DBU-Glycerol Solution: A CO2 Absorbent with High Desorption Ratio and Low Regeneration Energy.

1,8-Diazabicyclo[5.4.0]-undec-7-ene (DBU)-glycerol solution is employed as a promising CO2 absorbent. The regeneration of the CO2-loaded solution is of vital importance for its commercialization. It was investigated and compared with 30 wt % monoethanolamine (MEA). Variables affecting the absorption and desorption processes were studied, including the solvent composition, reaction temperature, and agitation. It shows that the absorption capacity for DBU-glycerol is comparable with 30 wt % MEA, and the desorption ratio for CO2-loaded DBU-glycerol mixture can reach as high as 95% in 60 min, 363 K at the 3:1 molar ratio of DBU to glycerol, while it is only 68% even after 165 min for CO2-saturated 30 wt % MEA. DBU-glycerol solution has higher cycling CO2 loading than 30 wt % MEA. Its cyclic capacity could keep above 90% after 10 cycles of absorption-desorption experiments. The desorption reaction is irreversible at the initial stage, and the reaction rate is expected as a first-order reaction from 349 to 377 K, and the apparent activation energy is 68.94 kJ/mol. Moreover, the heat duty of the reboiler during regeneration is estimated to be reduced by about 27% when compared with 30 wt % MEA.

An absorption mechanism and polarity-induced viscosity model for CO2 capture using hydroxypyridine-based ionic liquids.

A series of new hydroxypyridine-based ionic liquids (ILs) are synthesized and applied in CO2 capture through chemical absorption, in which one IL, i.e., tetrabutylphosphonium 2-hydroxypyridine ([P4444][2-Op]), shows a viscosity as low as 193 cP with an absorption capacity as high as 1.20 mol CO2 per mol IL. Because the traditional anion-CO2 absorption mechanism cannot provide an explanation for the influences of cations and temperature on CO2 absorption capacity, herein, a novel cation-participating absorption mechanism based on the proton transfer is proposed to explain the high absorption capacity and the existence of a turning point of absorption capacity with the increase of temperature for the capture of CO2 using [P4444][n-Op] (n = 2, 3, 4) ILs. Also, the relationship between the viscosity of ILs and the linear interaction energy is proposed for the first time, which can guide how to design and synthesize ILs with low viscosity. Quantum chemistry calculations, which are based on the comprehensive analysis of dipole moment, cation-anion interaction energy and surface electrostatic potential, indicate that the different viscosities of hydroxypyridine-based ILs and the changes after CO2 absorption mainly resulted from the different distribution of negative charges in the anion.

Plastron effect enhanced electrochemical CO2 reduction activity over hydrophobic three-dimensional nanoporous silver.

The electrochemical reduction of CO2 on catalyst surfaces is hindered by the inefficient mass transfer of CO2 in aqueous solutions. In this study, we employed an electrochemical reduction approach to fabricate a hydrophobic three-dimensional nanoporous silver catalyst with a plastron effect, aiming to enhance the CO2 diffusion. The resulting catalyst exhibited an exceptional performance with the FECO peaking at 95% at -0.65 V (vs. RHE) and demonstrated remarkable stability during continuous electrolysis for 48 hours. Control experiments, together with Tafel analysis, EIS measurements, and contact angle results, confirmed that the notable enhancement of performance was attributed to the hydrophobic porous structure that facilitated efficient storage and rapid mass transfer of low-solubility CO2 gas reactants.

The structure and properties of lignin isolated from various lignocellulosic biomass by different treatment processes.

The structure and properties of lignin can vary depending on the type of lignocellulosic biomass it comes from and the separation techniques used, and also affects its suitability for different applications. In this work, the structure and properties of lignin isolated from moso bamboo, wheat straw, and poplar wood by different treatment processes were compared. Results show that deep eutectic solvent (DES) extracted lignin exhibits well-preserved structures (including ß-O-4, ß-ß, and ß-5 linkages), a low molecular weight (Mn = 2300-3200 g/mol), and relatively homogeneous lignin fragments (1.93 < PDI < 2.33) compared to dealkaline lignin (DL) and milled wood lignin (MWL). Besides, lignin samples extracted by DES have a regular nanostructure, higher carbon residue content (>40 %), and excellent antioxidant properties (the free radical scavenging index >20). Among the three types of biomass, the structural destruction of lignin in straw is the most obvious, which is due to the degradation of ß-O-4 and ß-ß linkages during DES treatment. These findings can contribute to a better understanding of the structural changes that occur in various treatment processes from different lignocellulosic biomass, and help maximize the targeted development of their applications based on the characteristics of lignin.

Multistage treatment of bamboo powder waste biomass: Highly efficient and selective isolation of lignin components.

