Four Lanthanide(III) Metal–Organic Frameworks Fabricated by Bithiophene Dicarboxylate for High Inherent Proton Conduction

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(11), P. 13745 - 13755

Published: March 6, 2024

Currently, it is still a challenge to directly achieve highly stable metal–organic frameworks (MOFs) with superior proton conductivity solely through the exquisite design of ligands and attentive selection metal nodes. Inspired by this, we are intrigued multifunctional dicarboxylate ligand including dithiophene groups, 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid (H2DTD), lanthanide ions distinct coordination topologies. Successfully, four isostructural three-dimensional lanthanide(III)-based MOFs, [Ln2(DTD)3(DEF)4]·DEF·6H2O [LnIII = TbIII (Tb-MOF), EuIII (Eu-MOF), SmIII (Sm-MOF), DyIII (Dy-MOF)], were solvothermally prepared, in which effective transport will be provided coordinated or free solvent molecules, crystalline water framework components, as well large number electronegative S O atoms. As expected, Ln-MOFs demonstrated highest conductivities (σ) being 0.54 × 10–3, 3.75 1.28 1.92 10–3 S·cm–1 for respectively, at 100 °C/98% relative humidity (RH). Excitingly, Dy-MOF an extraordinary ultrahigh σ 1 30 RH. Additionally, plausible mechanisms emphasized.

Language: Английский

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Ligand-Functionalized MIL-68-type Indium(III) Metal–Organic Frameworks with Prominent Intrinsic Proton Conductivity

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(9), P. 4233 - 4248

Published: Feb. 20, 2024

Indium-based metal–organic frameworks (In-MOFs) have now become an attractive class of porous solids in materials science and electrochemistry due to their diverse structures promising applications. In the field proton conduction, find more crystalline MOFs with splendid proton-conductive properties, herein, five three-dimensional isostructural In-MOFs, MIL-68-In or MIL-68-In-X (X = NH2, OH, Br, NO2) using terephthalic acid (H2BDC) functionalized acids (H2BDC-X) as multifunctional linkages were efficiently fabricated. First, outstanding structural stability MOFs, including thermal water stability, was verified by analysis powder X-ray diffraction. Subsequently, H2O-mediated conductivities (σ) fully assessed compared. Notably, σ evinced a significant positive correlation between temperature relative humidity (RH) varied functional groups on organic ligands. Impressively, highest values are up 10–3–10–4 S/cm (100 °C/98% RH) change this order: MIL-68-In-OH (1.72 × 10–3 S/cm) > MIL-68-In-NH2 (1.70 MIL-68-In-NO2 (4.47 10–4 MIL-68-In-Br (4.11 (2.37 S/cm). Finally, computed activation energy under 98 68% RHs assessed, related conduction mechanisms speculated. Moreover, after electrochemical testing, these illustrate remarkable rigidity, laying meritorious material foundation for future

Language: Английский

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Inherent Ultrahigh Proton Conductivity of Two Highly Stable COOH-Functionalized Hafnium-Based Metal–Organic Frameworks

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 5, 2025

Although there has been some recent interest in the proton conductivity (σ) of highly stable carboxyl metal–organic frameworks (MOFs) made tetravalent metal ions, given their potential applications fuel cells and electrochemical sensing, research on MOFs constructed by hafnium(IV) ions needs to be expanded significantly. Based this, we used two common easily prepared phenylpoly(carboxylic acid) ligands, 1,2,4-phenyltricarboxylic acid 1,2,4,5-phenyltetracarboxylic acid, react with hafnium tetrachloride, respectively, creating porous hafnium(IV)-based MOFs, UiO-66-COOH-Hf (1) UiO-66-(COOH)2-Hf (2), same structure as UiO-66-Hf but different numbers free carboxylic groups. A series stability assays revealed that had excellent structural rigidity, including thermal water stability. More crucially, alternating current impedance experiments demonstrate σ varies positively humidity temperature, reaching up 10–3 S·cm–1 (1: 2.83 × 2: 4.35 S·cm–1) under right conditions (98% relative 100 °C). The latter roughly doubles former, which is due difference number groups, confirmed analysis conduction mechanism investigation. high intrinsic lays a solid foundation for future application affords new inspiration developing high-performance proton-conductive materials.

