Supported ionic liquid phases (SILP) are efficiently use for the construction of highly active, heterogeneous and recyclable catalysts. In this study, three strategies towards chemical immobilization of trifloaluminate ionic liquid catalyst into microporous/mesoporous silica support were investigated. The order of silica surface modification with trifloaluminate ILs components had crucial influence on the catalytic activity and stability which was tested in the model Diels-Alder reaction between isoprene and maleic anhydride in acetonitrile at room temperature. The best catalytic performance (maleic anhydride conversion > 97% in ten reaction cycles) was achieved for catalyst created through the synthesis of trifloaluminate ionic liquid in the first step with further bounding to the silica surface using 25 wt% of ionic liquid loading. The effective transformation of the Diels-Alder reaction to continuous flow synthesis led to 97% maleic anhydride conversion over 432 h with a TOF of 104.3 h-1 and significantly improved process sustainability.

A deep eutectic solvent (DES), composed of choline chloride and urea, demonstrated exceptional solubility properties, allowing the dissolution of 0.8 wt % of zinc oxide. This liquid system was used as both solvent and catalyst (DES 300 mol %; ZnO 7.8 mol %) for the transesterification of dimethyl terephthalate (DMTP) with various alcohols (1-butanol, 2-butanol, 2-ethylhexanol, 1-hexanol, and 1-octanol). For example, the use of 1-butanol caused full conversion of DMTP after 24 h at 120 degrees C. The synergistic effect of the DES and ZnO was demonstrated via a comparison with the catalytic efficiency of the components used separately. The advantage of the catalytic system is the lack of miscibility of the product with DES-ZnO, resulting in the formation of a biphasic system during the reaction, the shifting of the reaction equilibrium being the main driving force for this process. DES-ZnO was used in six consecutive reaction cycles without any significant drop in efficiency.

In this work, a novel acidic catalyst based on protic ionic liquid (1-metylimidazoluim triflate, [Hmim][OTf]) and ZnO was developed. First, analysis of the structure was developed by HRMS, FT-IR and Raman spectroscopy, NMR, and X-ray absorption spectroscopy. The obtained results revealed an alternative structure and mechanism of the formation of the ionic liquid/ZnO adduct ([Hmim][OTf])3Zn. The developed liquid system was created based on the molar ratio of ([Hmim][OTf])3Zn and was shown as an effective acidic catalyst and solvent in the alternative synthesis of plasticizers. In particular, ([Hmim][OTf])3Zn (10mol%) displayed catalytic efficiency for the esterification of succinic acid, adipic acid, and lactic acid with two alcohols 1-butanol and 2-etylhexanol. For 2-ethyl-1-hexanol, full conversion of succinic acid was achieved after 1h at 130 °C. The synergistic effect of the ionic liquid and ZnO was demonstrated by comparing the catalytic efficiency of the individual components. ([Hmim][OTf])3Zn was used in six consecutive reaction cycles without a significant decrease in catalytic efficiency. Additionally, structural studies provided the foundation for the rational design and development of an acidic catalyst, consequently leading to a more environmentally friendly and economically feasible process.

Aiming at sustainable solutions suitable for industrial-scale catalysis catalytic phase containing lipase and deep eutectic solvent (DES) was designed. To achieve this, both physical and chemical immobilizations of lipases were performed on the surface of silica and carbon materials. The catalytic activity of developed biosystem was tested in biotransformation of alpha-angelica lactone into butyl levulinate at 60 degrees C. The best results were achieved for Candida antarctica lipase B adsorbed on fumed silica suspended in choline chloride: glycerol (1:2) with the addition of 20 wt% of water. Under these conditions 99.9% conversion of alpha-angelica lactone and 100% selectivity to butyl levulinate were obtained after 45 min. The biocatalytic system maintained its activity for up to five consecutive reaction cycles with full conversion of lactone to ester. The heterogenization of the enzyme allowed the biocatalyst to be integrated into the bulk of the DES, which includes essential water. This combination resulted in the formation of a stable and easy-to-operate catalytic phase where reagents formed a second organic phase. The integration of cost-effective biocatalyst with process efficiency provides a greener alternative with significant potential for industrial use. The heterogenization of Candida antarctica lipase B adsorbed on fumed silica suspended in DES (choline chloride:glycerol) with the addition of 20 wt% of water allowed the biocatalyst to be integrated into the bulk of the DES. The biocatalytic system maintained its activity in the conversion of alpha-angelica lactone to butyl levulinate up to five reaction cycles. image

Figure 7. presents the scheme of ionic liquid immobilization on the silica surface. The file relates to the composite material manufactured for the NCN project OPUS, grant no. 2020/37/B/ST8/00693.