Bamboo pulp and papermaking produce a lot of bamboo powder waste, and its resource utilization is of great significance for biomass refining and environmental protection. Here, we propose an integrated approach involving mechanical activation, hydrothermal extraction, and deep eutectic solvents (DESs) multiple delignification for the efficient separation of bamboo powder. Among seven carboxylic acids based DESs, choline chloride (ChCl)-lactic acid (La) DES (1:1) is the most effective, with over 78.0% lignin removal and 88.9% cellulose retained after mechanical-hydrothermal (180 °C, 5 h)-DES (110 °C, 12 h) treatment. Notably, 84.7% of delignification is achieved after three times of ChCl-La DES treatment at 70, 90, and 110 °C respectively. The delignification rate is negatively correlated with the amount of carboxyl group in the DESs. The lower the pKa value, the higher the delignification rate. Additionally, the selectivity for lignin is improved with decreasing solvent polarity. DES treatment effectively degrades the guaiacyl unit lignin fractions and disrupts several ß-aryl-ether bonds (e.g., ß-O-4, ß-ß, and ß-5). Furthermore, DESs exhibit good recyclability, with less than 10% reduction in delignification after three cycles. Theory calculations confirm that ChCl-carboxylic acid DESs could compete with lignin to break hydrogen bonds in lignocellulosic biomass by providing their chloride, hydroxyl, and carboxyl groups. Overall, this study demonstrates the practical significance of multistage treatment for the effective fractionation of biomass into its three components.

Insights into the relationships between physicochemical properties, solvent performance, and applications of deep eutectic solvents.

Deep eutectic solvent (DES) is regarded as a new generation of green solvent due to its distinctive and tailorable physicochemical properties, such as low volatility, strong solubility, biodegradability, low-cost, environment-friendly, and feasibility of the structural design. As an alternative to traditional organic solvents and ionic liquids (ILs), DESs have been widely applied in many fields, such as organic chemical synthesis, electrochemical deposition, material preparation, biomass catalytic conversion, extraction and separation, detection and analysis, nanotechnology, gas absorption, and drug delivery. In this paper, through in-depth discussion on factors influencing the physicochemical properties of DESs, we summarized the relations between their composition, structure, and performance. Focusing on their solvent performance, we analyzed the latest research results of DESs with different physicochemical properties in various fields. It should be pointed out that designing and synthesizing DESs from the molecular structure aspect to regulate their physicochemical properties is the direction of accurately developing new functional applications of DESs.

The role of adsorbed oleylamine on gold catalysts during synthesis for highly selective electrocatalytic reduction of CO2 to CO.

The low-coordinated sites of electrocatalysts favour hydrogen evolution, while the edge sites are active for CO2 reduction. Oleylamine is used to stabilize nanoparticles by adsorbing on the low-coordinated sites. The hydrogen evolution reaction was dramatically suppressed and the FECO remained >93% from -0.4 to -0.8 V (vs. RHE) when oleylamine ligands existed on the surface of a gold catalyst. More H+ and electrons were involved in the CO evolution reaction, which changed the rate-limiting step from single-electron transfer to the chemical reaction step. The results establish that the surface-adsorbed surfactants during catalyst synthesis have an important effect on CO2 electrocatalytic reduction.

Enhanced hydrolysis of mechanically pretreated cellulose in water/CO2 system.

The aim of this work was to study promotion of ball milling and CO2 assistance on cellulose hydrolysis kinetics in water medium. Kinetic behaviors were analyzed based on first-order and shrinking core models. The results showed that cellulose hydrolysis is enhanced by ball milling and CO2 assistance. Ball milling reduced crystallinity and particle size of cellulose, resulting in high cellulose conversion, while hydrolysis promoted by CO2 assistance was weaker. Double-layer hydrolysis was observed for ball-milled cellulose, and rate constant in active layer is higher. Based on double-layer shrinking core model (DL-SCM), activation energy of cellulose conversion decreased from 73.6 to 39.8 kJ/mol when ball milling and CO2 assistance were applied. Hydrolysis active layer was about 0.9 µm, representing activated thickness of ball-milled cellulose. Hydrolysis promotion by crystallinity and particle size reduction was distinguished via DL-SCM, and crystal evolution possesses greater improvement than particle size decrease on hydrolysis of ball-milled cellulose.

Preparation of Silver Carbonate and its Application as Visible Light-driven Photocatalyst Without Sacrificial Reagent.

Visible light-driven photocatalyst is the current research focus and silver oxyacid salts with p-block elements are the promising candidates. In this research, Ag2 CO3 was prepared by a facile precipitation method and used to degrade the pollutants from waters. The results revealed that the silver carbonate with monoclinic structure quickly decomposed methyl orange and rhodamine B in less than 15 min under visible light irradiation. When it was recycled six times, the degradation of methyl orange still can reach 87% after 30 min. The calculated band gap of Ag2 CO3 was 2.312 eV with Valence band edge potential of 2.685 eV and Conduction band 0.373 eV vs NHE, which endowed the excellent photo-oxidation ability of silver carbonate. Photogenerated holes and ozone anion radicals were the primary active species in the photo-oxidization degradation of dye. The generation of metallic silver resulted from photocorrosion and the consequent reduction in the ozone anion radical amount led to the performance degradation of Ag2 CO3 . The simple preparation method and high photocatalytic performance of Ag2 CO3 increases its prospect of application in future.

