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Solvent-controlled extraction and precipitation are the most fundamental methods for obtaining hemicellulose from lignocellulosic biomass and purification processes. However, the dissolution and precipitation mechanisms involved have scarcely been mentioned. In this study, the molecular scale behavior of xylan-type hemicellulose during solvent-controlled extraction and precipitation is investigated using molecular dynamics (MD) simulations and density functional theory (DFT) calculations. To bring the model closer to the real extracted xylan, a high degree of polymerization (DP100) of xylan is established, and hemicelluloses with low DP (DP15 and DP50) are also investigated. Four phenomena are explained at the molecular level, including the influence of the polymerization degree and side chain on the solubility of xylan in water, the improvement of the xylan's solubility in NaOH, the precipitation of xylan in ethanol, and the acetyl group preservation of xylan in DMSO. This study contributes to an increased understanding of the dissolution and precipitation mechanisms of hemicellulose and provides a resource for the simulation of high DP hemicellulose, which gives a theoretical basis for the efficient extraction of high-purity hemicellulose as well as economic biorefining.

Cu/SiO 2 is one of the most promising catalysts for the furfural (FF) hydrogenation reaction but suffers from the difficulty of tailoring the microstructure and surface properties. Herein, we developed a MOF-derived Cu/SiO 2 catalyst (Cu/SiO 2 -MOF) for FF hydrogenation to 2-methyl furan (2-MF). In comparison with Cu/SiO 2 catalysts prepared from ammonia evaporation (Cu/SiO 2 -AE) and traditional impregnation (Cu/SiO 2 -TI), the copper species in Cu/SiO 2 -MOF could not only be anchored on the silica surface via forming Cu-O-Si bonds but also exposed many more active sites. In this way, a higher ratio of Cu + /(Cu + + Cu 0 ) and richer oxygen defects were constructed via strong metal-support interactions, which were responsible for the superior catalytic performance. In addition, it was found that the solvent effect on product distribution played an important role in adjusting the selectivity to 2-MF and cyclopentanone (CPO). The present work not only provides a deep insight into the catalytic mechanism of Cu/SiO 2 -MOF for the FF hydrogenation reaction but also sheds light on the design and synthesis of highly efficient catalysts for other heterogeneous catalysis fields.

The efficient production of γ-valerolactone (GVL) from renewable lignocellulose that is synthesized in plants by photosynthesis to replace the declining fossil resources conforms to the principles of circular economy. Compared to direct hydrogenation by H 2 molecules, catalytic transfer hydrogenation (CTH) of levulinic acid (LA) and/or its esters to GVL with organic alcohols as a hydrogen source is a much milder route. The synergistic catalysis between Lewis and Brønsted acids is indispensable in the CTH process. Considering that unsaturated coordinated Zr species could act as Lewis acid sites and phosphotungstic acid (PTA) could dissociate protons as Brønsted acid sites, UiO-66 (Zr) was thus "acidified" by encapsulating PTA in its channels to tune the ratio of Brønsted to Lewis acid sites as a bifunctional catalyst so as to better understand the catalytic structure-performance relationship in the CTH process. To address the dilemma of encapsulated PTA that is prone to leach, a rapid surface sealing strategy was adopted to establish a polyimide (PI) coating over the surface of UiO-66 introducing a space confinement effect via an anhydride-amine coupling reaction. The as-synthesized PTA/UiO-66@PI catalyst exhibited 100% of LA conversion, a 93.2% of GVL yield and high recyclability for at least five consecutive cycles. Moreover, a reaction pathway followed by esterification, hydrogenation and dealcoholization as well as a catalytic hydrogenation mechanism based on intermolecular hydride β-H transfer were proposed. Current work not only provides a high-performance and high-stability catalytic system to selectively produce GVL from LA or its esters, but also sheds light on the catalytic mechanism of the CTH process at the molecular level.

