Fracto-eutectogels: SDS fractal dendrites via counterion condensation in a deep eutectic solvent.

This thesis presents novel approaches and applications for deep eutectic solvents (DESs) based on readily available, renewable, and inexpensive compounds as extraction, reaction and detection media for inorganic compounds. Chapter 1 focuses on the selective extraction of metal salts and oxides, specifically phosphates, from incinerated sewage sludge ash (ISSA) using DESs that are based on natural products. The solubility behavior of the main components of ISSA as well as several metal salts and metal oxides in DESs is investigated and an empirical basis for possible applications is provided. The solubility can partly be correlated with the approximated pH value of the DESs: the tested phosphates and metal chlorides dissolve preferably in DESs containing urea or N,N’-dimethyl urea (DMU), which offer neutral to slightly basic conditions; in general, metal oxides enrich in DESs with carboxylic acids at strongly acidic pH value; and acetates dissolve best in DESs based on choline chloride (ChCl). From these findings, DESs were tested as environmentally friendly extraction media for phosphorus from ISSA. The first results show the feasibility of the approach, which may lead to a low-energy process. With the DES of DMU/mannose, an accumulation of phosphorus up to 31% was achieved, emphasizing the capability of biodegradable DESs as extraction media. In Chapter 2, DESs are introduced that are able to dissolve metal oxides and are used as reaction media to synthesize spinel-type ferrite nanoparticles MFe2O4 (M = Mg, Zn, Co, Ni). By employing DESs, the reactions towards phase-pure spinel ferrites proceed at much lower temperatures than usual for the respective solid-state reaction of the metal oxides and at the same temperatures as a synthesis with comparable calcination processes using metal salts. Best results for spinel-type ferrite nanoparticles were obtained with the DES consisting of ChCl/maleic acid. The method therefore reduces the overall required energy for the nanoparticle synthesis. The analysis of the cation distribution, particle size, band gap, and morphology showed that the properties of the gained nanoparticles are comparable to particles obtained by other methods, which illustrates the potential of DESs for the processing of metal oxides. Chapter 3 presents DESs as promising solvents for light rare earth elements (LREE) in solid–liquid separation on one hand and potent media for luminescence measurements of trivalent lanthanide ions in quantitative analysis on the other hand. The spectroscopic characteristics of lanthanide chlorides LnCl3 (Ln = Eu, Tb), respectively their aquo complexes, are described in a comprehensive study that demonstrates the significant enhancement of the phosphorescence emission intensity in DESs as polar and weakly coordinating solvent. Several DESs proved to be a stable environment for luminescent lanthanide ions towards external influences such as changes in temperature and moisture, which gives them an advantage over ionic liquids. It was found that water may even have a supporting role in certain eutectic systems that leads to a further increase in phosphorescence emission. By investigating the solubility of lanthanide sesquioxides Ln2O3 (Ln = La, Nd, Sm, Eu, Gd, Tb, Dy) in DESs, selectivities were identified that provide the basis for subsequent development of a separation process for LREE.

