99% at room temperature, superior to the reported proton-conducting MOFs. Molecular dynamics simulation further proves that the abundant hydrophilic atoms of the MOF keep the high water density in the pores in such a wide RH range, leading to the integrity of the hydrogen bonding networks to smoothly conduct protons. This work not only discovers a highly proton-conducting MOF in a wide RH range, but also provides a strategy to discover conductive MOFs by the portion of hydrophilic atoms in the MOFs, opening a cost-saving avenue to provide highly proton-conductive materials.

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“…As for MOF- 2 , intramolecular hydrogen bonds existed only between free water molecules in the hydrophilic channel (Figure b). This complex hydrogen bond system was an important factor for the excellent proton conduction performance of MOF materials. , The hydrogen bonding parameters for MOF- 1 and MOF- 2 are presented in Tables S4 and S5, respectively.…”

Section: Resultsmentioning

confidence: 99%

Comparative Analysis of Proton Conductivity in Two Zn-Based MOFs Featuring Sulfate and Sulfonate Functional Groups

Guo,

Wang,

Wei

et al. 2024

Inorg. Chem.

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Metal−organic frameworks (MOFs) have shown promising potential as proton-conducting materials due to their tunable structures and high porosity. In this study, two novel MOFs had been successfully synthesized, one containing sulfate groups (MOF-1; [Zn 4 (TIPE) 2 (SO 4 ) 4 (H 2 O)]•5H 2 O) and the other containing sulfonate groups (MOF-2; [Zn 2 (TIPE)(5-sip, and the effect of the two groups on the proton conductivity of Zn-based MOFs had been investigated and compared for the first time. The proton conductivity of these MOFs was systematically measured at different temperatures and humidity conditions. Remarkably, the results revealed significant differences in proton conductivity between the two sets of MOFs. At 90 °C and 98% RH, MOF-1 and MOF-2 achieved optimal proton conductivity of 4.48 × 10 −3 and 5.69 × 10 −2 S•cm −1 , respectively. This was due to the structural differences arising from the presence of different functional groups, which subsequently affected the porosity and hydrophilicity, thereby influencing the proton conductivity. Overall, this comparative study revealed the influence of sulfate and sulfonate groups on the proton conductivity of Znbased MOFs. This research provided a feasible idea for the development of advanced MOF materials with enhanced proton conductivity and opened up new possibilities for their application in proton devices.

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Effect of hydrogen-bonding networks in water on the proton conductivity properties of metal–organic frameworks

Cited by 7 publications

References 46 publications

Highly Tunable MOF Luminophores Featuring Anthracene Directed Assembly and Fluorescence Regulation

Highly Tunable MOF Luminophores Featuring Anthracene Directed Assembly and Fluorescence Regulation

Abundant Hydrophilic Atoms Enhanced the Proton Conductivity of a Stable Metal–Organic Framework in a Wide Relative Humidity Range

Comparative Analysis of Proton Conductivity in Two Zn-Based MOFs Featuring Sulfate and Sulfonate Functional Groups

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