Language: Английский

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Linkage Position-Controlled Synthesis of Diverse Zirconium Metal–Organic Frameworks with Prominent Intrinsic Proton Conductivities

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: 64(10), P. 5271 - 5283

Published: March 5, 2025

Herein, by engineering the geometries of organic linkers, two pyrrolo-pyrrole-based low-symmetry tetracarboxylate linkers (TAPPs) were successfully designed and subsequently used for construction new zirconium-based metal-organic frameworks (Zr-MOFs) (IAM-10 IAM-11). The reduction linker symmetry arises from both asymmetric pyrrolo-pyrrole core integration para- meta-benzoate coordination groups on linkers. Both MOFs are composed 8-connected Zr6 nodes 4-connected highly deformed TAPP4- with same scu topology, but distinct arrangements can be observed in structures. specific rhomb-shaped geometry together flexible m-benzoate through rotation peripheral phenyl rings allows this type TAPP to generate unique conformations MOF structures optimize bonds inorganic building blocks adapt final topologies. Furthermore, presence well-defined hydrophilic channels reported allowed us evaluate potential proton conduction. IAM-10 IAM-11 show prominent intrinsic conductivities 1.13 × 10-2 2.69 10-3 S cm-1 at 90 °C 95% RH, making them top-performing proton-conductive Zr-MOFs.

Language: Английский

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Exploration of single-crystal proton conduction in ordered networks

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 499, P. 215516 - 215516

Published: Nov. 1, 2023

Language: Английский

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Prominent Intrinsic Proton Conduction in Two Robust Zr/Hf Metal–Organic Frameworks Assembled by Bithiophene Dicarboxylate

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(23), P. 10786 - 10797

Published: May 21, 2024

To date, developing crystalline proton-conductive metal–organic frameworks (MOFs) with an inherent excellent proton-conducting ability and structural stability has been a critical priority in addressing the technologies required for sustainable development energy storage. Bearing this mind, multifunctional organic ligand, 3,4-dimethylthiophene[2,3-b]thiophene-2,5-dicarboxylic acid (H2DTD), was employed to generate two exceptionally stable three-dimensional porous Zr/Hf MOFs, [Zr6O4(OH)4(DTD)6]·5DMF·H2O (Zr-DTD) [Hf6O4(OH)4(DTD)6]·4DMF·H2O (Hf-DTD), using solvothermal means. The presence of Zr6 or Hf6 nodes, strong Zr/Hf–O bonds, electrical influence methyl group, steric effect thiophene unit all contribute their throughout wide pH range as well water. Their proton conductivity fully examined at various relative humidities (RHs) temperatures. Creating intricate rich H-bonded networks between guest water molecules, coordination solvent thiophene-S, –COOH, –OH units within framework assisted transfer. As result, both MOFs manifest maximum 0.67 × 10–2 4.85 10–3 S·cm–1 under 98% RH/100 °C, making them top-performing Zr/Hf-MOFs. Finally, by combining characteristics activation energies, potential conduction pathways were identified.

