Production of vanillin via oxidation depolymerization of lignin over Fe- and Mn-modified TS-1 zeolites.

Converting lignin into specific aromatic chemicals for utilization through depolymerization of lignin is an effective way to achieve high-value applications. There are many depolymerization methods that can do this, but there are problems such as harsh reaction conditions, low depolymerization efficiency and uncontrollable target products that need to be solved. This study reports a novel system for the oxidative depolymerization of alkali lignin using Fe- and Mn- modified TS-1 as a catalyst to assist in the highly selective production of vanillin. We also proposed a possible reaction pathway for the oxidative depolymerization of alkali lignin to produce vanillin catalyzed by Fe-Mn/TS-1 catalyst. The catalytic effects of TS-1, Fe/TS-1, and Fe-Mn/TS-1 catalysts on the oxidative depolymerization of lignin to produce phenolic monomers and vanillin were investigated. The results show that the modified catalysts can effectively improve the efficiency of linkage bond breaking in lignin, especially the ß-O-4 bond, in which the inter-band transitions of Fe and Mn play an important role. The synergistic effect of the bimetallic-loaded catalyst (Fe-Mn/TS-1) could catalyze the oxidative depolymerization of lignin more efficiently than the monometallic-loaded catalyst (Fe/TS-1). This lignin oxidative depolymerization system produced 40.59 wt% bio-oil including 12.24 wt% phenolic monomers and 16.17 wt% re-lignin after the addition of Fe-Mn/TS-1 catalyst, owning the highest phenolic monomer yield. Surprisingly, this lignin oxidative depolymerization system exhibited high yield for vanillin (8.36 wt%) production. These results demonstrated that the Fe-Mn/TS-1 catalytic system has potential to produce vanillin from lignin under mild conditions.

Effect of Lignin Structure Characteristics on the Performance of Lignin Based Phenol Formaldehyde Adhesives.

As the second most abundant biopolymer, lignin remains underutilized in various industrial applications. Various forms of lignin generated from different methods affect its physical and chemical properties to a certain extent. To promote the broader commercial utilization of currently available industrial lignins, lignin sulfonate (SL), kraft lignin (KL), and organosolv lignin (OL) are utilized to partially replace phenol in the synthesis of phenol formaldehyde (PF) adhesives. The impact of lignin production process on the effectiveness of lignin-based phenolic (LPF) adhesives is examined based on the structural analysis of the selected industrial lignin. The results show that OL has more phenolic hydroxyl groups, lower molecular weight, and greater number of reactive sites than the other two types of lignins. The maximum replacement rate of phenol by OL reaches 70% w/w, resulting in organosolv lignin phenolic (OLPF) adhesives with a viscosity of 960 mPa·s, a minimal free formaldehyde content of 0.157%, and a shear strength of 1.84 MPa. It exhibits better performance compared with the other two types of lignin-based adhesives and meets the requirements of national standards.

Preparation of Lignin-Based Nanoparticles with Excellent Acidic Tolerance as Stabilizer for Pickering Emulsion.

In this work, novel lignin-based nanoparticles (LßNPs) with high acidic tolerance were successfully prepared via electrostatic interaction between ß-alanine and lignin nanoparticles. The effects of the mass ratio of lignin nanoparticles to ß-alanine and pH value on the morphology and particle sizes of LßNPs were investigated with the aim of obtaining the ideal nanoparticles. The optimized LßNPs were spherical in shape with an average particle size of 41.1 ± 14.5 nm and exhibited outstanding structure stability under high acidic conditions (pH < 4). Subsequently, Pickering emulsions stabilized by LßNPs were prepared using olive oil as the oil phase. Additionally, the effects of pH value, droplet size, morphology, and storage stability on Pickering emulsions were also analyzed. The emulsions displayed excellent stability, and were stable against strongly acidic conditions (pH < 4) after 30 days of storage. The study presented a promising approach to preparing lignin-based nanoparticles with high acidic tolerance (an ideal type of stabilizer to prepare emulsions), and exhibited extremely high potential application values in the fields of drug delivery, food additives, and oily wastewater treatment.

Antimicrobial Peptide-Inspired Design of Amino-Modified Lignin with Improved Antimicrobial Activities.

