We here present four new fluorine-free ionic liquids (ILs) based on the non-nutritive sweetener saccharinate (Sac) anion coupled with pyrrolidinium, imidazolium, and phosphonium cations and their thermal, physicochemical, and electrochemical properties. The pyrrolidinium cation-based material is a solid at room temperature, whereas the other three materials are room-temperature ionic liquids (RTILs). By infrared spectroscopy, we find the ionic interactions to be controlled by the distinct conformers of the Sac anion, which in turn are cation-dependent. (P4444)(Sac) shows the lowest glass transition temperature, (Tg), the highest thermal stability and ionic conductivity, and the widest electrochemical stability window, up to 6 V. As an electrolyte in a symmetric supercapacitor, it enabled a specific capacitance of 204 F g–1 at 1 mV s–1, an energy density of 53 Wh kg–1 and a power density of 300 W kg–1 at a current density of 0.1 A g–1, and the capacitor retained 81% of its initial capacitance after 10,000 cycles at 60 °C. Altogether, these fluorine-free electrolytes have electrochemical properties promising for application in supercapacitors operating at elevated temperatures over a wide voltage range. 

Both untransformed poplar and genetically modified “zip-lignin” poplar, in which additional ester bonds were introduced into the lignin backbone, were subjected to mild alkaline and copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment. Our hypothesis was that the lignin in zip-lignin poplar would be removed more easily than lignin in untransformed poplar during this alkaline pretreatment, resulting in higher sugar yields following enzymatic hydrolysis. We observed improved glucose and xylose hydrolysis yields for zip-lignin poplar compared to untransformed poplar following both alkaline-only pretreatment (56% glucose yield for untransformed poplar compared to 67% for zip-lignin poplar) and Cu-AHP pretreatment (77% glucose yield for untransformed poplar compared to 85% for zip-lignin poplar). Compositional analysis, glycome profiling, and microscopy all supported the notion that the ester linkages increase delignification and improve sugar yields. Essentially no differences were noted in the molecular weight distributions of solubilized lignins between the zip-lignin poplar and the control line. Significantly, when zip-lignin poplar was utilized as the feedstock, hydrogen peroxide, catalyst, and enzyme loadings could all be substantially reduced while maintaining high sugar yields.

Amino acid ionic liquids (ILs) are the most interesting and effective for CO2 capture due to their low toxicity, biodegradability and fast reactivity towards CO2. Ionic nature of amino acid ILs can raise an environmental issue if the cation counterpart becomes toxic to the aquatic ecosystems and can become potential atmospheric pollutant. In this regard, choline based ILs are known to be promising scaffolds for the development of less toxic amino acid ILs. However, the existing choline amino acid ILs are highly viscous limiting their applicability as solvents. Ether functionalized choline based amino acid ILs with novel series of less toxic green ILs were explored with reduced viscosity and high CO2 capture capacity. A simple, economic, clean and environmentally benign method was utilized for the synthesis of novel choline based amino acid ILs using a commercially available and economical starting material 2-(dimethylamino)ethanol (deanol, a human dietary food supplement). Reported ILs have low viscosity with high CO2 capture capacity (1.62 mol of CO2 /mol of IL, 4.31 mol of CO2/kg of IL, 19.02 wt.% of CO2). Mechanism of [N1,1,6,2O4][Lys]+CO2 reaction and adduct structure was proposed by means of DFT and NMR.

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 activities of the melamine resins were attributed to the abundant Lewis basic N-sites capable of activating CO₂ molecules. Based on CO₂-temperature programmed desorption, the concentrations of surface basic sites for MMFR and MMFR250 were estimated to be 172 and 56 μmol/g, while the activation energies 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 activities and stabilities 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 the 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 activities (turnover frequency 207–2147 h^–1) and selectivities (>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 °C. Most importantly, these low-cost polymeric catalysts were reusable and demonstrated exceptional stability in a flow reactor (tested up to 13 days of 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 °C, 13 bar, solvent-free/co-catalyst-free) confirming their superiority over the previously reported catalytic materials.

This study investigates the application of mesoporous aluminosilicate material with hierarchical porosity to ultralow density wood fiber composite (ULD_WFC) for improving their mechanical properties. A 300 nm thickness Si–Al inorganic film was applied to the surface of the fibers. The mesoporous aluminosilicate material with many mesopores ranging from 2 to 20 nm was obtained. Their total pore volume and Brunauer–Emmett–Teller surface area were 0.193 cm3/g and 355.2 m2/g, respectively. Thermogravimetric analysis indicated that the thermostability of ULD_WFCs was affected by Si–Al compounds. But the residual weight of ULD_WFC with Si–Al compounds was 23.87% greater than composite without Si–Al compounds. The X-ray diffraction analysis indicated partial conversion of SiO2 to α-SiC. These conditions attributed to improving the mechanical properties of ULD_WFC. The modulus of elasticity, modulus of rupture, and internal bond strength of composite with Si–Al compounds increased by 547.4%, 240.0%, and 400.0%, respectively, as compared with uncoated ULD_WFC.

