CYCU-3: an Al(III)-based MOF for SO2 capture and detection.

The Al(III)-based MOF CYCU-3 exhibits a relevant SO2 adsorption performance with a total uptake of 11.03 mmol g-1 at 1 bar and 298 K. CYCU-3 displays high chemical stability towards dry and wet SO2 exposure. DRIFTS experiments and computational calculations demonstrated that hydrogen bonding between SO2 molecules and bridging Al(III)-OH groups are the preferential adsorption sites. In addition, photoluminescence experiments demonstrated the relevance of CYCU-3 for application in SO2 detection with good selectivity for SO2 over CO2 and H2O. The change in fluorescence performance demonstrates a clear turn-on effect after SO2 interaction. Finally, the suppression of ligand-metal energy transfer along with the enhancement of ligand-centered π* → π electronic transition was proposed as a plausible fluorescence mechanism.

Covalent organic frameworks as highly versatile materials for the removal and electrochemical sensing of organic pollutants.

The presence of persistent organic compounds in water has become a worldwide issue due to its resistance to natural degradation, inducing its environmental resilience. Therefore, the accumulation in water bodies, soils, and humans produces toxic effects. Also, low levels of organic pollutants can lead to serious human health issues, such as cancer, chronic diseases, thyroid complications, immune system suppression, etc. Therefore, developing efficient and economically viable remediation strategies motivates researchers to delve into novel domains within material science. Moreover, finding approaches to detect pollutants in drinking water systems is vital for safeguarding water safety and security. Covalent organic frameworks (COFs) are valuable materials constructed through strong covalent interactions between blocked monomers. These materials have tremendous potential in removing and detecting persistent organic pollutants due to their high adsorption capacity, large surface area, tunable porosity, porous structure, and recyclability. This review discusses various synthesis routes for constructing non-functionalized and functionalized COFs and their application in the remediation and electrochemical sensing of persistent organic compounds from contaminated water sources. The development of COF-based materials has some major challenges that need to be addressed for their suitability in the industrial configuration. This review also aims to highlight the importance of COFs in the environmental remediation application with detailed scrutiny of their challenges and outcomes in the current research scenario.

Evaluation of the catalytic activity of Zn-MOF-74 for the alcoholysis of cyclohexene oxide.

In the present work, nanocrystalline Zn-MOF-74 is shown to be a heterogeneous catalyst for the acid-catalyzed ring-opening alcoholysis of cyclohexene oxide. The results corroborated that accessible open metal sites within the material are critical conditions (Zn(ii) Lewis acid sites) for this reaction. Zn-MOF-74 was tested at three different temperatures (30, 40, and 50 °C) for the alcoholysis reaction. Furthermore, the cyclohexene oxide conversion was 94% in less than two days. A comparison of the catalytic activity with different crystal sizes of Zn-MOF-74 and the homogenous phase, zinc acetate, was conducted. Zn-MOF-74 exhibited excellent catalytic cyclability for three cycles without losing its activity. The material showed chemical stability by retaining its crystalline structure after the reaction and cyclability process.

MFM-300(Sc): a chemically stable Sc(III)-based MOF material for multiple applications.

Developing robust multifunctional metal-organic frameworks (MOFs) is the key to advancing the further deployment of MOFs into relevant applications. Since the first report of MFM-300(Sc) (MFM = Manchester Framework Material, formerly known as NOTT-400), the development of applications of this robust microporous MOF has only grown. In this review, a summary of the applications of MFM-300(Sc), as well as some emerging advanced applications, have been discussed. The adsorption properties of MFM-300(Sc) are presented systematically. Particularly, this contribution is focused on acid and corrosive gas adsorption. In addition, recent applications for catalysis based on the outstanding hemilabile Sc-O bond character are highlighted. Finally, some new research areas are introduced, such as host-guest chemistry and biomedical applications. This highlight aims to showcase the recent advances and the potential for developing new applications of this promising material.

MOF-based catalysts: insights into the chemical transformation of greenhouse and toxic gases.

Metal-organic framework (MOF)-based catalysts are outstanding alternative materials for the chemical transformation of greenhouse and toxic gases into high-add-value products. MOF catalysts exhibit remarkable properties to host different active sites. The combination of catalytic properties of MOFs is mentioned in order to understand their application. Furthermore, the main catalytic reactions, which involve the chemical transformation of CH4, CO2, NOx, fluorinated gases, O3, CO, VOCs, and H2S, are highlighted. The main active centers and reaction conditions for these reactions are presented and discussed to understand the reaction mechanisms. Interestingly, implementing MOF materials as catalysts for toxic gas-phase reactions is a great opportunity to provide new alternatives to enhance the air quality of our planet.