The World has abundant deposits of heavy crude oils. In the past, production of such heavy oil was disfavored due to discouraging economic feasibility and availability of lighter oils. Increasing demand and dwindling supply of crude oil have spurred efforts towards enhancing heavy oil recovery. Recently, applications of ionic liquids (ILs) for heavy oil recovery and catalytic upgrading have been reported. However, ILs are generally considered too expensive for industrial applications. Moreover, certain types of ILs are non-biodegradable and toxic. An alternative class of ILs called Deep Eutectic Solvents (DESs) have recently been discovered and investigated upon. A DES generally composed of two or more components that are capable of self-association, to form eutectic mixture with a melting point lower than that of each individual component. DESs are non-toxic, biodegradable, recyclable, nonflammable, environmentally friendly and cheap. Therefore, DESs have found application in fields like extraction/separation, solvent development/reaction medium, hydrometallurgy, etc. In this study, and for the first time to our knowledge, the effectiveness of two different types of DESs, Choline Chloride:Glycerol(1:2) and Choline Chloride:Urea(1:2), in enhancing heavy oil recovery is thoroughly investigated. Effect of the two DESs diluted with water on emulsification, altering wettability, spontaneous imbibitions, surface and interfacial tensions and tertiary residual heavy oil saturation reduction are studied experimentally at different temperatures. Heavy oil with 16 °API and formation brine from one of the Omani heavy oil fields was used. The core flood experiments were conducted at reservoir condition and using Berea sandstone core plugs. The results showed that the two DESs did not make emulsion with the heavy oil. They increased the IFT of oil-brine system. Moreover, the two DESs altered the wettability of the sandstone rock surfaces from strongly oil-wet to neutral-wet conditions. The core flooding runs at different temperatures showed high potential of using these DESs for enhancing heavy oil recovery; where 14-30% of water flooded residual heavy oil was recovered after injecting the DES solvents as tertiary recovery stage.

Purification of biodiesel prior to utilizing it as an alternative fuel is an essential industrial practice. Low glycerol content is one of the important pointers needed for passing the EN 14214 and ASTM D6751 international biodiesel standards. In this study, choline chloride (ChCl) as salt and ethylene glycol and 2,2,2-Trifluoroacetamide as hydrogen bond donors (HBDs) were employed to synthesize two ammonium salt-non glycerol based Deep Eutectic Solvents (DES). The physical properties of the synthesized DESs were measured and analyzed. These DESs were utilized to remove all the free glycerol from the palm oil-based biodiesel. The results indicated that all the tested DESs were able to remove all free glycerol successfully. The Central Composite Design (CCD) of the Response Surface Methodology (RSM) was used to to experiment design and optimization of total glycerol removal using ethylene glycol-based DESs and 2,2,2-Trifluoroacetamide-based DESs. The maximum total glycerol removal by ethylene glycol-based DESs was obtained at 0.66 ethylene glycol mole fraction and at DES/biodiesel molar ratio of 3 with removal efficiency of 23.85% as well as by 2,2,2-Trifluoroacetamide-based DESs at 0.60 2,2,2-Trifluoroacetamide mole fraction and at DES/biodiesel molar ratio of 2.93 with removal efficiency of 29.29%. The reusability of these DESs for removing free glycerol and total glycerol content from palm oil-based biodiesel was also investigated. This study proves that both ammonium salt-non glycerol based DESs can be successfully employed to remove the glycerol from palm oil-based biodiesel.