Arginine was produced via fermentation of sugars using the engineered microorganism Escherichia coli. Zeolite-Y adsorbents in the form of powder and extrudates were used to recover arginine from both a real fermentation broth and aqueous model solutions. An adsorption isotherm was determined using model solutions and zeolite-Y powder. The saturation loading was determined to be 0.2 g/g using the Sips model. Arginine adsorbed from a real fermentation broth using either zeolite-Y powder or extrudates both showed a maximum loading of 0.15 g/g at pH 11. This adsorbed loading is very close to the corresponding value obtained from the model solution showing that under the experimental conditions the presence of additional components in the broth did not have a significant effect on the adsorption of arginine. Furthermore, a breakthrough curve was determined for extrudates using a 1 wt % arginine model solution. The selectivity for arginine over ammonia and alanine from the real fermentation broth at pH 11 was 1.9 and 8.3, respectively, for powder, and 1.0, and 4.1, respectively, for extrudates. To the best of our knowledge, this is the first time recovery of arginine from real fermentation broths using any type of adsorbent has been reported.

Boric acid is known to enhance the kinetics of CO2 absorption by some active aqueous solutions. However, the mechanism of interaction of boric acid with CO2 in the presence of active molecules is not yet fully understood. In this work, the interaction and dynamics of ions in aqueous solutions of functionalized choline-based ionic liquids [N1,1,5,2OH][Threo] and [N1,1,5,2OH][Tau] in the presence of boric acid and CO2 was thoroughly investigated using a multinuclear NMR approach: 13C and 11B NMR spectroscopy, 11B NMR transverse relaxation, and 1H and 11B NMR diffusometry. 13C and 11B NMR spectroscopy revealed the formation of borate-based complexes as a result of a reaction between boric acid and the anions of the ILs at ionic liquid/boric acid molar ratios larger than ca. 0.15. The formation of these complexes and their dynamics were further investigated using 11B relaxation and 1H and 11B pulse-field-gradient (PFG) NMR. Plausible reaction mechanisms of boric acid with the anions of the ILs, formation of the borate complexes, and dissociation of these complexes facilitated by CO2 molecules are suggested.

Biofuels are essential for transitioning to a sustainable society. This switch can be achieved by introducing novel feedstocks and technologies for efficient and economically feasible biofuel production. Second-generation biofuels are particularly advantageous, as they are produced from nonedible lignocellulosic biomass derived primarily from agricultural byproducts. Ciona intestinalis, a marine filter feeder, is cultivated to produce fish feed from the invertebrate’s inner tissue body. This process generates also vast amounts of a renewable side stream, namely the tunicate’s external cellulose-rich tunic. The aim of the present study was to evaluate the potential of the C. intestinalis tunic as a novel feedstock for bioethanol production. For this purpose, organosolv fractionation of the tunic was optimized to increase cellulose content. Enzymatic saccharification of the pretreated biomass was assessed to identify the most promising materials, which were subsequently utilized as carbon source in fermentation trials. Under optimal conditions, a titer of 38.7 g/L of ethanol, with a yield of 78.3% of the maximum theoretical, was achieved. To the best of our knowledge, this is the first report whereby organosolv pretreated tunic biomass is valorized toward bioethanol production; the current work paves the way for incorporating tunicates in bioconversion processes for the generation of biofuels and other biobased chemicals.

The tunicate species Ciona intestinalis is a fast-growing marine invertebrate animal that contains cellulose in its outer part - the tunic. The high crystallinity and microfibril aspect ratio of tunicate cellulose make it an excellent starting material for the isolation of nanocellulose. In the present work, tunic from C. intestinalis was subjected to organosolv pretreatment followed by bleaching and acid-hydrolysis steps for the isolation of nanocrystals. Applying an intermediate enzymatic treatment step with a lytic polysaccharide monooxygenase (LPMO) from the thermophilic fungus Thermothelomyces thermophila was proved to facilitate the isolation of nanocellulose and to improve the overall process yield, even when the bleaching step was omitted. LPMOs are able to oxidatively cleave the glycosidic bonds of a polysaccharide substrate, either at the C1 and/or C4 position, with the former leading to introduction of carboxylate moieties. X-ray photoelectron spectroscopy analysis showed a significant increase in the atomic percentage of the C═O/O-C-O and O-C═O bonds upon the addition of LPMO, while the obtained nanocrystals exhibited higher thermal stability compared to the untreated ones. Moreover, an enzymatic post-treatment with LPMOs was performed to additionally functionalize the cellulose nanocrystals. Our results demonstrate that LPMOs are promising candidates for the enzymatic modification of cellulose fibers, including the preparation of oxidized-nanocellulose, and offer great perspectives for the production of novel biobased nanomaterials. ©