Heterogeneous catalysis, although known for over a century, is constantly improved and plays a key role in solving the present problems in chemical technology. Thanks to the development of modern materials engineering, solid supports for catalytic phases having a highly developed surface are available. Recently, continuous-flow synthesis started to be a key technology in the synthesis of high added value chemicals. These processes are more efficient, sustainable, safer and cheaper to operate. The most promising is the use of heterogeneous catalyst with column-type fixed-bed reactors. The advantages of the use of heterogeneous catalyst in continuous flow reactors are the physical separation of product and catalyst, as well as the reduction in inactivation and loss of the catalyst. However, the state-of-the-art use of heterogeneous catalysts in flow systems compared to homogenous ones remains still open. The lifetime of heterogeneous catalysts remains a significant hurdle to realise sustainable flow synthesis. The goal of this review article was to present a state of knowledge concerning the application of Supported Ionic Liquid Phase (SILP) catalysts dedicated for continuous flow synthesis.

Deep eutectic solvents (DESs) are an emerging class of materials that show promise for applications as inexpensive “designer” solvents with tunable properties. A detailed review of the current literature reveals a lack of predictive understanding of the microscopic mechanisms that govern the structure−property relationships in this class of solvents. They can dissolve both organic and inorganic compounds, including salts and metal oxides. Zinc oxide is used as a substrate for the synthesis of various task-specific materials, and has excellent antibacterial properties. In this work, both DES and a DES + ZnO combination were used for the first time as admixtures for cement composites, and were shown to improve the final properties of the cement matrix. The materials obtained exhibit good antibacterial properties, even with small amounts of zinc oxide, improved mechanical properties, and good durability when subjected to freezing–thawing cycles.

Nitrogen-doped carbon composites are prepared using simple precursors, such as glucose or urea and used as supports for Fe nanoparticles. The present work investigated two approaches for incorporating metal nanoparticles into the composite: traditional metal postloading and in situ formation of a metal/N-doped carbon catalyst. The impacts of the preparation technique on (i) the characteristics of the resulting iron oxides (Fe2O3 and Fe3O4) and (ii) the nanoparticle distribution on the support were determined. Microscopic surface characterization revealed that the postloading method promoted a uniform distribution of Fe nanoparticles (5-10 nm), which enhanced the activity and long-term stability of the catalytic system for the Baeyer-Villiger oxidation of cyclic ketones. The product yield reached 97% (5 h, 60 degrees C), and after the third reaction cycle, the yield remained at 96%. The proposed synthetic approach for preparing active and stable catalysts provides a new perspective for the inexpensive and sustainable synthesis of lactones.

The second research task carried out under the project concerns the synthesis of metallate ionic liquids and the physical and chemical properties characterization. The information relates to study performed for the NCN project OPUS, grant no. 2020/37/B/ST8/00693.

Dataset contains results obtained during the NCN project OPUS, grant no. 2020/37/B/ST8/00693. The file presents the catalytic activity of triflogallate (III) IL catalyst in cycloaddition between methyl/ethyl acrylate and cyclopentadiene.

In this work heterogeneous catalysts based on hybrid materials consisted of calcium and/or magnesium silicates and modern task-specific ionic liquids (supported ionic liquid phase material) dedicated particularly for continuous flow synthesis of fine chemicals with liquid reagents were designed. Pure SiO2 (as a reference sample), as well as magnesium (MgO-SiO2) or calcium (CaO-SiO2) silicates were used as supports for Lewis acidic trifloaluminate ionic liquids immobilized via chemical bound. The lowest ionic liquid loading was determined for SiO2 (15.58 wt%) and the highest for CaO-SiO2 (23.70 wt%). Resulted catalysts were used for the optimization of process parameters of the synthesis of beta-amino alcohols in batch reactor (molar ratio aniline: styrene oxide 1.1:1; 1 mol% of catalyst, 60 degrees C). Not only the most active (conversion of styrene oxide 100.0% and selectivity to main product 98.7%) but also stable in 3 cycles of the process was the catalyst based on MgO-SiO2. The activity of poorly recyclable precursor of ionic liquid used as an active phase Al(OTf)(3) was also lower (conversion 87.3% and selectivity 94.6%). Substrate scope confirmed the versatility of this method. The key achievement of the research was the confirmation of activity and stability of the most active catalyst in batch process for the aminolysis of epoxide in the presence of heterogeneous catalyst based on MgO-SiO2 in flow system through 72 h (conversion 81.1%, selectivity 95.9%). The proof of concept for the design of this catalytic system for production of selected fine chemicals is shown in this study. (c) 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

Supported ionic liquid phase (SILP) was used as a carrier for lipase from Aspergillus oryzae (LAO) and used as a biocatalyst for enantiomeric resolution of racemic ibuprofen via esterification leading to (S)-(+)-ibuprofen ester. Using native form of lipase, outstanding results were achieved, obtaining (S)-(+)-ibuprofen propyl ester with enantiomeric excess (ee) of 99.9% and high conversion of racemic ibuprofen after 24 h (α=34.8%) and respectively ee = 99.9% with α=45.2% after 48 h. Several hybrid materials composited with silica and metal-based oxides including magnesium, calcium, and zirconia were evaluated as supports for LAO with various surface characteristics. The selected ionic liquid 1-methyl-3-(triethoxysilylpropyl)imidazolium bis(trifluoromethylsulfonyl)imide was immobilized via the covalent bound onto the surface of solid material and in the second step LAO was anchored. Optimized results in enantiomeric resolution of racemic ibuprofen (35.23% conversion of rac-ibuprofen after 7 days with 95% ee of ester) were obtained for SILP biocatalyst based on MgO⋅ SiO2 (1:1) (ionic liquid loading 6.79%, enzyme loading 3.96%). This is proposed as a generic approach to tailoring supported ionic liquids phase biocatalysts for industrially-relevant reactions, to generate both environmentally and economically sustainable processes.

