Metal-organic frameworks (MOFs) are a class of porous crystalline materials showing great potential for applications such as catalysis, gas storage, molecular separations, energy storage and drug delivery. The properties that render them interesting stem from their structure (e.g. morphology, porosity or metal coordination and geometry). Thus, gaining a deeper understanding strongly relies on the availability and adequate use of advanced characterization tools, which can interrogate MOFs under realistic synthesis as well as catalysis (or sorption) conditions. Herein, we present an overview of the various characterization techniques specifically suitable for the study on the underlying chemistry of the formation mechanisms and adsorption properties of three archetypal MOFs, namely MIL-100, ZIF-8 and HKUST-1. A section on using MOFs as supports for metal atoms or complexes that can be used for catalysis on the robust Zr nodes of UiO-66 or NU-1000, and the characterization techniques used thereof, is presented as well. In addition, we discuss recent developments on the application of nano-spectroscopic characterization for MOF thin-films and explore the potential of MOFs as model systems in catalysis. The conclusions and outlook provide future research possibilities in the field of MOF characterization.
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http://dx.doi.org/10.1039/d0cs00635a | DOI Listing |
ACS Appl Nano Mater
November 2024
Institute of Solid State Physics, Graz University of Technology, Graz 8010, Austria.
Understanding the structure of thin films is essential for successful applications of metal-organic frameworks (MOFs), such as low k-dielectrics in electronic devices. This study focuses on the thin film formation of the 3D nanoporous MOF Cu(bdc)(dabco). The thin films are prepared by a layer-by-layer technique with varying deposition cycles (1 to 50).
View Article and Find Full Text PDFACS Appl Mater Interfaces
November 2024
Laboratorio de Fisicoquímica y Reactividad de Superficies (LaFReS), Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, 04510, Ciudad de México, Mexico.
The archetypical metal-organic framework (MOF), HKUST-1, has been systematically modified in both its organic and inorganic building blocks to introduce diversity in the metal centers and create defects within the network, achieving a variety of bimetallic hierarchical structures. These modifications changed the affinity of the MOFs for acid gases. The introduction of bimetallic sites mostly affects CO adsorption, while the hierarchical structure generates an increase in SO uptake capacity, allowing better performance in the separation of binary mixtures of these gases near room temperature.
View Article and Find Full Text PDFPhys Chem Chem Phys
October 2024
Université de Lorraine, CNRS, L2CM, F-57000 Metz, France.
The diverse structural tunability of 2-dimensional π-stacked layered metal-organic frameworks (2D MOFs) enables the control of charge carrier mobility to achieve specific photoconductive characteristics. This study demonstrates the potential of various theoretical methodologies and frameworks in establishing a correlation between structure and functionality for such purposes. Through a focus on the archetypal Ni(HITP) 2D MOF, we examine the impact of quantum confinement and stacking fault defects on the absorption spectra using our recently-developed Frenkel-Holstein Hamiltonian.
View Article and Find Full Text PDFChembiochem
November 2024
Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Bld. 330, Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen, 76344, Germany.
The integration of biocatalysts within metal-organic frameworks (MOFs) is attracting growing interest due to its potential to both enhance biocatalyst stability and sustain biocatalyst activity in organic solvents. However, the factors that facilitate the post-synthetic infiltration of such large molecules into MOF pores remain unclear. This systematic study enabled the identification of the influence of biocatalyst molecular size, molecular weight and affinity on the uptake by an archetypal MOF, NU-1000.
View Article and Find Full Text PDFJ Am Chem Soc
June 2024
Department of Chemistry, Stony Brook University, Stony Brook, New York 11794, United States.
In metal-organic frameworks (MOFs) the interplay between the dynamics of individual components and how these are constrained by the extended lattice can yield unusual emergent phenomena. For the archetypal Zr-MOF, UiO-66, we explore the cooperative dynamics of a Zr-node transformation that gives rise to negative thermal expansion (NTE). Using synchrotron X-ray scattering, with powder diffraction and pair distribution function (PDF) analyses, we identify lattice hysteresis and a thermal ramp-rate-dependence of the thermal expansion.
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