68391-54-8

PROBLEM TO BE SOLVED: To provide a novel ionic liquid that is liquid at a room temperature and is hydrophilic, particularly water-soluble, and use thereof.SOLUTION: This invention provides a hydrophilic room-temperature ionic liquid including a cation and an anion, the cation being a quaternary ammonium cation of the formula (I), and the anion being a carboxylate anion, where R represents a 1-5C straight-chain or branched-chain alkylene group, and n represents an integer of 1-3.

Disclosed herein are embodiments of a heterogeneous catalyst system and methods of using the same to convert CO2-derived compounds to formate, formic acid, or a mixture thereof. The disclosed heterogeneous catalyst systems exhibit superior reactivity and stability in comparison to homogeneous catalyst systems and also can convert a variety of CO2-derived compounds to formate, formic acid, or mixtures thereof, in high yields using economical and environmentally friendly reaction conditions.

In this work, neoteric and biodegradable ionic liquids (ILs) based on various hydroxyl ammonium cations and formic acid anions have been used as media for biocatalytic oxidoreductions catalyzed by different metalloproteins. The effect of these ILs on the biocatalytic behavior and structure of solubilized enzymes was investigated using cytochrome c (cyt c) as a model protein. The use of IL-based media enhances the tolerance of cyt c against the denaturing effect of H2O2 and increases (up to 20 fold) its catalytic efficiency compared to that observed in buffer. This beneficial effect strongly correlates with the concentration of ILs used, as well as the chaotropicity of their cations. UV-vis, circular dichroism and Fourier transform infrared (FT-IR) spectroscopic studies indicated that, the effect of ILs on the catalytic behavior of cyt c could be correlated with slight structural changes on the protein molecule and/or perturbations of the heme microenvironment. The use of hydroxyl ammonium-based ILs as reaction media increased (up to 4-fold) the decolorization activity of cyt c. All ILs used were recycled and successfully reused three times indicating the potential application of these novel ILs as environmentally friendly media for biocatalytic processes of industrial interest.

In this work sixteen hydroxyl ammonium Protic Ionic Liquids derived from a proton transfer reaction between four different substituted amines and four different low molecular weight aliphatic and alicyclic carboxylic acids have been synthesized. The synthesized PILs were structurally characterized by NMR and FT-IR spectroscopy whereas two of their more important physicochemical properties namely viscosity and glass transition temperature (Tg) were evaluated. The effect of alkyl chain length and substitution on the anionic and cationic component of the PILs scaffold has been discussed for the studied properties. It seems that Tg values are mainly affected by the carboxylate anion structure whereas viscosity is controlled mainly by the structural features of the cationic part of the PILs. In order to estimate their environmental impact and reinforce their “green” character, biodegradation studies, as well as toxicity evaluation experiments have also been conducted. The synthesized PILs can be confidently labelled as green considering that they are not toxic or present low toxicity to the nauplii of the brine shrimp A. salina whereas they show biodegradability levels between 41–64%, according to the manometric respirometric method which measures the biological oxygen demand (BOD5) by microorganisms in order to degrade PILs via bio-oxidation in five days.

An integrated process of CO2 capture and in situ hydrogenation into formate was achieved in 95-99% yield using a tunable ethoxyl-functionalized amidine and Rh/bisphosphine system, being regarded as an alternative carbon capture and utilization approach to supply fuel-related products, to circumvent the energy penalty in carbon capture and storage. CO2 was captured by non-volatile amidine derivatives with simultaneous activation to form zwitterionic amidinium carbonate, and subsequent hydrogenation was facilitated by Rh/bisphosphine. The adsorption capacity and hydrogenation efficiency can be optimized by tuning the ethoxyl side chain. Particularly, the alkanolamidine bearing an intramolecular hydrogen donor derived from 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU) gave both a high CO2 uptake (molar ratio of 0.95:1) and excellent hydrogenation yield (99%). Furthermore, the silica-supported alkanolamidine was readily recovered and reused with the retention of good performance. This kind of carbon capture and utilization pathway could be a potential energy-saving option for industrial upgrading of CO2 from waste to fuel-related products in a carbon neutral manner.

We designed ionic liquid bis(2-hydroxyethyl)ammonium formate [BHEA][HCO2] for use as a solvent and hydrogen donor for hydrogenation. Catalytic hydrogenation of aromatic ketones, nitro groups, and olefins with PdCl2 in [BHEA][HCO2] generated the corresponding reduction products. Selective reduction of aromatic ketones over aliphatic ketones was observed. Hydrogenolysis of benzyl ethers and benzyl amines also proceeded. All these reactions were successfully carried out in good to excellent yields under mild and nonflammable conditions. In addition, the ionic liquid and Pd source can be reused several times.