Biomass-Based Hydrothermal Carbons for the Contaminants Removal of Wastewater: A Mini-Review.

The preparation of adsorbents with eco-friendly and high-efficiency characteristics is an important approach for pollutant removal, and can relieve the pressure of water shortage and environmental pollution. In recent studies, much attention has been paid to the potential of hydrothermal carbonization (HTC) from biomass, such as cellulose, hemicellulose, lignin, and agricultural waste for the preparation of adsorbents. Hereby, this paper summarizes the state of research on carbon adsorbents developed from various sources with HTC. The reaction mechanism of HTC, the different products, the modification of hydrochar to obtain activated carbon, and the treatment of heavy metal pollution and organic dyes from wastewater are reviewed. The maximum adsorption capacity of carbon from different biomass sources was also evaluated.

A cellulose nanofibril-reinforced hydrogel with robust mechanical, self-healing, pH-responsive and antibacterial characteristics for wound dressing applications.

BACKGROUND: Bacterial infection in wounds has become a major threat to human life and health. With the growth use of synthetic antibiotics and the elevated evolution of drug resistant bacteria in human body cells requires the development of novel wound curing strategies. Herein, a novel pH-responsive hydrogel (RPC/PB) was fabricated using poly(vinyl alcohol)-borax (PB) and natural antibiotic resveratrol grafted cellulose nanofibrils (RPC) for bacterial-infected wound management. RESULTS: In this hydrogel matrix, RPC conjugate was interpenetrated in the PB network to form a semi-interpenetrating network that exhibited robust mechanical properties (fracture strength of 149.6 kPa), high self-healing efficiency (> 90%), and excellent adhesion performance (tissue shear stress of 54.2 kPa). Interestingly, the induced RPC/PB hydrogel showed pH-responsive drug release behavior, the cumulative release amount of resveratrol in pH 5.4 was 2.33 times than that of pH 7.4, which was adapted well to the acidic wound microenvironment. Additionally, this RPC/PB hydrogel exhibited excellent biocompatibility and antioxidant effect. Moreover, in vitro and in vivo results revealed that such RPC/PB hydrogel had excellent antibacterial, skin tissue regeneration and wound closure capabilities. CONCLUSION: Therefore, the generated RPC/PB hydrogel could be an excellent wound dressing for bacteria-infected wound healing.

Research Progress on the Preparation and High-Value Utilization of Lignin Nanoparticles.

Lignin nanoparticles, the innovative achievements in the development and utilization of lignin, combine the structural characteristics of nanomaterials and lignin molecules and have a wide range of applications. In this review, we summarize the methods for preparing lignin nanoparticles by solvent exchange method, mechanical method, biological enzymatic method, interface polymerization/crosslinking method, and spray freezing method, and emphatically introduce the application prospects of lignin nanoparticles in ultraviolet protection, antibacterial, nano-filler, drug delivery, and adsorption, aiming to provide a certain reference direction for additional high-value applications of lignin nanoparticles.

Porous Carbon Spheres Derived from Hemicelluloses for Supercapacitor Application.

With the increasing demand for dissolving pulp, large quantities of hemicelluloses were generated and abandoned. These hemicelluloses are very promising biomass resources for preparing carbon spheres. However, the pore structures of the carbon spheres obtained from biomass are usually poor, which extensively limits their utilization. Herein, the carbon microspheres derived from hemicelluloses were prepared using hydrothermal carbonization and further activated with different activators (KOH, K2CO3, Na2CO3, and ZnCl2) to improve their electrochemical performance as supercapacitors. After activation, the specific surface areas of these carbon spheres were improved significantly, which were in the order of ZnCl2 > K2CO3 > KOH > Na2CO3. The carbon spheres with high surface area of 2025 m2/g and remarkable pore volume of 1.07 cm3/g were achieved, as the carbon spheres were activated by ZnCl2. The supercapacitor electrode fabricated from the ZnCl2-activated carbon spheres demonstrated high specific capacitance of 218 F/g at 0.2 A/g in 6 M KOH in a three-electrode system. A symmetric supercapacitor was assembled in 2 M Li2SO4 electrolyte, and the carbon spheres activated by ZnCl2 showed excellent electrochemical performance with high specific capacitance (137 F/g at 0.5 A/g), energy densities (15.4 Wh/kg), and good cyclic stability (95% capacitance retention over 2000 cycles).

