Search

The utilization of plant polyphenols as catalyst carriers holds promise for environmentally friendly catalysis. However, challenges such as the inhomogeneous distribution of organic ligands often hinder their effectiveness. In this study, lignin–metal supramolecular framework were formed through ionic coordination self-assembly, achieved by oxidative ammonolysis modified lignin. The specific spatial domain-limiting effect of lignin–metal supramolecular framework ensures the dispersion and stability of catalyst active sites. Carbon-coated trimetallic catalysts (Ru–FeNi@OALC) derived from lignin–metal supramolecules exhibit promising performance, with low overpotentials for the oxygen evolution reaction (OER, η10 = 290 mV) and the hydrogen evolution reaction (HER, η10 = 52 mV), surpassing commercial noble metal catalysts. Additionally, these catalysts demonstrate long-lasting water-splitting performance, highlighting their potential for sustainable catalytic reactions. Molecular simulations and DFT theoretical calculations elucidate the feasibility of lignin oxidative ammonolysis modification and reveal the coordination mechanism. Furthermore, the abundant defects and disorder in the coordination polymer-derived carbon materials optimize electron transfer processes and accelerate reaction kinetics. This construction strategy towards designable polyphenol–metal supramolecular framework presents a promising avenue for the green synthesis of a variety of metal/carbon composite catalysts, contributing to sustainable catalysis and environmental protection. [ABSTRACT FROM AUTHOR]

Graphite anodes experience co‐intercalation of K+ ions and solvent in ether‐based electrolytes, which enables ultrafast kinetics of potassium‐ion storage. The potassium‐ion storage mechanisms of amorphous soft carbon (SC) and hard carbon (HC) anodes in ether‐based electrolytes are ambiguous. Herein, the co‐intercalation mechanisms of SC and HC in ether‐based electrolytes are elucidated. The solvated K+ intercalates with a solvation structure, which avoids the sluggish desolvation process. Thus, HC and SC anodes display excellent rate capabilities. Moreover, the SC anode forms ternary K‐graphite intercalation compounds during the potassiation process. It is also demonstrated that solvated K+ is not only stored in the spacing between graphene nanodomains but can also be stored in the closed pores of HC, enabling higher capacities than pure K+ intercalation in ester‐based electrolytes. Nevertheless, the co‐intercalation causes the large volume expansion of SC and HC, giving rise to irreversible structural damage and capacity decay of SC and HC. The strong interaction between K+ ions and ether molecules is the main reason for the co‐intercalation. A thick and organic‐rich solid electrolyte interphase film formed in ester‐based electrolytes can hinder the co‐intercalation in ether‐based electrolytes. [ABSTRACT FROM AUTHOR]

Lignin valorization is a challenge for chemical and materials scientists due to its complex molecular structure and intra- and inter-molecular assembly. Although catalytic conversion of lignin into small aromatic organic molecules has been widely investigated, it faces the problems of low selectivity and complex products. Herein, we report a direct electrochemical conversion method for the selective oxidation of industrial lignin to produce short-chain carboxylic acids (SCCAs) with a wide range of concentrations. In an electrolytic cell, lignin is chemically converted to SCCAs by H2O2 with titanium silicate-1 (TS-1) as a catalyst. H2O2 is generated in situ by the recombination of H+ and HO2− in a three-compartment cell by separately introducing hydrogen (H2) and oxygen (O2) as the sources of protons and HO2− into the anode and cathode compartments. We have achieved a record-high concentration of SCCAs up to 109.8 mg mL−1 through the catalytic depolymerization of lignin. A high concentration of SCCAs of 80.1 mg mL−1 could also be achieved at a cell voltage of 2.13 V by coupling the 2e−-ORR and water oxidation using air and 1 M aqueous H2SO4 solution as feedstocks. Our approach could eliminate the additional economic consumption and environmental hazards caused by the transportation and storage of commercially concentrated and stabilized H2O2. Aside from the SCCAs produced in this process, the formation of new carboxyl groups in the lignin residue during the oxidation reaction greatly broadens the application potential of industrial lignin. [ABSTRACT FROM AUTHOR]

Common precursors for carbon materials typically include petroleum‐based polymers or MOF materials. However, these materials often encounter challenges such as metal aggregation, high cost, and metals leaching. In this work, a novel of approach lignin‐metal supramolecular framework complex (MSF@Lignin) is introduced. These complexes are formed through oxidative ammonolysis of lignin (OAL) to synthesize a nitrogen‐doped carbon‐encapsulated CoRu nanocatalyst (CoRu@OALC) via in situ carbonization. CoRu@OALC exhibited exceptional performance in both HER (90 mV) and OER (200 mV) at the current density of 10 mA cm−2, with an overall water splitting voltage of 1.5 V and outstanding stability under high density. During the pyrolysis process, metal became encapsulated by lignin‐derived carbon, occurring within the temperature range of 600–700 °C. In the catalytic process, active sites are primarily located within the defects in lignin‐derived carbon, showcasing a unique "self‐healing" phenomenon within the carbon layer. Oxygen‐containing intermediates (*OH, *O, and *OOH) facilitated the reconstruction of defects on the carbon layer, while the hydrogen‐containing intermediates (*H) contributed to the reappearance of a defect‐rich structure. [ABSTRACT FROM AUTHOR]

The supermolecule-mediated method is employed to prepare an organic molecule aggregate (OMA) precursor called MCAL in which the dopant agent (melamine-cyanuric acid supramolecular (MCA)) and biomass molecule (alkali lignin (AL)) are uniformly mixed. Direct pyrolysis of OMA yields lignin-derived highly nitrogen-doped turbine-like carbon (LNTC), which serves as a high-performance anode for potassium-ion capacitors. [Display omitted] Potassium-ion hybrid capacitors (PIHCs) represent a burgeoning class of electrochemical energy storage devices characterized by their remarkable energy and power densities. Utilizing amorphous carbon derived from sustainable biomass presents an economical and environmentally friendly option for anode material in high-rate potassium-ion storage applications. Nevertheless, the potassium-ion storage capacity of most biomass-derived carbon materials remains modest. Addressing this challenge, nitrogen doping engineering and the design of distinctive nanostructures emerge as effective strategies for enhancing the electrochemical performance of amorphous carbon anodes. Developing highly nitrogen-doped nanocarbon materials is a challenging task because most lignocellulosic biomasses lack nitrogen functional groups. In this work, we propose a general strategy for directly carbonizing supermolecule-mediated lignin organic molecular aggregate (OMA) to prepare highly nitrogen-doped biomass-derived nanocarbon. We obtained lignin-derived, highly nitrogen-doped turbine-like carbon (LNTC). Featuring a three-dimensional turbine-like structure composed of amorphous, thin carbon nanosheets, LNTC demonstrated a capacity of 377 mAh g−1 when used as the anode for PIHCs. This work also provides a new synthesis method for preparing highly nitrogen-doped nanocarbon materials derived from biomass. [ABSTRACT FROM AUTHOR]

