Microwave-assisted DES fabrication of lignin-containing cellulose nanofibrils and its derived composite conductive hydrogel.

Deep eutectic solvents (DES) have been regarded as green solvents in the biorefinery of lignocellulosic biomass, but long duration time has severely limited efficiency. The microwave-assisted DES pretreatment along with enzymatic hydrolysis and high-pressure homogenization process was proposed to produce lignin-containing cellulose nanofibrils (LCNF) from corncob. Benefiting from microwave-assisted DES pretreatment, the duration time was greatly shortened; meanwhile the effects of different kinds of DES on the resultant LCNF were investigated. The results showed that, the microwave-assisted DES fabricated LCNF (M-LCNF) was successfully obtained, exhibiting good nano size, thermal stability, colloidal stability, and fluorescence. M-LCNF was further introduced into phytic acid (PA) enhanced poly(acrylamide-co-acrylic acid) (P(AM-co-AA)) network and constructed composite conductive hydrogels (PLP). The obtained hydrogels exhibited good mechanical strength, UV blocking ability, fluorescence, and conductivity. A simple battery assembled with the resultant PLP as electrolyte had an out voltage of 2.41 V. The composite conductive hydrogel showed good sensing performance towards different stimuli (e.g., stretching and compression) and human motions in real time. It is expected that this research would provide an alternative way for green fabrication of LCNF and potential application of LCNF in flexible sensors.

Enhancing photocatalytic destruction of lignin via cellulose derived carbon quantum dots/g-C3N4 heterojunctions.

Lignocellulosic biomass exhibits a promising potential for production of carbon materials. Nitrogen and phosphorus co-doped carbon quantum dots (N,P-CQDs) were fabricated via (NH4)2HPO4 assisted hydrothermal treatment of cellulose pulp fibers. The as-prepared N,P-CQDs were characterized by HRTEM, FTIR, fluorescence and UV-vis, and then incorporated into g-C3N4 (CN) through sonication and liquid deposition, forming N,P-CQDs/sonication treated g-C3N4 (C-SCN) composites, which were then explored as photocatalysts. The photocatalytic ability of C-SCN towards model lignin was further analyzed. The results showed that, the fluorescence intensity and photoluminescence performance of N,P-CQDs were much higher than that of CQDs; the heterojunction was successfully constructed between the composites of N,P-CQDs and SCN; the incorporation of N,P-CQDs enhanced the visible light absorption, but reduced the band gap of the composite heterojunction; the resultant photocatalysts exhibited a good photocatalytic ability of model lignin via catalyze the fracture of ß-O-4' ether bond and CC bond, i.e., the photocatalytic degradation ratio reached up to 95.5 %; and the photocatalytic reaction generated some valuable organics such as phenyl formate, benzaldehyde, and benzoic acid. This study would promote the high value-added utilization of lignocellulosic resources especially in the transformation of lignin, conforming the concept of sustainable development.

Upgrading lignin macromolecular by green and recyclable ternary deep eutectic solvents.

Lignin is the most abundant natural aromatic macromolecule in the nature, but its high value-added utilization has been seriously hindered by the highly random and branched structures and the high difficulty in separation and purification. A microwave-assisted ternary deep eutectic solvent (DES) composed by formic acid, lactic acid and choline chloride was developed for lignin pretreatment. The effects of three types of DES on main characteristics of lignin were investigated, and the corresponding dissolution mechanism was proposed. The results showed that, the microwave-assisted ternary DES pretreatment showed an obvious improvement on main characteristics of regenerated lignin, e.g., a higher purity, lower molecular weight with reduced dispersity, improved thermal stability, higher phenolic hydroxyl content, and increased antioxidative activity in comparison with control. It is expected that the lignin macromolecular can be facile regulated and upgraded by the proposed ternary DES.

Enhancing sludge methanogenesis with changed micro-environment of anaerobic microorganisms by Fenton iron mud.