A major challenge to make use of lignin as an antimicrobial material is the weak antimicrobial activity of industrial lignin. Inspired by the antimicrobial mechanism of actions of antimicrobial peptides, alkyldiamines were employed as lysine mimics for lignin modifications. Accordingly, aminoalkyl-modified lignins with different degrees of substitution of amino groups and different hydrophobicity were synthesized. The chemical structure, properties, and antimicrobial activities of the as-prepared aminoalkyl lignins were thoroughly characterized with state-of-the-art technologies. The results indicated that aminobutyl lignin showed enhanced antimicrobial activity against S. aureus and E. coli and performed even better than copper ions. The antimicrobial mechanism of action of the as-prepared aminobutyl lignin was similar to that of polylysine, which damaged the cell membrane, leading to the leakage of intracellular molecules and death of the cell. This study provides a feasible approach to afford modified lignin with enhanced antimicrobial performance, which would facilitate the high-value valorization of lignin as biological materials.

Recent advances in lignin-based 3D printing materials: A mini-review.

With the growing global population and rapid economic development, the demand for energy and raw materials is increasing, and the supply of fossil resources as the main source of energy and raw materials has reached a critical juncture. However, our overexploitation and overconsumption of fossil resources have led to serious problems, including environmental pollution, climate change, and ecosystem destruction. In the face of these challenges, we must recognize the negative impacts of the shortage of fossil resources and actively seek sustainable alternative sources of energy and resources to protect our environment and sustainable development in the future. Three-dimensional (3D) printing, an additive manufacturing technology, has been used in many fields to manufacture complex and high-precision products. While traditional manufacturing processes typically produce large amounts of waste and emissions that are harmful to the environment, 3D printing is much more energy efficient compared to traditional manufacturing methods, which helps to lower energy costs and reduce reliance on non-renewable energy sources. The development of low-carbon and environmentally friendly 3D printing materials can help to reduce carbon emissions and environmental pollution and realize the goal of sustainable development. Lignin, as the second largest renewable green biomass resource after cellulose, has great potential for manufacturing low-carbon and environmentally friendly 3D printing materials. This review presents some recent studies on the applications of lignin and its derivatives in photo-curing 3D printing, including the preparation and performance of lignin-based photosensitive prepolymers, lignin-based reactive diluents, lignin-based photo-initiators, and lignin-based additive. This review also provides recent studies on the preparation and performance of lignin-based thermoplastic polymer for Fused Deposition Modeling (FDM) 3D printing. Finally, the future challenges and industrialization prospects of lignin-based 3D printing materials are discussed.

Two-Pronged Approach: Synergistic Tuning of the Surface and Carbon Core to Achieve Yellow Emission in Lignin-Based Carbon Dots.

In this study, yellow emissive lignin-based carbon dots (Y-CDs) were successfully prepared through a synergistic approach to adjust its surface and carbon core states. The lignin was initially effectively oxidized and carboxymethylated to impart abundant -COOH onto the precursor, which eventually adjusts the surface state of the CDs. Subsequently, α-naphthol was employed during the solvothermal treatment of lignin with the aim of elevating the sp2 domain content in the CDs and, thus, adjusting its carbon core state. The obtained Y-CDs possessed abundant carboxyl groups and nanoscale spherical shape with an average diameter of 5.21 nm. Meanwhile, the energy gap of Y-CDs was 2.46 eV and the optimal emission wavelength was 561 nm under the excitation wavelength of 410 nm. Synergistic adjusting carbon core and surface of the Y-CDs would alter the surface charge distribution and promote the delocalization of π electrons, and thus lead to a red shifting with the emission wavelength of 154 nm. Furthermore, a shape memory film with excellent recovery performance and fluorescent properties was designed by embedding the Y-CDs into polyvinyl alcohol (PVA) polymer. The incorporation of Y-CDs could impart the film with considerable high-value applications in the fields of intelligent sensing, biomedicine, and tissue engineering.

High value valorization of lignin as environmental benign antimicrobial.

