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Herein, we present an integrated upper division chemistry laboratory experiment involving the synthesis, characterization, and evaluation of catalytic metal–organic frameworks (MOFs). Experiments are designed to facilitate the solvothermal synthesis and characterize MOFs, including UiO-66, UiO-66-NH2, and UiO-66-NO2. The MOFs are employed as catalysts in oxidative desulfurization (ODS) of an organic sulfur-containing compound, dibenzothiophene (DBT), in a laboratory experiment. To investigate the composition and structure of the MOFs, powder X-ray diffraction (PXRD) and elemental analysis (EA), respectively, are employed. Using Fourier transform infrared (FT-IR) spectroscopy, students evaluate the different organic linkers found in the MOFs. Students then investigate the effects of the electronic environment of the organic linker of the MOFs on the ODS of DBT. Students find that all three porous and crystalline MOFs oxidize DBT, but UiO-66-NO2 exhibits the most efficient catalytic conversion.more » « lessFree, publicly-accessible full text available July 23, 2025
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Here, we report an air-free approach to infiltrate isostructural metal–organic frameworks (MOFs), M-MOF-74 (M = Cu, Mn, Zn, Mg), with conjugated acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ). The TCNQ@M-MOF-74 compounds exhibit a striking correlation between their bulk conductivities and the open d shell variants (Cu, Mn), arising from TCNQ p-doping of the MOFs. Importantly, conjugation of the guest molecule is a prerequisite for inducing electrical conductivity in these systems.more » « less
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An intriguing new class of two-dimensional (2D) materials based on metal–organic frameworks (MOFs) has recently been developed that displays electrical conductivity, a rarity among these nanoporous materials. The emergence of conducting MOFs raises questions about their fundamental electronic properties, but few studies exist in this regard. Here, we present an integrated theory and experimental investigation to probe the effects of metal substitution on the charge transport properties of M-HITP, where M = Ni or Pt and HITP = 2,3,6,7,10,11-hexaiminotriphenylene. The results show that the identity of the M-HITP majority charge carrier can be changed without intentional introduction of electronically active dopants. We observe that the selection of the metal ion substantially affects charge transport. Using the known structure, Ni-HITP, we synthesized a new amorphous material, a-Pt-HITP, which although amorphous is nevertheless found to be porous upon desolvation. Importantly, this new material exhibits p-type charge transport behavior, unlike Ni-HITP, which displays n-type charge transport. These results demonstrate that both p- and n-type materials can be achieved within the same MOF topology through appropriate choice of the metal ion.more » « less