Conductive materials have been demonstrated to enhance sludge methanogenesis, but few researches have concentrated on the interaction among conductive materials, microorganisms and their immediate living environment. In this study, Fenton iron mud with a high abundance of Fe(III) was recycled and applied in anaerobic reactors to promote anaerobic digestion (AD) process. The results show that the primary content of extracellular polymeric substances (EPS) such as polysaccharides and proteins increased significantly, possibly promoting microbial aggregation. Furthermore, with the increment of redox mediators including humic substances in EPS and Fe(III) introduced by Fenton iron mud, the direct interspecies electron transfer (DIET) between methanogens and interacting bacteria could be accelerated, which enhanced the rate of methanogenesis in anaerobic digestion (35.21 ± 4.53% increase compared to the control). The further analysis of the anaerobic microbial community confirmed the fact that Fenton iron mud enriched functional microorganisms, such as the abundance of CO2-reducing (e.g. Chloroflexi) and Fe(III)-reducing bacteria (e.g., Tepidimicrobium), thereby expediting the electron transfer reaction in the AD process via microbial DIET and dissimilatory iron reduction (DIR). This work will make it possible for using the recycled hazardous material - Fenton iron mud to improve the performance of anaerobic granular sludge during methanogenesis.

Structure regulated 3D flower-like lignin-based anode material for lithium-ion batteries and its storage kinetics.

As a green sustainable material, lignin-derived porous carbon (LPC) exhibits great application potential when used as the anode material in lithium-ion batteries (LIBs), but the applications are limited by the heterogeneity of the lignin precursor. Therefore, it is crucial to reveal the relationship among lignin properties, porous carbon structure and the kinetics of lithium-ion storage. Herein, LPCs from fractionated lignin have been prepared by an eco-friendly and recyclable activator. The structure of the LPCs was regulated by adjusting the molecular weight, linkage abundance and glass transition temperature (Tg) of lignin macromolecules. As the anode material of LIBs, the prepared 3D flower-like LPCE70 could achieve a reversible capacity of 528 mAh g-1 at a current density of 0.2 A g-1 after 200 cycles, 63 % higher than that of commercial graphite. Furthermore, kinetic calculations of lithium-ion storage behavior of LPCs were firstly used to confirm the contribution ratio of diffusion-controlled behavior and capacitive effect. Lignin with a high linkage abundance could yield LPCE70 with the largest interlayer spacing and specific surface area to maximize lithium-ion storage from both diffusion-controlled and capacitive contributions of specific capacities. This work provides a green, facile and effective pathway for value-added utilization of lignin in LIBs.

Fabrication of a Carbonized Cellulose Nanofibrils/Ti3C2Tx MXene/g-C3N4 Heterojunction for Visible-Light-Driven Photocatalysis.

Photocatalytic degrading pollutants driven by visible-light irradiation has attracted tremendous attention. One strategy of preparing carbonized cellulose nanofibrils/Ti3C2Tx MXene/g-C3N4 (CMCN) as a photocatalyst was developed. The as-prepared CMCN was comprehensively characterized in terms of the chemical composition, chemical and crystal structure, morphology, and photoelectrochemical properties. The CMCN was explored as a photocatalyst and exhibited good photocatalytic performance in degrading MB (96.5%), RhB (95.4%), and TC (86.5%) under visible-light conditions. In addition, the CMCN as a photocatalyst exhibited good reusability and stability. It is found that the incorporation of cellulose nanofibrils provided a high carbon content, a high porosity, and a large specific surface area, enhanced the electron transfer, improved the photocatalytic performance, and ensured a semiconductor with a high stability. It is believed that this study would provide an effective approach to preparing a photocatalyst and broaden the potential application of cellulose nanofibrils in photocatalysis.

Spider-web-inspired cellulose nanofibrils networking polyaniline-encapsulated silica nanoparticles as anode material of lithium-ion batteries.

As the promising anode material of lithium-ion batteries (LIBs), SiO2 has high theoretical capacity, but the volume expansion severely hinders its application. To address the challenge, inspired by the highly flexible spider-web architecture, the SiO2@carbonized polyaniline/carbonized 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (SiO2@cPANI/cTOCNFs) composite was designed, and fabricated via carbonizing the freeze-dried SiO2@PANI/TOCNFs. The resultant SiO2@cPANI/cTOCNFs composite exhibited unique spider-web-like nanostructures, providing a double-layer carbon network to protect SiO2 anode material. The results showed that, the SiO2@cPANI/cTOCNFs composite as anode material of LIBs offered a reversible capacity of 1103 mAh g-1 at a current density of 0.1 A g-1 after 200 cycles, and gave a capacity of 302 mAh g-1 after 1000 cycles at a current density of 1 A g-1, exhibiting excellent cycling stability. This study provides a strategy of spider-web-inspired cellulose nanofibrils networking polyaniline-encapsulated silica nanoparticles as anode material of LIBs.

Combination of hydrothermal and chemi-mechanical pretreatments to enhance enzymatic hydrolysis of poplar branches and insights on cellulase adsorption.