Lignin is a natural aromatic polymer of p-hydroxyphenylpropanoids with various biological activities. Noticeably, plants have made use of lignin as biocides to defend themselves from pathogen microbial invasions. Thus, the use of isolated lignin as environmentally benign antimicrobial is believed to be a promising high value approach for lignin valorization. On the other hand, as green and sustainable product of plant photosynthesis, lignin should be beneficial to reduce the carbon footprint of antimicrobial industry. There have been many reports that make use of lignin to prepare antimicrobials for different applications. However, lignin is highly heterogeneous polymers different in their monomers, linkages, molecular weight, and functional groups. The structure and property relationship, and the mechanism of action of lignin as antimicrobial remains ambiguous. To show light on these issues, we reviewed the publications on lignin chemistry, antimicrobial activity of lignin models and isolated lignin and associated mechanism of actions, approaches in synthesis of lignin with improved antimicrobial activity, and the applications of lignin as antimicrobial in different fields. Hopefully, this review will help and inspire researchers in the preparation of lignin antimicrobial for their applications.

Preparation of Nitrogen and Sulfur Co-Doped Fluorescent Carbon Dots from Cellulose Nanocrystals as a Sensor for the Detection of Rutin.

The poor water solubility, large particle size, and low accessibility of cellulose, the most abundant bioresource, have restricted its generalization to carbon dots (CDs). Herein, nitrogen and sulfur co-doped fluorescent carbon dots (N, S-CDs) were hydrothermally synthesized using cellulose nanocrystals (CNC) as a carbon precursor, exhibiting a small particle size and excellent aqueous dispersion. Thiourea was selected as a nitrogen and sulfur dopant to introduce abundant fluorescent functional groups into N, S-CDs. The resulting N, S-CDs exhibited nanoscale size (6.2 nm), abundant functional groups, bright blue fluorescence, high quantum yield (QY = 27.4%), and high overall yield (16.2%). The excellent optical properties of N, S-CDs endowed it to potentially display a highly sensitive fluorescence "turn off" response to rutin. The fluorescence response for rutin allowed a wide linear range of 0-40 mg·L-1, with a limit of detection (LOD) of 0.02 µM, which revealed the potential of N, S-CDs as a rapid and simple sensing platform for rutin detection. In addition, the sustainable and large-scale production of the N, S-CDs in this study paves the way for the successful high-value utilization of cellulose.

Ultrasonic assisted enhanced catalytic effect of perovskite to promote depolymerization of lignin.

The search for renewable energy sources to replace fossil fuel has made lignin a promising carbon-containing resource. In this paper, LaNiO3 perovskite catalyst supported by mesoporous carrier with specific pore structure was prepared by the pore filling of MCM-41 with citrate complex precursors of nickel and lanthanum. Then the catalysts applied to maize straw lignin depolymerization. The results of low-angle XRD, N2 adsorption-desorption, IR spectroscopy and SEM confirmed that the catalyst has been successfully manufactured. Based on the yield of phenolic monomer, low molecular weight lignin derived bio-oil and high molecular weight lignin derived bio-oil as standard, the catalyst showed best catalytic effect when the reaction temperature was 250 °C, the reaction time was 6 h, the ratio of lignin to catalyst mass was 5: 1 and with ultrasonic assist. The yield of phenolic monomer was 11.46 wt% and that of bio-oil was 68.0 wt%. In general, this method is an excellent embodiment of the principle of Lignin-first as well as an excellent strategy for the production of value-added phenolics and high-quality bio-oils from lignin. It plays an important role in promoting the high value utilization of lignin in the future.

In-situ compatibilized starch/polyacylonitrile composite fiber fabricated via dry-wet spinning technique.