In this study, the application of different chemical and enzymatic treatment methods for the fractionation of the birch outer bark components was evaluated. More specifically, untreated and steam exploded, hydrothermally and organosolv treated bark samples were incubated with enzyme mixtures that consisted of cellulases, hemicellulases and esterases, and the effect of enzymes was analyzed with ³¹P NMR and {¹³C-¹H} HSQC. The biocatalysts performed the cleavage of ester bonds resulting in reduction of methoxy and aliphatic groups in the remaining solid fraction, whereas the aromatic fraction remained intact. Moreover, the suberin and lignin fraction were isolated chemically and their properties were characterized by gas chromatography (GC-MS), ³¹P NMR, {¹³C-¹H} HSQC and gel permeation chromatography (GPC). It was demonstrated that the lignin fraction was enriched in guaiacyl phenolics but still contained some associated aliphatic acids and carbohydrates, whereas the suberin fraction presented a polymodal pattern of structures with different molecular weight distributions. This work will help in getting a deeper fundamental knowledge of the bark structure, the intermolecular connection between lignin and suberin fractions, as well as the potential use of enzymes in order to degrade the recalcitrant bark structure toward its valorization.

Unlike conventional electrolytes, ionic liquid (IL)-based electrolytes offer higher thermal stability, acceptable ionic conductivity, and a higher electrochemical stability window (ESW), which are indispensable for the proper functioning of Li-ion batteries. In this study, fluorine-free electrolytes are prepared by mixing the lithium furan-2-carboxylate [Li(FuA)] salt with the tetra(n-butyl)phosphonium furan-2-carboxylate [(P₄₄₄₄)(FuA)] IL in different molar ratios. The anion of these electrolytes is produced from biomass and agricultural waste on a large scale and, therefore, this study is a step ahead toward the development of renewable electrolytes for batteries. The electrolytes are found to have T_onset higher than 568 K and acceptable ionic conductivities in a wide temperature range. The pulsed field gradient nuclear magnetic resonance (PFG-NMR) analysis has confirmed that the (FuA)⁻ anion diffuses faster than the (P₄₄₄₄)⁺ cation in the neat (P₄₄₄₄)(FuA) IL; however, the anion diffusion becomes slower than cation diffusion by doping Li salt. The Li⁺ ion interacts strongly with the carboxylate functionality in the (FuA)⁻ anion and diffuses slower than other ions over the whole studied temperature range. The interaction of the Li⁺ ion with the carboxylate group is also confirmed by ⁷Li NMR and Fourier transform infrared (FTIR) spectroscopy. The transference number of the Li⁺ ion is increased with increasing Li salt concentration. Linear sweep voltammetry (LSV) suggests lithium underpotential deposition and bulk reduction at temperatures above 313 K.

We synthesized tetra(n-butyl)phosphonium furoate [P₄₄₄₄][FuA] ionic liquid (IL) by the reaction of tetra(n-butyl)phosphonium hydroxide and 2-furoic acid using water as a solvent at room temperature. The thermal stability and phase behavior of the IL are investigated through thermogravimetry (TGA) and differential scanning calorimetry (DSC), while the ionic conductivity measurement is carried out using impedance spectroscopy. Hybrid carbon-based material composed of multi walled carbon nanotubes (MWCNTs) and activated charcoal is fabricated and used as electrodes. The effect of potential scan rate, temperature and voltage on the electrochemical performance of the capacitor is thoroughly investigated through cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS). The results showed that the internal resistance and specific capacitance are highly dependent on the temperature and voltage, and a high specific capacitance of 141.4 F g⁻¹ (5 mV s⁻¹) from CV and 182 F g⁻¹ (1 A g⁻¹) from GCD at 100 °C is achieved, indicating an excellent electrochemical performance. The capacitor demonstrated 29.0 Wh kg⁻¹ energy density and 13.3 kW kg⁻¹ power density at 20 °C and 3 V potential, while 177 Wh kg⁻¹ energy density and 82 kW kg⁻¹ power density are achieved at higher temperature (100 °C). The FTIR analysis of the capacitor after electrochemical studies confirmed that no changes have occurred in the structure of the IL, indicating high electrochemical stability of the IL for supercapacitor applications in an extended temperature (−20 to 100 °C) and a wide potential range (3 V to 4.6 V).

