| 1. |
- Khokarale, Santosh G., et al.
(författare)
-
One-Pot, Metal-Free Synthesis of Dimethyl Carbonate from CO2 at Room Temperature
- 2020
-
Ingår i: Sustainable Chemistry. - : MDPI. - 2673-4079. ; 1:3, s. 298-314
-
Tidskriftsartikel (refereegranskat)abstract
- Herein, we report on the metal-free, one-pot synthesis of industrially important dimethyl carbonate (DMC) from molecular CO2 under ambient conditions. In this process, initially the CO2 was chemisorbed through the formation of a switchable ionic liquid (SIL), [DBUH] [CH3CO3], by the interaction of CO2 with an equivalent mixture of organic superbase 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and methanol. The obtained SIL further reacted with methyl iodide (CH3I) to form DMC. The synthesis was carried out in both dimethyl sulfoxide (DMSO) and methanol. Methanol is preferred, as it not only served as a reagent and solvent in CO2 capture and DMC synthesis, but it also assisted in controlling the side reactions between chemical species such as CH3I and [DBUH]+ cation and increased the yield of DMC. Hence, the use of methanol avoided the loss of captured CO2 and favored the formation of DMC with high selectivity. Under the applied reaction conditions, 89% of the captured CO2 was converted to DMC. DBU was obtained, achieving 86% recovery of its salts formed during the synthesis. Most importantly, in this report we describe a simple and renewable solvent-based process for a metal-free approach to DMC synthesis under industrially feasible reaction conditions.
|
|
| 2. |
- Vucetic, Nemanja, et al.
(författare)
-
Tuned Bis-Layered Supported Ionic Liquid Catalyst (SILCA) for Competitive Activity in the Heck Reaction of Iodobenzene and Butyl Acrylate
- 2020
-
Ingår i: Catalysts. - : MDPI. - 2073-4344. ; 10:9
-
Tidskriftsartikel (refereegranskat)abstract
- A thorough experimental optimization of supported ionic liquid catalyst (SILCA) was performed in order to obtain a stable and efficient catalyst for the Heck reaction. Out of fifteen proposed structures, propyl imidazolium bromide-tetramethylguanidinium pentanoate modified SiO2 loaded with PdCl2 appeared to be the most stable and to have a good activity in the reaction between butylacrylate and iodobezene, resulting in a complete conversion in 40 min at 100 °C, in four consecutive experiments. This study elucidated on the stability of the catalytic system with an ionic liquid layer during the catalyst synthesis but also under reaction conditions. In the bis-layered catalyst, the imidazolium moiety as a part of internal layer, brought rigidity to the structure, while in external layer pentanoic acid gave sufficiently acidic carboxylic group capable to coordinate 1,1,3,3-tetramethylguanidine (TMG) and thus, allow good dispersion of Pd nanoparticles. The catalyst was characterized by means of XPS, FT-IR, TEM, ICP-OES, ζ-potential, EDX, TGA, and 13C NMR. The release and catch mechanism was observed, whereas Pd re-deposition can be hindered by catalyst poisoning and eventual loss of palladium.
|
|
| 3. |
- Khokarale, Santosh G., et al.