An integration of different pretreatments is important to overcome recalcitrance and realize efficient bioconversion of lignocellulosic biomass. This study aims at the effects of combination of hydrothermal pretreatment and different chemi-mechanical pretreatments on enzymatic hydrolysis, and understanding the enzymes adsorption mechanism. The combination of hydrothermal and chemi-mechanical pretreatments effectively improved the enzymatic hydrolysis of poplar substrates, in which the enzymatic hydrolysis of substrates pretreated by hydrothermal pretreatment + Fenton pretreatment + mechanical refining (HFM) was the highest (92.39% of glucose conversion yield, and 20.88 g/L of glucose concentration). The substrates' main characteristics were obviously changed after combined pretreatments, such as swelling ability and specific surface area of substrates were increased. The Langmuir adsorption model (R2 > 0.98) and pseudo second-order adsorption kinetic model (R2≈1) were well suitable to describe the adsorption of enzymes on substrates, meanwhile the adsorption mechanism was summarized.

Fabricating lignin-containing cellulose nanofibrils with unique properties from agricultural residues with assistance of deep eutectic solvents.

Lignocellulosic biomass-derived nanocellulose has been attracting more and more attentions due to its distinguished advantages and various applications, but its development has been restricted by the preparation especially with environmental friendly approach. Herein, lignin-containing cellulose nanofibrils (LCNF) was prepared from corncob via the combined pretreatment of choline chloride-based DES (ChCl-DES) and enzymatic hydrolysis followed by high-pressure homogenization. The effects of different types of ChCl-DES on the properties of LCNF were investigated and compared. The results showed that LCNF can be successfully fabricated through the combined pretreatments; the LCNF had an average diameter of 60-90 nm, exhibited good fluorescence, high thermal stability (up to 353 °C of Tmax), hydrophobicity, stability, and redispersibility in organic solvent; AC-LCNF showed well oriented arrangement, the highest hydrophobicity and fluorescence, and distinguished redispersibility especially in DMSO. ChCl-DES as one green and sustainable approach would realize efficient separation and high value-added utilization of agricultural residues.

Facile preparation of cellulose nanofibrils (CNFs) with a high yield and excellent dispersibility via succinic acid hydrolysis and NaClO2 oxidation.

An efficient and low-cost approach to preparing CNFs with succinic acid hydrolysis and NaClO2 oxidation is explored. High-temperature-short-time hydrolysis can depolymerize the cellulose, whereas the dispersibility of the CNFs is hugely enhanced by NaClO2 oxidation under alkaline condition. The degradation of cellulose in succinic acid hydrolysis follows first-order reaction kinetics and is severely influenced by the hydrolysis temperature, moreover, the molecular chains of the cellulose are seriously cracked under the optimized condition. The NaClO2 oxidation greatly improves the zeta potential (-36.2 mV) and the dispersibility of the CNFs. The obtained CNFs have an ultimate yield of 94.6%, and the diameter distribution is mainly within 20-40 nm. In addition, some amount of carboxyl groups in the cellulose will be instead of the hydroxyl groups, and the crystallinity of the CNFs is significantly increased.

A complex of oxidised chitosan and silver ions grafted to cotton fibres with bacteriostatic properties.

The laccase/TEMPO system was employed to oxidise the C6 primary hydroxyl group on the chitosan (CS) to form a carboxyl group to obtain oxidised chitosan (C-COS). The silver-oxidised chitosan complex(C-COS-Ag) was prepared by reacting C-COS with silver nitrate, then C-COS-Ag and cotton fibres were subjected to a reaction to prepare bacteriostatic fibres. FT-IR and XPS analysis showed that: Ag+ and C-COS were combined in these forms: Ag, [Ag(NH3)2] OH, -COOAg, and Ag2O. C-COS-Ag was combined with cotton fibres by way of ester bonds. The inhibition zone of bacteriostatic fibres was all greater than 11 mm. After 50 washing tests, the bacteriostatic effect of bacteriostatic fibres remained at above 99 %. The amount of silver ions that had migrated from the bacteriostatic fibre was 3.336 mg/kg.

Nanocomposites derived from licorice residues cellulose nanofibril and chitosan nanofibril: Effects of chitosan nanofibril dosage on resultant properties.