Airborne pollutants including particulate matter (PM) and microorganisms threaten public health. Fibrous filters in personal protection equipment have shown good PM removal ability but a poor biocidal effect. Herein, a series of highly biocompatible amino acid-grafted enzymatic hydrolysis lignin derivatives (EHL-AA-x) with both cationic/anionic groups were synthesized by nucleophilic substitution. The structures of EHL-AA-x were characterized by NMR, FT-IR, GPC, DLS, potentiometric titration, surface charge and elemental analysis. In vitro biological assays showed that the inhibition efficiency of EHL-AA-x against Gram-negative bacteria increased from 10 to 57% when the grafting amount of amino acids varied from 0 to 0.62 mmol g−1 at a concentration of 10 mg mL−1, while that against Gram-positive bacteria reached 99%. It is not only 4 times higher than that of birch wood hydrotropic lignin, but also comparable to that of lignin/nanosilver composites. The morphological changes observed by SEM indicated that EHL-AA-x damaged the cell membrane of bacteria, suggesting a membrane disruption mechanism. QCM-D and AFM analysis showed that the increase of electrostatic and hydrophobic interactions between EHL-AA-x and bacteria is the key factor for the improvement of the antimicrobial activity. Subsequently, a mask fabricated from the optimal EHL-AA-x-coated non-woven fabrics could inhibit >95% bacteria in 30 min, while a number of living bacteria were detected on the inner layer of the control commercial mask. In addition, the mask with EHL-AA-x could prevent the adhesion of bacteria by the formation of anionic and cationic hydration layers. Using this strategy, ideal lignin-based antimicrobial materials with good bacteriostatic activity and anti-bio-adhesion properties could be designed and used in personal protection equipment. [ABSTRACT FROM AUTHOR]

Dissipative particle dynamics simulations are performed to systematically investigate the effects of hydrophobicity and compatibility on the inner phase separated structures (core-shell type or Janus type) of polymer nanoparticles self-assembled from a series of polymer blends in aqueous solution. Moreover, the temperature-dependent core-shell-to-Janus phase transition of a thermo-sensitive polymer blend is captured and explored by dissipative particle dynamics simulations for the first time. Our simulations reveal that both hydrophobicity and compatibility among blended polymers and the solvent play important roles in controlling the inner structures (core-shell or Janus) of polymer blend nanoparticles in aqueous solution. The phase separated structures of the studied polymer blend nanoparticles can be well predicted by using the criteria based on Neumann's triangle concept, which is derived from the corresponding interfacial tensions among the polymers and water. Besides, it was found that the hydrophobicity change of the blended thermo-responsive block copolymer induced by temperature plays a major role in the reversible transition from core-shell structure to Janus structure of the thermo-sensitive polymer blend nanoparticles. The present work is expected to provide some guidelines for designing and preparing novel polymer nanoparticles with desired structures and facilitating their applications in switching devices, nano-sensors, drug delivery system, etc. [ABSTRACT FROM AUTHOR]

As a natural fluorescent material, the fluorescent property and mechanism of lignin were elusive until now, which hindered the high value application of lignin fluorescence. Herein, we firstly probed the previous studies on lignin fluorescence and the results indicated that lignin microstructure was an important factor for its complex fluorescence property because of fluorophore interaction and aggregation behavior. Following the rules, lignin fluorescence was explored by analyzing its aggregation fluorescence behaviors and basic fluorescence properties based on the theory of traditional conjugated luminescence and aggregation-induced emission. It was demonstrated that intermicellar aggregation of loose lignin micelle made no substantial effect on lignin fluorescence, while intramicellar aggregation could induce the enhancement of lignin fluorescence before the micellar compactness exceeded a critical value. Combined with the physicochemical structures and fluorescence properties of lignin, aggregation-induced conjugation from phenylpropane units was believed as the main sources of the visible emission of lignin and different phenylpropane aggregates consequently formed the multi-fluorophore system in lignin micelle. Furthermore, lignin aggregation fluorescence behavior has great potential in its microstructure analysis and a case study of pH/ionic strength-induced solution behavior analysis was presented. This work provided a totally new prospective for lignin fluorescence. Multi-scale aggregation behaviors in lignin micelle together resulted in the complex but solvable fluorescent property. Unlabelled Image • A general understanding for the mechanism of lignin fluorescence was provided. • The model of lignin aggregation fluorescence behavior was initially established. • Lignin fluorescence showed great potential in its microstructure analysis. [ABSTRACT FROM AUTHOR]

Sustainable co-production of materials and chemicals is essential to green production and reduction of contaminations. This work presents a sustainable production process for the co-production of porous carbon and calcium chloride using renewable lignin as the carbon precursor. The utilization of CaO as a hard template agent facilitates the creation of porous carbons through the homogeneous mixing of lignin precursors and CaO. Theoretically, it is possible to obtain carbon dioxide with high purity from the subsequent acid etching process. CaCl 2 with high purity as a value-added product can be obtained by a straightforward crystallization process with a calcium collection efficiency of >93%. In this work, the formation mechanism of the pore structure evolution of LPC was elucidated by exploring the structural evolution of CaO during the reaction process. The obtained LPC has a hierarchical porous structure and specific surface areas around 700 m2 g−1. The obtained porous carbons showed excellent electrochemical performances as the cathodes of zinc ion hybrid capacitors. This combined sustainable production process could be developed as a practical process for the production of calcium chloride and porous carbons. This work opens up a pathway for the development of sustainable comprehensive resource utilization from renewable biomass for the production carbon electrode materials and producing chemicals. [Display omitted] [ABSTRACT FROM AUTHOR]

We developed a simple and practical method to prepare pH-responsive lignin-based complex micelles in green solvents using purified alkali lignin. Alkali lignin (AL) was quaternized and further self-assembled into lignin-based complex micelles with sodium dodecyl benzenesulfonate (SDBS) in an ethanol/water mixture. The FT-IR and 1 H NMR spectra indicated the successful grafting of quaternary ammonium groups on AL. TEM images showed that the complex micelles were uniform spherical nanoparticles. The complex micelles also exhibited rich phase behaviors responding to pH changes. Ibuprofen (IBU) was used as a drug model and more than 74.44% could be encapsulated via hydrophobic interactions. The in vitro release behavior of IBU was pH-dependent and exhibited controlled release properties. Therefore, more than 75% of IBU could be preserved in simulated gastric fluid (SGF, pH 1.2), and over 90% could be released smoothly in simulated intestinal fluid (SIF, pH 7.4). This work suggests a novel strategy for fabricating an oral drug delivery carrier and is of significance for the value-added utilization of lignin. [ABSTRACT FROM AUTHOR]

A novel coprecipitation process was developed to prepare lignin/silica hybrids using sodium metasilicate and alkali lignin (AL) from pulping black liquor. AL was first modified by quaternization to synthesize quaternized alkali lignin (QAL). The QAL/SiO 2 hybrids with different contents of lignin, which were prepared via the coprecipitation of QAL and sodium metasilicate in aqueous solution, were microspheres having a diameter of 300–400 nm and that were analyzed by SEM, TEM, FT-IR, XPS, XRD, and TG analysis. Interestingly, these novel QAL/SiO 2 hybrids showed excellent UV-absorption performance and could effectively protect the polyurethane (PU) film from UV radiation when they were blended with PU. The UV transmittance of the PU film was reduced from 13.4% to 0.1% below 315 nm and from 74.8% to 9.7% below 400 nm when the content of the QAL/SiO 2 hybrids increased from 0 to 1.0 wt%. Furthermore, the mechanical properties were also improved owing to the good compatibility between the QAL/SiO 2 hybrids and PU. The results of this study are of significant and practical importance to the value-added utilization of lignin. [ABSTRACT FROM AUTHOR]

