Advanced Uranium Removal with Pure, Nonfluorinated Ionic Liquids: Fine-Tuning Hydrophilic and Hydrophobic Properties for Enhanced Selectivity.

Ionic liquids (ILs) have significant potential for eco-friendly extraction of uranium from aqueous solutions, which is critical for nuclear technology, fuel cycle management, and environmental protection. This study examines the impact of the adjustable hydrophobic/hydrophilic properties of ILs on the removal of uranium(VI) (UO22+) from aqueous solutions utilizing both a novel hydrophilic IL (1-butoxyethyl-1-methylmorpholinium butoxyethylphosphite - Mor1-2O4-BOEP) and 1-heptyl-1-methylmorpholinium heptylphosphite (Mor1-7-HP) as an example of a hydrophobic IL with a similar structure. The transfer mechanism of uranyl ions from water to organic or solid phases closely depends on the physicochemical properties of ILs, especially their hydrophobicity. The hydrophobic Mor1-7-HP extracts uranyl via neutral complex formation as UO2(NO3)2-(Mor1-7-HP)2. Conversely, hydrophilic Mor1-2O4-BOEP induced selective precipitation as UO2(NO3)-(BOEP), transferring uranyl to the solid phase. Optimization of the working parameters, in terms of acidity of the aqueous solution and amount of ILs used, allowed the extraction of over 98% of U(VI). The stoichiometry of the organic complex and the precipitate was determined using physicochemical techniques. These tunable H-phosphonate-based ILs have advantages over traditional solvent extraction and conventional ILs, allowing easier handling, improved selectivity, and lower environmental impact. This work advances uranium separation techniques with applications in hydrometallurgy, particularly in the treatment of wastewater and radioactive waste for sustainable uranium recovery.

Enhanced Electrochemical Performance in Supercapacitors through KCu-Cy Based Metal-Organic Framework Electrodes.

In the realm of electronics and electric energy storage, the convergence of organic and metallic materials has yielded promising outcomes. In this study, we introduce a novel metal-organic polymer synthesized from Cyamelurate and copper (KCu-Cy) and explore its application as an electrode for a supercapacitor. This material was pressed onto a stainless-steel grid as a thin film and synthesized on nickel foam. Comprehensive characterization was carried out to confirm the synthesis, ensure phase purity, and investigate atomic interactions. Single Crystal X-ray Diffraction (SCXRD) and Powder X-ray Diffraction (PXRD) analyses verified the synthesis and phase purity, shedding light on atomic arrangements. Fourier Transform Infrared Spectroscopy (FTIR) analyses provided insights into characteristic peaks within the material. Thermal Gravimetric Analysis (TGA) gauged stability and durability. Electrochemical performance was assessed through cyclic voltammetry. Notably, the nickel-supported electrodes, devoid of binders, exhibited exceptional specific capacity, reaching 1210.89 F/g at a scan rate of 5 mV/s, in contrast to 363.73 F/g for the pressed thin film on the stainless-steel grid, which incorporated a conductive agent and binder. Cu-Cy displayed impressive cyclization resistance, with a capacity retention of 90 % even after 11000 cycles. These findings underline the promise of Cu-Cy as a high-performance electrode material for supercapacitors, particularly in binder-free configurations, and suggest its potential in advanced energy storage applications.

Theoretical investigation of hydrogen sulfide capture from methane binary mixture using s-heptazine-based metal-organic framework.