(författare)
-
Metal free synthesis of ethylene and propylene carbonate from alkylene halohydrin and CO2 at room temperature
- 2019
-
Ingår i: RSC Advances. - : The Royal Society of Chemistry. - 2046-2069. ; 9:58, s. 34023-34031
-
Tidskriftsartikel (refereegranskat)abstract
- Herein we describe a metal free and one-pot pathway for the synthesis of industrially important cyclic carbonates such as ethylene carbonate (EC) and propylene carbonates (PC) from molecular CO2 under mild reaction conditions. In the actual synthesis, the alkylene halohydrins such as alkylene chloro- or bromo or iodohydrin and organic superbase, 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) reacted equivalently with CO2 at room temperature. The syntheses of cyclic carbonates were performed in DMSO as a solvent. Both 1,2 and 1,3 halohydrin precursors were converted into cyclic carbonates except 2-bromo- and iodoethanol, which were reacted equivalently with DBU through n-alkylation and formed corresponding n-alkylated DBU salts instead of forming cyclic carbonates. NMR analysis was used to identify the reaction components in the reaction mixture whereas this technique was also helpful in terms of understanding the reaction mechanism of cyclic carbonate formation. The mechanistic study based on the NMR analysis studies confirmed that prior to the formation of cyclic carbonate, a switchable ionic liquid (SIL) formed in situ from alkylene chlorohydrin, DBU and CO2. As a representative study, the synthesis of cyclic carbonates from 1,2 chlorohydrins was demonstrated where the synthesis was carried out using chlorohydrin as a solvent as well as a reagent. In this case, alkylene chlorohydrin as a solvent not only replaced DMSO in the synthesis but also facilitated an efficient separation of the reaction components from the reaction mixture. The EC or PC, [DBUH][Cl] as well as an excess of the alkylene chlorhydrin were separated from each other following solvent extraction and distillation approaches. In this process, with the applied reaction conditions, >90% yields of EC and PC were achieved. Meanwhile, DBU was recovered from in situ formed [DBUH][Cl] by using NaCl saturated alkaline solution. Most importantly here, we developed a metal free, industrially feasible CO2 capture and utilization approach to obtain EC and PC under mild reaction conditions.
|
|
| 4. |
- Nuri, Ayat, et al.
(författare)
-
Synthesis and Characterization of Palladium Supported Amino Functionalized Magnetic-MOF-MIL-101 as an Efficient and Recoverable Catalyst for Mizoroki–Heck Cross-Coupling
- 2020
-
Ingår i: Catalysis Letters. - : Springer. - 1011-372X .- 1572-879X. ; 150:9, s. 2617-2629
-
Tidskriftsartikel (refereegranskat)abstract
- Magnetic particles were prepared by a hydrothermal method and then successively covered by Metal–Organic-Frameworks MIL-101-NH2 with a high surface area. This was followed by deposition of Pd(OAc)2 on Fe3O4–NH2@MIL-101-NH2 particles. The final catalyst was characterized with FT-IR, nitrogen physisorption, thermogravimetry (TGA), scanning electron microscopy (SEM) combined with energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), wide-angle X-ray diffraction spectroscopy (XRD) and X-ray photoelectron spectroscopy (XPS). The prepared magnetic catalyst was effectively used in the Heck coupling reaction in the presence of an inorganic base. The reaction parameters such as the base type, amounts of catalyst and solvents, temperature, and substrates ratios were optimized. The catalyst was then magnetically separated, washed, and reused 7 times without losing significantly catalytic activity.
|
|
| 5. |
- Shukla, Shashi Kant, 1983-, et al.
(författare)
-
Melting point of ionic liquids
- 2020
-
Ingår i: Encyclopedia of ionic liquids. - Singapore : Springer. - 9789811067396 ; , s. 1-9
-
Bokkapitel (övrigt vetenskapligt/konstnärligt)
|
|
| 6. |
- Pezoa-Conte, R., et al.