Condensation, dark color and low extraction yield of lignin have hindered the full valorization of biomass during lignocellulosic fractionation. Herein, we introduce a novel biomass fractionation concept that addresses the issue of lignin's spatial confinement. Building upon this concept, we have devised an environmentally friendly and straightforward strategy. This approach involves a combination of selective carboxylation at the Cγ-OH position using citric acid and etherification at the Cα-OH position using butanol. The objective is to mitigate the spatial confinement of lignin and stabilize its active intermediates for lignin extraction. Consequently, up to 91.4 ± 0.2% lignin with a light color can be separated from the recalcitrant softwoods, as a UV blocker to improve the performance of sunscreen cream. The cellulosic residue can be enzymatically digested to glucose with a yield of 80%. The initiated biomass fractionation theory and strategy in this study provide a new concept for the isolation of lignin and full valorization of lignocellulose, promoting the development of a sustainable economy. [ABSTRACT FROM AUTHOR]

This work demonstrated a facile one-pot in-situ method to prepare lignin-based carbon/ZnO (LC/ZnO) nanocomposites by using lignin that was extracted from paper pulping waste liquor as the carbon source. The morphological, physical and optical properties of the prepared LC/ZnO nanocomposites was characterized with Scanning electron microscope (SEM), Transmission electron microscopy (TEM), Thermal-gravimetric analysis (TGA), Raman, X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analyses. The resulting LC/ZnO is composed of highly dispersed ZnO nanoparticles embedded on a lignin-based carbon nanosheet. The typical D and G bonds of carbon materials obviously appeared. The TGA shows that the LC contents could be controlled. The BET surface area of the LC/ZnO was much larger than the BET surface area of the pure ZnO. The prepared LC/ZnO nanocomposites exhibited excellent photocatalytic performance for the degradation of organic dyes. LC/ZnO that contained ∼6.38% lignin-based carbon exhibited an excellent photo-degradation efficiency of methyl orange as high as 98.9% under sunlight irradiation for 30 min, superior to the performance of pure ZnO and other reported ZnO/GRs. The improved photocatalytic performance was attributed to a homogeneous structure and stronger absorption ability for organic dyes. The mechanism exploration experiment showed that h + was the main active specie. Meanwhile, the photocatalytic electron transfer mechanism was also investigated. In addition, this work demonstrates a green and valuable pathway for the high-value-added utilization of lignin. [ABSTRACT FROM AUTHOR]

Polyvinylpyrrolidone (PVP) is an antifouling polymer to resist the adsorption of protein on solid surface. Effects of PVP on the enzymatic hydrolysis of pretreated lignocelluloses and its mechanism were studied. Adding 1 g/L of PVP8000, the enzymatic digestibility of eucalyptus pretreated by dilute acid (Eu-DA) was increased from 28.9% to 73.4%, which is stronger than the classic additives, such as PEG, Tween and bovine serum albumin. Compared with PEG4600, the adsorption of PVP8000 on lignin was larger, and the adsorption layer was more stable and hydrophilic. Therefore, PVP8000 reduced 73.1% of the cellulase non-productive adsorption on lignin and enhanced the enzymatic hydrolysis of lignocelluloses greatly. [ABSTRACT FROM AUTHOR]

A new two-step lignin depolymerization strategy was developed, in which the benzylic alcohols in lignin was methylated under microwave irradiation, followed by a hydrogenolysis for the cleavage of β O 4 bond with Pd/C as the catalyst. The results showed that an efficient and selective catalytic methylation of benzylic alcohols was achieved with various lignin model compounds, and the acidic environment promoted the methylation of benzylic alcohol. Methylation of benzylic alcohol increased the β O 4 bond cleavage rate by 55.9%, and improved products selectivity. Preliminary study of lignin depolymerization illustrated that methylation pretreatment of benzylic alcohols facilitated lignin depolymerization to produce aromatic monomers and reduced the oxygen content of aromatic monomers. [ABSTRACT FROM AUTHOR]

Phosphorylated kraft lignin (PKL), a novel lignin polymer, has potential application in the preparation and modification of inorganic materials. In this article, the adsorption characteristics of PKL at the solid/liquid interface were investigated under different pH conditions. Quartz crystal microbalance combined with dissipation monitoring (QCM-D), UV spectroscopy, and atomic force microscopy (AFM) were applied for monitoring the adsorption. The adsorbed amount of PKL gradually decreased as a function of pH increment on the gold covered QCM-D crystals, which were pretreated with an adsorbed layer of poly(diallyldimethylammonium chloride) (PDAC). This was also the case for quartz slide substrates pretreated with PKL/PDAC multilayers by the method relying on the layer-by-layer (LBL) electrostatic self-assembly. The hydrophobicity of adsorbed PKL films increased with increasing pH from 3 to 12. In the course of this process, the adsorption morphology changed from a compact rigid state to a less compact soft state. Under acidic conditions, the adsorption is governed mainly by cation-π interaction between PKL and PDAC, and the adsorption configuration is mushroom-like. Under neutral and alkaline conditions, the cation-π interaction is less relevant owing to the longer distances between the anionic groups in PKL and the cation in PDAC. This causes stretching of the molecular chains in PKL, while the adsorption configuration changes to a planar pancake structure so that the electrostatic interaction dominates. The knowledge on adsorption characteristics of PKL at different pH values is helpful to prepare some lignin-based composite materials. [ABSTRACT FROM AUTHOR]

Two pretreatment methods to overcome recalcitrance of lignocelluloses, sulfite pretreatment (SPORL) and dilute acid (DA), were conducted to pretreat softwood masson pine and hardwood eucalyptus for enzymatic hydrolysis. In the presence of corresponding pre-hydrolysates, adding moderate cetyltrimethylammonium bromide (CTAB) could enhance the enzymatic hydrolysis of the SPORL-pretreated substrates, but had no enhancement for the DA-pretreated substrates. The results showed that sodium lignosulfonate (SL) in pre-hydrolysates and CTAB together had a strong enhancement on the enzymatic hydrolysis of lignocelluloses. The compound of commercial lignosulfonate SXSL and CTAB (SXSL-CTAB) could enhance the substrate enzymatic digestibility (SED) of SPORL-pretreated masson pine from 27.1% to 71.0%, and that of DA-pretreated eucalyptus from 37.6% to 67.9%. The mechanism that CTAB increased the adsorption of SL on lignin to form more effective steric hindrance and reduced the non-productive adsorption of cellulase on lignin by neutralizing the negative charge of SL was proposed. [ABSTRACT FROM AUTHOR]

Using a simple method, we developed a new family of alkyl sulfonic acid modified lignosulfonate (ASLSs) with simultaneously improved sulfonation degrees and molecular weights via one step. Direct sulfonation occurred on both phenolic and alcoholic hydroxyl groups of alkali lignin raw material with 1,4-butylenesulfone used as sulfonation agent. A sulfonation degree of 3.86 mmol/g had been achieved which presents as one of the highest sulfonation degrees among those of reported LSs, to date.1H-NMR and Fourier transform infrared spectroscopy measurements confirmed the efficient sulfonation. Furthermore, the dispersion properties were investigated in low-rank coal-water slurry (CWS). ASLS3 showed better viscosity-reduction effect than naphthalene sulfonate formaldehyde condensate (FDN) in CWS with dosages from 0.6% to 1.0 wt%. ASLS3 had the similar sulfonation degree with FDN; however, the large steric hindrance, soft long alkyl chain-C4H8-SO3H, and their efficient anchoring effect of ASLSs contributed to their improved dispersion properties. [ABSTRACT FROM PUBLISHER]