SU-101: a Bi(III)-based metal-organic framework as an efficient heterogeneous catalyst for the CO2 cycloaddition reaction.

A non-porous version of SU-101 (herein n-SU-101) was evaluated for the CO2 cycloaddition reaction. The findings revealed that open metal sites (Bi3+) are necessary for the reaction. n-SU-101 displays a high styrene oxide conversion of 96.6% under mild conditions (3 bar and 80 °C). The catalytic activity of n-SU-101 demonstrated its potential application for the cycloaddition of CO2 using styrene oxide.

Detection of SO2 using a chemically stable Ni(II)-MOF.

The MOF-type Ni2(dobpdc) shows a high chemical stability towards SO2, high capacity for SO2 capture at low pressure (4.3 mmol g-1 at 298 K and up to 0.05 bar), and exceptional cycling performance. Fluorescence experiments demonstrated the SO2 detection properties of Ni2(dobpdc) with a remarkable SO2 detection selectivity. Finally, time-resolved photoluminescence experiments provided a plausible mechanism of SO2 detection by this Ni(II)-based MOF material.

Zinc-aluminum layered double hydroxide and double oxide for room-temperature oxidation of sulfur dioxide gas.

Sulfur dioxide (SO2) gas at trace levels challenges the consumption of fuel gases and cleaning of flue gases originating from diverse anthropogenic sources. We have demonstrated Zn-Al layered double hydroxide (LDH) and layered double oxide (LDO) as low-cost and effective adsorbents in removing lowly concentrated SO2 gas at room temperature. Water in the adsorbent bed significantly improved the performance, where the maximum adsorption capacity of 38.0 mg g-1 was achieved for LDO. Based on the spectroscopic findings, the adsorbed gas molecules were oxidized to surface-bound sulfate/bisulfate species, showing complete mineralization of SO2 molecules. By employing an inexpensive NaOH-H2O2 solution-based regeneration strategy, we successfully regenerated the spent LDO, significantly restoring its gas uptake capacity. The regenerated oxide exhibited an increased gas uptake capacity ranging from 38.0 to 98.5 mg g-1, highlighting the practicality and economic feasibility of our approach. LDH/LDO materials are promising regenerable adsorbents for removing low concentrations of SO2 gas in ambient conditions.

Encapsulation of dopamine within SU-101: insights by computational chemistry.

Encapsulating and protecting dopamine from oxidation is a difficult challenge. We propose to use SU-101 BioMOF as a dopamine host, where we study different adsorption scenarios by a robust computational approach. Our results show that dopamine encapsulation is feasible with the formation of non-covalent interactions within the SU-101 pores. These computational results have been corroborated experimentally.

Gas-phase organometallic catalysis in MFM-300(Sc) provided by switchable dynamic metal sites.

MFM-300(Sc) was explored as a catalyst for the gas-phase hydrogenation of acetone. The catalysis results support the presence of non-permanent open Sc(III) sites within the structure due to the requirement of Lewis acid sites for the reaction to proceed. The open Sc(III) sites are generated in situ due to the presence of hemilabile Sc-O bonds. MFM-300(Sc) showed high mechanical and chemical stability, and the crystalline structure was maintained after the catalytic reaction. The catalytic activity of the material was quantified by performing a gas-phase reaction using a continuous flow reactor. The acetone conversion in MFM-300(Sc) was estimated to be 27.7% with no loss of activity after catalytic cycles.

Engineering Catalysis within a Saturated In(III)-Based MOF Possessing Dynamic Ligand-Metal Bonding.

Metal-organic frameworks have developed into a formidable heterogeneous catalysis platform in recent years. It is well established that thermolysis of coordinated solvents from MOF nodes can render highly reactive, coordinatively unsaturated metal complexes which are stabilized via site isolation and serve as active sites in catalysis. Such approaches are limited to frameworks featuring solvated transition-metal complexes and must be stable toward the formation of "permanent" open metal sites. Herein, we exploit the hemilability of metal-carboxylate bonds to generate transient open metal sites in an In(III) MOF, pertinent to In-centered catalysis. The transient open metal sites catalyze the Strecker reaction over multiple cycles without loss of activity or crystallinity. We employ computational and spectroscopic methods to confirm the formation of open metal sites via transient dissociation of In(III)-carboxylate bonds. Furthermore, the amount of transient open metal sites within the material and thus the catalytic performance can be temperature-modulated.