Research on nanocomposite film from natural polymers such as cellulose and chitosan is of great importance to promote the development and highly efficient utilization of green and renewable bioresources. In this study, enzymatic pretreatment cellulose nanofibril (ETCNF) derived from licorice residues was prepared, and further processed into nanocomposite film with addition of chitosan nanofibril (CHN). This study focused on the effects of CHN dosage on the main properties of resultant nanocomposite film in terms of crystallinity, thermal stability, light transmittance, hydrophobicity, mechanical properties, and antibacterial activity. The results showed that ETCNF/CHN nanocomposite film exhibited good hydrophobicity especially at higher dosage of CHN, good light transmittance and mechanical properties (tensile strain can reach 39.6 MPa for ETCNF/CHN-10.0%). The as-prepared ETCNF/CHN nanocomposite film also showed good antibacterial activity against Escherichia coli. It was expected that the ETCNF/CHN nanocomposite film would help to realize transformation and high value-added utilization of these biomass residues.

Insight on adsorption of cellulase on wet ground corncob residues and its evaluation by multivariate linear analysis.

Understanding the adsorption behavior and the interaction between substrates and enzymes are critical to improving enzymatic hydrolysis efficiency and reducing bioconversion cost. Herein, the adsorption of cellulase on wet ground corncob residues was studied, and the effects of main characteristics of wet ground corncob residues on adsorption capacity were quantitatively analyzed with the combination of principal component analysis and multiple linear regression models. The results showed that the adsorption of cellulase on wet ground corncob residues was fitted well with Langmuir isotherm adsorption and pseudo second-order kinetics model, the adsorption rate and adsorption capacity were greatly enhanced with increasing grinding time; the multiple linear regression models describing the relationship between main characteristics of corncob residues and adsorption capacity to cellulase were established; the significance of these characteristics were in the following order: average particle size, crystallinity index, specific surface area, surface lignin concentration, water retention value, and surface charge density.

Improving enzymatic hydrolysis of mechanically refined poplar branches with assistance of hydrothermal and Fenton pretreatment.

The combination of different pretreatment methods can effectively overcome recalcitrance of lignocellulosic biomass to ensure its highly efficient conversion into bio-based products. In this study, the combined pretreatments of chemical methods (hydrothermal treatment and Fenton treatment) with mechanical refining were used to improve the enzymatic hydrolysis efficiency of poplar branches. The results indicated that hydrothermal pretreatment and Fenton pretreatment can effectively improve the enzymatic hydrolysis of poplar substrates, e.g., the maximum glucose conversion yield and glucose concentration reached 92.4% and 20.8 g/L, respectively. The pre-hydrolysates contained some valuable components such as monosaccharides, oligosaccharides, acetic acid, furfural, and hydroxymethylfurfural. The main characteristics (specific surface area, water retention value, fines content, and surface lignin concentration) of poplar substrates were obviously changed by the combined pretreatment, which benefit the enzymatic hydrolysis.

Color evolution of poplar wood chips and its response to lignin and extractives changes in autohydrolysis pretreatment.

Combining chemi-mechanical pulping with autohydrolysis pretreatment is an efficient and value-added utilization approach for lignocellulosic biomass in paper industry. To further promote the utilization of autohydrolyzed biomass in chemi-mechanical pulping, the color evolution of poplar wood chips in autohydrolysis pretreatment and its chromogenic mechanism were investigated by using CIELab color system, FT-IR, NMR and GPC. The results showed that the total color difference ΔE* increased obviously, which were remarkable as the combined hydrolysis factor (CHF) increased. The lignin content led to a more significant influence on the color of poplar wood chips than the extractives. The autohydrolysis pretreatment with a higher CHF accelerated the degradation and subsequent condensation of lignin, resulting in the formation of chromophoric groups, such as Hibbert ketone, quinones and quinone methides. It is of great significance for biomass refinery and paper industry to reveal the color evolution of poplar wood chips caused by autohydrolysis pretreatment from the point of view of chemical components' structure.

Fabricating cellulose nanofibril from licorice residues and its cellulose composite incorporated with natural nanoparticles.

It is important to make full utilization of industrial biomass residues. Pulp was prepared from licorice residues by soda-anthraquinone pulping followed by peroxyacetic acid bleaching. Cellulose nanofibril was obtained by enzymatic pretreatment followed by homogenization of the pulp (ETCNF). The effects of enzymatic pretreatment on ETCNF were investigated. Chitosan nanofibril (CHN) and lignin nanoparticles (LNPs) were prepared and used for ETCNF composites, respectively. The results showed that ETCNF exhibited clear nanofibrillar structure and a highly relative colloidal stability, and a much higher crystallinity index and thermal stability compared to TEMPO-medicated oxidized one; the cellulose composite films incorporated with CHN or LNPs exhibited good thermal stability and hydrophobicity. Compared with ETCNF film, ETCNF@LNPs-5.0% film showed higher UV-blocking ability and thermal stability, but reduced light transmittance, while ETCNF@CHN-5.0% film showed improved mechanical properties and similar light transmittance. This study would expend licorice residues as potential materials for CNF and its applications.