Alkaline anion exchange membrane fuel cells (AEMFC) have gained interest due to their potential as electrochemically energy conversion devices and a competitive alternative to the more extensively studied commercialized proton exchange membrane fuel cells (PEMFCs). Nevertheless, their development impedes the limited ion conductivity, chemical and mechanical stability in an alkaline medium of anion exchange membranes (AEMs). The ionic conductivity of AEM is lower than that of a proton exchange membrane (PEM) because the mobility of hydroxide ions is inherently lower than that of protons [1]. Deep eutectic solvents (DESs) as green solvents can overcome this issue.The main idea of this research is to fabricate a deep eutectic solvent-supported polymer-based AEM for alkaline fuel cell application by electrospinning technique. Poly(vinyl alcohol) (PVA) is one of the potential polymers for the development of AEM due to its water solubility, biodegradability, high fiber forming ability, non-toxicity, and high chemical and thermal stability [2]. This work aims to achieve high ionic conductivity, chemical and mechanical stability by two methods: swelling polyvinyl alcohol (PVA)-based nanofibers into DES and encapsulating DES inside the PVA-nanofibers together with optimizing fabrication methods.In this study, polymer electrolytes as potential AEMs were first prepared using the swelling method, where electrospun PVA nanofibers were fabricated via the electrospinning technique, followed by swelling in a series of DESs. To prepare the DES solutions, choline chloride (ChCl) and ethylene glycol (EG) were mixed at different molar ratios. The cross-linking of pure PVA fibers with glutaraldehyde in ethanol (see Figure 1B) and DES uptake and the presence of voids as channels for ion conduction (see Figure 1C) were successfully confirmed with a scanning electron microscopy (SEM, Crossbeam500, Zeiss). The ionic conductivity of swelled in DES PVA-based membranes were evaluated by electrochemical impedance spectroscopy (Metrohm Autolab) at room temperature and was equal to 0.336 mS/cm. The presence of DES in the membrane was confirmed with FTIR spectroscopy (FT-IR spectrometer, Nicolet iS10): a slight C-N+ peak at 953 cm-1 from ChCl has proven interaction between PVA and DES with FTIR spectroscopy, meaning that DES is present in the fiber. In addition, the nitrogen content in the obtained membrane was determined by CHNS elemental analysis (Elemental Vario micro cube) as 3.32 wt.%.In order to overcome high weight loss in the swelling method, the encapsulation method was suggested as an alternative option, which is based on the encapsulation of DES into the PVA solution by mixing them, varying the amount of DES added, and then preparing fibers using electrospinning. Observing the morphology of DES-encapsulated PVA nanofibers with a scanning electron microscope (SEM, Crossbeam500, Zeiss), as the content of DES in the solution increased, there was an observed rise in the average diameter of the nanofibers (see Figure 1D). Encapsulation of DES in PVA nanofibers was primarily confirmed by transmission electron microscope (TEM, JEM -1400 Plus, JEOL): PVA appears lighter due to its decreased density, proving that DES is present inside the fibers. Also, the same tendency was observed with the results of FTIR spectroscopy (FT-IR spectrometer, Nicolet iS10) as for the swelling method, meaning that DES is present in the fiber. According to CHNS elemental analysis (Elemental Vario micro cube), nitrogen content was lower than for the swelling method - 0.70 wt.%. The ionic conductivity was evaluated as 0.364 mS/cm by electrochemical impedance spectroscopy (Metrohm Autolab) at room temperature, which was almost the same as for the swelling method.As a result, very flexible and visually transparent electrospun DES-supported PVA-based AEMs were obtained via the swelling and encapsulation method.

The effects of a hydrogen bond acceptor and hydrogen bond donor on carbon dioxide absorption via natural deep eutectic solvents were studied in this work. Naturally occurring non-toxic deep eutectic solvent constituents were considered; choline chloride, b-alanine, and betaine were selected as hydrogen bond acceptors; lactic acid, malic acid, and fructose were selected as hydrogen bond donors. Experimental gas absorption data were collected via experimental methods that uses gravimetric principles. Carbon dioxide capture data for an isolated hydrogen bond donor and hydrogen bond acceptor, as well as natural deep eutectic solvents, were collected. In addition to experimental data, a theoretical study using Density Functional Theory was carried out to analyze the properties of these fluids from the nanoscopic viewpoint and their relationship with the macroscopic behavior of the system, and its ability for carbon dioxide absorption. The combined experimental and theoretical reported approach work leads to valuable discussions on what is the effect of each hydrogen bond donor or acceptor, as well as how they influence the strength and stability of the carbon dioxide absorption in deep eutectic solvents. Theoretical calculations explained the experimental findings, and combined results showed the superiority of the hydrogen bond acceptor role in the gas absorption process, with deep eutectic solvents. Specifically, the cases in which choline chloride was used as hydrogen bond acceptor showed the highest absorption performance. Furthermore, it was observed that when malic acid was used as a hydrogen bond donor, it led to low carbon dioxide solubility performance in comparison to other studied deep eutectic solvents. The cases in which lactic acid was used as a hydrogen bond donor showed great absorption performance. In light of this work, more targeted, specific, deep eutectic solvents can be designed for effective and alternative carbon dioxide capture and management.

