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      Deep eutectic solvents as highly active catalysts for the fast and mild glycolysis of poly(ethylene terephthalate)(PET)

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          Abstract

          Urea/metal salt DESs can catalyze PET degradation into a monomer with high selectivity in a short time under mild conditions.

          Abstract

          Deep eutectic solvents (DESs) have attracted broad attention due to their low cost, easy preparation, low toxicity, good biological compatibility and similar characteristics to those of ionic liquids (ILs). In this study, we found that not only the glycolysis time is sharply shortened under mild reaction conditions, but also the high selectivity of monomer bis(hydroxyalkyl) terephthalate (BHET) is obtained when DESs were used as catalysts. Then, the influences of technological parameters on PET degradation were investigated and the optimization conditions were obtained. Under the optimization conditions of ethylene glycol (EG) (20 g), catalyst ( n(urea)/ n(ZnCl 2) 4/1, 0.25 g), PET (5 g), and atmospheric pressure at 170 °C for 30 min, the conversion of PET and selectivity of BHET were 100% and 83%, respectively. This time is equal to that taken by a supercritical method under 15.3 MPa at 450 °C. In addition, the degradation mechanism of PET wastes catalyzed by DESs is proposed through the experiments and DFT calculations. The high catalytic activity is attributed to the synergetic catalysis of H-bonds and coordination bonds formed between the DES catalyst and EG.

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          Most cited references29

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          Natural Deep Eutectic Solvents – Solvents for the 21st Century

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            Deep eutectic solvents: sustainable media for nanoscale and functional materials.

            Deep eutectic solvents (DESs) represent an alternative class of ionic fluids closely resembling room-temperature ionic liquids (RTILs), although, strictly speaking, they are distinguished by the fact that they also contain an organic molecular component (typically, a hydrogen bond donor like a urea, amide, acid, or polyol), frequently as the predominant constituent. Practically speaking, DESs are attractive alternatives to RTILs, sharing most of their remarkable qualities (e.g., tolerance to humidity, negligible vapor pressure, thermostability, wide electrochemical potential windows, tunability) while overcoming several limitations associated with their RTIL cousins. Particularly, DESs are typically, less expensive, more synthetically accessible (typically, from bulk commodity chemicals using solvent/waste-free processes), nontoxic, and biodegradable. In this Account, we provide an overview of DESs as designer solvents to create well-defined nanomaterials including shape-controlled nanoparticles, electrodeposited films, metal-organic frameworks, colloidal assemblies, hierarchically porous carbons, and DNA/RNA architectures. These breakthroughs illustrate how DESs can fulfill multiple roles in directing chemistry at the nanoscale: acting as supramolecular template, metal/carbon source, sacrificial agent (e.g., ammonia release from urea), and/or redox agent, all in the absence of formal stabilizing ligand (here, solvent and stabilizer are one and the same). The ability to tailor the physicochemical properties of DESs is central to controlling their interfacial behavior. The preorganized "supramolecular" nature of DESs provides a soft template to guide the formation of bimodal porous carbon networks or the evolution of electrodeposits. A number of essential parameters (viscosity, polarity, surface tension, hydrogen bonding), plus coordination with solutes/surfaces, all play significant roles in modulating species reactivity and mass transport properties governing the genesis of nanostructure. Furthermore, DES components may modulate nucleation and growth mechanisms by charge neutralization, modification of reduction potentials (or chemical activities), and passivation of particular crystal faces, dictating growth along preferred crystallographic directions. Broad operational windows for electrochemical reactions coupled with their inherent ionic nature facilitate the electrodeposition of alloys and semiconductors inaccessible to classical means and the use of cosolvents or applied potential control provide under-explored strategies for mediating interfacial interactions leading to control over film characteristics. The biocompatibility of DESs suggests intriguing potential for the construction of biomolecular architectures in these novel media. It has been demonstrated that nucleic acid structures can be manipulated in the ionic, crowded, dehydrating (low water activity) DES environment-including the adoption of duplex helical structures divergent from the canonical B form and parallel G-quadruplex DNA persisting near water's boiling point-challenging the misconception that water is a necessity for maintenance of nucleic acid structure/functionality and suggesting an enticing trajectory toward DNA/RNA-based nanocatalysis within a strictly anhydrous medium. DESs offer tremendous opportunities and open intriguing perspectives for generating sophisticated nanostructures within an anhydrous or low-water medium. We conclude this Account by offering our thoughts on the evolution of the field, pointing to areas of clear and compelling utility which will surely see fruition in the coming years. Finally, we highlight a few hurdles (e.g., need for a universal nomenclature, absence of water-immiscible, oriented-phase, and low-viscosity DESs) which, once navigated, will hasten progress in this area.
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              Asymmetric cooperative catalysis of strong Brønsted acid-promoted reactions using chiral ureas.

              Cationic organic intermediates participate in a wide variety of useful synthetic transformations, but their high reactivity can render selectivity in competing pathways difficult to control. Here, we describe a strategy for inducing enantioselectivity in reactions of protio-iminium ions, wherein a chiral catalyst interacts with the highly reactive intermediate through a network of noncovalent interactions. This interaction leads to an attenuation of the reactivity of the iminium ion and allows high enantioselectivity in cycloadditions with electron-rich alkenes (the Povarov reaction). A detailed experimental and computational analysis of this catalyst system has revealed the precise nature of the catalyst-substrate interactions and the likely basis for enantioinduction.
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                Author and article information

                Journal
                GRCHFJ
                Green Chemistry
                Green Chem.
                Royal Society of Chemistry (RSC)
                1463-9262
                1463-9270
                2015
                2015
                : 17
                : 4
                : 2473-2479
                Affiliations
                [1 ]Beijing Key Laboratory of Ionic Liquids Clean Process
                [2 ]Key Laboratory of Green Process and Engineering
                [3 ]Institute of Process Engineering
                [4 ]Chinese Academy of Sciences
                [5 ]Beijing 100190
                Article
                10.1039/C4GC02401J
                82aec38d-d6d4-4677-adbc-4b6f60931a8c
                © 2015
                Product
                Self URI (article page): http://xlink.rsc.org/?DOI=C4GC02401J

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