Effect of the molecular structure of lignosulfonate-based polyoxyethylene ether (LS-PEG) on the enzymatic hydrolysis of Avicel and corn stover was investigated. With the increase of PEG contents and M w of LS-PEG, glucose yield of corn stover increased from 16.7% to 51.9%. When LS-PEG was compounded with cationic surfactant cetyltrimethylammonium bromide (CTAB), the enhancement of glucose yield of corn stover was further increased from 45.3% to 62.8%. Sulfonic group of LS-PEG preferentially interacted with quaternary ammonium group of CTAB by the electrostatic attraction to form a similar non-ionic surfactant CTAB-LS-PEG. CTAB-LS-PEG showed electrically neutral and more hydrophobic, and blocked more nonproductive adsorption of cellulase on the lignin. Therefore, CTAB-LS-PEG enhanced enzymatic hydrolysis efficiency of lignocelluloses more significantly. The understanding developed in this study can help to develop potential approaches and strategies for effective application of lignosulfonate to improve bioconversion of lignocellulosic biomass. [ABSTRACT FROM AUTHOR]

The second generation biofuel butanol can be produced by acetone-butanol-ethanol (ABE) fermentation, but the separation from the broth is still challenging. Therefore, dipotassium hydrogen phosphate was investigated as salting-out agent. The ABE fermentation broth was enriched by a prefractionator after being preheated. The enriched ABE solution was salted out by K2HPO4 solutions at different temperatures. The water in the supplemented ABE solution was largely removed by the salting-out method. The energy requirements for the prefractionator and the butanol column were significantly reduced. The total energy demand for the recovery of acetone, butanol, and ethanol by salting-out and subsequent distillation was optimized. With the salting-out process, the entire salting-out and distillation method turned out to be more energy-saving than the conventional one. [ABSTRACT FROM AUTHOR]

Effect of the molecular structure of lignin-based polyoxyethylene ether (EHL–PEG) on enzymatic hydrolysis of Avicel and corn stover was investigated. With the increase of PEG contents and molecular weight of EHL–PEG, glucose yield of corn stover increased. EHL–PEG enhanced enzymatic hydrolysis of corn stover significantly at buffer pH 4.8–5.5. Glucose yield of corn stover at 20% solid content increased from 32.8% to 63.8% by adding EHL–PEG, while that with PEG4600 was 54.2%. Effect of EHL–PEG on enzymatic hydrolysis kinetics of cellulose film was studied by quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). An enhancing mechanism of EHL–PEG on enzymatic hydrolysis kinetics of cellulose was proposed. Cellulase aggregates dispersed by EHL–PEG excavated extensive cavities into the surface of cellulose film, making the film become more loose and exposed. After the maximum enzymatic hydrolysis rate, the film was mainly peeled off layer by layer until equilibrium. [ABSTRACT FROM AUTHOR]

Rational design of efficient, stable, and inexpensive bifunctional electrocatalysts for oxygen evolution reactions (OER) and hydrogen evolution reactions (HER) is a key challenge to realize green hydrogen production via electrolytic water splitting. Herein, Ru nanoparticles and FeNi alloy heterojunction catalyst (Ru−FeNi@NLC) encapsulated via lignin‐derived carbon was prepared by self‐assembly precipitation and in situ pyrolysis. The designed catalyst displays excellent performance at 10 mA cm−2 with low overpotentials of 36 mV for HER and 198 mV for OER, and only needs 1.48 V for overall water splitting. Results and DFT calculations show the unique N‐doped lignin‐derived carbon layer and Ru−FeNi heterojunction contribute to optimized electronic structure for enhancing electron transfer, balanced free energy of reactants and intermediates in the sorption/desorption process, and significantly reduced reaction energy barrier for the HER and OER rate‐determining steps, thus improved reaction kinetics. This work provides a new in situ pyrolysis doping strategy based on renewable biomass for the construction of highly active, stable and cost‐effective catalysts. [ABSTRACT FROM AUTHOR]

Rational design of efficient, stable, and inexpensive bifunctional electrocatalysts for oxygen evolution reactions (OER) and hydrogen evolution reactions (HER) is a key challenge to realize green hydrogen production via electrolytic water splitting. Herein, Ru nanoparticles and FeNi alloy heterojunction catalyst (Ru−FeNi@NLC) encapsulated via lignin‐derived carbon was prepared by self‐assembly precipitation and in situ pyrolysis. The designed catalyst displays excellent performance at 10 mA cm−2 with low overpotentials of 36 mV for HER and 198 mV for OER, and only needs 1.48 V for overall water splitting. Results and DFT calculations show the unique N‐doped lignin‐derived carbon layer and Ru−FeNi heterojunction contribute to optimized electronic structure for enhancing electron transfer, balanced free energy of reactants and intermediates in the sorption/desorption process, and significantly reduced reaction energy barrier for the HER and OER rate‐determining steps, thus improved reaction kinetics. This work provides a new in situ pyrolysis doping strategy based on renewable biomass for the construction of highly active, stable and cost‐effective catalysts. [ABSTRACT FROM AUTHOR]

Water-soluble lignin-based polyoxyethylene ether (EHL–PEG), prepared from enzymatic hydrolysis lignin (EHL) and polyethylene glycol (PEG1000), was used to improve enzymatic hydrolysis efficiency of corn stover. The glucose yield of corn stover at 72 h was increased from 16.7% to 70.1% by EHL–PEG, while increase in yield with PEG4600 alone was 52.3%. With the increase of lignin content, EHL–PEG improved enzymatic hydrolysis of microcrystalline cellulose more obvious than PEG4600. EHL–PEG could reduce at least 88% of the adsorption of cellulase on the lignin film measured by quartz crystal microbalance with dissipation monitoring (QCM-D), while reduction with PEG4600 was 43%. Cellulase aggregated at 1220 nm in acetate buffer analyzed by dynamic light scattering. EHL–PEG dispersed cellulase aggregates and formed smaller aggregates with cellulase, thereby, reduced significantly nonproductive adsorption of cellulase on lignin and enhanced enzymatic hydrolysis of lignocelluloses. [ABSTRACT FROM AUTHOR]

The salting-out effect of tripotassium phosphate on the liquid–liquid equilibria of the (water + acetone + 1-butanol + ethanol) system was investigated at 298.15 K. The water content of the organic phase decreased from 60.00% to 7.11% after the additions of tripotassium phosphate at 298.15 K. The experimental results were correlated with an excellent agreement by using the Othmer–Tobias equation where acetone, 1-butanol, and ethanol were taken as one fictitiously chemical compound. The salting-out effect of tripotassium phosphate under saturated conditions on this system was studied at different temperatures as well. A saturated solution of tripotassium phosphate at 333.15 K was used as an extractant to enrich acetone, 1-butanol and ethanol. When the salting-out factor was greater than 2/2, the recovery of acetone, 1-butanol and ethanol was approximately 100%. There was insignificant amount of tripotassium phosphate that dissolved in the organic phase. [ABSTRACT FROM AUTHOR]

Abstract: The modification of alkali lignin with laccase was investigated. The structural change of lignin was analyzed. The sulfonation reactivity was measured by the content of sulfonic group. The results showed the sulfonation reactivity increased to some extent under the condition of atmosphere pressure, but decreased under the condition of 0.3 MPa oxygen pressure. The analysis of Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) showed the cleavage of various ether linkages and demethylation took place in the structure of lignin to certain extent during modification with laccase, which contributed to the improvement of sulfonation reactivity. Under the condition of 0.3 MPa oxygen pressure, the ratio of s/g (guaiacyl/syringyl) increased after modification, which reduced the sulfonation reactivity of lignin. Simultaneously partial polymerization reaction, such as 4-O-5′, β-5, 5-5 and other reaction in the aromatic ring decreased the activity sites of C2, C5 and C6. Abundant polymerization reaction of α-O increased steric hindrance of C2 and C6 in aromatic ring, resulting in low sulfonation reactivity of lignin. [Copyright &y& Elsevier]