SO2 capture and detection using a Cu(II)-metal-organic polyhedron.

The SO2 adsorption-desorption capacity at room temperature and 1 bar of the metal-organic polyhedron MOP-CDC was investigated. In addition, the qualitative solid-state absorption-emission properties of this material (before and after SO2 exposure) were measured and tested, and it demonstrated remarkable capability for SO2 detection. Our results represent the first example of fluorimetric SO2 detection in a MOP.

Mercury remediation from wastewater through its spontaneous adsorption on non-functionalized inverse spinel magnetic ferrite nanoparticles.

In this study, inverse spinel cubic ferrites MFe2O4 (M = Fe2+, and Co2+) have been fabricated for the high-capacity adsorptive removal of Hg(II) ions. The PXRD analysis confirmed ferrites with the presence of residual NaCl. The surface area of Fe3O4 (Fe-F) and CoFe2O4 (Co-F) material was 69.1 and 45.2 m2 g-1, respectively. The Co-F and Fe-F showed the maximum Hg(II) adsorption capacity of 459 and 436 mg g-1 at pH 6. The kinetic and isotherms models suggested a spontaneous adsorption process involving chemical forces over the ferrite adsorbents. The Hg(II) adsorption process, probed by X-ray photoelectron spectroscopy (XPS), confirmed the interaction of Hg(II) ions with the surface hydroxyl groups via a complexation mechanism instead of proton exchange at pH 6 with the involvement of chloride ions. Thus, this study demonstrates a viable and cost-effective solution for the efficient remediation of Hg ions from wastewater using non-functionalized ferrite adsorbents. This study also systematically investigates the kinetics and isotherm mechanism of Hg(II) adsorption onto ferrites and reports one of the highest Hg(II) adsorption capacities among other ferrite-based adsorbents.

Switchable Metal Sites in Metal-Organic Framework MFM-300(Sc): Lewis Acid Catalysis Driven by Metal-Hemilabile Linker Bond Dynamics.

Uncommon reversible guest-induced metal-hemilabile linker bond dynamics in MOF MFM-300(Sc) was unraveled to switch on/switch off catalytic open metal sites. The catalytic activity of this MOF with non-permanent open metal sites was demonstrated using a model Strecker hydrocyanation reaction as a proof-of-concept. Conclusively, the catalytic activity was evidenced to be fully reversible, preserving the conversion performance and structure integrity of MFM-300(Sc) over multiple cycles. These experimental findings were corroborated by quantum-calculations that revealed a reaction mechanism driven by the Sc-open metal sites. This discovery paves the way towards the design of new effective and easily regenerable heterogeneous MOF catalysts integrating switchable metal sites.

Application of hybrid MOF composite in extraction of f-block elements: Experimental and computational investigation.

An attempt was made to understand the sorption behaviour of UO22+, Th4+ and Eu3+ on novel hybrid metal-organic framework composites, FeBDC@CoBDC. The XRD pattern revealed the composite nature of the hybrid MOF materials, while FTIR and Raman spectroscopic analyses evidenced the presence of different functional moieties. The thermal stability of the hybrid MOF composites was investigated through thermogravimetric analysis. The sorption predominantly followed Langmuir isotherm with sorption capacity of 189 mg g-1, 224 mg g-1 and 205 mg g-1 for UO22+, Th4+ and Eu3+ respectively. The sorption proceeded through chemisorption following pseudo 2nd order rate kinetics. The processes were found to be thermodynamically favourable and endothermic in nature. However, they were entropically driven. Multiple contacts of complexing agents were necessary for quantitative elution of f-elements from loaded MOF. The MOF showed moderate stability towards radiation exposure. DFT calculation was used for the optimization of structures, estimation of bond length and estimation of binding energy. In hybrid MOF composites, the Fe atom was having six coordination with 4 O atoms of BDC moieties and 2 O atoms of -OH groups. The O atoms of BDC and -OH groups were coordinated to Eu, Th and U atoms during their sorption.