CONTEXT: MOFs are promising candidates for the capture of H2S and CO2 from raw biogas. The presence of H2S residues in natural gas pipelines can cause corrosive damage and reduce energy efficiency. H2S capture from biogas presents several challenges due to its high toxicity and its corrosiveness. Microporous MOFs incorporating Lewis basic sites have demonstrated efficient capture of small and polar gas molecules such as CO2 and H2S from gas binary mixtures. In the quest to design and investigate functional materials to support the energy transition, specifically for the purification of RNG gas, we theoretically investigated the potential of s-heptazine-based IRH-1 for H2S capture from CH4 mixtures. IRH-1 exhibited significantly higher adsorption capacities for H2S (2.60 mmol/g) and CO2 (2.68 mmol/g) compared to CH4 (0.98 mmol/g) at 100 kPa and 298 K simulated by GCMC. All computed average energies for H2S were below 20 kJ/mol, indicating an exothermic physisorption behavior within the pores of IRH-1. IAST revealed remarkable H2S selectivity of IRH-1 for CH4/H2S binary mixtures at 5%, 10%, 15%, and 20% of H2S at 100 kPa. METHODS: GCMC simulations were performed with the BIOVIA Materials Studio 5.0 package using LJ potentials and UFF parameters to investigate the adsorption of pure H2S gas in the IRH-1 material. The IAST method was used to predict the adsorption behavior of H2S in different H2S/CH4 gas mixtures. The IAST calculations were performed using the Python package pyIAST, which allows the prediction of adsorption isotherms for mixed gases based on the adsorption isotherms for pure gases by numerical integration of the Gibbs adsorption approach.

Effect of Crystal Morphology on Electrochemical Performances of IRH-2 and IRH-2/PANI Composite for Supercapacitor Electrodes.

In the context of recent progress in designing metal-organic framework (MOF)-based supercapacitor electrodes, we report herein the successful growth of two different crystal morphologies of a cerium-based MOF, octahedral crystals named IRH-2-O and elongated square-bipyramidal crystals named IRH-2-ESBP (IRH = Institute de Recherche sur l'Hydrogène). The identical crystal structure of both materials was confirmed by powder X-ray diffraction (PXRD). Furthermore, scanning electron microscopy and energy-dispersive X-ray mapping analysis corroborated this fact and showed the crystal shape variation versus the surface composition of synthesized materials. Fourier transform infrared spectroscopy, UV-vis spectroscopy, and PXRD were used to confirm the purity of pristine MOFs as well as desired MOF//PANI composites. Cyclic voltammetry and electrochemical impedance spectroscopy highlighted the effect of crystal shape on the electrochemical performance of IRH-2 MOFs; the specific capacitance tripled from 43.1 F·g-1 for IRH-2-O to 125.57 F·g-1 for IRH-2-ESBP at 5 mV·s-1. The cycling stability was notably ameliorated from 7 K for IRH-2-O to 20 K for IRH-2-ESBP. Regarding the composites, the cell voltage was notably ameliorated from 1.8 to 1.95 V. However, the electrochemical performance of IRH-2/PANI composites was drastically decreased due to instability in the acidic media. To the best of our knowledge, our work is the first work that related the MOF crystal shape and the electrochemical performance.

Flexible and porous 2D layered structures based on mixed-linker metal-organic frameworks for gas sorption studies.

Layered structures of flexible mixed-linker metal-organic frameworks termed IRHs-(4 and 5) (IRH = Institut de Recherche sur l'Hydrogène) were synthesized by mixing cyclam, tetrakis(4-carboxyphenyl)benzene (TCPB), and copper and zinc metal salts respectively. The new materials characterized by single-crystal X-ray diffraction exhibited the features of HOFs and MOFs. Their structures are formed by coordination and hydrogen bonds that link metallocyclam (with Cu or Zn) and TCPB to a 2D sheet which is further packed to form a 3D structure with 1D microchannels. Remarkably, the as-synthesized IRHs-(4 and 5) contain DMF in the channels that can be exchanged with DCM and afterward removed from the framework by heating without losing their single-crystallinity. This enabled an easy elucidation of the structural transformations by single-crystal and powder X-ray diffraction analyses. Experimental studies of single-component adsorption isotherms of pure CO2, CH4, and N2 gases have been carried out for all activated IRHs. Based on the obtained adsorption isotherms, theoretical calculations using Ideal Adsorbed Solution Theory (IAST) have been performed to predict the selectivity of equimolar CO2/CH4 and CO2/N2 (1 : 1) binary mixtures. The simulations predicted outstanding selectivity for CO2/N2 than for CO2/CH4 at low pressures, reaching 185 for IRH-4 and 130 for IRH-5 at 1 bar.