This paper presents the results on gasification kinetic data, influence of the different models on predicted gasification rates, reaction order and comparison of gasification reactivity of the chars prepared in different conditions as well as that among the feedstock (algal and woody chars). A fresh water alga, Chlorococcum humicola and three types of woody biomass were pyrolyzed separately in a thermogravimetric analyzer (TGA) and in an entrained flow reactor (EFR), and the resultant chars were then gasified in the temperature range 700–1000 °C under CO2 to compare their intrinsic kinetics and to determine the transition temperatures between kinetic control and intraparticle diffusion control. The transition temperature was dependent on both sample and pyrolysis condition. Activation energy and frequency factor were determined using three kinetic models (volumetric, grain and random pore). The activation energy of different chars was determined to be in the range of 180–307 kJ/mol. Among the models, the random pore model was found to be predicting the weight loss profile most accurately except for the algal and a woody char from EFR. The reaction order and reactivity were found to be varying significantly with the pyrolysis condition of the chars.

Electrochemical reduction of CO2 removed from biosyngas into value-added methanol (CH3OH) provides an attractive way to mitigate climate change, realize CO2 utilization, and improve the overall process efficiency of biomass gasification. However, the economic and environmental feasibilities of this technology are still unclear. In this work, economic and environmental assessments for the stand-alone CO2 electrochemical reduction (CO2R) toward CH3OH with ionic liquid as the electrolyte and the integrated process that combined CO2R with biomass gasification were conducted systematically to identify key economic drivers and provide technological indexes to be competitive. The results demonstrated that costs of investment associated with CO2R and electricity are the main contributors to the total production cost (TPC). Integration of CO2R with CO2 capture/purification and biomass gasification could decrease TPC by 28%-66% under the current and future conditions, highlighting the importance of process integration. Energy and environmental assessment revealed that the energy for CO2R dominated the main energy usage and CO2 emissions, and additionally, the energy structure has a great influence on environmental feasibility. All scenarios could provide climate benefits over the conventional coal-to-CH3OH process if renewable sources are used for electricity generation.

The conductive multiwalled carbon nanotubes (MWCNTs)-graphene sheets (rGOs)-cellulose fiber was prepared with an eco-friendly wet-spinning method in which ionic liquid (IL) was used as both green solvent and dispersant. It was found that the selected IL 1-ethyl-3-methylimidazolium diethyl phosphate (EmimDep) shows remarkable capacities for dissolving cellulose and dispersing MWCNTs, and the synergistic effect of MWCNTs, rGOs, and cellulose results in a high electrical conductivity of 1195 S/m of MWCNTs-rGOs-cellulose fibers. Macropores and the double-layer structure of MWCNTs and rGOs can be observed by SEM in the studied fibers, and the number of macropores decreased with increasing rGOs amount, which is consistent with the result of the specific surface area. In addition, the prepared MWCNTs-rGOs-cellulose fibers present a nearly perfect electrical double-layer structure. The MWCNTs-rGOs-cellulose fiber with a mass ratio of 2:3:1 shows the best performance as the electrode candidate, with an electrical conductivity of 1195 S/m, specific capacitance of 597 mF/cm2, and specific surface area of 91 m2/g. Furthermore, the results from the molecular dynamics (MD) simulation evidenced that EmimDep can disperse CNTs effectively at 363.15 K, 1 atm compared to rGOs; the synergy effect of CNT and rGO exhibit great potential to enhance the dispersion than each individual component.

In this work, CO2 absorption capacities in a series of aqueous N-alkyl-N-methylmorpholinium-based ILs with acetate as the counterpart anion were investigated. Among these ILs, N-butyl-N-methylmorpholinium acetate ([Bmmorp][OAc]) with the highest CO2 absorption capacity was screened for thermodynamic modeling. The non-random two-liquid model and the Redlich–Kwong equation of state (NRTL-RK model) were used to describe the phase equilibria. The CH4 absorption capacity in the aqueous [Bmmorp][OAc] was also measured in order to verify the results predicted from the thermodynamic modeling, and the comparison shows the reliability of the model prediction. The parameters were embedded into the commercial software Aspen Plus. After that, the aqueous [Bmmorp][OAc] solutions with 30–40 wt % of water were selected to carry out process simulation for CO2 separation from biogas, and it was found that using these aqueous [Bmmorp][OAc] gave rise to lower energy usage and smaller size of equipment than other physical solvents. The results suggest that aqueous [Bmmorp][OAc] solution can be used as an alternative to organic solvents and has the potential to decrease the cost of CO2 separation.

Depolymerization and modification of lignin have been achieved simultaneously in a one-pot chemical reaction. Two heteroelement-rich modifiers, imidazol-1-yl phosphonic dichloride and 1H-1,2,4-triazol-1-yl phosphonic dichloride, were selected to react with lignin in this work. The modified lignin (m-lignin) is demonstrated as an effective lubricating additive for [choline][amino acid] ([CH][AA]) bioionic liquids. Different characterization techniques have been utilized to study the lignin depolymerization, reaction between lignin and modifiers and m-lignin/[CH][AA] interaction. The effect of the molecular structure of the modifiers on the rheological and tribological properties of m-lignin/[CH][AA] lubricants was systematically investigated. Density function theory is used to calculate the electronic structure of lignin, m-lignin, and [CH][AA]. The atomic natural charge analysis revealed the most negative charge on nitrogen bonded to a phosphorus atom and the strongest capability of forming hydrogen bonding with [CH][AA]. The introduced nitrogen and phosphorus elements not only increase the hydrogen bonding density in m-lignin/[CH][AA] but also enhance the polarity of the m-lignin, both of which facilitate a strong adhesion of lubricant on a metal surface and thus promote lubrication. A larger fraction of heteroatom groups in m-lignin contributes to a better lubrication property of these lubricants