(författare)
-
Deconstruction of the green alga Ulva rigida in ionic liquids : closing the mass balance
- 2015
-
Ingår i: Algal Research. - : Elsevier. - 2211-9264. ; 12, s. 262-273
-
Tidskriftsartikel (refereegranskat)abstract
- Algae are known to grow at high rates compared to terrestrial plants that contain comparable amounts of carbohydrates by weight. Therefore, this renders them attractive in terms of any biorefinery concept. In this work the green alga Ulva rigida, containing 40 wt.% of carbohydrates was pretreated with a switchable ionic liquid (SIL), distillable ionic liquid (DIL) and low-viscosity ionic liquid (LVIL). The SIL DBU–MEA–SO2 was prepared from a mixture of mono-ethanolamine (MEA) and 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) that was coupled with sulfur dioxide (SO2), whereas the DIL [TMGH+][EtCO2−] (1,1,3,3-tetramethylguanidine propionate) was synthesized by a simple acid–base neutralization reaction. Consequently, the LVIL [HDBU+][5OF−] protonated 1,8-diazabicyclo-[5,4,0]-undec-7-ene- 2,2,3,3,4,4,5,5-octafluoro-1-pentoxide was used as received. The treatments were carried out in the temperature range of 100–160 °C for 6 h. The products obtained after the treatments were analyzed using different techniques like ICP, OES, SEM, TEM, TGA, FTIR and carbohydrate determination by GC. Upon treatment with DIL up to 67 wt.% of carbohydrates could be dissolved. For the first time, processing of U. rigida was carried out in ionic liquids so that the mass balance of the process was obtained. It can be concluded that 1,1,3,3-tetramethylguanidine propionate shows significant potential when aiming at releasing carbohydrates from algal biomass that, consequently, can be applied in the production of platform chemicals and/or biofuels such as bioethanol.
|
|
| 7. |
- Saeid, Soudabeh, et al.
(författare)
-
Synthesis and Characterization of Metal Modified Catalysts for Decomposition of Ibuprofen from Aqueous Solutions
- 2020
-
Ingår i: Catalysts. - : MDPI. - 2073-4344. ; 10:7
-
Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- The presence of pharmaceuticals in surface water, drinking water, and wastewater has attracted significant concern because of the non-biodegradability, resistance, and toxicity of pharmaceutical compounds. The catalytic ozonation of an anti-inflammatory pharmaceutical, ibuprofen was investigated in this work. The reaction mixture was analyzed and measured by high-performance liquid chromatography (HPLC). Liquid chromatography-mass spectrometry (LC-MS) was used for the quantification of by-products during the catalytic ozonation process. Ibuprofen was degraded by ozonation under optimized conditions within 1 h. However, some intermediate oxidation products were detected during the ibuprofen ozonation process that were more resistant than the parent compound. To optimize the process, nine heterogeneous catalysts were synthesized using different preparation methods and used with ozone to degrade the ibuprofen dissolved in aqueous solution. The aim of using several catalysts was to reveal the effect of various catalyst preparation methods on the degradation of ibuprofen as well as the formation and elimination of by-products. Furthermore, the goal was to reveal the influence of various support structures and different metals such as Pd-, Fe-, Ni-, metal particle size, and metal dispersion in ozone degradation. Most of the catalysts improved the elimination kinetics of the by-products. Among these catalysts, Cu-H-Beta-150-DP synthesized by the deposition–precipitation process showed the highest decomposition rate. The regenerated Cu-H-Beta-150-DP catalyst preserved the catalytic activity to that of the fresh catalyst. The catalyst characterization methods applied in this work included nitrogen adsorption–desorption, scanning electron microscopy, transmission electron microscopy, and Fourier-transform infrared spectroscopy. The large pore volume and small metal particle size contributed to the improved catalytic activity.
|
|
| 8. |
- Sjöblom, Magnus, et al.
(författare)
-
Enzyme-Assisted CO2 Absorption in Aqueous Amino Acid Ionic Liquid Amine Blends
- 2020
-
Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society. - 2168-0485. ; 8:36, s. 13672-13682
-
Tidskriftsartikel (refereegranskat)abstract
- The influence of carbonic anhydrase (CA) on the CO2 absorption rate and CO2 load in aqueous blends of the amino acid ionic liquid pentaethylenehexamine prolinate (PEHAp) and methyl diethanolamine (MDEA) was investigated and compared to aqueous monoethanolamine (MEA) solutions. The aim was to identify blends with good enzyme compatibility, several fold higher absorption rates than MDEA and superior desorption potential compared to MEA. The blend of 5% PEHAp and 20% MDEA gave a solvent with approximately five-fold higher initial absorption rate than MDEA and a two-fold higher regeneration compared to MEA. Experiments in a small pilot absorption rig resulted in a mass transfer coefficient (KGa) of 0.48, 4.6, and 15 mol (m3 s mol fraction)−1 for 25% MDEA, 5% PEHAp, 20% MDEA, and 25% MEA, respectively. CA could maintain approximately 70% of its initial activity after 2 h incubation in PEHAp MDEA blends. Integration of CA with amine-based absorption resulted in a 31.7% increase in mass of absorbed CO2 compared to the respective non-enzymatic reaction at the optimal solvent: CA ratio and CA load. Combining novel blends and CA can offer a good compromise between capital and operating costs for conventional amine scrubbers, which could outperform MEA-based systems.
|
|
| 9. |
- Bui, Thai Q., et al.