As a result of strict regulations of phthalate plasticizers, alternative non-phthalate forms are desired and increasingly used. This work presents a synthetic method for alternative plasticizers (dialkyl succinates and adipates) via esterification of succinic and adipic acid with alcohols: butan-1-ol and 2-ethylhexan-1-ol. Ionic liquids were synthesized by the reaction of triethylamine with over-equimolar (1:2.7) amounts of sulfuric(VI) acid, which were used as an acidic catalyst and solvent. The two-phase liquid–liquid system was formed during the reaction due to immiscibility of the esters with the ionic liquid. This phenomenon is a driving force of this process, shifting the equilibrium toward the product formation. As a result, dialkyl succinates and adipates were obtained in high yields (99%) and selectivities (>99%), under mild reaction conditions at 70–80 °C and using a 4:1 molar ratio of alcohol to acid and 15 mol% of catalyst. The catalyst was recycled 10 times without any loss of activity. This alternative method is highly competitive: it involves a simple procedure for product isolation as well as a high yield and purity of the resulting esters. These advantages make this method sustainable and promising for industrial applications.

Following our previous studies on the molecular level structure of (co)oligoesters obtained via anionic homo- and co-polymerization of novel β-substituted β-lactones, prepared by the atmospheric pressure carbonylation reaction of respective epoxides, the boric acid biocatalyzed ring-opening (co)polymerization of δ-valerolactone has been studied. As a co-monomer the 6-methy-ε-caprolactone, prepared by the one-pot oxidation of respective alcohol, and ethylene glycol as polymerization initiator were used. The obtained copolymers were characterized by 1H-NMR, GPC and ESI-MS, respectively in order to confirm their chemical structures and identity. Subsequently, tandem mass spectrometry (MS-MS studies) via collision-induced dissociation were utilized to characterize the fragmentation pattern. ESI-MS and NMR analyses confirmed the formation of random linear copolymer chains composed of different polyester repeat units. MS-MS experiments showed that fragmentation proceeds via ester bound cleavage along the (co)polyester chains. The innovative aspect of this contribution is related to the elaboration of the telechelic (co)polymers end-capped with hydroxyl end groups and well-defined molecular architectures, which could facilitate the development of new flexible macromolecular systems for potential biomedical applications.

A stability survey of a basic N-doped carbon catalyst in a continuous flow process together with a study of process parameters affecting the batch system and their correlation to the flow protocol is described.

Low solubility of terephthalic acid in common solvents makes its industrial production very difficult and not environmentally benign. Ionic liquids are known for their extraordinary solvent properties, with capability to dissolve a wide variety of materials, from common solvents to cellulose, opening new possibilities to find more suitable solvents for terephthalic acid. This work presents studies on the solubility of terephthalic acid in ionic liquids, and demonstrates that terephthalic acid is soluble in ionic liquids, such as 1-ethyl-3-methylimidazolium diethylphosphate, 1-butyl-3-methylimidazolium acetate, and dialkylimidazolium chlorides up to four times higher than in DMSO. Additionally, the temperature effect and correlation of ionic liquid structure with solubility efficiency are discussed.

Based on MS analysis, the mechanism of the Baeyer-Villiger oxidation of cyclic ketones with hydrogen peroxide using metal triflates (Ga(OTf)(3)and Er(OTf)(3)) as catalysts was proposed. In the case of cyclohexanone as a substrate, dimeric, trimeric and tetrameric peroxide structures were detected.

A highly active biocatalyst based on a hybrid platform was designed for the conversion of α-angelica lactone to alkyl levulinates.

Inexpensive Brønsted acidic ionic liquids based on trimethylamine and sulfuric acid are proposed as both solvents and catalysts in the synthesis of alternative plasticizer bis(2-ethylhexyl) terephthalate, which has a broad spectrum of applications in plasticization processes. The utilization of 50 mol % of Brønsted ionic liquid led to the full conversion of terephthalic acid after 8 h of reaction at 120 °C. Additionally, a 100% selectivity of bis(2-ethylhexyl) terephthalate was obtained. The advantage of the presented reaction system is based on the formation of a biphasic system during the reaction. The bottom phase consists of an ionic liquid and water, and the upper phase is created by the ester and unreacted alcohol. This phenomenon helps overcome the equilibrium of the reaction and drives it towards a high yield of product. The presented new approach is proposed as a safe, cost-effective, and alternative method to conventional processes with organometallic compounds that, in turn, leads to greener and a more economically viable technology.