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This paper reports a new method for dissolving cellulose based on phosphonium ionic liquids (PILs). The method has the potential to produce novel cellulosic and cellulose composite materials in an environmentally friendly way. PILs with melting points less than 100 °C and mixtures of dimethylformamide and PILs were used, and are recommended here, d...
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... is the most abundant biorenewable material, which consists of polydisperse glucose polymer chains that form hydrogen-bonded supramolecular structures ( Figure 1). ...
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... illustrated in Figure 1, cellulose consists of an intricate network of intramolecu- lar and intermolecular hydrogen bonds, which is the cause of the difficulty in dissolving cellulose. When DMF is added, the cellulose pulp swells and as a result causes the dis- tance between cellulose strands to increase, allowing the ionic liquid to interact with the hydroxyl functional groups of the cellulose quicker than when DMF is not present. ...
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... Among effective ILs in biomass pretreatment are nitrogen-containing heterocycles and ammonium salts with oxygen-containing functional groups [58][59][60]. However, the high efficiency in cellulose dissolution has been demonstrated by the phosphonium salts as well [24,61]. Recent research has highlighted a number of structure-capacity patterns for effective cellulose dissolution in organic salts, which have been emphasized [62,63]. ...
In the present study, the synthesis of oxygen-containing quaternary phosphonium salts (oxy-QPSs) was described. Within this work, structure-property relationships of oxy-QPSs were estimated by systematic analysis of physical-chemical properties. The influence of the oxygen-containing substituent was examined by comparing the properties of oxy-QPSs in homology series as well as with phosphonium analog-included alkyl side chains. The crystal structure analysis showed that the oxygen introduction influences the conformation of the side chain of the oxy-QPS. It was found that oxy-QPSs, using an aprotic co-solvent, dimethylsulfoxide (DMSO), can dissolve microcrystalline cellulose. The cellulose dissolution in oxy-QPSs appeared to be dependent on the functional group in the cation and anion nature. For the selected conditions, dissolution of up to 5 wt% of cellulose was observed. The antimicrobial activity of oxy-QPSs under study was expected to be low. The biocompatibility of oxy-QPSs with fermentative microbes was tested on non-pathogenic Saccharomyces cerevisiae, Lactobacillus plantarum, and Bacillus subtilis. This reliably allows one to safely address the combined biomass destruction and enzyme hydrolysis processes in one pot.
... As a very promising alternative to fossil fuels, biomass is increasingly drawing attention. Biomass is widely abundant, distributed worldwide and relatively inexpensive and has been used to produce various value-added chemicals [45][46][47][48][49][50][51]. Biomass transformation into valuable chemicals not only has revived the green chemistry principles but has also paved the way to alleviate the current high reliance on fossil fuels [48]. ...
Deep eutectic solvents (DESs) have emerged as promising green solvents, due to their versatility and properties such as high biodegradability, inexpensiveness, ease of preparation and negligible vapor pressure. Thus, DESs have been used as sustainable media and green catalysts in many chemical processes. On the other hand, lignocellulosic biomass as an abundant source of renewable carbon has received ample interest for the production of biobased chemicals. In this review, the state of the art of the catalytic use of DESs in upgrading the biomass-related substances towards biofuels and value-added chemicals is presented, and the gap in the knowledge is indicated to direct the future research.
... By separating the biomass into individual cellulose strands, downstream processes can efficiently convert it into ethanol using enzymes or other catalyzed reactions. Ionic Liquids (ILs) are a class of solvents that are non-volatile, non-flammable, and thermally stable, with low melting points [1][2][3][4][5][6][7][8]. There are several ILs with the potential to dissolve cellulose, but many of them operate at higher temperatures and are ineffective even in low concentrations of water [1,[5][6][7]9]. ...
... Higher temperatures can be required to dissolve cellulose, as the ILs typically have high viscosities in their pure form, and the hydrogen bonds and conformations of the hydroxymethyl groups of the cellulose bundle can change at elevated temperatures [1,10,11]. Water inhibits the cellulose dissolution in ILs by solvating the anion with increasing water concentration, leading to less sustained interaction with the cellulose bundle [1][2][3][4][5][6][7][8]12]. ...