Lithium silicates have attracted great attention in recent years due to their potential use as high-temperature (450-700 °C) sorbents for CO 2 capture. Lithium orthosilicate (Li 4 SiO 4 ) can theoretically adsorb CO 2 in amounts up to 0.36 g CO 2 per g Li 4 SiO 4 . The development of new Li 4 SiO 4 -based sorbents is hindered by a lack of knowledge of the mechanisms ruling CO 2 adsorption on Li 4 SiO 4 , especially for eutectic mixtures. In this work, the structural, electronic, thermodynamic and CO 2 capture properties of monoclinic phases of Li 4 SiO 4 and a binary (Li 3 NaSiO 4 ) eutectic mixture are investigated using density functional theory. The properties of the bulk crystal phases as well as of the relevant surfaces are analysed. Likewise, the results for CO 2 -lithium silicates indicate that CO 2 is strongly adsorbed on the oxygen sites of both sorbents through chemisorption, causing an alteration not only in the chemical structure and atomic charges of the gas, as reflected by both the angles and bond distances as well as atomic charges, but also in the cell parameters of the Li 4 SiO 4 and Li 3 NaSiO 4 systems, especially in Li 4 SiO 4 (001) and Li 3 NaSiO 4 (010) surfaces. The results confirm strong adsorption of CO 2 molecules on all the considered surfaces and materials followed by CO 2 activation as inferred from CO 2 bending, bond elongation and surface to CO 2 charge transfer, indicating CO 2 chemisorption for all cases. The Li 4 SiO 4 and Li 3 NaSiO 4 surfaces may be proposed as suitable sorbents for CO 2 capture in wide temperature ranges.

Type V natural deep eutectic solvents based on monoterpenoids (cineole, carvone, menthol, and thymol) are studied using a combined experimental and molecular modeling approach. The reported physicochemical properties showed low viscous fluids whose properties were characterized as a function of temperature. The theoretical study combining quantum chemistry and classical molecular dynamics simulations provided a nanoscopic characterization of the fluids, particularly for the hydrogen bonding network and its relationship with the macroscopic properties. The considered fluids constitute a suitable type of solvents considering their properties, cost, origin, and sustainability in different technological applications and sow the possibility of developing type V NADES from different types of molecules, especially in the terpenoid family of compounds.

Electrochemical oxidation is a promising and effective method for lignin depolymerization owing to its selective oxidation capacity and environmental friendliness. Herein, the electrooxidation of non-phenolic alkyl aryl ether monomers and β-O-4 dimers was experimentally (by cyclic voltammetry, in situ spectroelectrochemistry, and gas chromatography-mass spectroscopy) and theoretically (by DFT calculations) explored in detail. Compared to the reported literature (T. Shiraishi, T. Takano, H. Kamitakahara and F. Nakatsubo, Holzforschung, 2012, 66(3), 303-309), 1-(4-ethoxyphenyl)ethanol showed a distinguishable oxidation pathway, where the resulting carbonyl product surprisingly underwent a bond cleavage on alkyl-aryl ether to ultimately produce a quinoid like compound. In contrast, β-O-4 dimers, like 2-phenoxy-1-phenethanol and 2-phenoxyacetophenone also demonstrated electrochemical oxidation induced by C β -O and C α -C β bond cleavages. For the oxidation products, the presence of the C α -hydroxyl group in dimers was the key to selectively generate aldehyde-containing species under mild electrochemical conditions, otherwise it produces alcohol-containing products following a different mechanism compared to the C α [double bond, length as m-dash]O containing dimers.

The low voltage electrowetting response of a LiCl aqueous solution on a freshly cleaved surface of highly oriented pyrolytic graphite (HOPG) is presented. For applied voltages below 1 V, the energy stored in the electrical double layer (EDL) is insufficient to drive the spreading of the drop due to the pinning of the three phase contact line at the step edges. Electrochemical impedance spectroscopy shows a dramatic increase in capacitance above 1 V, which provides a sufficient electrowetting force for depinning the contact line, resulting in a subsequent decrease of the contact angle. The transition of the interfacial capacitance from the EDL to the many-fold high capacitance of the pseudocapacitor drives the electrowetting transition on the HOPG surface. The observed changes in the capacitances above 1 V are correlated with the cyclic voltammetry and atomic force microscopy results, which show that the Cl- ions intercalate into the graphite galleries upon acquiring sufficient energy to overcome the van der Waals attraction between the graphene layers through the side of the step edge of the basal planes. To the best of our knowledge, this is the first study on the voltage dependent intercalation mediated transition of interfacial capacitance driving the spreading of an aqueous electrolyte drop on the HOPG surface, which provides a fundamental understanding of the mechanism and opens up potential applications in microfluidics and charge storage technologies.

As a common physicochemical phenomenon, protonation can cause molecules, atoms or ions with lone-pair electrons to become charged, and can further cause some changes in their physical and chemical properties. Our study first focused on the molecular protonation process and accompanying transitions of the oil/water interface properties in an electric field. The relationship between the protonation degree increment and applied voltage was proposed as a guide for controlling the protonation via applying an electric field. Besides the protonation degree, the water solubility of the oily target molecule obviously increased at 30 V for 600 s along with electric field-driven protonation. At the same time, the electrical conductivity and the underwater interface wettability of oil phase transitioned. These property transitions are anticipated to guide the further improvement and updating of promising protonation functions.