Polycarboxylate-type superplasticizers (PCs) containing different side chains and sulfonic groups have been synthesized, and the effect of side chains and sulfonic groups on their performance in cementitious systems has been intensively investigated by measuring zeta potential, thickness of absorption layer, paste fluidity, rheological properties as well as the setting time in this paper. Results show that the PC containing both short poly(ethylene oxide) (PEO) side chains and long PEO side chains with the molar ratio of 1:1 has a better dispersibility than the PC containing only short PEO side chains or only long PEO side chains in cement suspensions. The shorter the side chain of the PC, the longer the setting time of cement paste incorporating it. An appropriate increase of sulfonic group content is beneficial for the improvement of dispersibility for the PC and leads to no obvious change for the setting time. It also suggests that there is a geometrical balance between the PEO side chains and sulfonic groups for the performance of PC. This work is not only helpful for understanding the relationship of molecular structure of PCs and their performance, but also further designing optimum molecular structure of PC to meet the requirement in different concrete system. [ABSTRACT FROM AUTHOR]

Lignosulfonate is a type of macromolecular surfactant widely used as interfacial additive in various industrial fields and it is produced during chemical pulping process. In this paper, we present a new effective method for measurement of the critical aggregation concentration (CAC) of sodium lignosulfonate (SL) in water solution, with which a value of 0.38 g L−1 was obtained. Through the determination of CAC and observation by DLS, the state and dynamics of the formation of the SL micelles were disclosed. The results showed that SL was the state of individual molecules when its mass concentration was less than CAC; the individual SL molecules started to aggregate above CAC and thus micelles formed and grew with increasing SL concentration. The SL solution was quickly frozen and the structures of SL molecules or micelles were observed by ESEM, revealing that the spherical micelles were the main form of SL in the solution. Based on the results, the spherical hollow vesicular structure is proposed as a model of the aggregated micelles of SL in the solution. [ABSTRACT FROM AUTHOR]

Abstract: Lignosulfonate is an anionic surfactant from pulp processing industries. Alcohols are often used as cosurfactants in the application of surfactant. The improvement of straight-chain alcohols with different alkyl chain lengths as cosurfactant on the physicochemical properties of calcium lignosulfonate (CL) aqueous solution has been investigated. The results indicate that small amounts of straight-chain alcohols with longer alkyl chains are helpful in improving the surface activity of CL, especially when the number of carbon atoms in alcohols is 10 or larger. The adsorption amount of CL solutions with additives of longer chain alcohols on TiO2 particles increases greatly, and the zeta potential of TiO2 particles adsorbing CL rises significantly. It can be concluded that there is a cooperative effect of the longer chain alcohols on lignosulfonate to form a tighter adsorption layer at the interface. The steric hindrance increases with the increasing amount of adsorption, and the static repulsive force increases with the increasing zeta potential. Therefore, the effect of CL on the stability of the TiO2 suspension is enhanced dramatically by addition of longer chain alcohols. This understanding can lead to further development in expanding the functionalities of the lignosulfonate through manipulation of the adsorption capacity of CL on solid particles and enhance the dispersive ability of CL on solid suspensions by adding longer straight-chain alcohols. [Copyright &y& Elsevier]

This article studies the physicochemical characteristic of two anionic dispersants—sulphonated acetone-formaldehyde resin (SAF) and naphthalene sulfonate-formaldehyde condensate (FDN)—at coal-water interface, including contact angle, adsorption amount, thickness of adsorbed film, and zeta potential, using four different ranks of coals. The results show that SAF has better wetting property than FDN on coal surface. The adsorption amount of SAF in coal-water interface is greater than that of FDN, and that the thickness of adsorbed films of SAF and FDN on Datong coal measured by x-ray photoelectron spectroscopy (XPS) are respectively 6.38 nm and 2.11 nm. Moreover, the measurements of zeta potentials in coal-water interface show that SAF has greater capacity in charging coal surface with electronegativity. Based on the investigation, the adsorption models of SAF and FDN on different rank of coals are presented. [ABSTRACT FROM AUTHOR]

Five purified calcium lignosulfonate (CL) fractions with different molecular weights were obtained by fractionation using ultrafiltration and dialysis. The influence of molecular weight on their physicochemical properties was investigated by determining the properties of five fractions. TEM and ESEM imaging indicated that CL has a globular structure to form locally regular colloidal assemblies with the diameter of approximately 200 ∼ 300 nm. Fraction3 (Mw is 7621) with the molecular weight of 5,000-l0,000 has more sulfonic and carboxyl group, so the highest zeta potential (-36 mV) can be charged on the TiO2 particles. With the increase of molecular weight, the hydrophobicity and surface activity of CL in aqueous solution increase, so Fraction5 (Mw is 21646) which molecular weight is more than 30000 has the biggest adsorption amount. The adsorption characteristic of CL on solid-water interface have great impact on the dispersive properties of TiO2 particle in aqueous solution and the higher adsorption capacity is helpful to improve the dispersive ability of CL. On the other hand, the surface charge of TiO2 particle absorbing CL is another important factor to the dispersive ability of CL. Furthermore, when the CL concentration in TiO2 suspension is less than 4 mg/mL, Fraction3 has the best dispersive ability because the electrostatic repulsion effect is controlling factor. The dispersive ability of CL increases with the increase of molecular weight when the CL concentration in TiO2 suspension is more than 4 mg/mL, so Fraction5 has the best dispersive ability owing to the steric hindrance effect. [ABSTRACT FROM AUTHOR]

Abstract: In order to use lignosulfonates (a by-product of pulp and paper processes) as an effective dispersant of coal water slurry five purified sodium lignosulfonate (SL) samples with different molecular weights were prepared by fractionation using ultrafiltration and dialysis. The effect of SL on the apparent viscosity of coal water slurry (CWS) was investigated. The adsorption behavior of the SL on the coal water interface has much greater effect on the viscosity of coal water slurry. The higher adsorption amount and compact adsorption film of SL on the coal surface help reduce the viscosity of CWS, and the zeta potential is also an important factor, which is influenced by the sulfonic and carboxyl group contents of the lignosulfonate molecule. Furthermore, the SL with its molecular weight ranging from 10,000 to 30,000 has both a higher adsorbed amount and zeta potential on the coal surface and the best effect on reducing the viscosity of the coal water slurry. [Copyright &y& Elsevier]

Abstract: A new type of water-soluble polymer, sulphonated acetone–formaldehyde resin (SAF), was developed as dispersant for the preparation of highly-loaded coal water slurry (CWS). In this study, in order to evaluate the practical use in industry, the SAF and a naphthalene sulfonate formaldehyde condensate are used to prepare CWS using four Chinese coals with different coalification degrees. The evaluation of the properties of CWS shows that SAF has better ability in reducing CWS viscosity at lower dosage than naphthalene sulfonate formaldehyde condensate, and that the CWS prepared from SAF has excellent stability within 48h and exhibits shear-thinning apparent viscosity/shear rate behavior at lower dosage. Based on the results, the SAF is an effective and promising dispersant for highly-loaded CWS. [Copyright &y& Elsevier]

