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New methods for the preparation of metal–organic frameworks UiO-66 and NH2-UiO-66 with a hierarchical porous structure were developed using the MW-assisted technique under atmospheric pressure. The synthesized nanostructured meso-UiO-66 and meso-NH2-UiO-66 matrices were utilized as Au nanoparticle carriers. The resulting Au@meso-UiO-66 and Au@NH2-UiO-66 nanohybrids were studied in the reaction of phenylacetylene hydroamination with aniline into imine ([phenyl-(1-phenylethylydene)amine]) for the first time. Their catalytic behavior is significantly determined by a combination of factors, such as a small crystal size, micro–mesoporous structure, and functionality of the UiO-66 and NH2-UiO-66 carriers, as well as a high dispersion of embedded gold nanoparticles. The Au@meso-UiO-66 and Au@NH2-UiO-66 nanocatalysts demonstrate high activities (TOF), with conversion and selectivity values over 90. This excellent catalytic performance is comparable or even better than that demonstrated by heterogeneous systems based on conventional inorganic and inorganic supports known from the literature. [ABSTRACT FROM AUTHOR]

Composite materials have been used based on coordination polymers or microporous metal-organic frameworks (MOFs) combined with mesoporous matrices for adsorption-related techniques, which enable outflanking some adverse phenomena manifested during pristine components operation and enhance the performance and selectivity of the resulting materials. In this work, for the first time, the novel HKUST-1@BPS composites synthesized by the microwave-assisted (MW) technique starting from microporous HKUST-1 (Cu3(btc)2) MOF and biporous silica matrix (BPS) with bimodal mesopore size distribution were comparatively studied as materials for liquid-phase adsorption techniques utilizing the high-performance liquid chromatography (HPLC) method and benzene as a model adsorbate. It was established that the studied HKUST-1@BPS composites can function as stationary phases for HPLC, unlike the pristine HKUST-1 and bare BPS materials, due to the synergetic effect of both components based on the preliminary enhanced adsorbate mass transfer throughout the silica mesopores and, subsequently, its penetrating into HKUST-1 micropores. The suggested mechanism involves the initial deactivation of open metal Cu2+ sites in the HKUST-1 framework structure by isopropanol molecules upon adding this polar component into the mobile phase in the region of the isopropanol concentration of 0.0 to 0.2 vol.%. Thereafter, at the medium range of varying the isopropanol concentration in the eluent of 0.2 to 0.3 vol.%, there is an expansion of the previously inaccessible adsorption centers in the HKUST-1@BPS composites. Subsequently, while further increasing the isopropanol volume fraction in the eluent in the region of 0.3 to 5.0 vol.%, the observed behavior of the studied chromatographic systems is similar to the quasi-normal-phase HPLC pattern. According to the obtained thermodynamic data, benzene adsorption into HKUST-1 micropores from solutions with a vol.% of isopropanol in the range of 0.4 to 5.0 follows the unique entropy-driven mechanism previously described for the MIL-53(Al) framework. It was found that HKUST-1 loading in the composites and their preparation conditions have pronounced effects on their physicochemical properties and adsorption performance, including the adsorption mechanism. [ABSTRACT FROM AUTHOR]

A series of flexible metal–organic frameworks (MOFs) belonging to the MIL-53 family, such as MIL-53(Al), its amino-functionalized analog NH2-MIL-53(Al), and MIL-53(Al) type materials with Al3+ ions and mixed benzene-1,4-dicarboxylate and 2-aminobenzene-1,4-dicarboxylate linkers (MixLR) in various proportions were prepared in a nanocrystalline form using MW-activation under atmospheric pressure according to the original solvothermal procedure. The MIL-53(Al) and NH2-MIL-53(Al) samples feature nanocrystals with sizes of 200–300 nm, while MixLR matrices synthesized in this manner are composed of small nanoparticles with sizes of about 20–30 nm. MIL-53(Al) type materials (MIL-53(Al), NH2-MIL-53(Al) and MixLR) were probed in the adsorption of a typical herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) in an aqueous medium. This study revealed a strong impact of the flexibility and porosity of the synthesized MIL-53(Al) type matrices on their physicochemical characteristics. MIL-53(Al) type materials show much higher 2,4-D adsorption rates than an activated carbon matrix (CSAC). The structural characteristics of the studied MIL-53(Al) type materials were established with a high resolution X-ray powder diffractometer equipped with a synchrotron radiation source. The obtained results can be used for the development of advanced adsorbents based on MIL-53(Al) type materials for water remediation. [ABSTRACT FROM AUTHOR]

To date, metal-organic frameworks (MOFs) have been recognized as promising solid phases in high-performance liquid chromatography (HPLC). This research aimed to elucidate the role of the physico-chemical characteristics of the microporous HKUST-1 metal-organic framework in its operation as a selective adsorbent in HPLC. For this, the HKUST-1 samples were prepared by microwave-assisted synthesis and a solvothermal procedure. According to the chromatographic examinations, the HKUST-1 material synthesized in the microwave fields shows an efficient performance in the selective adsorption of aromatic compounds with different functionalities. This study revealed a significant impact of the preparation procedure on the mechanism of the liquid-phase adsorption on the HKUST adsorbents under conditions of the HPLC. An effect of the elution solvent with the different coordination ability to the Cu2+ sites in the HKUST-1 structure on the adsorption selectivity was observed. [ABSTRACT FROM AUTHOR]

Graphical abstract Iodobenzene methoxycarbonylation is catalyzed by novel Pd@MOFs nanohybrids. Low-loaded nanocatalysts – 0.1–0.5 wt.% Pd on MOFs – demonstrate a superior activity compared to conventional systems. The catalytic performance of the Pd@MOFs is affected by the framework nature, Pd content and preparation procedure. Abstract This paper reports for the first time iodobenzene methoxycarbonylation over Pd-containing catalysts based on MOF materials differed in topology, texture properties and organic and inorganic building blocks: MIL-53(Al) (AlOHbdc, bdc = benzene-1,4-dicarboxylate), NH 2 -MIL-53(Al) (AlOHabdc, abdc = 2-aminobenzene-1,4-dicarboxylate), NH 2 -MIL-101(Al) (Al 3 Oabdc) 3 , and ZIF-8 (Zn(MeIm) 2 , MeIm = 2-methylimidazolate). Low-loaded nanocatalysts (0.1–0.5 wt.% Pd) based on MIL-53(Al) and ZIF-8 demonstrated a superior activity as compared to those on conventional supports such as silica and alumina. The catalytic performance of the synthesized nanocatalysts is affected both by the MOF support nature and Pd loading. Another important factor governing the performance of the Pd/MOF catalysts is the preparation procedure of the metal–organic matrices which affects their crystal size and morphology. This effect was studied for ZIF-8 materials. [ABSTRACT FROM AUTHOR]