A series of deep eutectic solvents (DESs) were prepared using glycerol and choline chloride (ChCl), and Fourier transform infrared spectrometer (FT-IR) was used to analyze the spectra of glycerol, choline chloride and DESs based on glycerol and choline chloride. Then DESs were used as the additives of mobile phase to optimize chromatographic behavior of caffeic acid in high performance liquid chromatography (HPLC). A 17-run Box-Behnken design (BBD) was employed to evaluate effect of DESs as additives by analyzing the maximum theoretical plate number. Three factors, reaction temperature (60 °C, 80 °C, 100 °C), molar ratio of glycerol and choline chloride (2 : 1, 3 : 1, 4 : 1, n/n), and volume percent of additives (0.05%, 0.10%, 0.15%, v/v), were investigated in BBD. The optimum experiment condition was that of reaction temperature (80 °C), molar ratio of glycerol and ChCl (3 : 1, n/n), and volume percent of additive (0.10%, v/v). The mean chromatographic theoretical plate number of the caffeic acid this condition was 1567.5, and DESs as additives shorten the retention time and modify the chromatogram shape, proving DESs as additives for effective theoretical plate number and column efficiency in HPLC.

Results on the extraction of ferulic acid from palm pressed fiber using deep eutectic solvent (DES) of choline chloride‐acetic acid (ChCl‐AA) and choline chloride‐citric acid (ChCl‐CA) are reported. Acetic acid was found to be a better hydrogen bond donor to choline chloride than citric acid for the extraction of ferulic acid. Influence of water content in both DES was investigated whereby ChCl‐AA and ChCl‐CA experienced a drop in viscosity from 9.678 to 1.429 and 22.658 ± 1.655 mm2/s, respectively as the water content in the DES increased from 0 to 50 wt%. The drop in viscosity contributed to higher extraction efficiency in which 41,155 ± 940 mg/kg ferulic acid was obtained after 6 h reflux when ChCl‐AA with 30 wt% water was used for the extraction compared to 30,940 ± 621 mg/kg when neat ChCl‐AA was used. Further increase in water content in the DES however, did not lead to higher extraction efficiency. Although viscosity of the DES could be improved with the addition of water, there is a threshold where the DES could tolerate the presence of water without changing its solvent behavior. Surface response model revealed that interaction between heating duration and water content in DES, as well as second order effect of both heating duration and water content in DES played important roles in the extraction of ferulic acid from oil palm pressed fiber. The optimum condition for extraction of ferulic acid from palm pressed fiber was heating for 6 h with DES containing 30 wt% water.