... The stability of the cellulose bundle is dependent on the intra-strand (within a strand) and inter-strand (between strands) hydrogen bonding network [3,4,60]. Recent studies have shown that breaking the intra-strand hydrogen bonds is the critical step in the cellulose dissolution process [3,4,60]. ...
All-atom molecular dynamics simulations are utilized to determine the properties and mechanisms of cellulose dissolution using the ionic liquid tetrabutylphosphonium chloride (TBPCl)–water mixture, from 63.1 to 100 mol%water. The hydrogen bonding between small and large cellulose bundles with 18 and 88 strands, respectively, is compared for all concentrations. The Cl, TBP, and water enable cellulose dissolution by working together to form a cooperative mechanism capable of separating the cellulose strands from the bundle. The chloride anions initiate the cellulose breakup, and water assists in delaying the cellulose strand reformation; the TBP cation then more permanently separates the cellulose strands from the bundle. The chloride anion provides a net negative pairwise energy, offsetting the net positive pairwise energy of the peeling cellulose strand. The TBP–peeling cellulose strand has a uniquely favorable and potentially net negative pairwise energy contribution in the TBPCl–water solution, which may partially explain why it is capable of dissolving cellulose at moderate temperatures and high water concentrations. The cellulose dissolution declines rapidly with increasing water concentration as hydrogen bond lifetimes of the chloride–cellulose hydroxyl hydrogens fall below the cellulose’s largest intra-strand hydrogen bonding lifetime.
... If cellulose in wastes such as cornstalks post-growing season, dead trees, and sawmill scraps can be economically extracted from the biomass, the resulting biomass feedstock could be used for both commodity and specialty chemical production. In this regard, ionic liquids (ILs) have shown promise as solvents for the dissolution of cellulosic biomass [1][2][3][4][5][6][7][8][9]. ILs are a class of materials that possess low melting points, are non-flammable and nearly non-volatile, and demonstrate chemical and thermal stability under a range of operating conditions, making them well suited for industrial processes [1][2][3][4][5][6][7][8][9]. ...
... In this regard, ionic liquids (ILs) have shown promise as solvents for the dissolution of cellulosic biomass [1][2][3][4][5][6][7][8][9]. ILs are a class of materials that possess low melting points, are non-flammable and nearly non-volatile, and demonstrate chemical and thermal stability under a range of operating conditions, making them well suited for industrial processes [1][2][3][4][5][6][7][8][9]. For example, alkylimidazolium-based ILs such as 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) have been studied and shown to be effective; however, elevated temperatures (323 to 373 K) are required to dissolve high concentrations [1,[5][6][7]. ...
... The increased length of the alkyl chains in the TBP molecule may make it less reactive than a tetramethylphosphonium or tetraethylphosphonium hydroxide, due to the steric hinderance in contacting the acidic hydrogen [62]. Additionally, the TBPCl-water solution should be more stable than the TBPH-water solution, as the chloride anion is less reactive than the hydroxide anion [3,62]. It is also possible that the mentioned reactions could contribute to the loss of cellulose dissolution in the TBPH-water solution at lower water concentrations, as the TBPCl-dimethylformamide (DMF) co-solvent mixture is capable of dissolving cellulose with the pure TBPCl IL at 343 K [3]. ...