Synthesis of Silver Nanoparticles and Detection of Glucose via Chemical Reduction with Nanocellulose as Carrier and Stabilizer.

The application of silver nanoparticles (AgNPs) in antibacterial materials, glucose detection, etc., is of broad interest for researchers around the world. Nanocellulose with many excellent properties can be used as a carrier and stabilizer to assist in the synthesis of AgNPs. In this study, cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs) were used to assist in the synthesis of AgNPs under the reduction of glucose and detection of glucose concentration under different conditions. Transmission electron microscopy (TEM) analysis showed that the AgNPs in the nanocellulose-AgNPs (NC-AgNPs) system were roughly spherical and randomly distributed on the nanocellulose. In the whole reaction system, when the concentration of nanocellulose is 0.11 mg/mL, the concentration of silver ammonia solution is 0.6 mM, and the mixing time is 2.5 h, according to the UV-Vis analysis, the absorbance of CNF-AgNPs at 425 nm exhibited a good linear relationship (R2 = 0.9945) with the glucose concentration range (5-50 µM), while the absorbance of CNC-AgNPs at 420 nm showed a good linear relationship (R2 = 0.9956) with the glucose concentration range (5-35 µM). The synthesis of NC-AgNPs can be further developed into a sensor with higher sensitivity and higher stability for detecting glucose concentration and a material with antibacterial effects.

Preparation and Characterization of Size-Controlled Lignin Nanoparticles with Deep Eutectic Solvents by Nanoprecipitation.

Lignin nanomaterials have wide application prospects in the fields of cosmetics delivery, energy storage, and environmental governance. In this study, we developed a simple and sustainable synthesis approach to produce uniform lignin nanoparticles (LNPs) by dissolving industrial lignin in deep eutectic solvents (DESs) followed by a self-assembling process. LNPs with high yield could be obtained through nanoprecipitation. The LNPs were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). Distinct LNPs could be produced by changing the type of DES, lignin sources, pre-dropping lignin concentration, and the pH of the system. Their diameter is in the range of 20-200 nm and they show excellent dispersibility and superior long-term stability. The method of preparing LNPs from lignin-DES with water as an anti-solvent is simple, rapid, and environmentally friendly. The outcome aids to further the advancement of lignin-based nanotechnology.

Building a Bridge from Papermaking to Solar Fuels.

Black liquor, an industrial waste product of papermaking, is primarily used as a low-grade combustible energy source. Despite its high lignin content, the potential utility of black liquor as a feedstock in products manufacturing, remains to be exploited. Demonstrated here in is the use of black liquor as a primary feed-stock for synthesizing graphene quantum dots that exhibit both up-conversion and photoluminescence when excited using visible/near-infrared radiation, thereby enabling the photosensitization of ultraviolet-absorbing TiO2 nanosheets. In addition, these graphene quantum dots can trap photo-generated electrons to realize the effective separation of electron-hole pairs. Together, these two processes facilitate the solar-powered generation of H2 from H2 O, and CO from H2 O-CO2 , using broadband solar radiation.

Production of Flocculants, Adsorbents, and Dispersants from Lignin.

Currently, lignin is mainly produced in pulping processes, but it is considered as an under-utilized chemical since it is being mainly used as a fuel source. Lignin contains many hydroxyl groups that can participate in chemical reactions to produce value-added products. Flocculants, adsorbents, and dispersants have a wide range of applications in industry, but they are mainly oil-based chemicals and expensive. This paper reviews the pathways to produce water soluble lignin-based flocculants, adsorbents, and dispersants. It provides information on the recent progress in the possible use of these lignin-based flocculants, adsorbents, and dispersants. It also critically discusses the advantages and disadvantages of various approaches to produce such products. The challenges present in the production of lignin-based flocculants, adsorbents, and dispersants and possible scenarios to overcome these challenges for commercial use of these products in industry are discussed.

Ionic Liquid-Mediated Homogeneous Esterification of Cinnamic Anhydride to Xylans.

A new functional biopolymer was synthesized through an ionic liquid-mediated homogeneous grafting of cinnamic anhydride to xylans. The ionic liquid used was 1-allyl-3-methylimidazolium chloride (AMIMCl) ionic liquid. Xylans with degrees of substitution (DS) between 0.11 and 0.57 were accessible in a completely homogeneous system by changing catalysts (NaOH, KOH and LiOH), time, reaction temperature, and cinnamic anhydride/xylan molar ratio. The chemical structure and the thermal stability of the derivatives were characterized by Fourier transform infrared spectroscopy (FT-IR), 13C-NMR spectroscopy, and thermogravimetry. The thermal stability of the derivatives was reduced compared with the original xylan. Possible applications of the cinnamic anhydride-acylated xylan derivatives include wet-end papermaking, organic-inorganic composite films, and hydrogels.

