Stabilization of Palladium-Nanoparticle-Decorated Postsynthesis-Modified Zr-UiO-66 MOF as a Reusable Heterogeneous Catalyst in C–C Coupling Reaction
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SUBMITTER: Mohammadi L
PROVIDER: S-EPMC9996586 | biostudies-literature | 2023 Feb
REPOSITORIES: biostudies-literature
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Project description:Metal-organic frameworks (MOFs) are emerging as leading candidates for nanoscale drug delivery, as a consequence of their high drug capacities, ease of functionality, and the ability to carefully engineer key physical properties. Despite many anticancer treatment regimens consisting of a cocktail of different drugs, examples of delivery of multiple drugs from one MOF are rare, potentially hampered by difficulties in postsynthetic loading of more than one cargo molecule. Herein, we report a new strategy, multivariate modulation, which allows incorporation of up to three drugs in the Zr MOF UiO-66 by defect-loading. The drugs are added to one-pot solvothermal synthesis and are distributed throughout the MOF at defect sites by coordination to the metal clusters. This tight binding comes with retention of crystallinity and porosity, allowing a fourth drug to be postsynthetically loaded into the MOFs to yield nanoparticles loaded with cocktails of drugs that show enhancements in selective anticancer cytotoxicity against MCF-7 breast cancer cells in vitro. We believe that multivariate modulation is a significant advance in the application of MOFs in biomedicine, and anticipate the protocol will also be adopted in other areas of MOF chemistry, to easily produce defective MOFs with arrays of highly functionalised pores for potential application in gas separations and catalysis.
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Project description:This investigation explores optimum synthetic conditions for novel polymer-metal organic framework hybrid composites composed of Zr-terephthalate-based MOF UiO-66 and conductive polyaniline (PANI) nanofibers in an effort to optimize conductivity while minimizing MOF structural deformation. Successful syntheses of self-assembled PANI nanofibers in PANI@UiO-66 and PANI@UiO-66-NH2 composites were confirmed using scanning electron microscopy, infrared spectroscopy, and powder X-ray diffraction. The polymer-MOF composites show different bonding synergies to the PANI nanofibers depending on the organic linker used. Electronic properties of the post-synthetically modified PANI@UiO-66 and PANI@UiO-66-NH2 were investigated using UV-vis diffuse reflectance spectroscopy. Sheet resistivity of the self-assembled polymer-MOF composites was determined under an inert atmosphere at room temperature using four-point probe measurements to confirm tunable semiconductivity ranging from 40 to 2 mS/sq. Furthermore, the effects of aniline oxidation on the crystallinity and coordination of UiO-66 and UiO-66-NH2 were determined through analysis of these results.
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Project description:Metal-organic frameworks have been utilized as heterogeneous catalysts for the degradation of chemical warfare agents, typically organophosphorous nerve agents. Vibrational spectroscopy techniques coupled with nuclear magnetic resonance (NMR) were utilized to study the adsorption and degradation of dimethyl phosphite (DMP), a simulant molecule of the organophosphorus nerve agent Soman (GD), by Zr- and Hf-UiO-66 as a function of particle size, defect type, and defect density. Defective Zr- and Hf-UiO-66 have been synthesized via a modulated synthesis protocol to engineer missing linker and missing cluster defects into the crystal structure. The adsorption of DMP to UiO-66 was observed to be surface-limited, suggesting maximal DMP adsorption occurs with maximized external surface area. In addition, Hf-UiO-66 samples engineered with large quantities of missing cluster defects are observed to more efficiently hydrolyze DMP into phosphonic acid when compared to less-defective samples. The increase in reactivity is attributed to the greater accessibility of the internal particle volume and, thus, access to a higher number of Lewis-acidic open metal sites, facilitated by missing cluster defects. Taken together, these two observations indicate that to create maximally efficient MOF catalysts for chemical warfare agent degradation one must obtain frameworks with large surface area to maximize adsorption of the simulant as well as a large accessible free volume obtained through the introduction of missing cluster defects to maximize the degradation of the simulant at the Lewis acid sites found in the interior of the framework.
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Project description:Defect engineering in metal-organic framework compounds has allowed for improvements in catalysis-based functionalities, gas sensing, and gas storage. Metal-organic framework UiO-66 compounds with Zr- and Hf-based metal secondary building units were studied with Raman and infrared vibrational spectroscopy. Missing linker and missing cluster defects were engineered into the crystal structure via a modulated synthesis technique. Missing cluster defects in Hf-UiO-66 are first characterized by powder X-ray diffraction (PXRD) whereby two low-angle peaks were fit to extract the relative quantity of reo topology in four defective samples. A monotonic red-shift of the Raman-active Hf-O coordination bond vibration is interpreted as a signature of missing cluster defects, resulting from less-rigid charge-balancing monocarboxylate formate ions replacing the dicarboxylate linker molecule. This signature is hypothesized to be independent of the topology in which the defects appear. Missing linker defects in Zr-UiO-66 are characterized by infrared absorption spectroscopy by the quenching of C-C and C-H vibrational modes confined to the linker molecule. Together, Raman and infrared vibrational spectroscopies coupled with standard characterization techniques are employed to directly probe the nature of defects as well as offer new characterization tools for missing cluster defects in UiO-66.