Lignin, one of the most naturally abundant polymers, has been successfully incorporated into ethylene glycol (EG) and poly(ethylene glycol) (PEG) in this work and fortified lubricating properties were achieved in EG/lignin and PEG/lignin. The molecular interaction between lignin and EG (or PEG) has been revealed as hydrogen bonding, which serves as the dominating factor that determines the thermal, rheological, and tribological properties of the mixed systems of EG/lignin and PEG/lignin. The physicochemical properties of the mixed lubricants are tightly related to the state of internal hydrogen bonding (EG–EG, PEG–PEG, EG–lignin, PEG–lignin, and lignin–lignin) and are well correlated to their lubrication properties. Generally, larger lignin fractions lead to better lubricating performance in both EG and PEG systems. Lignin liquefaction in PEG has been addressed by catalytic degradation with the presence of sulfuric acid, which was then neutralized by triethanolamine for lubricant development. Lignin in PEG significantly improves the lubricating property at higher pressure conditions, where a wear reduction of 94.6% was observed. Lignin fortified EG and PEG based lubricants show outstanding noncorrosive characteristic to the mostly used metal materials such as aluminum and iron.

Isolation of lignins from hardwood and softwood biomass samples, containing 26.1% and 28.1% lignin, respectively, has been performed with the use of alkaline and organosolv pretreatment methods. The effect of catalyst loading, ethanol content, particle size, and pretreatment time on the yields and properties of the isolated lignins were investigated. Alkaline lignins had higher carbohydrate content - up to 30% - and exhibited higher molecular weights in the range of 3000 Da, with a maximum phenolic hydroxyl content of 1 mmol g^-1 for birch and 2 mmol g^-1 for spruce. Organosolv lignins, on the other hand, showed high purity - 93% or higher - despite the more extensive biomass dissolution into the pretreatment medium; they also exhibited a lower range of molecular weights between 600 and 1600 Da depending on the source and pretreatment conditions. Due to the lower molecular weight, phenolic hydroxyl content was also increased, reaching as high as 4 mmol g^-1 with a simultaneous decrease in aliphatic hydroxyl content as low as 0.6 mmol g^-1. Efficient lignin dissolution of 62% for spruce and 69% for birch, achieved at optimal pretreatment conditions, was combined with extensive hemicellulose removal

Squalene and docosahexaenoic acid (DHA) have gained substantial market share as dietary supplements and vital nutraceuticals due to their beneficial effects on human health. Marine fish are the main commercial source of these nutraceuticals, but a growing global demand, issues of sustainability, and an expanding vegan and vegetarian population has prompted the search for alternatives. Oils obtained from oleaginous microorganisms such as microalgae, diatoms, certain fungi, and thraustochytrids are alternatives to fish oils for omega-3 fatty acids. Among these, DHA is now being mined from thraustochytrids due to its highest proportion in their lipids, however, this strategy is not cost-effective. One way to offset such elevated production costs is to simultaneously extract other high value-added biological products from these oleaginous microorganisms. Here, we propose a novel biorefinery process based on single-step purification of squalene from total lipids extracted from an oleaginous thraustochytrid cultivated on non-edible forest biomass. To render the process economically feasible and sustainable, additional squalene-free lipids were exploited for enrichment of DHA; whereas leftover lipids generated as by-product during the process were tested as a novel biolubricant.

Lignin hydrogenolysis has recently been studied extensively as it was shown to result in high monomer yields. Most of these reactions were conducted in liquid solvents, which have shown large impacts on product types and yields. Because adsorption is the first step to any heterogeneous catalyst reactions, this work aims to understand how solvent affects lignin adsorption on Ni(111) and Cu(111) surfaces. To achieve this, density functional theory calculations were employed to investigate β-O-4 lignin dimer (a model compound) adsorption conformations in both vacuum and liquid ethanol. In vacuum, it was found that lignin prefers to adsorb strongly on Ni(111) and weakly on Cu(111) with both aromatic rings parallel to the surface. Solvated adsorption was modeled using both implicit and explicit models. It was found that an explicit model is required to accurately describe the lignin-solvent interactions. With the explicit solvation model, it was predicted that the lignin dimer adsorbs on a Ni(111) surface but not on Cu(111). Furthermore, to circumvent the computationally expensive liquid interface calculations, a thermodynamic cycle method was developed to quickly estimate the solvated lignin dimer adsorption energy from the gas phase adsorption energy and the solvation energies. This model quantifies the effects from the solvent on lignin dimer adsorption, including the contributions from the lignin-solvent and the solvent-metal interactions, and suggests how to design both catalyst and solvent to tune lignin adsorption. 