Deep Eutectic Solvents (DESs) for the Isolation of Willow Lignin (Salix matsudana cv. Zhuliu).

Deep eutectic solvents (DESs) are a potentially high-value lignin extraction methodology. DESs prepared from choline chloride (ChCl) and three hydrogen-bond donors (HBD)-lactic acid (Lac), glycerol, and urea-were evaluated for isolation of willow (Salix matsudana cv. Zhuliu) lignin. DESs types, mole ratio of ChCl to HBD, extraction temperature, and time on the fractionated DES-lignin yield demonstrated that the optimal DES-lignin yield (91.8 wt % based on the initial lignin in willow) with high purity of 94.5% can be reached at a ChCl-to-Lac molar ratio of 1:10, extraction temperature of 120 °C, and time of 12 h. Fourier transform infrared spectroscopy (FT-IR) , 13C-NMR, and 31P-NMR showed that willow lignin extracted by ChCl-Lac was mainly composed of syringyl and guaiacyl units. Serendipitously, a majority of the glucan in willow was preserved after ChCl-Lac treatment.

Lignocellulosic biomass pretreatment with a lignin stabilization strategy and valorization toward multipurpose fractionation.

Lignocellulosic biomass has emerged as a promising alternative with sustainable advantages for the production of a wide range of renewable products and value-added chemicals. In this study, a pretreatment strategy that use a fully recyclable acid hydrotrope (p-TsOH aqueous solution) to extract lignin and employ glyoxylic acid (GA) to stabilize lignin was proposed for biomass valorization toward multipurpose fractionation. 83.0 % of lignin was dissolved out by p-TsOH hydrotrope (80 wt%) with GA addition to form GA-stabilized product at 80 o C for 15 min. The stabilized lignin was subsequently used as an additive in the preparation of lignin-based suncream. Notably, the incorporation of 4 wt% lignin nanospheres into an SPF15 sunscreen yielded a measured SPF of 59.94. Furthermore, the depolymerization of uncondensed lignin into aromatic monomers yielded a high lignin-oil yield of 84.2 %. Additionally, direct heating of the pretreatment liquor facilitated the conversion of monosaccharides into furfural, achieving a desired yield of 53.7 % without the addition of any acid catalyst. The pretreatment also enhanced the enzymatic hydrolysis of glucan, resulting in a saccharification yield of 98.4 %. Moreover, short-term ultrasonication of the pretreated substrate yielded pulp suitable for papermaking. Incorporating 15 wt% fibers into the produced paper sheets led to a 5.3 % increase in tear index and a 25.4 % increase in tensile index. This study presents a viable pretreatment strategy for the multipurpose fractionation of lignocellulosic biomass, offering potential avenues for biomass valorization.

Effect of Pulping Waste Liquid on the Physicochemical Properties and the Prediction Model of Wheat Straw Residue Granular Fuels.

Herein, wheat straw residue and pulping waste liquid were collected from pulping mill and mixed to prepare bio-based granular fuels by using compression molding technology, and to explore the comprehensive utilization of the industrial waste of pulping and papermaking. The effects of pulping waste liquid on granular fuel properties were analyzed systemically. Further study of the function of pulping waste liquid, cellulose and hemicellulose was used to replace wheat straw residue and avoid the interference factors. Therefore, the prediction models of granular fuels were established with influencing factors that included cellulose, hemicellulose and pulping waste liquid. The granular fuels had the best performance with 18.30% solid content of pulping waste liquid. The highest transverse compressive strength of granular fuel was 102.61 MPa, and the activation energy was 81.71 KJ·mol-1. A series of curve fitting prediction models were established to clarify the forming process of granular fuel, and it turned out that the pulping waste liquid could improve the adhesion between solid particles and increase their compression resistance.

Facile sulfation of cellulose via recyclable ternary deep eutectic solvents for low-cost cellulose nanofibril preparation.