(författare)
-
Mesoporous Melamine-Formaldehyde Resins as Efficient Heterogeneous Catalyst for Continuous Synthesis of Cyclic Carbonates from Epoxides and gaseous CO2
- 2020
-
Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 8:34, s. 12852-12869
-
Tidskriftsartikel (refereegranskat)abstract
- Herein we report the application of inexpensive mesoporous melamine-formaldehyde resins (MMFR and MMFR250) obtained by a novel template-free and organosolvent-free hydrothermal method as efficient heterogeneous catalysts for direct synthesis of cyclic carbonates from CO2 and epoxides (epichlorohydrin, butylene oxide and styrene oxide). The catalytic activity of the melamine resins was attributed to the abundant Lewis basic N-sites capable of activating CO2 molecules. Based on CO2-Temperature programmed desorption, the concentration of surface basic sites for MMFR and MMFR250 were estimated to be 172 and 56 µmol/g, while the activation energy of CO2 desorption (strength of basic sites) were calculated to be 92.1 and 64.5 kJ/mol. We also observed considerable differences in the catalytic activity and stability of polymeric catalysts in batch and in continuous-flow mode; due to the existence of a synergism between adsorption of CO2 and cyclic carbonates (poison). Our experiments also revealed important role of catalyst surface chemistry and CO2 partial pressure upon catalyst poisoning. Nevertheless, owing to their unique properties (large specific surface area, large mesoporous and CO2 basicity) melamine resins presented excellent activity (turnover frequency 207-2147 h-1), selectivity (>99%) for carbonation of epoxides with CO2 (20 bar initial CO2 or CO2:epoxide mole ratio ~1.5) under solvent-free and co-catalyst-free conditions at 100-120 oC. Most importantly, these low-cost polymeric catalysts were reusable and demonstrated exceptional stability in a flow reactor (tested upto 13 days time on stream, weight hourly space velocity 0.26-1.91 h-1) for continuous cyclic carbonate production from gaseous CO2 with different epoxides (conversion 76-100% and selectivity >99%) under industrially relevant conditions (120 oC, 13 bar, solvent-free/co-catalyst-free) confirming their superiority over the previously reported catalytic materials.
|
|
| 10. |
- Ismail, Norafiqah, et al.
(författare)
-
Investigating the potential of membranes formed by the vapor induced phase separation process
- 2020
-
Ingår i: Journal of Membrane Science. - : Elsevier. - 0376-7388 .- 1873-3123. ; 597
-
Forskningsöversikt (refereegranskat)abstract
- About 100 years ago, Zsigmondy and Bachmann invented a new method to induce phase inversion, the so-called vapor induced phase separation (VIPS). Since then many researchers have demonstrated this method in membrane fabrication. Here we present a review on membrane fabrication via VIPS to provide insights into membrane formation parameters in order to achieve desired properties for different applications. The key factors upon membrane preparation including solution parameters (i.e. polymer type and concentration, type of solvent, and additives) as well as operating parameters (i.e. exposure time, relative humidity, dissolution temperature, and vapor temperature) are comprehensively discussed. Furthermore, the design of a fouling-resistance membrane by the VIPS process has recently gained attention and is elaborated in details. The applications of the produced membranes via VIPS in water and wastewater treatment, gas separations, electrochemical applications (i.e. secondary batteries and supercapacitors) as well as in medical and biological applications are summarized and an outlook for future investigation is presented.
|
|
