98%
921
2 minutes
20
Herein, we report transformation of a metal-organic gel (MOG) to a crystalline metal-organic framework (MOF) and solvent-dependent gelation/crystallization solvothermal reactions of a tetracarboxylic acid, namely 4,4'-dinitro-2,2',6,6'-tetracarboxybiphenyl, and ZnSO. The results provide structural insights into MOGs at the molecular level and also help in the synthesis of crystalline MOFs that are otherwise difficult to obtain.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1039/d2cc04724a | DOI Listing |
Angew Chem Int Ed Engl
August 2025
College of Environmental Science and Engineering, State Key Laboratory of Water Pollution Control and Green Resource Recycling, Tongji University, Shanghai, 200092, P.R. China.
Metal-organic gels (MOGs), an innovative subset of metal-organic frameworks (MOFs), feature hierarchically porous architecture and self-shaping monolithic morphologies, demonstrating them significantly potential for advanced applications in catalysis, gas storage, and energy conversion. Despite their functional versatility, the synthesis of MOGs remains empirical, as the actual formation mechanisms are largely unexplored. Here, a multiscale characterization strategy integrating time-resolved in-situ small-angle X-ray scattering (SAXS), Zr K-edge X-ray absorption fine structure (XAFS), and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) analyses are systematically employed to elucidate the formation mechanism of UiO-66(Zr) gel.
View Article and Find Full Text PDFInorg Chem
March 2025
GDMPA Key Laboratory for Process Control and Quality Evaluation of Chiral Pharmaceuticals, and Guangzhou Key Laboratory of Analytical Chemistry for Biomedicine, School of Chemistry, South China Normal University, Guangzhou 510006, P. R. China.
Zirconium metal-organic cages (Zr-MOCs) that assemble from zirconocence-based clusters and carboxylate-based ligands have been widely used as building blocks for constructing various MOC-based materials with diverse applications because of their high stability and solubilities. However, in this work, we found that the structures of a series of Zr-MOCs are quite flexible when heated at 60 °C in an ,'-dimethylformamide solution, in which they are completely disassembled into fragments and reassembled into amorphous metal-organic gels (MOGs). The transformation mechanism was investigated via proton nuclear magnetic resonance, electrospray ionization mass spectrometry, infrared spectroscopy, X-ray photoelectron spectroscopy, and other techniques, which revealed that cyclopentadiene (CP) breaks out of the [ZrCP(μ-OH)(μ-O)] cluster and remains in solution, whereas the trinuclear [Zr(μ-OH)(μ-O)] cluster dimerizes into a hexanuclear [Zr(μ-OH)(μ-O)] cluster and forms amorphous MOGs with terephthalic acid-based ligands.
View Article and Find Full Text PDFChem Sci
December 2024
Key Laboratory of Eco-chemical Engineering, International Science and Technology Cooperation Base of Eco-chemical Engineering and Green Manufacturing, College of Chemistry and Molecular Engineering, School of Materials Science and Engineering, Qingdao University of Science and Technology China inorc
Metal-organic gels (MOGs) are emerging soft materials with distinct metal active centers, multifunctional ligands and hierarchical porous structures, showing promising potential in the field of electrocatalysis. However, the reconfiguration of MOGs during the electrocatalytic process remains underexplored, with current studies in early developmental stages. To deeply investigate the application of MOG materials in electrocatalysis, the compositional transformations and structural changes under an electrochemical activation method were studied in detail, leading to high-performance OER pre-electrocatalysts.
View Article and Find Full Text PDFDalton Trans
June 2024
Department of Organic and Inorganic Chemistry, University of the Basque Country, UPV/EHU, P.O. 644, Bilbao E-48080, Spain.
The synthesis, characterization and photocatalytic hydrogen evolution reaction (HER) performance of a series of metal-organic gels (MOGs) constructed from titanium(IV)-oxo clusters and dicarboxylato linkers (benzene-1,4-dicarboxylato and 2-aminobenzene-1,4-dicarboxylato) are described. All the MOGs exhibit a microstructure comprised of metal-organic nanoparticles intertwined into a highly meso-/macroporous structure, as demonstrated by cryogenic transmission electron microscopy and gas adsorption isotherms. Comprehensive chemical characterization enabled the estimation of the complex formula for these defective materials, which exhibit low crystallinity and linker vacancies.
View Article and Find Full Text PDFInorg Chem
April 2024
Department of Chemistry, Indian Institute of Technology Kharagpur, 721302 Kharagpur, India.
The solvothermal conversion of metal-organic gels (MOGs) to crystalline metal-organic frameworks (MOFs) represents a versatile and ingenious strategy that has been employed for the synthesis of MOF materials with specific morphologies, high yield, and improved functional properties. Herein, we have adopted an solvothermal conversion of bimetallic MOGs to crystalline bimetallic MOFs with the aim of introducing a redox-active metal heterogeneity into the monometallic counterpart. The formation of bimetallic and solvothermal sol-gel-crystal and sol-crystal transformation is found to depend on the solvent systems used.
View Article and Find Full Text PDF