Here we present a new method to treat cellulose with a sulfamic acid-urea-choline chloride (ternary deep eutectic solvent) system, which can realize both swelling and sulfation of cellulose. This can greatly reduce the energy consumption in the process of cellulose nanoization, and use it to successfully prepare food packaging films for eliminating odors. We hope that due its simplicity and resource-efficiency, this method will have a widespread influence on currently used (nano) cellulose modification protocols.

Preparation of Dissolving Pulp by Combined Mechanical and Deep Eutectic Solvent Treatment.

Grasses are potential candidate to replace wood as a raw material for pulping and paper making, and several processes have been developed to produce grass pulp. In this study, wheat straw was used as raw material, and the possibility of sequential treatment with a mechanical method and deep eutectic solvent (DES) to prepare high-quality dissolving pulp was explored. Firstly, the wheat straw was mechanically treated, and then the wheat straw was delignified using a choline chloride-lactic acid deep eutectic solvent. The results showed that the optimal treatment conditions of deep eutectic solvent were 110 °C, 6 h, and a solid-liquid ratio (ratio of pulp to DES) of 1:40. The removal rate of lignin was 82.92%, the glucose content of pulp was increased by 11.42%. The DES recovery rate was further calculated, and the results showed that the DES recovery rate was more than 50% with rotary evaporation. The pulp viscosity after bleaching was 472 mL/g, and the α-cellulose accounted for 81.79%. This treatment has advantages in biomass refining, and the total utilization rate of wheat straw reaches 72%. This study confirmed that combined mechanical and deep eutectic solvent treatment can effectively remove lignin from wheat straw to produce high-quality wheat straw dissolving pulp.

Structural regulatory mechanism of phosphotungstate acid decorated graphene oxide quantum dots-chitosan aerogel and its application in ciprofloxacin degradation.

Chitosan modified AGQD (amine modified graphene oxide quantum dots) and then combined with H3PW12O40 to obtain CSx@AGQD-HPW12 via facile process and applied for CIP removal through pre-adsorption and photocatalytic processes. The application of chitosan could regulate the morphology and photoelectric properties effectively. CS0.5@AGQD-HPW12 was found to have the optimal CIP removal performance among all the products, the corresponding adsorption removal efficiency and pre-adsorption photocatalysis process were 72.1 % and 98.8 %, respectively. Results of toxicity assessment confirmed photocatalytic degradation process could mitigate the ecotoxicity of CIP effectively. The optimal TOC (total organic carbon) removal efficiency was about 52.1 %. Possible pathways for CIP degradation and reaction mechanism were proposed based on the results of intermediates analysis and trapping experiments. This demonstrated a novel approach to chitosan application and an eco-friendly way to remove CIP by adsorption-photocatalysis process.

Switchable Deep Eutectic Solvents for Lignin Dissolution and Regeneration.

Deep eutectic solvents (DESs) are promising for lignin dissolution and extraction. However, they usually possess high polarity and are difficult to recycle. To overcome this drawback, a variety of switchable ionic liquids (SILs) composed of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and alcohols was synthesized and screened. According to the thermodynamic modeling suggestions, the selected DBU-HexOH SIL was coupled with hydrogen-bond donors to form switchable-DES (SDES) systems with moderated viscosity, conductivity, and pH while maintaining switchability. The SDESs produced a well-improved lignin and lignin model compound solubility compared with those of SILs; charging CO2 into SDES (SDESCO2) caused a further increase in solubility. The solubility (25 °C) of syringic acid, ferulic acid, and milled wood lignin in SDESCO2 reached 230.57, 452.17, and 279.12 mg/g, respectively. Such SDES-dissolved lignin can be regenerated using acetone as an anti-solvent. The SDES-regenerated lignin exhibited a well-preserved structure with no noticeable chemical modifications. Furthermore, the SDESCO2 lignin possessed a higher molecular weight (Mw = 10,340 g/mol; Mn = 7672 g/mol), improved uniformity (polydispersity index = 1.35), and a higher guaiacyl lignin unit content compared with the original milled wood lignin. The SDES system proposed in the present work could benefit the fractionation of lignin compounds and facilitate downstream industrial processes.

Strength Enhancement of Regenerated Cellulose Fibers by Adjustment of Hydrogen Bond Distribution in Ionic Liquid.