Comparative study on different pretreatment on enzymatic hydrolysis of corncob residues.

Under the situation of increasingly severe challenge of energy consumption, it is of great importance to make full use of bioresources such as forestry and agricultural residues. Herein, the corncob residues generated after processing corncob were enzymatically hydrolyzed to yield fermentable sugars. To overcome the recalcitrance of corncob residues, three kinds of pretreatment methods, i.e., sulfonation, PFI refining, and wet grinding, were applied; their effects on enzymatic hydrolysis and main characteristics of corncob residues substrate were investigated. The results showed that the enzymatic digestibility of the substrate was greatly enhanced by employing each method. The wet grinding exhibited obvious advantages, e.g., the conversion yield of cellulose to glucose and glucose concentration reached 96.7% and 32.2 g/L after 59 h of enzymatic hydrolysis, respectively. The improvement in enzymatic hydrolysis was mainly attributed to the altered characteristics of the substrate such as swelling ability, specific surface area, and particle size and distribution.

Facile fabrication of cellulose composite films with excellent UV resistance and antibacterial activity.

Research on biodegradable cellulose composite film with unique properties is of significance to alleviate current dependency on petroleum-based polymers, and to promote highly efficient utilization of lignocellulosic biomass. Lignin nanoparticles (LNPs) have been considered as a promising material for high value-added products. In this study, LNPs were prepared from corncob lignin via anti-solvent precipitation method, and then characterized by FTIR, TGA, AFM, and NMR. The CNF@CLNPs composite film was fabricated by blending CLNPs with CNF. The results showed that the CLNPs had an average diameter of about 118 nm, meanwhile the main structures and properties of corncob lignin were maintained. The CNF@CLNPs composite film exhibited a high ultraviolet resistance, and a good antibacterial activity against both Escherichia coli and Staphylococcus aureus. It is expected that the CNF@CLNPs composite film would have potential applications in outdoor materials and food packaging.

Characterization and comparison of lignin derived from corncob residues to better understand its potential applications.

Lignocellulosic biomass is regarded as an ideal renewable resource for replacing traditional fossil fuels. Corncob residues (CRs) generated after hemicelluloses pre-extraction of corncobs were potential feedstocks to produce lignin-based products. Three lignin fractions, i.e., dioxane lignin (DL), milled-wood lignin (MWL), and enzymatic mild acidolysis lignin (EMAL), were isolated from CRs and characterized by HPLC, GPC, FT-IR, NMR, and TGA to reveal characteristics of CRs lignin to better understand its potential applications. The results showed that the yield of DL, MWL and EMAL were 12.8%, 14.7% and 15.6%, respectively. The molecular weight of DL, MWL and EMAL were 2001, 5391, and 2629 g/mol, respectively. The EMAL and MWL had similar structural features including guaiacyl and syringyl units, ß-O-4' aryl ether, p-coumaric acids, ferulates, and phenylcoumarans, while the structure of DL was relatively simple. It is expected that this work will provide some useful information for the utilization of CRs in view of biorefinery.

Fabrication of optically transparent and strong nanopaper from cellulose nanofibril based on corncob residues.

In this study, a strong and optically transparent nanopaper was fabricated from cellulose nanofibril (CNF) of corncob residues, an abundant byproduct from the processing of corncobs. Two processes were applied to successfully generate CNF from corncob residues. The resultant CNF mainly consists of fibers with diameter (height) of about 1.0 - 5.0 nm on average. The results showed that the as-prepared cellulose nanopaper (CNP) exhibited good strength, optical and thermal properties, with the tensile strength and tensile fracture strain of CNP being 65.3 MPa and 2.3%, respectively; the optical transmittance was close to 90% in the visible range; the highest degradation peak temperature was about 290 °C; the water contact angle at 30 s was 68.2°; A-CNP showed much higher optical properties and hydrophobicity, similar thermal ability, but slightly lower strength properties, compared with B-CNP. It can be seen that corncob residues are suitable choice of raw material for cellulose nanopaper, and is expected to find similar applications in flexible electronics and energy products as those of other raw materials used for this purpose.