This work presents a novel method for generating in-situ low friction tribofilms in lubricated contacts using α-amino acid L-methionine as additive. Methionine is an environmentally acceptable natural organosulphur compound that is typically used in food industry. Our approach relies in the use of steel surfaces functionalized with tungsten carbide particles that are tailored to interact with methionine via a tribo-chemical reaction. The results show that after an induction period, the friction drops dramatically by 60% down to values of 0.06 when methionine was used as additive in lubricated tungsten carbide functionalized surfaces. The low friction could only be achieved by the coexistence of tungsten from the functionalized surfaces and sulphur from methionine, which led to the presence of tribo-chemically generated tribofilms. Ab-initio simulations indicate that the tribo-chemical reaction for forming tungsten disulphide is energetically favourable, thus attributing the observed friction reduction mechanism to the in-situ formation of this compound during the sliding process. The concept of functionalizing surfaces to react with specific additives opens up a wide range of possibilities, which allows tuning surfaces to target specific additive interactions. This synergy can be exploited for using novel green additive technology, thus allowing more environmentally friendly formulations with outstanding tribological performance.

The current practice of landfilling fly ash generated by waste incineration is nonsustainable, so alternative ways of using this material are needed. Silanization effectively immobilizes the heavy metal contaminants in the incineration fly ash and enables its circular utilization because silanized fly ash (SFA) has market value as a low-cost filler for polymer composites. This study examines the ecoefficiency of a thermal insulation panel that consists of a polyurethane (PU) foam core sandwiched between two epoxy composite skins prepared by reinforcing glass fibers (GF) and SFA in epoxy resin. The ecoefficiency of such panels was evaluated by comparing their life cycle environmental externality costs (LCEE) to their life cycle costs (LCC). The LCEE was calculated by monetizing the panels’ environmental impacts, which were quantified by performing a life cycle assessment (LCA). The results revealed that the ecoefficiency of the composite panels is positive (47%) and superior to that of market incumbent alternatives with PU foam or rockwool cores and steel skins. The two market incumbents have negative ecoefficiencies, primarily due to their high LCEE. The environmental performance of the panel with SFA–GF epoxy composite skins can be further improved by using lignin-based epoxy resin or thermoplastic polypropylene as the polymer matrix of composite skins. Overall, application as a filler in fabricating polymer composite skins of sandwich panels is an upcycling pathway of SFA that combines circular economy prospects with sustainability benefits.

In this study, a biobased phenolic adhesive was successfully developed by entirely substituting both petroleum-based phenol and formaldehyde with an unmodified corn stover biorefinery lignin and glyoxal (a biobased dialdehyde), respectively. Lignin-glyoxal resins were synthesized using an alkaline catalyst with a molar ratio of lignin to glyoxal of 1:2. Chemical, thermal, and mechanical properties of the lignin, lignin-based resins, and final adhesives were assessed following appropriate standard test methods. The analysis of lignins and lignin-based resin molar mass was performed using gel permeation chromatography. The lignin-glyoxal resin was found to have a 3-fold higher average molecular weight than the starting lignin, demonstrating the successful integration of lignin into the polymeric resin network. The curing of the formulated adhesives was studied using differential scanning calorimetry and dynamic mechanical analysis. Although the lignin-glyoxal resin had a higher curing temperature (167 °C) than a conventional phenol-formaldehyde resin (142 °C) and the formulated lignin-formaldehyde resin (146 °C), the rate and degree of cure were similar or better than the other two resins. The adhesion strengths of the formulated adhesives were determined using single-lap-joint veneer samples cured according to recommended press parameters for commercial adhesives. The lignin-glyoxal adhesive had a relatively high dry adhesion strength (3.9 MPa), with over 90% wood failure, but failed the wet adhesion test (boiling water test). Although the formulated lignin-glyoxal adhesive failed the boiling water test, it had excellent stability at room temperature water, remaining intact after 1 week during the water immersion test. The high dry adhesion strength makes this class of lignin-based formaldehyde-free adhesives a unique biobased glue for the production of interior grade plywood and oriented strand boards.

Microbial treatment of biodegradable wastes not only ensures neutralization of harmful substances such as volatile organic compounds but also enables valorization and bio-circularity within the society. Single cell protein (SCP) is a value-added product that can be obtained from biodegradable waste materials such as food waste via microbial fermentation. In this article, SCP derived from potato starch waste was demonstrated as a viable alternative to existing plant/animal proteins used in the production of films, for example, packaging applications. Flexible glycerol-plasticized SCP films were prepared through compression molding, and tensile tests revealed strength and stiffness similar to other plasticized protein films. The oxygen barrier properties were significantly better compared to the common polyethylene packaging material, but as with other highly polar materials, the SCP material must be shielded from moisture if used in, for example, food packaging. The biodegradation test revealed a similar degradation pattern as observed for a household compostable bag. The results showed that SCP-based bioplastic films can be considered as potential alternative to the existing plant/animal protein films and certain synthetic polymers. An important advantage with these protein materials is that they do not cause problems similar to microplastics.