An in-situ compatibilized starch (St) and polyacrylonitrile (PAN) composite spinning solution was designed by preparing starch-graft-polyacrylonitrile (St-g-PAN) through graft copolymerizing acrylonitrile from soluble starch and using ammonium cerium nitrate (CAN) as initiator. As dimethyl sulfoxide (DMSO) was used as the solvent, St/St-g-PAN/PAN/DMSO spinning solution was prepared and St/St-g-PAN/PAN composite fibers were obtained by dry-wet spinning technique. The effects of air gap, coagulation bath, hot drawing and stretching, and thermal-setting process were studied in detail. Fourier transform infrared spectroscopy (FT-IR), solid state nuclear magnetic resonance (13C NMR), thermogravimetric analysis (TGA), X-ray diffraction analysis (XRD), and scanning electron microscopy (SEM) were used to characterize the structure and morphology of the copolymer and the fibers. Single fiber strength tester and sonic orientation instrument were performed to measure the fiber mechanical properties and orientation degrees. The results showed that as the grafting ratio ~150.0% and the reacting mixture containing St ~9.8%, St-g-PAN ~81.6%, and homo-PAN ~8.6% in DMSO solution with 6.0 wt% in concentration were used, the spinning parameters such as air gap ~35 mm, coagulation bath concentration ~70%, temperature ~25 °C, and positive stretching ~48%, hot drawing and stretching 6 times at 80 °C, thermal-setting at 90 °C for 3 h under constant length mode were met, composite fibers with breaking strength 3.41 cN·dtex-1, breaking elongation 14.41%, sonic orientation factor 0.625, moisture recovery ratio 10.53% under standard condition (1 atm, 22 °C, and relative humidity 65%), and boiling water shrinkage ratio 9.60% were obtained. The as prepared composite fiber was better than common viscose fiber 2.11 cN·dtex-1 and cotton fiber ~3.24 cN·dtex-1 and expected to be used in the fields of medical gauze, bandage, protective clothing, et al. besides of common textiles. The in-situ compatibilization method can be applied in preparation of other composite polymer materials.

Lignin-First Depolymerization of Lignocellulose into Monophenols over Carbon Nanotube-Supported Ruthenium: Impact of Lignin Sources.

Lignin-first depolymerization of lignocellulosic biomass into aromatics is of great significance to sustainable biorefinery. However, it remains a challenge, owing to the variance between lignin sources and structures. In this study, ruthenium supported on carbon nanotubes (Ru/CNT) exhibits efficient catalytic activity toward lignin hydrogenolysis to exclusively afford monophenols in high yields. Catalytic tests indicate that the yields of aromatic monomers are related to lignin sources and decrease in the order: hardwoods > herbaceous plants > softwoods. Experimental results demonstrate that the scission of C-O bonds and the high selectivity to monomeric aromatic compounds over the Ru/CNT catalyst are enhanced by avoiding side condensation. Furthermore, the fabricated Ru/CNT shows good reusability and recyclability, applicability, and biomass feedstock compatibility, rendering it a promising candidate for lignin valorization. These findings pave the way for rational design of highly active and stable catalysts to potentially address challenges in lignin chemistry.

Lignin-based electrospinning nanofibers for reversible iodine capture and potential applications.

The capture of radioactive iodine has recently attracted much attention due to the release of radioactive iodine during nuclear waste disposal and disasters. Exploring highly efficient, sustainable, and eco-friendly materials for capturing radioactive iodine has great significance in developing safe nuclear energy. We reported highly efficient, natural, lignin-based, electrospun nanofibers (LNFs) for reversible radioiodine capture. Abundant iodine adsorption sites, such as functional groups and the interaction between the intermolecular forces exist in LNFs. The capacity of the LNFs for the saturated adsorption of iodine was found to be 220 mg·g-1, which is higher than that of the majority of bio-based adsorbents studied. Moreover, the LNFs exhibited an excellent recycling behavior, and their absorption capacity remained at 84.72% after 10 recycles. Therefore, the results imply that the lignin-based nanofibers can act as a natural, sustainable and eco-friendly packed material for the purification columns in industrial applications. The results demonstrate that the novel, nanostructured, natural biomass, as an ideal candidate has the potential for practical nuclear wastewater purification.

Ni12P5/P-N-C Derived from Natural Single-Celled Chlorella for Catalytic Depolymerization of Lignin into Monophenols.

Lignin is exceptionally abundant in nature and is regarded as a renewable, cheap, and environmentally friendly resource for the manufacture of aromatic chemicals. A novel Ni12P5/P-N-C catalyst for catalytic hydrogenolysis of lignin was synthesized. The catalysts were prepared by simple impregnation and carbonization using the nonprecious metal Ni taken up by the cell wall of Chlorella in Ni(NO3)2 solution. There were only two steps in this process, making the whole process very simple, efficient, and economical. Ni12P5 was uniformly distributed in the catalyst. During the hydrogenolysis of lignin, after 4 h reaction at 270 °C, the yield of bio-oil reached 65.26%, the yield of monomer reached 9.60%, and the selectivity to alkylphenol reached 76.15%. The mixed solvent of ethanol/isopropanol (1:1, v/v) is used as the solvent for the hydrogenolysis of lignin, which not only had excellent hydrogen transferability but also improved the yield of bio-oil, inhibiting the generation of char. No external hydrogen was used, thus avoiding safety issues in hydrogen transport and storage.