Abstract: Environmental concerns have stimulated interest in utilizing plant-derived materials in various industrial fields. The main objective of the present study was to synthesize a new type of high-performance lignin series dispersant of coal–water slurry (CWS) from wheat straw alkali lignin (WAL), and determine the affecting factors in the reaction and the application performance for CWS preparation. The experimental results showed that the inherent viscosity and the sulfonic group content of the modified wheat straw alkali lignin (MSL) are the key factors affecting its dispersing effect for CWS. In the reaction, the reactant mass concentration and the sulfonating agent amount were changed to obtain the MSL with different inherent viscosities and sulfonic group contents, and the MSL with intermediate inherent viscosity (6.0 ml/g) and higher sulfonic group content (1.80 mmol g−1) was found to have excellent dispersing effect for CWS. The MSL obtained from optimized process was used as dispersant for CWS preparation, the studies of the properties of CWS showed that MSL has similar dispersing effect with naphtalenesulfonate–formaldehyde condensate, and far better dispersing effect than lignosulphonate. Recently this kind of new dispersant has been applied in several power plants in China. [Copyright &y& Elsevier]

Abstract: The water-soluble sulphonated acetone–formaldehyde (SAF) resin was synthesized by a reaction among acetone, formaldehyde and sodium sulfite. It is applied as a dispersant of a coal–water slurry, and the influence of the synthesis processing parameter on the inherent viscosity and the dispersing ability of the SAF resin was investigated. The composite SAF resin was regarded as an aliphatic high polymer containing block hydrophilic and hydrophobic structures in the molecular chain, which show little surface activity. The dispersing ability of the SAF resin dispersant in a coal–water slurry was evaluated, and the effect of the SAF mass concentration on the rheological property of the slurries was determined. The results showed that the SAF resin has potential to be developed as a new type of dispersant of a coal–water slurry. [Copyright &y& Elsevier]

Four purified sodium lignosulfonate (SL) samples with different molecular weights were prepared by fractionation using ultrafiltration. The effect of the molecular weights of SL on the apparent viscosity of coal‐water slurry (CWS) was investigated by studying the adsorption amounts and the zeta potentials in the coal‐water interface. The results show that the adsorption behavior of the dispersants in the coal‐water interface is the key factor to affect the dispersing effect, that the higher adsorption amount and compact adsorption film help reduce the viscosity reduction of CWS, and that the zeta potential is also an important factor influenced by the sulfonic group and carboxy contents of the lignosulfonate molecule. Furthermore, SL with a molecular weight ranging from 10000 to 50000 has both a higher adsorbed amount and zeta potential on the coal surface and the best effect on reducing the viscosity of the coal‐water slurry. [ABSTRACT FROM AUTHOR]

[Display omitted] • Dual carbon skeleton structure is constructed in situ, which improves the conductivity and cycle stability of the cathodes. • Nitrogen introduced enhance the adsorption of sodium ion, which promotes the intercalation/deintercalation of sodium ions in NVPFO cathodes. • This delicately designed dual carbon coating layer enhances the rate capabilities and the cycling stabilities of NVPFO cathodes. The cathode material of sodium-ion batteries, Na 3 V 2 (PO 4) 2 F 3-y O z (NVPFO), with its NASICON structure, exhibits greater stability and a higher average discharge potential compared with sodium vanadium phosphate (NVP). Owing to its low intrinsic conductivity, the electrochemical performance and cycle stability of NVPFO is unsatisfactory. In this study, a sol–gel method was implemented, by using melamine-cyanic acid-lignin supermolecule precursor (MCL) and citric acid (CA) as carbon sources in the preparation of NVPFO process, in which a double-carbon coating structure was established. The distinctiveness of this dual carbon source can result in the tremendous pyrolysis gases, created by the MCL during the calcination process, exploding the outer CA layer, through which sodium vanadium oxyfluorophosphate (NVPFO/MCLC@C) was produced with a dual carbon coating containing an outer coral-like carbon layer and an interior nitrogen-doped carbon layer. Nitrogen doping enables MCLC to adsorb Na+ with a pseudocapacitive behavior. The specific capacity of the NVPFO is 117.3 mAh/g at a current density of 0.1 A/g, and 52.8 mAh/g at a current density of 10.0 A/g. The capacity retention rate was 80.0 % after 1100 cycles at a current density of 1.0 A/g. In this work, a dual carbon coating strategy has been proposed to enhance the rate performance and long cycle stability of NVPFO cathode materials, which could be a potential approach for the cathode coating engineering of sodium-ion batteries. [ABSTRACT FROM AUTHOR]

Gel‐based adhesives show promising prospects in epidermal bioelectronics because of their potential applications in physiological signal collection and electrical stimulation. An ideal epidermal adhesive should exhibit robust adhesion for lamination and poor adhesion for easy peeling, in addition to strain‐insensitivity in electrical properties for motion‐artifact‐free physiological signal collection. Here, lignosulfonate‐derived organohydrogel adhesives with anisotropic and tunable adhesion, together with unprecedented strain‐insensitivity are synthesized. The organohydrogel exhibits a high interfacial toughness of 728 J m−2 on fresh porcine skin, while the adhesion can be screened by covering a denatured silk fibroin. An anisotropic adhesive with an adhesion heterogeneity is designed, showing a 14.2‐fold difference in adhesion strength along two different directions for on‐demand attachment and removal. The adhesive can transform into a highly porous structure, which has only a 3% resistance increase at 100% strain. The strain‐insensitivity of the adhesive lies in the strong interaction of ions and the 3D porous structure, which enables motion‐artifact‐free and high‐quality electrophysiological signal collection within the strain range of the human skin. The lignosulfonate‐derived on‐demand organohydrogel adhesive is expected to be used in epidermal bioelectronics, human‐machine interaction, metaverse, and beyond. [ABSTRACT FROM AUTHOR]

Synopsis: This study presents a thiocyanogen-modulated alkali activation strategy for preparing N, S co-doped lignin hierarchical porous carbon (NSLHPC). Thiocyanate acts as a surface modulation mediator to introduce nitrogen and sulfur heteroatoms via oxygen replacement reaction. NSLHPC exhibits excellent electrochemical performance and long cycling lifespan in both symmetric supercapacitors and zinc-ion hybrid capacitors. [Display omitted] • Thiocyanogen-modulated alkali activation strategy for the preparation of NSLHPC. • Oxygen replacement reaction between KSCN and lignin carbon for N, S co-doping. • NSLHPC exhibits an impressive SSA of 2705.3 m2/g and a pore volume of 3.27 cm3/g. • NSLHPC presents remarkable electrochemical performance in aqueous supercapacitors. • DFT calculations reveal that N, S co-doping reduces the adsorption energy barrier of Zn2+. Constructing heteroatom-doped porous carbons with distinct charge storage properties is significant for high-energy–density supercapacitors, yet it remains a formidable challenge. Herein, we employed a thiocyanogen-modulated alkali activation strategy to synthesize N and S co-doped lignin hierarchical porous carbon (NSLHPC). In this process, thiocyanogen serves as a surface modulation mediator to substitute oxygen with nitrogen and sulfur species, while the combination of KOH activation and MgO template generates numerous nanopores within the carbon structure. The three-dimensional interconnected nanosheet architecture facilitates rapid ion transfer and enhances accessibility to active sites. Density functional theory (DFT) calculations demonstrate that introducing N and S heteroatoms through oxygen substitution reduces the adsorption energy barrier of Zn2+. Consequently, the optimized NSLHPC exhibits a remarkable specific capacitance of 438F/g at 0.5 A/g in 6 M KOH, delivering an energy density of 10.4 Wh/kg in the symmetric supercapacitor and an impressive energy density of 104.9 Wh/kg in the zinc-ion hybrid capacitor. The NSLHPC cathode also shows an excellent lifespan with capacitance retention of 99.0 % and Columbic efficiency of 100 % over 10,000 cycles. This study presents innovative strategies for engineering high-performance porous carbon electrode materials by emphasizing pore structure modulation and N, S co-doping as crucial approaches. [ABSTRACT FROM AUTHOR]

