This work presents a comparative study between Ionic Liquids (ILs) along with the neoteric IL-based Deep Eutectic Solvents (DESs) for the thermal dehydrogenation of ethylene diamine-bisborane (EDAB). For the selection of potential reaction media, a screening of the potential DES solvent was carried out using the COnductor-like Screening MOdel Segment Activity Coefficient (COSMO-SAC) model to study the solubility of EDAB in the solvent. On the basis of their obtained Infinite Dilution Activity Coefficient (IDAC) value, the following solvents from the IL and the DES family were selected: 1-butyl-3-methylimidazolium methanesulfonate ([BMIM][MeSO 3 ]) and 1-butyl-3-methylimidazolium methanesulfonate:urea ([BMIM][MeSO 3 ]:[urea]) at a molar ratio of 1:1. The latter is considered a DES owing to the addition of hydrogen bond donor, namely, urea. A 1 H− 1 H Nuclear Overhauser Effect SpectroscopY (NOESY) technique NMR spectrum between [BMIM][MeSO 3 ] and urea was also carried out to elucidate the formation of DES. It was observed that the EDAB/DES system produced 3.2 equiv of hydrogen with a lower induction time when compared to 3.7 equiv of hydrogen at the same temperature (105 °C) for the IL-based solvent. This was also confirmed from the TGA analysis of the reaction mixture. Gas Chromatography (GC) analysis was further performed in order to determine the purity of the released hydrogen gas. 1 H NMR characterization of the residual EDAB/DES and EDAB/IL complexes reaffirmed the role of IL and DES as a catalyst medium. 11 B NMR analysis was further performed in order to confirm the existence of sp 2 boron moieties.

This work reports the thermal dehydrogenation of chemical hydrides, namely, ammonia borane (AB) and ethylene diamine bisborane (EDAB), in the presence of neoteric ionic liquids (ILs) based on methyl carbonate anions. Initially, the COSMO-SAC model was performed to predict the infinite dilution activity coefficient values for the solubility of AB and EDAB on the pyrrolidinium-and ammonium-based cations. Based on the screening study, 1-butyl-1-methylpyrrolidinium methyl carbonate[Bmpyr][CH 3 CO 3 ] and tributylmethylammonium methyl carbonate [TBMA][CH 3 CO 3 ] were selected for our dehydrogenation studies. It was observed that the latter performed remarkably well in terms of equivalents of hydrogen released, which is primarily due to the higher stability of the intermediate in the polar medium of ILs. Here, [TBMA][CH 3 CO 3 ] gave a cumulative release of 3.50 equiv of hydrogen with EDAB at 105 °C. The 1 H NMR spectroscopy technique confirmed the catalytic sum solvent role of ILs. The electronic structure elucidation of individual ILs and IL−chemical hydride complexes was then performed at the M06-2X/6-311++G(d,p) level of theory. The DFT calculations, along with the highest occupied molecular orbital−lowest unoccupied molecular orbital analysis, pointed out the fact that the active sites mainly existed within the methyl carbonate anions. Overall, the dehydrogenation pathway was initiated by the formation of hydrogen-bonded interactions between the protic moieties of the hydrides and the anionic part of the ILs, respectively.

With countries and regions setting strict targets for adopting renewable and sustainable technologies, worldwide demand for energy storage has surged dramatically. Novel materials and new storage chemistry solutions are being explored to realize storage technologies for the next generation. This step-change includes fundamental research in the design of new electrolytes. Ionogels are gaining popularity in electrochemical applications because of their ability to overcome the drawbacks of their liquid counterparts while retaining certain beneficial qualities of the latter. The present study reports the preparation of a novel quasi-solid ionogel through the confinement of the ionic liquid (IL) trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide ([P 66614 ][TFSI]) into a matrix of titania (TiO 2 ) by a simple one-pot sol−gel process. The properties of the ionogel have been studied via field emission scanning electron microscopy (FESEM), rheology, Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and cyclic voltammetry (CV). The ionogel manifests shear-thinning viscoelastic behavior. The integrity of the IL remains unaffected after its confinement in TiO 2 . Thermal stability analysis shows little mass loss of the ionogel up to a temperature of ∼93 °C, favoring its utilization in hightemperature applications. The ionogel demonstrates a double-layer capacitive behavior with an impressive operating potential window (OPW) of 4 V (−4 to +4 V), substantiating its applicability and excellent stability in the electrochemical domain. The formation of the weakly coordinating ionogel is analyzed using density functional theory (DFT). The electronic structures of the precursors and the ionogel are elucidated at the B3LYP/LANL2DZ level of theory. The quantum chemical (QC) calculations reveal that the interaction of the IL with the cross-linker results in some dimensional changes due to alterations in the vibrational frequencies of the respective groups present in the ionogel system.

The demand for effective and secure chemical hydrogen storage systems impedes hydrogen's usage as an alternative energy carrier. This work reports the use of morpholine borane (MB) as a novel, efficient, and widely viable chemical hydrogen storage material for mobile applications. Herein, for the first time, hydrogen generation from the thermolytic dehydrogenation of MB in the presence of ionic liquid (IL) media is reported. Initially, the COSMO-SAC model was utilized to determine the most appropriate solvent. [Bmim][HSO 4 ] proved to be an excellent catalytic solvent media with maximum solubility in the morpholine borane complex. Thermal dehydrogenation experiments were conducted separately on solid-state and MB-IL systems at 60 and 80 °C in a vacuum-sealed experimental setup. After a prolonged heating period, the solid-state dehydrogenation of the MB complex released 0.62 equiv of hydrogen, whereas the dehydrogenation of the MB-IL system at 60 and 80 °C released 1.75 and 1.46 equiv of hydrogen in a shorter time. The residue products were characterized using 1 H and 11 B nuclear magnetic resonance (NMR). 1 H NMR validated IL's activity as a catalytic solvent without affecting its structural identity, whereas 11 B NMR helped establish an intra-and intermolecular dehydrogenation mechanism connected with MB. As confirmed by the density functional theory-based transition state calculations, the intramolecular dehydrogenation pathway results in a dehydrocoupled product with minimal energy required for the dehydrogenation reaction.

Deep eutectic solvents (DESs) based on metal halide salts are highly catalytic, low toxic, reusable, cost-effective, and have higher thermal stability than their analogue ionic liquids (ILs). In this work, we have reported the formation mechanism of metal salt-based DESs at the molecular level along with their charge-transfer analysis and thermodynamics associated with their formation using density functional theory. The DES systems analyzed in the present work were choline chloride and tin(II)chloride (DES1) and choline chloride and zinc(II)chloride (DES2), both in a molar ratio of 1:2, respectively. An excellent correlation is obtained between the theoretically calculated IR spectra of the DES systems and the previously reported experimental findings for the formation of the complex systems. The DESs were found to be stable systems due to traditional hydrogen bonding and electrostatic interactions resulting in the ionic species [Sn 2 Cl 5 ] − and [Zn 2 Cl 5 ] − and are elucidated with the help of electronic structure calculations. CHELPG partial charge analysis and natural bond orbital analysis suggest a charge transfer from Cl − (chloride) to Ch + (choline) and metal salts in the DES structures. The atom-in-molecules and noncovalent interaction (NCI) analysis suggest a strong electrostatic interaction within the DES2 system as compared to DES1. Higher stability and reactivity are observed in the DES2 system based on the frontier molecular orbital analysis. Our analysis offers important insights into the formation mechanism of these economic IL analogues.