Green solvents-based molecular weight controllable fractionation process for industrial alkali lignin at room temperature.

The molecular weight is one of the most important factors influencing the utilization of industrial lignin obtained from chemical pulping process. In this paper, a facile operative green solvent system was successfully developed for molecular weight-controllable fractionation of industrial alkali lignin (IAL) at room temperature. The results showed that through adjusting the ratio of water, ethanol and γ-Valerolactone (GVL), the industrial lignin was fractionated into six levels with molecular weight stepwise controllable from low to high. The fractionation is a physical process according to FTIR and 2D-HSQC NMR analysis, and the chemical structure of lignin has not changed. Additionally, the polydispersity of fractionated lignin with higher molecular weight tends to be narrower. The content of hydroxyl and carboxyl group is higher for the fractionated lignin with lower molecular weight, which would be beneficial for the chemical reactivity in the down-stream application.

Correlation between physicochemical characteristics of lignin deposited on autohydrolyzed wood chips and their cellulase enzymatic hydrolysis.

Enzymatic hydrolysis is a method to generate biofuel from biomass, and autohydrolysis is a popular method to pretreat biomass prior to enzymatic hydrolysis. The primary aim of the present study was to determine the role of lignin produced in the autohydrolysis process on the enzymatic hydrolysis of biomass. The HSQC and 31P NMR analyses confirmed that ß-O-4 of lignin was reduced, while ß-5, ß-ß, and S/G-ratio of lignin were increased with intensifying the hydrolysis intensity.The increase in the hydrolysis intensity significantly enhanced the condensed and non-condensed phenolic OH group of lignin. Interestingly, the cellulase enzyme adsorbed more on lignin that had more phenolic content, and its association with lignin reduced its activity for hydrolyzing cellulose microcrystals. Strong negative correlations were observed between the enzymatic hydrolysis yield and the condensed S-OH (r2 = 0.978) and G-OH (r2 = 0.961) of lignin generated in the autohydrolysis process.

Study on the mechanism of inhibiting the calcification of anaerobic granular sludge induced by the addition of trace signal molecule (3O-C6-HSL).

Microbiota quorum sensing (QS) induced by 3O-C6-HSL (N-(ß-ketocaproyl)-DL-homoserine lactone) inhibited the calcification of anaerobic granular sludge (AnGS), and the mechanism of promoting the activity recovery of calcified AnGS was studied in this paper. Through research, it was speculated that 3O-C6-HSL acted on calcified AnGS residual microorganisms to trigger QS. It enriched many functional microorganisms. For example, it promoted the growth of Methanospirillum. The CO2 could be consumed quickly by Methanospirillum and reduced the calcium carbonate formation. The increase of microbial biomass would promote the activity of sludge. What's more, the pore size and porosity of sludge would increase, so the mass transfer channel will be broadened at same time. All those, could help the calcified AnGS quickly restore the activity and anaerobic system recover normal, which provided a new idea for the emergency rescue of anaerobic system in the future.

Nitrogen-doped lignin-derived biochar with enriched loading of CeO2 nanoparticles for highly efficient and rapid phosphate capture.

Development of lignin-derived carbon adsorbents with ultrahigh phosphate adsorption activity and rapid adsorption kinetics is of great importance, yet limited success has been achieved. Herein, we develop a CeO2 functionalized N-doped lignin-derived biochar (Ce@NLC) via a cooperative modification strategy for effective and fast phosphate capture. The novel modification strategy not only contributes greatly to the loading of well-dispersed CeO2 nanoparticles with a smaller size, but also significantly increases the relative concentration of Ce(III) species on Ce@NLC. Consequently, an enhanced capture capacity for phosphate (196.85 mg g-1) as well as extremely rapid adsorption kinetics were achieved in a wide operating pH range (2-10). Interestingly, Ce@NLC exhibited a strong phosphate adsorption activity at even low-concentration phosphorus-containing water. The removal efficiency and final P concentration reached 99.87% and 2.59 µg P L-1 within 1 min at the phosphate concentration of 2 mg P L-1. Experiments and characterization indicated that Ce(III) species plays a predominant role for the phosphate capture, and ligand exchange, together with electrostatic attraction, are the main adsorption mechanism. This work develops not only an efficient carbon-based adsorbent for phosphate capture, but also promotes the high-value application of industrial lignin.