Derived from lignocellulosic biomass, sustainable hard carbon has emerged as a promising low-cost anode material for sodium-ion batteries (SIBs). However, the intricate formation process of the hard carbon microstructure remains unclear. This study investigates the structural differences and pyrolysis behaviors of pine lignin and its graded variants obtained through a lignin molecular sieving engineering strategy. Moreover, it delves into the relationship between the microstructure of lignin-derived hard carbon and its sodium-ion storage characteristics. Pristine pine lignin, along with ethanol-isolated lignin, acetone-isolated lignin, and residual lignin, serves as a precursor for synthesizing hard carbon materials. Quantitative analysis via31P NMR spectroscopy reveals the highest content of polar functional groups in ethanol-isolated lignin. Interestingly, hard carbon derived from ethanol-isolated lignin exhibits the smallest closed pore volume, leading to the lowest plateau capacity of sodium-ion storage. Conversely, hard carbon derived from acetone-dissolved lignin displays the highest plateau capacity owing to its largest closed pore volume formed in the carbonization process. The origin of open and closed pore structures of hard carbons is thoroughly analyzed. [ABSTRACT FROM AUTHOR]

The development of high‐performance carbon anode for sodium‐ion batteries is limited by the sluggish kinetics and structural instability. Expanded interlayer spacing, nitrogen doping, and mesoporous structure engineering have emerged as promising strategies to overcome these challenges. Simultaneously achieving graphene nanodomains construction, high‐efficient nitrogen doping, and rational mesoporous structure engineering is challenging. Herein, a strategy of pyrolyzing SiO2@ lignin amine urea‐formaldehyde resin is proposed for deliberate manipulation of graphene nanodomains, edge‐nitrogen doping, and specific mesoporous distribution in amorphous lignin‐derived carbon based on polycondensation‐template. The obtained carbon material exhibits a nitrogen‐doping level of 6.03 at% with a high edge‐nitrogen ratio of up to 84.4%, high‐ connectivity mesoporous structure, and graphene nanodomains with expanded interlayer spacing. The optimized carbon material delivers a reversible capacity of 234 mAh g−1 at 100 mA g−1, superior rate capability of 129 mAh g−1 at 2 A g−1, and excellent cycling stability. In addition, the surface‐dominated sodium‐ion storage mechanism is identified by in situ electrochemical impedance spectroscopy. Furthermore, the optimized carbon can function as an outstanding anode for full cells. This work proposes a new avenue for designing high‐performance carbon for low‐cost and high‐rate sodium‐ion batteries. [ABSTRACT FROM AUTHOR]

Antibiotic resistance and the rise of untreatable bacterial infections pose severe threats to human health. Silver nanoparticles (AgNPs) have emerged as a promising antibacterial solution due to their broad-spectrum effectiveness. However, their relatively high cytotoxicity has limited their widespread application. In this study, ferulic acid (FA) was used as a reducing agent, while silver oxide served as a silver precursor to rapidly prepare FA-derived lignin (FAL) coated AgNPs (AgNPs@FAL) with a size ranging from 34.8 to 77.1 nm. Density functional theory (DFT) calculations indicated that the coating of FAL endowed AgNPs@FAL with high stability, preventing the oxidation of AgNPs prior to antibacterial applications. Cell experiments further indicated that AgNPs@FAL exhibited lower cell toxicity (∼80 % viability of normal kidney cells cultured at 25 μg/mL AgNPs@FAL) compared to fully exposed commercially available citrate-modified AgNPs (AgNPs@CA). Antibacterial experiments revealed that the minimum inhibitory concentrations (MIC) of AgNPs@FAL against E. coli and S. aureus were 12.5 μg/mL and 25 μg/mL, respectively, surpassing the antibacterial effect of AgNPs@CA, as well as ampicillin and penicillin. Additionally, AgNPs@FAL was capable of disrupting E. coli and S. aureus biofilm formation. This novel AgNPs@FAL formulation presents a promising antibacterial solution, addressing limitations observed in conventional drugs. • A novel, rapid and straightforward method to produce AgNPs@FAL was developed. • DFT calculation revealed reduction of Ag 2 O by FA and AgNPs shielded by FAL. • AgNPs@FAL has a low cytotoxicity, high stability and antibacterial properties. [ABSTRACT FROM AUTHOR]

• Utilizing aminated lignin as a precursor for N-doping modification of Ni. • The charges redistribution between Ni and NC carriers endows superior performance. • DFT unveils the energy barrier of ethanol coupling reaction on the Ni-N-C site. • N-doped engineering Ni for synthesis of higher alcohols from bioethanol. The selective conversion of biomass-derived ethanol into higher alcohols is a desirable but challenging process for the efficient production of value-added chemicals from alternative carbon sources. However, the current catalysts used in ethanol coupling exhibit low conversion rates and yields towards the formation of higher alcohols, necessitating significant improvements in their efficiency for practical applications. In this work, a lignin-derived N-doped carbon- supported Ni catalyst for ethanol coupling was designed and synthesized. The Ni@NC catalyst, synthesized using diethylenetriamine as the nitrogen source with a mass ratio of nitrogen source to lignin of 2:1 and a molar ratio of metal to lignin of 20:1, demonstrated excellent performance, with an ethanol conversion rate of 81.1% and a yield of C 4+ alcohols reaching 35.3%. Experimental results and density functional theory (DFT) calculations suggest that nitrogen-doped lignin, in appropriate quantities, along with the metal active component, forms a Ni-N-C structure that controls charge redistribution between the support and the Ni catalyst. This structure hinders the interaction of reaction intermediates and inhibits the production of by-products in the decomposition reaction, resulting in a higher yield of C 4+ alcohols. This study presents a more cost-effective and efficient approach for developing ethanol-coupling catalysts and holds promise for expanding the utility of lignin-derived catalysts. [ABSTRACT FROM AUTHOR]

Remote controllable photothermal elastomers can realize precise non-contact control through the photothermal conversion effect, highlighting a new routine for light energy utilization and a promising direction for smart materials. Developing biomass-based photothermal materials is an important strategy to promote the realization of carbon neutrality and improve the environmental friendliness of photothermal elastomers. In this work, green biomass lignin was demonstrated as an efficient photothermal agent for preparing smart elastomer composites with versatile functionalities, owing to the fact that the conjugated structures in lignin could effectively promote electron transitions from low-energy orbitals to high-energy states and the visible and near-infrared (NIR) light energy absorbed by lignin was mainly released in the form of non-radiative transition. A high photothermal conversion efficiency of 53.7% was obtained for low molecular weight alkaline lignin with the photothermal temperature exceeding 280 °C under NIR irradiation (808 nm, 1.25 W cm−2). Under the stimulation of NIR light, the alkaline lignin/polyethylene elastomer (POE) composite exhibited a good light-triggered shape memory effect, excellent light-controlled self-repairing properties with the self-repairing efficiency as high as 98.2% (808 nm, 1.25 W cm−2, 20 min), and strong photothermal bactericidal activity. Meanwhile, a series of functional applications were demonstrated based on the excellent photothermal effect of lignin, such as photothermal engines, photothermal generators and photothermal switches, which endowed lignin-based elastomer composites with considerable application prospects in smart materials for precise remote driving of robots, machines, sensors, sterilization and self-repairing equipment, etc., promoting the sustainable development and high-value utilization of biomass lignin. [ABSTRACT FROM AUTHOR]