Production of tung oil biodiesel and variation of fuel properties during storage.

The crude Tung oil with 4.72 mg KOH/g of acid value (AV) was converted by direct transesterification, and the reaction mixture was quantified. The phase distribution data showed that 38.24% of excess methanol, 11.76% of KOH, 10.13% of soap and 4.36% of glycerol were in the biodiesel phase; 0.35% of biodiesel dissolved in the glycerol phase. Tung oil biodiesel as well as its blends with 0(#) diesel was investigated under different storage conditions. The results indicated that higher temperature greatly influenced the storage stability, especially when the volume fraction of Tung oil biodiesel is increased in the blends.

A sustainable woody biomass biorefinery.

Woody biomass is renewable only if sustainable production is imposed. An optimum and sustainable biomass stand production rate is found to be one with the incremental growth rate at harvest equal to the average overall growth rate. Utilization of woody biomass leads to a sustainable economy. Woody biomass is comprised of at least four components: extractives, hemicellulose, lignin and cellulose. While extractives and hemicellulose are least resistant to chemical and thermal degradation, cellulose is most resistant to chemical, thermal, and biological attack. The difference or heterogeneity in reactivity leads to the recalcitrance of woody biomass at conversion. A selection of processes is presented together as a biorefinery based on incremental sequential deconstruction, fractionation/conversion of woody biomass to achieve efficient separation of major components. A preference is given to a biorefinery absent of pretreatment and detoxification process that produce waste byproducts. While numerous biorefinery approaches are known, a focused review on the integrated studies of water-based biorefinery processes is presented. Hot-water extraction is the first process step to extract value from woody biomass while improving the quality of the remaining solid material. This first step removes extractives and hemicellulose fractions from woody biomass. While extractives and hemicellulose are largely removed in the extraction liquor, cellulose and lignin largely remain in the residual woody structure. Xylo-oligomers, aromatics and acetic acid in the hardwood extract are the major components having the greatest potential value for development. Higher temperature and longer residence time lead to higher mass removal. While high temperature (>200°C) can lead to nearly total dissolution, the amount of sugars present in the extraction liquor decreases rapidly with temperature. Dilute acid hydrolysis of concentrated wood extracts renders the wood extract with monomeric sugars. At higher acid concentration and higher temperature the hydrolysis produced more xylose monomers in a comparatively shorter period of reaction time. Xylose is the most abundant monomeric sugar in the hydrolysate. The other comparatively small amounts of monomeric sugars include arabinose, glucose, rhamnose, mannose and galactose. Acetic acid, formic acid, furfural, HMF and other byproducts are inevitably generated during the acid hydrolysis process. Short reaction time is preferred for the hydrolysis of hot-water wood extracts. Acid hydrolysis presents a perfect opportunity for the removal or separation of aromatic materials from the wood extract/hydrolysate. The hot-water wood extract hydrolysate, after solid-removal, can be purified by Nano-membrane filtration to yield a fermentable sugar stream. Fermentation products such as ethanol can be produced from the sugar stream without a detoxification step.

Properties of Tung oil biodiesel and its blends with 0# diesel.

Tung oil was used to produce biodiesel by transesterification with methanol catalyzed by potassium hydroxide and the influence of the transesterification temperatures on the properties of the Tung oil biodiesel was investigated. FT-IR, UV, and GC-MS results indicated that the triconjugated double bonds of Tung oil were stable during the transesterification procedure between 25 and 60 degrees C. The results of properties showed that Tung oil biodiesel had a low cold filter plugging point (CFPP, -19 degrees C) and a higher kinetic viscosity (KV, 7.070 mm(2)/s). Acid value (AV), KV, and CFPP increased with the increase of storing time. Blending Tung oil biodiesel with 0(#) diesel could improve its stability. B20 or lower blends could still meet the specification of ASTM D7467 after storage for a month. They were more stable than pure Tung oil biodiesel.

Preparation, application, and optimization of Zn/Al complex oxides for biodiesel production under sub-critical conditions.

Biodiesel produced by transesterification is a promising green fuel in the future. A new heterogeneous catalyst, Zn/Al complex oxide, was prepared for biodiesel production. The results showed that the catalyst derived from a hydrotalcite-like precursor with a zinc/aluminum atom ratio of 3.74:1 and calcined at 450 degrees C gave the highest conversion of 84.25%. Analysis of XRD, XPS, FI-IF, TG-DTA, BET and alkalinity tests demonstrated that it is the unique structure of hydrotalcite-like compound precursor that gave the catalyst a high alkalinity greater than 11.1. The optimal reaction condition for Zn/Al complex oxide was under methanol sub-critical condition: 200 degrees C, 2.5MPa, 1.4% (wt) catalyst dosage, and 24:1 methanol to oil ratio. Under these conditions, the conversion reached 84.25% after 90min, which was better than Mg/Al complex oxides. The excellent tolerance to water and free fatty acid was exhibited when the oil feed had fewer than 6% FFA or 10% water content with a conversion greater than 80%.