Thermodynamic, structural, and transport properties of tetrabutylphosphonium hydroxide (TBPH) and tetrabutylphosphonium chloride (TBPCl)–water mixtures have been investigated using all-atom molecular dynamics simulations in response to recent experimental work showing the TBPH–water mixtures capability as a cellulose solvent. Multiple transitional states exist for the water—ionic liquid (IL) mixture between 70 and 100 mol% water, which corresponds to a significant increase in water hydrogen bonds. The key transitional region, from 85mol% water–92.5mol% water, which coincides with the mixture’s maximum cellulose solubility, reveals small and distinct water veins with cage structures formed by the TBP+ ions, while the hydroxide and chloride ions have moved away from the P atom of TBP+ and are strongly hydrogen bonded to the water. The maximum cellulose solubility of the TBPH–water solution at approximately 91 . 1 mol% water, appears correlated with the destruction of the TBP’s interlocking structure in the simulations, allowing the formation of water veins and channeling structures throughout the system, as well as changing from a subdiffusive to a near-normal diffusive regime, increasing the probability of the IL’s interaction with the cellulose polymer. A comparison is made between the solution properties of TBPH and TBPCl with those of alkylimidazolium-based ILs, for which water appears to act as anti-solvent rather than a co-solvent.
... Natural deep eutectic solvents, NADESs, which meet green chemistry objectives and are composed of naturally occurring substances from cellular metabolites [9], are considered to be suitable alternatives for organic solvents, ILs, and even for common DESs [10]. Among a diverse list of applications [4,[11][12][13][14][15][16][17][18][19], the use of DESs and NADESs in biofuel [8,[20][21][22] and bio-oil [23,24] production, as reaction media or extractive agents [25][26][27][28][29][30][31][32][33][34][35], and as media to tune intermolecular interactions [36] are of special importance to researchers. ...
... Illustration of the overall biorefinery process to produce bioenergy from biowaste/biomass. Plant-based biomass is a natural, renewable, organic source of carbon [62,77] for conversion to fuel products or valorization to produce biobased chemicals [20,21,26,28,34,35,[78][79][80][81][82][83][84][85][86][87]. Biomass conversion into fuels and value-added chemicals decreases the world's need for fossil fuels and can effectively reduce CO2 emissions by combining chemical methods and photosynthesis [88]. ...
... Of all the types of biomass feedstock, lignocellulosic biomass is the most abundant type [89], prevalent in the cell walls of hardwoods, softwoods, energy crops, and other plants [90,91]. The primary constituents of lignocellulosic biomass are carbohydrate polymers such as cellulose and hemicellulose, embedded in a lignin matrix, as illustrated in Figure 2. Plant-based biomass is a natural, renewable, organic source of carbon [62,77] for conversion to fuel products or valorization to produce biobased chemicals [20,21,26,28,34,35,[78][79][80][81][82][83][84][85][86][87]. Biomass conversion into fuels and value-added chemicals decreases the world's need for fossil fuels and can effectively reduce CO 2 emissions by combining chemical methods and photosynthesis [88]. ...
Valorization of lignocellulosic biomass and food residues to obtain valuable chemicals is essential to the establishment of a sustainable and biobased economy in the modern world. The latest and greenest generation of ionic liquids (ILs) are deep eutectic solvents (DESs) and natural deep eutectic solvents (NADESs); these have shown great promise for various applications and have attracted considerable attention from researchers who seek versatile solvents with pretreatment, extraction, and catalysis capabilities in biomass- and biowaste-to-bioenergy conversion processes. The present work aimed to review the use of DESs and NADESs in the valorization of biomass and biowaste as pretreatment or extraction solvents or catalysis agents.
... The number of potential ion combinations available is estimated to generate 10 12 of ILs [93,95]. The most efficient ILs reported for the dissolution of cellulose are mainly composed of a salt with halide, phosphonate, formate, or acetate as an anion and imidazolium, pyridinium, choline, or phosphonium as a cation [96][97][98][99][100][101][102][103]. As compared to NMMO and DMAc/LiCl, ILs have exhibited a capability of dissolving high molecular weight cotton linter (DP~4745) [96]. ...