Thin Ni and Cr coatings are commonly electrodeposited from aqueous electrolytes [1,2]. These often contain series of additives, whose role is to improve the leveling and adhesion of deposited films to the substrate, decrease internal stress, and limit the hydrogen evolution reaction (HER). However, certain additives, such as thiourea as well as Cr(VI) compounds are highly hazardous [1,2]. Therefore, due to the increasing environmental awareness of the society, the electrolytes containing these constituents require replacement by green alternatives, such as Deep Eutectic Solvents (DESs).DESs, usually composed of quaternary ammonium salt and hydrogen bond donor, i.e. ethylene glycol, have wider electrochemical potential window than H2O, which in principle enables obtaining metallic coatings without the HER [3]. However, due to the low conductivity and high viscosity of DESs, it is necessary to use additives, i.e. nicotinic acid, improving these physico-chemical properties and enhancing the electrodeposition process. However, due to the unavoidable presence of water (DESs are hygroscopic), H2O can be considered an additive to DESs. The addition of H2O can be beneficial since it improves the ion mobility, and therefore increases the reduction rate [4]. The current studies focus on understanding the effect of water content on the physico-chemical properties, and the structure of DESs. However, a little is known on the influence of H2O on the electrodeposition of Ni and Cr, especially on the nucleation and growth, the effect of the morphology and chemical composition of deposited films. Therefore, an in-depth study on this topic is required.The electrolytic reduction of Ni and Cr cations in choline chloride – ethylene glycol (1ChCl:2EG) on glassy carbon and steel substrates was investigated in function of water content. This study was performed by means of electrochemical techniques, such as linear sweep voltammetry and chronoamperometry. The obtained deposits were analyzed with surface sensitive methods, i.e. scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. In order to bring the understanding on the influence of H2O as an additive on the early stage electrodeposition of Ni and Cr from DES, a combination of computational modelling with UV-vis spectroscopy was involved. This approach allowed correlating the observed electrochemical behavior of Ni and Cr cations with certain water concentrations. Establishing such relationship is of high relevance, as it may enable optimizing the process parameters for Ni and Cr electroreduction from DESs. [1] N. V. Mandich and D. L. Snyder. Modern Electroplating, chapter Electrodeposition of Chromium, pages 205–248. John Wiley & Sons, Inc., New Jersey, 5 edition, 2010.[2] G. DiBari. Modern Electroplating, chapter Electrodeposition of Nickel, pages 79-114. John Wiley & Sons, Inc., New Jersey, 5 edition, 2010.[3] E.L. Smith, A.P. Abbot, K.S. Ryder, Deep Eutectic Solvents (DESs) and Their Application, American Chemical Society Publications, 2014, pp. 11060 – 11082.[4] M. Lukaczynska, E.A. Mernissi Cherigui, A. Ceglia, K. Van den Bergh, J. De Strycker, H. Terryn, and J. Ustarroz, Influence of water content and applied potential on the electrodeposition of Ni coatings from deep eutectic solvents, Electrochimica Acta, 319: 690-704, 2019.

Deep eutectic solvents (DESs) have emerged as an alternative to both common organic solvents and ionic liquids (ILs). DESs share physicochemical properties with ILs such as low vapor pressure, high thermal stability, high viscosity while offering advantages such as low toxicity, lower cost, and ease of preparation. Moreover, DESs are attractive candidates for electrochemical applications due to their large voltage windows and solubility properties. DESs as a solvent class share a general composition of a hydrogen bond donor (HBD), typically a polyol, amide, or acid, and a hydrogen box acceptor (HBA), usually a quaternary ammonium or phosphonium salt. At a specific molar composition of a HBD and HBD, the DES forms a eutectic mixture resulting in a large melting point depression due to extensive hydrogen bonding between the components.Despite being widely studied, the microscopic structures of DESs have remained largely uncharacterized. Herein, we present a multitechnique NMR study of two DESs: glyceline (glycerol + choline chloride) and ethaline (ethylene glycol + choline chloride). Fast-field cycling 1H relaxometry, pulsed field gradient diffusion, nuclear Overhauser effect spectroscopy (NOESY), 13C NMR relaxation, and pressure-dependent NMR experiments are deployed to sample a range of frequencies and modes of motion of the polyol and choline components of the DES. Generally, translational and rotational diffusion of polyols are more rapid than those of choline while short-range rotational motions observed from 13C relaxation indicate slow local motion of glycerol at low choline chloride (ChCl) content. We show how the additional hydroxyl group present in glycerol contributes to not only higher viscosities, but a larger perturbation of the hydrogen bonding network by the addition of ChCl.Additionally, we have investigated the solubility properties of several lithium salts (LiTFSI, LiFSI, LiPF6, LiBF4, and LiOAc) in these DESs and utilized the same suite of NMR techniques to understand how they act as solvents. We observe that due to anion effects, the heterogeneities present in DES result in differential solvation for some species where there is a distinction of lithium salts co-existing in these holes as well as the bulk. The large changes in the structural organization of DESs that result from the presence of lithium salts will serve as a guide to the design of a new class of electrolytes for lithium-ion batteries.

