Search Results (5)

Considering the importance of organic functionalization of MOFs, we here report a simple, tunable and efficient one-step post-modification procedure for introducing amino and carboxylic groups into the mesoporous metal–organic framework Al- and Cr-MIL-101-NH₂ based on its reaction with alkyl bromides. This procedure allows also access to polyfunctionalized MIL-101 decorated with both carboxylic and primary amino groups. Other chemical functions, such as alcohols and alkynes, were also successfully introduced by this method. Full article

Metal–organic frameworks (MOFs) are hybrid inorganic–organic 3D coordination polymers with metal sites and organic linkers, which are a “hot” topic in the research of sorption, separations, catalysis, sensing, and environmental remediation. In this study, we explore the molecular mechanism and kinetics of interaction of the new copper porphyrin aluminum metal–organic framework (actAl-MOF-TCPPCu) compound 4 with a vapor of the volatile organic sulfur compound (VOSC) diethyl sulfide (DES). First, compound 4 was synthesized by post-synthetic modification (PSM) of Al-MOF-TCPPH₂ compound 2 by inserting Cu²⁺ ions into the porphyrin ring and characterized by complementary qualitative and quantitative chemical, structural, and spectroscopic analysis. Second, the interaction of compound 4 with DES vapor was analyzed dynamically by the novel method of in situ time-dependent attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy at controlled humidity levels. The sorbent–adsorbate interactions, as analyzed by the shifts in IR peaks, indicate that the bonding includes the hydroxy O-H, carboxylate COO⁻, and phenyl groups. The kinetics of sorption obeys the Langmuir pseudo-first-order rate law. The pre-adsorption of water vapor by compound 4 at the controlled relative humidity under static (equilibrium) conditions yields the binary stoichiometric adsorption complex (Al-MOF-TCPPCu)_1.0(H₂O)_8.0. The pre-adsorption of water vapor makes the subsequent sorption of DES slower, while the kinetics obey the same rate law. Then, static pre-adsorption of water vapor was followed by static sorption of DES vapor, and the ternary adsorption complex (Al-MOF-TCPPCu)_1.0(H₂O)_8.0(DES)₃.₈ was obtained. Despite the pre-adsorption of significant amounts of water, the binary complex adsorbs a large amount of DES: ca. 36.6 wt. % (per compound 4). Finally, the ternary complex is facilely regenerated by gentle heating under vacuum. Compound 4 and related MOFs are promising for adsorptive removal of vapor of DES and related VOSCs from dry and humid air. Full article

A sulfur-containing metal–organic framework, donated as UiO-66-NSMe, was prepared by the post-synthetic modification (PSM) of UiO-66-NH₂ with 2-(Methylthio)benzaldehyde, and the successful synthesis of PSM was confirmed by X-ray photoelectron spectroscopy (XPS), FT-IR and ¹H NMR studies. According to the characteristics of mercury thiophilic, UiO-66-NSMe could be used as a luminescent sensor for Hg²⁺ detection with a high selectivity and sensitivity (K_sv = 2.5 × 10⁴ M⁻¹; LOD = 20 nM), which could be attributed to the coordination between sulfur sites and Hg²⁺ based on XPS results. In practical applications, UiO-66-NSMe yielded satisfactory recovery rates (ranging from 96.1% to 99.5%) when it was employed for detecting Hg²⁺ in spiked environmental samples. Furthermore, UiO-66-NSMe was successfully employed to detect mercury (II) residues with the in situ rapid nondestructive imaging in simulated fresh agricultural products. Thus, this PSM strategy could provide good guidance for environmental protection methodologies in the future. Full article

Mixed Matrix Membranes (MMM) with enhanced selectivity and permeability are preferred for gas separations. The porous metal-organic frameworks (MOFs) materials incorporated in them play a crucial part in improving the performance of MMM. In this study, Zeolitic imidazolate frameworks (ZIF-90) are selected to fabricate Polyetherimide (PEI) MMMs owing to their lucrative structural and chemical properties. This work reports new controlled post-synthetic modifications of ZIF-90 (50-PSM-ZIF-90) with ethanolamine to control the diffusion and uptake of CO₂. Physical and chemical properties of ZIF-90, such as stability and presence of aldehyde functionality in the imidazolate linker, allow for easy modulation of the ZIF-90 pores and window size to tune the gas transport properties across ZIF-90-based membranes. Effects of these materials were investigated on the performance of MMMs and compared with pure PEI membranes. Performance of the MMMs was evaluated in terms of permeability of different gases and selective separation of CO₂ and H₂ gas. Results presented that the permeability of all membranes was in the following order, i.e., P(H₂) > P(CO₂) > P(O₂) > P(CH₄) > P(C₂H₆) > P(C₃H₈) > P(N₂), demonstrating that kinetic gas diffusion is the predominant gas transport mode in these membranes. Among all the membranes, permeability of pure PEI membrane was highest for all gases due to the uniform porous morphology. The pure PEI membrane showed highest permeability of H₂, which is 486.5 Barrer, followed by 49 Barrer for O₂, 29 Barrer for N₂, 142 Barrer for CO₂, 41 Barrer for CH₄, 40 Barrer for C₂H₆ and 39.6 Barrer for C₃H₈. Results also confirm the superiority of controlled PSM-ZIF-90-PEI membrane over the pure PEI and ZIF-90-PEI membranes in CO₂ and H₂ separation performance. The 50-PSM-ZIF-90 PEI membrane exhibited a 20% increase in CO₂ separation from methane and a 26% increase over nitrogen compared to the ZIF-90-PEI membrane. The 50-PSM-ZIF-90 PEI membrane showed 15% more H₂/O₂ separation and 9% more H₂/CH₄ separation than ZIF-90 PEI membrane. Overall, this study represents the role of controlled PSM in enhancing the property of new materials like ZIF and its application in MMMs fabrication to develop a promising approach for the CO₂ capture and separation. Full article

Metal-organic frameworks (MOFs) are a new class of microporous materials that possess framework flexibility, large surface areas, “tailor-made” framework functionalities, and tunable pore sizes. These features empower MOFs superior performances and broader application spectra than those of zeolites and phosphine-based molecular sieves. In parallel with designing new structures and new chemistry of MOFs, the observation of unique breathing behaviors upon adsorption of gases or solvents stimulates their potential applications as host materials in gas storage for renewable energy. This has attracted intense research energy to understand the causes at the atomic level, using in situ X-ray diffraction, calorimetry, Fourier transform infrared spectroscopy, and molecular dynamics simulations. This article is developed in the following order: first to introduce the definition of MOFs and the observation of their framework flexibility. Second, synthesis routes of MOFs are summarized with the emphasis on the hydrothermal synthesis, owing to the environmental-benign and economically availability of water. Third, MOFs exhibiting breathing behaviors are summarized, followed by rationales from thermodynamic viewpoint. Subsequently, effects of various functionalities on breathing behaviors are appraised, including using post-synthetic modification routes. Finally, possible framework spatial requirements of MOFs for yielding breathing behaviors are highlighted as the design strategies for new syntheses. Full article