To improve the physical strength of regenerated cellulose fibers, cellulose dissolution was analyzed with a conductor-like screening model for real solvents in which 1-allyl-3-methylimidazolium chloride (AMIMCl) worked only as a hydrogen bond acceptor while dissolving the cellulose. This process could be promoted by the addition of urea, glycerol, and choline chloride. The dissolution and regeneration of cellulose was achieved through dry-jet and wet-spinning. The results demonstrated that the addition of hydrogen bond donors and acceptors either on their own or in combination can enhance the tensile strength, but their effects on the crystallinity of the regenerated fibers were quite limited. Compared with the regenerated fibers without any additives, the tensile strength was improved from 54.43 MPa to 139.62 MPa after introducing the choline chloride and glycerol, while related the crystallinity was only changed from 60.06% to 62.97%. By contrast, a more compact structure and fewer pores on the fiber surface were identified in samples with additives along with well-preserved cellulose frameworks. Besides, it should be noted that an optimization in the overall thermal stability was obtained in samples with additives. The significant effect of regenerated cellulose with the addition of glycerol was attributed to the reduction of cellulose damage by slowing down the dissolution and cross-linking in the cellulose viscose. The enhancement of the physical strength of regenerated cellulose fiber can be realized by the appropriate adjustment of the hydrogen bond distribution in the ionic liquid system with additives.

Lipase induced highly hydrophobic nanofibrillated cellulose film for strain sensor application.

An environmental-friendly lipase induced highly hydrophobic NFC film was fabricated through lipase induced dimethyl adipate (DA) esterification followed by silver nanowires (AgNWs) coating for strain sensor application. Due to the lipase activation, the substitution degree (DSNMR) of 0.18 was achieved, which was three times higher than that of the control sample (without lipase treatment of NFC-DA). As a result, the water contact angle (WCA) of lipase induced adipated-NFC film was reached to 105 ± 3° from 50 ± 2.3° of NFC-DA. In addition, the cellulose structure and performance were well maintained after lipase induced esterification, confirmed by AFM, SEM, TG/DTG, and XRD analysis. After AgNWs coating and annealing, the hydrophobic NFC film-based strain sensor exhibited excellent sensitivity towards human motion, such as finger/wrist movement in real-time, even under wet conditions. Overall, a highly hydrophobic NFC film-based strain sensor was fabricated, which has promising application in wearable devices for human motion monitoring.

Rapid and efficient microwave-assisted guanidine hydrochloride deep eutectic solvent pretreatment for biological conversion of castor stalk.

Microwave-assisted guanidine hydrochloride deep eutectic solvents (DESs) was developed for rapid and efficient pretreatment of castor stalk. The DES synthesized with guanidine hydrochloride and lactic acid showed a better delignification (92.02%) and enzymatic saccharification yield (96.3%) than choline chloride and lactic acid DES resulted. In addition, high-purity (up to 98%) lignin was recovered from the pretreatment liquor. The good recyclability of the guanidine hydrochloride-based DES was also proven with up to 90% cellulose hydrolysis with third-time recycled DES without post purification. The proposed microwave-assisted guanidine hydrochloride/lactic acid DES showed its great potentials as a highly effective and recyclable pretreatment solvent for future biorefinery strategies.

Effects of Lipase and Xylanase Pretreatment on the Structure and Pulping Properties of Wheat Straw.

Based on the reduction of environmental pollution, a biological enzyme assisted alkali-oxygen pulping method was explored to improve the delignification efficiency and fiber accessibility of wheat straw and improve the properties of wheat straw pulp. In this paper, lipase and xylanase were used to pretreat wheat straw and the effects of different enzyme types and enzyme dosage on the microstructure and pulp properties of wheat straw were investigated and experimented. The results showed that the lipase can remove fat and wax on the surface of wheat straw, while xylanase degraded the hemicellulose components, such as xylan, of wheat straw fiber, destroyed the structure of the lignin-carbohydrate complex, increasing lignin removal as a result and enhancing the impregnating, diffusion and penetration of alkali. Compared with wheat straw without enzyme pretreatment, the skeleton of wheat straw pretreated by enzyme became looser, the internal cavity appeared and the wall cavity became thin and transparent. The fines decreased obviously and the length of fibers increased. After combined pretreatment with lipase (15 U·g-1) and xylanase (15 U·g-1), the pulping performance of wheat straw was improved and the tensile index (97.37 N·m·g-1), brightness (40.9% ISO) and yield (58.10%) of the pulp increased by 12.9%, 19.9% and 9.9%, respectively. It can be seen that enzyme pretreatment is a green and effective approach to improving the alkali-oxygen pulping performance of wheat straw.