Language: Английский

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Icing on the Cake: Imidazole-Anchored Strategy To Enhance the Proton Conductivity of Two Isostructural Ce(IV)/Hf(IV) Metal–Organic Frameworks

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(51), P. 21309 - 21321

Published: Dec. 13, 2023

In the field of proton conduction, acquisition crystalline metal-organic frameworks (MOFs) with high stability and ultrahigh conductivity has been great research value is worth continuous exploration. Here, we greenly synthesized a three-dimensional porous MOF (MOF-801-Ce) by using [(NH4)2Ce(NO3)6 fumaric acid as starting materials solvothermally Hf-UiO-66-NO2 HfCl4 2-nitroterephthalic materials. A series measurements have shown that both MOFs exhibit good water stability, acid-base thermal demonstrate outstanding conductivity. At 100 °C 98% relative humidity (RH), conductivities (σ) could be 2.59 × 10-3 S·cm-1 for MOF-801-Ce 0.89 Hf-UiO-66-NO2. To pursue higher conductivity, further adopted evaporation approach to encapsulate imidazole molecules in pores two compounds, achieving imidazole-encapsulated MOFs, Im@MOF-801-Ce Im@Hf-UiO-66-NO2. As expected, their σ values were significantly boosted almost an order magnitude up 10-2 S·cm-1. Finally, proton-conductive mechanisms explored light structural information, gas adsorption/desorption, other tests. The these durability conduction capability manifested they promise electrochemical fields.

Language: Английский

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A Highly Stable Multifunctional Bi-Based MOF for Rapid Visual Detection of S^2– and H₂S Gas with High Proton Conductivity

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(26), P. 33865 - 33876

Published: June 21, 2024

Metal organic frameworks (MOFs) constructed with bismuth metal have not been widely reported, especially multifunctional Bi-MOFs. Therefore, developing MOFs is of great significance due to the increasing requirements materials. In this work, a 3D Bi-MOF (Bi-TCPE) multifunctionality was successfully constructed, demonstrating high thermal stability, water porous structure, and strong blue fluorescence emission. We evaluated properties Bi-TCPE in detecting anions (S2-, Cr2O72-, CrO42-) aqueous solution, along rapid visual detection H2S gas proton conduction. terms anion detection, achieved trace S2- solutions, while Ksv value 1.224 × 104 M-1 limit (LOD) 1.93 μM through titration experiments. Furthermore, could sensitively detect Cr2O72- CrO42-, values 1.144 1.066 M-1, respectively, LOD reached 2.07 2.18 μM. Subsequently, we conducted experiments, results indicated that selectively at extremely low concentrations (2.08 ppm) fast response time (<10 s). also observed significant color changes under both UV light sunlight. developed test paper for gas. Finally, conductivity Bi-TCPE, experimental showed 4.77 10-2 S·cm-1 98% RH 90 °C, achieving an excellent unmodified encapsulated MOFs. addition, stability conduction experiments (it remained stable after 21 consecutive days testing 12 cycles testing), relatively application value. These indicate MOF material potential.

Language: Английский

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U-type π-conjugated phosphorescent ligand sensitized lanthanide metal–organic frameworks for efficient white-light-emitting diodes

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(39), P. 13872 - 13877

Published: Jan. 1, 2023

Lanthanide metal-organic framework (Ln-MOF) based phosphors for light-emitting diodes (LEDs) play an important role in the fields of solid-state lighting and display. The rational design organic antennae to address drawback low extinction coefficients lanthanide ions is highly desired. In this work, we provide a new strategy achieve energy transfer molecule with through-space conjugated folded structure, which can strengthen skeleton rigidity facilitate triplet state transfer. Consequently, one U-type π-conjugated 2,6-bis(3,5-dicarboxylphenoxy) pyridine (H4L) was selected as light gatherer sensitize construction Ln-MOFs [Ln(HL)(H2O)3]n (Eu-MOF Tb-MOF), exhibit long-lived luminescence lifetime (0.88 ms Eu-MOF 1.31 Tb-MOF) high quantum yields (50.87% 85.64% Tb-MOF). Furthermore, white LED device colour rendering index (89) fabricated using mixture commercial blue phosphor.

Language: Английский

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Defect-containing metal–organic framework materials for sensor applications

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 12(1), P. 38 - 58

Published: Dec. 11, 2023

Defective MOFs: unique properties and electrochemical sensor applications. Overview of construction principles, mechanisms,

Language: Английский

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