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 5-fold higher initial absorption rate than MDEA and a 2-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.

Bio-based wood materials are preferable for composites because of their sustainability, but adequately dispersing wood fibers in polymers can be difficult and costly. Our approach was to pretreat the wood with a green solvent system, allowing the composite to be extruded in a single step, simplifying the process, and reducing the overall cost. This study investigates the fibrillation of untreated wood sawdust (W) and deep eutectic solvent-treated wood sawdust (DESW) using a one-step twin-screw extrusion (TSE) process. The results of the analysis of wood fractions and optical microscopy confirmed that the one-step extrusion process resulted in fibrillation of both treated and untreated wood material. The width of the original wood particles was reduced by more than 99% after a one-step TSE for both untreated and DES-treated wood. The size reduction of the DESW was slightly greater than that of the untreated wood, and fibrillation was further confirmed by rheological analysis. The fibrillated wood was then compounded with polypropylene (PP) to produce a wood fiber-polypropylene composite with 50 wt % wood content. The elastic modulus of both untreated and treated extruded composites was higher than that of neat PP. The tensile strength and strain at break for the DESW-PP composite slightly increased in comparison to the untreated W-PP composite. Furthermore, DES treatment of wood resulted in a darker color and increased hydrophobicity of the material.

Beech sawdust was treated with a ternary solvent system based on binary aqueous ethanol with partial substitution of ethanol by acetone at four different water contents (60, 50, 40, and 30%v/v). In addition to standard, i.e., noncatalyzed treatments, the application of inorganic acid in the form of 20 mm H2SO4 was evaluated. The various solvent systems were applied at 180 °C for 60 min. The obtained biomass fractions were characterized by standard biomass compositional methods, i.e., sugar monomer and oligomer contents, dehydration product contents of the aqueous product, and lignin, cellulose, and hemicellulose contents in isolated solid fractions. More advanced analyses were performed on the lignin fractions, including quantitative 13C NMR analyses, 1H–13C HSQC analysis, size exclusion chromatography, and pyrolysis-GC/MS, and the aqueous product, in the form of size exclusion chromatography and determination of total phenol contents. The picture emerging from the thorough analytical investigation performed on the lignin fractions is consistent with that resulting from the characterization of the other fractions: results point toward greater deconstruction of the lignocellulosic recalcitrance upon higher organic solvent content, replacing ethanol with acetone during the extraction, and upon addition of mineral acid. A pulp with cellulose content of 94.23 wt % and 95% delignification was obtained for the treatment employing a 55/30/15 EtOH/water/acetone mixture alongside 20 mm H2SO4. Furthermore, the results indicate the formation of two types of organosolv furan families during treatment, which differ in the substitution of their C1 and C5. While the traditional lignin aryl–ether linkages present themselves as indicators for process severity for the nonacid catalyzed systems, the distribution of these furan types can be applied as a severity indicator upon employment of H2SO4, including their presence in the isolated lignin fractions.

A titanium phosphate sorbent with linked active units (LTP) is synthesized. XRD, ³¹P MAS NMR, and TGA techniques are used to disclose the relation between the ion-exchange units of −HPO₄ (crystalline α-TiP) and of −H₂PO₄ (amorphous TiP1) type. The reported kinetics data of TiP1 sorbent in batch mode have been reprocessed according to the nonlinear approach in order to explore further the sorption mechanism. It was found that the data could be well described by the pseudo-second-order model in the case of Ni²⁺ ions. Consequently, fixed-bed column sorption experiments of Ni²⁺ ions on LTP were designed, and the effects of both the amount of nickel(II) ions in the feed solution and the flow rates on the sorption equilibrium were studied. The ion-exchange capacity is estimated to be 1.6 m_eq·g^–1 during the first four cycles before decreasing to 1.2 m_eq·g^–1 for cycles five and six. The experimental data were simulated following the Thomas model, and desorption experiments with HCl were performed. Observations show that regeneration and reutilization of the LTP ion-exchanger are possible through at least six cycles. It is revealed that the sorption performances in column conditions could be undoubtedly predicted from the corresponding batch sorption data.