Lignocellulose flow fuel cells are promising technologies for large scale generation of renewable electricity at low temperature. However, most of them have low electron transfer kinetics and require pre-reaction and redox mediators in anolytes for a liquid-phase catalytic reaction, which leads to low power density, energy consumption and resource waste. Herein, we develop a new low temperature and high-power density lignin flow fuel cell (LFFC) catalyzed by CoMn-LDH electrocatalysts with superhydrophilic intercalation on the anode to efficiently degrade lignin and transfer electrons rapidly. The experiments and DFT calculations show that CoMn-LDH exhibits high adsorption capacity for lignin due to its superhydrophilic intercalation, and has good electrical conductivity due to the greater overlap of antibonding orbitals and high continuity at the Fermi level. Moreover, the abundant oxygen defects of CoMn-LDH can depolymerize lignin effectively. Thus, the prepared CoMn-LDH electrocatalyst enables fast charge transfer and high catalytic efficiency. The power density of the designed LFFC reached 269.3 mW cm−2, and the generated electrical energy is 294.7 mW h based on 1.0 g of lignin, which are obviously higher than those of the reported LFFCs. Furthermore, it can work stably for more than 9 h at 0.3 V and 413.5 mA cm−2, and successfully power a 1.5 V LED pattern with only a 1 cm2 active membrane. It presents a promising approach for developing high-power density LFFCs towards a sustainable society. [ABSTRACT FROM AUTHOR]

The exploitation of bio‐based materials derived from renewable resources represents a pivotal strategic approach in addressing environmental pollution and alleviating the scarcity of fossil resources. 2,5‐Furandicarboxylic acid (FDCA) is the most potential substitute for terephthalic acid. Lignin is the most abundant aromatic biomass resource. However, the preparation of high‐performance lignin/FDCA‐based bio‐polyesters remains a formidable challenge. Herein, a multifunctional lignin‐modified polyester elastomer (LFPEe) is designed using FDCA‐based polyester oligomer (PPeF) and lignin (AOH) as building blocks. The LFPEe exhibits superior mechanical properties with the optimum tensile strength, fracture strain, and elastic recovery ratio up to 58.9 MPa, 610% and 88.9%, respectively, attributing to the formation of dual cross‐linking network with nanophase separation structure. Furthermore, leveraging the inherent characteristics of lignin, the LFPEe demonstrates excellent light‐controlled shape memory and excellent UV shielding performance. This innovative work not only breaks the performance dependence of FDCA‐based polyester on high molecular weight but also highlights a novel paradigm for value‐added utilization of lignin in sustainable bio‐polyesters. [ABSTRACT FROM AUTHOR]

This study employs a combined computational and experimental approach to elucidate the mechanisms governing the interaction between lignin and urea, impacting lignin dissolution and subsequent aggregation behavior. Molecular dynamics (MD) simulations reveal how the urea concentration and temperature influence lignin conformation and interactions. Higher urea concentrations and temperatures promote lignin dispersion by disrupting intramolecular interactions and enhancing solvation. Density functional theory (DFT) calculations quantitatively assess the interaction energy between lignin and urea, supporting the findings from MD simulations. Anti-solvent precipitation demonstrates that increasing the urea concentration hinders the self-assembly of lignin nanoclusters. The findings provide valuable insights for optimizing lignin biorefinery processes by tailoring the urea concentration and temperature for efficient extraction and dispersion. Understanding the influence of urea on lignin behavior opens up avenues for designing novel lignin-based materials with tailored properties. This study highlights the potential for the synergetic application of MD simulations and DFT calculations to unravel complex material interactions at the atomic level. [ABSTRACT FROM AUTHOR]

In this work, the coordination-based energy sacrificial bonds have been constructed in the interphase between lignin and polyolefin elastomer to prepare high performance lignin-based thermoplastic elastomers (TPEs). The strength and toughness of lignin-based TPEs can be adjusted by choosing different nitrogen heterocyclic compounds as reactive assistants and Fe3+ or Zn2+ as metal coordination centers. It was demonstrated that 3-Amino-1,2,4-triazole with three nitrogen atoms in the heterocyclic ring and one nitrogen branch chain could form the most efficient coordination bond system and generate the best mechanical performance. The system with ferric iron as coordination center exhibited better enhancement effect than divalent zinc. By adjusting the nitrogen-containing reactive additives or metal salts as coordination centers, the mechanical performance of the lignin-based TPE can be regulated, which provides a method for making green bio-composites with good strength and toughness, and also promotes the high value utilization of lignin in polymer materials. [ABSTRACT FROM AUTHOR]

The inherent challenges posed by lignin, such as its high heterogeneity, complex structure and dark color, have impeded its widespread high-value utilization. In the present study, a green cosolvent system comprising ethanol (EtOH) and dimethyl carbonate (DMC) was employed for the fractional separation of alkali lignin. Through careful manipulation of the solvent ratio, interactions between the solvents and lignin were effectively regulated, leading to the reduction of lignin heterogeneity and the isolation of lignin fractions with distinct properties. Notably, a high yield of up to 35.65% of lignin with desirable characteristics, including a light color, low molecular weight, and high hydroxyl groups content, was achieved. Furthermore, this specific lignin fraction exhibited enhanced UV absorption and antioxidative properties, rendering it highly suitable for potential applications in sun protection products. When incorporated as micro-nano particles, it exhibited great compatibility with hand creams and elevated their sun protection factor (SPF). This innovative approach not only presents a green and straightforward lignin fractionation process but also highlights the untapped potential of lignin in the realm of sun protection applications. [Display omitted] • Lignin was fractionated by sequentially dissolving in a green ethanol/DMC cosolvent. • Lignin with light color showed enhanced UV absorption and antioxidant activity. • Light-color lignin nanoparticles were prepared and improved the SPF of hand cream. [ABSTRACT FROM AUTHOR]

Extraction of native-like lignin from lignocellulose is crucial for maximizing the value of all three major components of biomass. In this study, molecular dynamics was employed to reveal the essence of lignin condensation during the pretreatment of biomass with a promising acidic hydrotropic solution (AHS) at the molecular level. Diols were discovered to effectively suppress the excessive acidity of p-toluenesulfonic acid (pTsOH) in AHS while maintaining its solubilizing effect below a minimal hydrotropic concentration (MHC). The experimental results confirmed that the combined use of 1,4-butanediol and pTsOH can extract native-like lignin under mild conditions. The retention of lignin's β-O-4 linkages can exceed 90%, and the lignin extraction rate was over 80%. The obtained lignin can enhance the efficacy of chemical sunscreens, doubling the sun protection factor (SPF). Simultaneously, the residual cellulose was readily hydrolyzed into glucose by cellulase. This strategy demonstrates excellent adaptability to various biomass sources, including herbaceous species, hardwoods, and highly recalcitrant softwoods. The work lays the theoretical foundation for the precise control of biomass component separation using AHS, contributing to the development of mild and efficient component separation technologies in the future. [ABSTRACT FROM AUTHOR]