Cotton is an important, worldwide cash crop and is considered as a ubiquitous resource offering the purest form of cellulose in nature. By far, the most industrially exploited natural resources containing cellulose are wood and cotton. Cellulose derived from either wood or cotton has the same chemical structure. Hydrogels are jellylike materials consisting of substantially hydrophilic cross-linked network filled with water. Upon replacing water with air, hydrogels are able to form aerogels. Cellulose and its derivatives can be used to prepare hydrogels with tailored absorbability and adsorbability. In the first section of this review, we discuss recent progress in the dissolution of high molecular weight cotton-derived cellulose as the dissolution of cellulose is an important step in preparing cellulose-based hydrogels. In the second section, we focus on the preparation of various cotton cellulose-based hydrogels and their derivatives by physical, chemical, and photocatalytic processes and their current applications. The third section includes the preparation and application of cellulose-based aerogels, which are a specific dry form of hydrogels. Overall, this review covers recent research developments in cotton cellulose-based hydrogels and their broad spectrum of applications in agriculture, environment, energy, health, and medicine.
... Imidazolium-based ILs are the most frequently-studied ILs in toxicology while phosphonium-based ILs the least-commonly studied, despite great industrial interest in the latter [14]. In recent times, phosphonium-and ammonium-based ILs have shown potential for biomass-processing [19][20][21][22]. Thus, this study was aimed to study phosphonium-and ammonium-based ILs with anions like hydroxyl, acetate, phenylalanine, and taurine as potential solvents for biomass dissolution. ...
... This subsequently allows for a quicker interaction between cellulose and IL. 150 This hypothesis was confirmed by NMR studies, in which the interactions between the IL [C 4 mim][CH 3 COO] and aprotic, organic solvents were investigated. 151 Their investigation showed that ethyl acetate facilitated the most enhanced interaction between the IL and cellulose (Alicell-Super). ...
Lignocellulosic biomass has gained extensive research interest due to its potential as a renewable resource, which has the ability to overtake oil-based resources. However, this is only possible if the fractionation of lignocellulosic biomass into its constituents, cellulose, lignin and hemicellulose, can be conducted more efficiently than is possible with the current processes. This article summarizes the currently most commonly used processes and reviews the fractionation with innovative solvents, such as ionic liquids and deep eutectic solvents. In addition, future challenges for the use of these innovative solvents will be addressed.
Ionogels have established themselves as an intriguing type of composites, owing to their distinctive properties, including superior thermal stability, non‐flammability, tunable electrochemical stability window, and high ionic conductivity. Hybrid materials based on ionic liquids (ionogels) are held together by interfaces arising out of intermolecular interactions, including electrostatic, van der Waals, solvophobic, steric, and hydrogen bonding. The interfaces within the ionic liquid (ILs) and its multifaceted interplay with the encapsulating matrix greatly influence the physicochemical and electronic/ionic interactions within the composite resulting in exceptional characteristics, allowing for the design of ionogels for targeted applications. Though ionogels have shown superior properties comparable to neat ILs, they still exhibit relatively low mechanical strength, limiting their application in several practical technologies. Simultaneous enhancement of mechanical durability while retaining high ionic conductivity is indispensable, which requires understanding interfaces and related influencing parameters. This review provides a synergetic comprehension, focusing on the interactive forces and factors affecting the conductivity, stability, and robustness of ionogels. Correlating with interfaces, several strategies, including the implications of nanofiller incorporation on the electromechanical properties of ionogel, are also elaborated. Finally, a primer is provided on the application of ionogels in sensors and energy harvesting technologies.
Lignocellulose is one of the most promising renewable bioresources for the production of chemicals. For sustainable and competitive biorefineries, effective valorization of all biomass fractions is crucial. However, current efforts in lignocellulose fractionation are limited by the use of either toxic or suboptimal solvents that do not always allow producing clean and homogeneous streams. Here, we present a computational screening approach that covers more than 8000 solvent candidates for the processing of lignocellulosic biomass. The automated screening identified highly effective, non-intuitive solvents based on physico-chemical properties, solubilities of the biomass fractions, and environmental, health and safety properties. Solubility experiments for the lignin and cellulose fraction confirmed the applicability of the proposed framework in biomass processing. In addition to the traditional “lignin-first” approaches, we identified solvents applicable for the complete dissolution of biomass. Furthermore, we elucidated particular structural patterns in solvents featuring high lignin solubility. The most promising solvents attained lignin solubilities of more than 33 wt%.