Sorptionfixed-bed column experiments were performed using atitanium phosphate ion-exchanger composed of−H2PO4units [TiO(OH)(H2PO4)·H2O]. Model mine water containingfive divalent metal ions (Cu2+,Zn2+,Mn2+,Ni2+,and Co2+) and a few closed-mine water samples were treated to evaluate the sorptionpreference of the material. For thefirst time, dynamic ion-exchange capacities(estimated to be between 3.2 and 4.2 mequiv g−1) and static ion-exchange uptakes(calculated to be between 3.1 and 3.5 mequiv g−1) were obtained for the same TiP1sorbent and data were discussed in terms of sorption behavior. It was found thatsorption processes on TiP1 in model and closed-mine waters during a columnexperiment could be accurately predicted from the corresponding batch experiment(including the sorbent’s capacities in different types of waters). A competitivesorption phenomenon in favor of Cu2+on TiP1 was established for all cases, pointingtoward the possibility of isolating pure copper concentrate from closed-mine waters.The relatively high amounts of calcium and magnesium ions present in mine waters did not appear to considerably affect theselectivity of TiP1 material. Exploratory experiments for sorbent regeneration and desorption using a low concentration of nitricacid were demonstrated.

With the explosion of global demands for electrified mobility systems and a surge in rural energy transport mechanisms augmented by the scarcity of key metals, carbon by design has become a transformational pathway to fill the gap as an energy material of choice. The development of functional carbon from renewables with outstanding electrostatic double-layer capacitance is still in its infancy, as there is a significant gap in understanding the relationship between the tunable structure and properties of the bioresources both before and after their controlled carbonization. Herein, we report carbon fiber networks (CFNs) with highly controllable intact structure manufactured from four functional lignins originating from different types of processing residues, demonstrating excellent electrochemical efficacies, which makes them promising self-standing electrodes in supercapacitors. This study also underpins the feasibility and importance of preparing CFNs with highly oriented structure, which endows superior specific capacitance and cycle stability compared to the CFNs with randomly oriented fibers. The randomly oriented CFNs reached a specific capacitance value of 456 F g^–1 under current densities of 1 A g^–1 and a cycle stability of 73.6%, while the CFNs with an orientation factor of 0.87 exhibited significant improvement of the specific capacitance by approximately 15% (529 F g^–1) and the cycle stability reached 95% after 10 000 charge–discharge cycles. The high specific capacitance and excellent overall electrochemical properties of the highly oriented CFNs make them a cost-effective and greener material of choice for energy storage devices. 

In this study, a facile synthesis method was employed to create lignin-castor oil-based oleogels by modifying organic lignin with two silane coupling agents. The resulting oleogels demonstrated outstanding lubricating and antioxidation properties, establishing them as promising green lubricating greases. Compared with the pure castor oil, the oxidation induction time (OIT) value of the synthesized oleogels was significantly increased from 20 s (pure castor oil) to 1959 s (oleogel with 20 wt % lignin), indicating an effective improvement of the oxidation resistance. The steel contacts lubricated by the synthesized oleogel also had lower wear than those lubricated by pure castor oil, signifying the better lubricating properties of oleogels. The oleogel with 20 wt % lignin showed the lowest wear, which was around 64% lower than that of pure castor oil. The exceptional performance and environmentally sustainable composition of these oleogels, with the biomass content exceeding 80%, allow them to be used as green lubricating greases for industrial applications. Overall, this study provides valuable insights into the development of high-performance, eco-friendly lubricants.

The high recalcitrance of plant cell walls is an obstacle for effective chemical or biological conversion into renewable chemicals and transportation fuels. Here, we investigated the utilization of both oxygen (O₂) and hydrogen peroxide (H₂O₂) as co-oxidants during alkaline–oxidative pretreatment to improve biomass fractionation and increase enzymatic digestibility. The oxidative pretreatment of hybrid poplar was studied over a variety of conditions. Employing O₂ in addition to H₂O₂ as a co-oxidant during the two-stage alkaline pre-extraction/copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment process resulted in a substantial improvement in delignification relative to using H₂O₂ alone during the second-stage Cu-AHP pretreatment, leading to high overall sugar yields even at H₂O₂ loadings as low as 2% (w/w of the original biomass). The presence of H₂O₂, however, was both critical and synergistic. Performing analogous reactions in the absence of H₂O₂ resulted in approximately 25% less delignification and 30% decrease in sugar yields. The lignin isolated from this dual oxidant second stage had high aliphatic hydroxyl group content and reactivity to isocyanate, indicating that it is a promising substrate for the production of polyurethanes. To test the suitability of the isolated lignin as a source of aromatic monomers, the lignin was subjected to a sequential Bobbitt’s salt oxidation followed by a formic acid-catalyzed depolymerization process. Monomer yields of approximately 17% (w/w) were obtained, and the difference in yields was not significant between lignin isolated from our Cu-AHP process with and without O₂ as a co-oxidant. Thus, the addition of O₂ did not lead to significant lignin crosslinking, a result consistent with the two-dimensional heteronuclear single-quantum coherence NMR spectra of the isolated lignin.