After biomass fractionation using deep eutectic solvents (DES), solvent recovery is an essential step. Recovery of lignin from DES by liquid–liquid extraction (LLX) may provide large energy savings compared to cold water precipitation. Lignin that is dissolved in DES from biomass fractionation is inhomogeneous, meaning it has various fractions with different molar weights and possibly variations in functional group densities. Therefore, it is important to compare recoverability of every lignin fraction by LLX with cold-water precipitation. In this work, the recovery of lignin from a DES comprised of 30 wt% choline chloride and 70 wt% lactic acid was studied. Using as much as 30 wt% choline chloride is beneficial to limit leaching of lactic acid. Three cross-current extractions were performed using 2-MTHF. This method recovered 95% of the lignin fractions around 2000 g/mol and 85% of the lignin fractions around 10,000 g/mol. No inter-aromatic ether bonds were found in the lignin remaining in the DES raffinate by heteronuclear single quantum coherence spectroscopy (HSQC), indicating the remaining lignin in the DES has a highly condensed nature. Cold water precipitation could fully recover the lignin fractions above 4000 g/mol using 3.5 kg water per kg DES. However, only half of the lignin fraction of 1000 g/mol was recovered. Briefly, LLX is more suitable for the recovery of low molar weight fractions, while cold water precipitation is more suitable for the heavy molar weight fractions. For industrial applications, a combination of both approaches is essential for full lignin recovery.

Density functional theory assessed molecular insights into asphaltene interactions within silica and calcium carbonate surface with deep eutectic solvents

Koenigia Weyrichii (F. Schmidt) T.M. Schust. et Reveal, which grows on the Kola Peninsula, contains a significant amount of flavonoids in the aerial parts of the plant, rapidly builds up biomass, and is resistant to various climatic conditions. This makes K. Weyrichii a promising source of biologically active substances (BAS) in the Arctic zone. A relatively new method for extracting biologically active substances from plants is the use of deep eutectic solvents (DES), for example, a mixture of choline chloride with glycerol, which has shown high efficiency in the extraction of flavonoids from other plants. Previously, DES was not used for the extraction of biologically active substances from K. Weyrichii. The aim of this work is to evaluate the efficiency of ultrasonic extraction using traditional solvents (water, ethanol) and DES choline chloride + glycerol and to optimize the extraction conditions. Comparison of the total content of polyphenols, flavonoids, antioxidative, and antiradical activity in various extracts is carried out. It was found that the most favorable conditions for extraction are: water content in DES – 17.5 wt%, temperature – 65 °C, and time – 3 hours. At the same time, under identical extraction conditions (temperature and time), more target substances can be extracted with 60% ethanol than with DES. However, DES can be seen as an alternative to using ethanol. The data obtained can be useful for the further development of innovative technologies of the extraction of biologically active substances from plant material. Also, K. Weyrichii may be considered as a source of biologically active substances in cosmetics and the food industry.

Thermal behavior, solvatochromic parameters, and metal halide solvation of the novel water-based deep eutectic solvents

Wood delignification with aqueous solutions of deep eutectic solvents

Gallic acid (GA) (3,4,5-trihydroxybenzoic acid), which is a natural secondary metabolite and widely isolated from various plants, is for the first time employed as a hydrogen bond donor (HBD) for preparing a deep eutectic solvent (DES) with choline chloride (ChCl) as a hydrogen bond acceptor (HBA). This DES has been applied as an extractant to separate gycerol from biodiesel. The finding indicates that a DES could be formed at a molar ratio of ChCl to GA of 5 : 1, 6 : 1, and 7 : 1. The characterization of the synthesized DES shows its acidic polar property with a pH of lower than its constituents, density of lower than biodiesel, and the viscosity within the range reported for previously prepared DES. Functional groups analysis using FTIR indicated the presence of all functional groups from GA and ChCl in the DES structure, along with the absence of any new spectral peaks, suggesting that there was no chemical reaction involved in the DES formation. Its ability to reduce the glycerol concentration in the biodiesel in the range of 74.6 to 99.8 % denotes its capability as a potential extractant for separation of glycerol from biodiesel.