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Project description:We have designed a functionalized metal-organic framework (MOF) of UiO topology as a support, with an extremely high surface area, adjustable pore sizes and stable crystalline coordination polymeric structure and implanted copper (Cu) nanoparticles thereon. The core three dimensional Zr-derived MOF (UiO-66-NH2) was modified with a biguanidine moiety following a covalent post-functionalization approach. The morphological and physicochemical features of the material were determined using analytical methods such as FT-IR, SEM, TEM, EDX, atomic mapping, XRD and ICP-OES. The SEM and XRD results justified the unaffected morphology of Zr-MOF after structural modifications. The as-synthesized UiO-66-biguanidine/Cu nanocomposite was catalytically explored in the aryl and heteroaryl Buchwald-Hartwig C-N and Ullmann type C-O cross coupling reactions with excellent yields. A library of biaryl amine and biaryl ethers was synthesized over the catalyst under mild and green conditions. Furthermore, the catalyst was isolated by centrifugation and recycled 11 times with no significant copper leaching or change in its activity.
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Project description:We report a novel synthetic procedure for the high-yield synthesis of metal-organic frameworks (MOFs) with fcu topology with a UiO-66-like structure starting from a range of commercial ZrIV precursors and various substituted dicarboxylic linkers. The syntheses are carried out by grinding in a ball mill the starting reagents, namely, Zr salts and the dicarboxylic linkers, in the presence of a small amount of acetic acid and water (1 mL total volume for 1 mmol of each reagent), followed by incubation at either room temperature or 120 °C. Such a simple "shake 'n bake" procedure, inspired by the solid-state reaction of inorganic materials, such as oxides, avoids the use of large amounts of solvents generally used for the syntheses of Zr-MOF. Acidity of the linkers and the amount of water are found to be crucial factors in affording materials of quality comparable to that of products obtained under solvo- or hydrothermal conditions.
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Project description:Although Zr-based metal-organic frameworks (MOFs) exhibit robust chemical and physical stability in the presence of moisture and acidic conditions, their susceptibility to nucleophilic attacks from bases poses a critical challenge to their overall stability. Herein, we systematically investigate the stability of Zr-based UiO-66 (UiO = University of Oslo) MOFs in basic solutions. The impact of 11 standard bases, including inorganic salts and organic bases, on the stability of these MOFs is examined. The destruction of the framework is confirmed through powder X-ray diffraction (PXRD) patterns, and the monitored dissolution of ligands from the framework is assessed using nuclear magnetic resonance (NMR) spectroscopy. Our key findings reveal a direct correlation between the strength and concentration of the base and the destruction of the MOFs. The summarized data provide valuable insights that can guide the practical application of Zr-based UiO-66 MOFs under basic conditions, offering essential information for their optimal utilization in various settings.
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Project description:By rigorous control of water, missing-cluster defects in Zr-based UiO-66 were generated to a remarkable extent without the need of acidic modulators. The presence of missing-cluster defects created hierarchical pore structures, which had a profound effect on the catalytic performance.
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Project description:This work reports on the fabrication, optimization and characterization of ultrathin films containing submicrometer particles (sMPs) of the hydrophilic and water stable UiO-66-COOH(Zr) metal organic framework (MOF). MOF particles of ≈200 nm have been synthesized and assembled at the air-water interface by the Langmuir-Blodgett technique. The use of different solvents, mixtures of solvents and surfactants has been investigated in order to improve the stability of MOF dispersions and reduce particle aggregation. The compact MOF/surfactant films containing 10 wt % octadecylphoshonic acid (ODP) have been deposited on substrates of different nature by Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) methods, showing that the presence of even only one MOF/ODP monolayer can increase the water contact angle of highly hydrophilic substrates such as mica or glass up to 120°. These films were characterized by scanning electron microscopy, grazing incidence X-ray diffraction, Fourier transform infrared spectroscopy and atomic force microscopy, revealing the formation of a continuous film where ODP molecules adopt an almost vertical position and cover MOF particles. Moreover, the presence of MOF particles significantly enhances the surface roughness and allows ultrathin, hydrophobic coverage to be obtained. Finally, it has been shown that the crystallinity and the porosity of the MOF remains almost unaltered in MOF/ODP films.
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Project description:In this work, a bimetallic MOF UiO-66 Ce-Zr to degrade bisphenol A (BPA) in water was synthesised. The material exhibited a remarkable degradation efficiency of 84.3% under UV irradiation for 240 minutes. Combining cerium (Ce) and zirconium (Zr) in the MOF structure enhanced the catalytic activity and reinforced its structural stability. Comprehensive characterisation was performed using PXRD, FT-IR, SEM-EDS, XPS, and N₂ adsorption-desorption isotherms. Scavenger tests confirmed that hydroxyl (˙OH) and superoxide (˙O₂⁻) radicals played a crucial role in the photocatalysis. The material demonstrated excellent reusability, maintaining high performance over three cycles with minimal structural changes. Furthermore, a toxicological evaluation of the degradation by-products was conducted using UPLC-MS, reaffirming the potential of the material as an efficient water treatment system. This study underscores the potential of UiO-66 Ce-Zr as a stable and effective photocatalyst for water treatment applications, particularly in removing emerging pollutants such as BPA.
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