Study on polysaccharide polyelectrolyte complex and fabrication of alginate/chitosan derivative composite fibers.

Sodium alginate (SA) blending with quaternary ammonium chitosan (QAC) polysaccharide polyelectrolyte complex (PEC) system was chosen to research the binary blending of anionic and cationic polyelectrolytes in detail and to fabricate SA/QAC composite fibers. The potential charge and the rheology of the PEC solution were characterized through Zeta Laser Particle Size Analyzer and DV-C Rotary Rheometer, the structure and properties of the composite fiber were examined by FT-IR, XRD, SEM, EDS, and YG004 single fiber strength meter. The results showed that as the mass ratio of SA to QAC increased from 0/1 to 10/1, the state of the binary solution in water changed from transparent uniform solution to turbid solution with flocculent precipitate, then back to uniform solution, accompanied by the electrical potential change. Moreover, the electrical potential also depended on salt in solution. By using this uniform PEC solution with the mass ratio of SA to QAC 10/1 and concentration 5.5 wt% in water, SA/QAC composite fibers with excellent performances of breaking strength 2.37 cN·dtex-1 and breaking elongation 14.11%, good antibacterial and hydrophobic properties were fabricated via green wet-spinning process. The FT-IR and EDS determination indicated there formed egg-box between SA and Ca2+, cross-linked network between glutaraldehyde(GA) and SA, QAC, respectively. Depending on its mechanical, natural, and antibacterial properties, the SA/QAC composite fiber has advantages in wound dressing, medical gauze, medical absorbable suture, and tissue engineering.

State-of-the-Art: Applications and Industrialization of Lignin Micro/Nano Particles.

As a new product of high-value utilization of lignin, lignin micro/nano particles (LMNPs) have attracted the attention of researchers due to their non-toxicity, corrosion-resistance, UV resistance, and other excellent characteristics and potential application value. This article outlined the main preparation methods of LMNPs at the current stage, summarized and compared them from three perspectives of preparation technology, final product state and product composition. Subsequently, based on the different focuses of the properties of LMNPs, their application research progress as fillers, UV blockers, drug delivery carriers, among others, were introduced. Then a concise analysis of the technical and economic assessment and life cycle assessment of LMNPs in the process of industrialization was made. Finally, the main problems at present and the future development directions were analyzed and prospected to provide references for the deep processing of forest resources and the development of bio-based nanomaterials.

Fluorescent N-functionalized carbon nanodots from carboxymethylcellulose for sensing of high-valence metal ions and cell imaging.

A convenient and sensitive reversible-fluorescence sensing platform for accurate monitoring of high-valence metal ions is still very challenging. As a green kind of fluorescent carbon nanomaterials, carbon dots (CDs) have captured considerable attention because of the stable fluorescence property and low cost. Herein, we fabricated a type of nitrogen-functionalized carbon dots (N-CDs) from CMC as a fluorescent reversible sensing platform for detecting various high-valence metal ions. N-CDs with a mean size of 2.3 nm were obtained and possessed 22.9% quantum yields (QY). A label-free fluorescent probe for detection of high-valence metal ions (Fe3+, Cr6+, Mn7+) was established via the fluorescence quenching response. Among them, the detection limit (LOD) toward Fe3+ ions reached 0.8 µM. We have explored the quenching mechanism of N-CDs to explain the valence state-related electron-transfer fluorescence quenching between high-valence metal ions and N-CDs. Moreover, the valence state-related fluorescence quenching phenomenon of N-CDs in aqueous solution could be effectively recovered by introducing a reducing agent (Ti3+). This "turn off-on" fluorescence recovery system of N-CDs could be applied in different applications covering the selective detection of environmental high-valence metal ions and cellular imaging.