In order to manufacture environmentally friendly particle boards and enhance local resources, the lignins of Sorghum bicolor and Andropogon gayanus characterized using RMN 13C and MALDI TOF have the same structures. T...In order to manufacture environmentally friendly particle boards and enhance local resources, the lignins of Sorghum bicolor and Andropogon gayanus characterized using RMN 13C and MALDI TOF have the same structures. They contents Guaiacyl (G), Syringyl (S), p-hydroxyphenylpropane (H) and functional groups of phenols, flavonoids and secondary alcohols. The total phenol content determinated using Folin-Ciocalteu reagent is respectively 20.97 and 15.42 mg eqgallic acid/g of extract. The power of their adhesives is different. The Internal Bond (IB) of particleboards manufactured with these adhesives are respectively 0.37 MPa and 0.41 MPa. These lignins can be used as antioxydants.展开更多
Lignins were isolated and purified from alkali treated prehydrolysate of corn stover. The paper presents the structural features of lignins in a series purification processes. Fourier transform infrared spectroscopy, ...Lignins were isolated and purified from alkali treated prehydrolysate of corn stover. The paper presents the structural features of lignins in a series purification processes. Fourier transform infrared spectroscopy, ultraviolet-vis spectroscopy and proton nuclear magnetic resonance spectroscopy were used to analyze the chemical structure. Thermogravimetric analysis was applied to follow the thermal degradation, and wet chemical method was used to determine the sugar content. The results showed that the crude lignin from the prehydrolysate of corn stover was a heterogeneous material of syringyl, guaiacyl and p-hydroxyphenyl units, containing associated polysaccharides, lipids, and melted salts. Some of the crude lignin was chemically linked to hemicelluloses （mainly xylan）. The lipids in crude lignin were probably composed of saturated and/or unsaturated long carbon chains, fatty acids, tdterpenols, waxes, and derivatives of aromatic. The sugar content of purified lignin was less than 2.11%, mainly composed of guaiacyl units. DTGmax of purified lignin was 359 ℃. The majority of the hydroxyl groups were phenolic hydroxyl groups. The main type of linkages in purified lignin was β-O-4. Other types of linkages included β-5, β-β and α-O-4.展开更多
Brassica crops,which are of worldwide importance,provide various oil,vegetable and ornamental products,as well as feedstocks for animal husbandry and biofuel industry.Cinnamoyl-Co A reductase(CCR)is the entry point to...Brassica crops,which are of worldwide importance,provide various oil,vegetable and ornamental products,as well as feedstocks for animal husbandry and biofuel industry.Cinnamoyl-Co A reductase(CCR)is the entry point to the lignin pathway and a crucial locus in manipulation of associated traits,but CCRassociated metabolism and traits in Brassica crops have remained largely unstudied except in Arabidopsis thaliana.We report the identification of 16 CCR genes from Brassica napus and its parental species B.rapa and B.oleracea.The Bn CCR1 and Bn CCR2 subfamilies displayed divergent organ-specificity and participation in the yellow-seed trait.Their functions were dissected via overexpression of representative paralogs in B.napus.Bn CCR1 was expressed preferentially in G-and H-lignin biosynthesis and vascular development,while Bn CCR2 was expressed in S-lignin biosynthesis and interfascicular fiber development.Bn CCR1 showed stronger effects on lignification-related development,lodging resistance,phenylpropanoid flux control,and seed coat pigmentation,whereas Bn CCR2 showed a stronger effect on sinapate biosynthesis.Bn CCR1 upregulation delayed bolting and flowering time,while Bn CCR2 upregulation weakened the leaf vascular system in consequence of suppressed G-lignin accumulation.Bn CCR1 and Bn CCR2 were closely but almost oppositely linked with glucosinolate metabolism via inter-pathway crosstalk.We conclude that Bn CCR1 and Bn CCR2 subfamilies offer great but differing potential for manipulating traits associated with phenylpropanoids and glucosinolates.This study reveals the CCR1–CCR2 divergence in Brassicaceae and offers a resource for rapeseed breeding for lodging resistance,yellowseed traits,and glucosinolate traits.展开更多
In order to efficiently explore and use woody biomass,six lignin fractions were isolated from dewaxed Caragana sinica via successive extraction with organic solvents and alkaline solutions.The lignin structures were c...In order to efficiently explore and use woody biomass,six lignin fractions were isolated from dewaxed Caragana sinica via successive extraction with organic solvents and alkaline solutions.The lignin structures were characterized by Fourier transform infrared spectroscopy(FT-IR) and 1D and 2D Nuclear Magnetic Resonance(NMR).FT-IR spectra revealed that the "core" of the lignin structure did not significantly change during the treatment under the conditions given.The results of 1H and 13C NMR demonstrated that the lignin fraction L2,isolated with 70% ethanol containing 1% NaOH,was mainly composed of β-O-4 ether bonds together with G and S units and trace p-hydroxyphenyl unit.Based on the 2D HSQC NMR spectrum,the ethanol organosolv lignin fraction L1,extracted with 70% ethanol,presents a predominance of β-O-4′ aryl ether linkages(61% of total side chains),and a low abundance of condensed carbon-carbon linked structures(such as ββ′,β-1′,and β-5′) and a lower S/G ratio.Furthermore,a small percentage(ca.9%) of the linkage side chain was found to be acylated at the γ-carbon.展开更多
Pyrolytic lignin, the water-insoluble fraction in bio-oil, often shows a high content and has strong intermolecular interactions with other compounds in bio-oil. In order to obtain pure pyrolytic lignin and facilitate...Pyrolytic lignin, the water-insoluble fraction in bio-oil, often shows a high content and has strong intermolecular interactions with other compounds in bio-oil. In order to obtain pure pyrolytic lignin and facilitate the utilization of aqueous phase obtained from water extraction of bio-oil, methanol–water extraction method was employed to further separate the bio-oil water-insoluble phase in this paper. Different technologies, including Fourier transform infrared spectroscopy, gel permeation chromatography, and nuclear magnetic resonance, were adopted to characterize the structures of pyrolytic lignins with different activities obtained through this method. Both the heating value and the polymerization degree of high-molecular-weight pyrolytic lignin were higher than those of low-molecular-weight pyrolytic lignin. The molecular weight distribution of high-molecular-weight pyrolytic lignin was relatively wider, among which the contents of dimers to pentamers all accounted for 12% –18%,while the low-molecular-weight pyrolytic lignin mainly consisted of trimers(75.38%). The pyrolytic lignins had similar basic structures, both of which contained syringyl and guaiacyl units, whereas the low-molecular-weight pyrolytic lignin had more abundant syringyl units, reactive carbonyl groups and hydroxyl groups. Meanwhile,thermogravimetric study revealed that the final char residue yield of low-molecular-weight pyrolytic lignin was lower than that of high-molecular-weight pyrolytic lignin.展开更多
<span style="line-height:1.5;font-family:Verdana;">In the present work</span><span style="line-height:1.5;font-family:Verdana;">,</span><span "="" style=&q...<span style="line-height:1.5;font-family:Verdana;">In the present work</span><span style="line-height:1.5;font-family:Verdana;">,</span><span "="" style="line-height:1.5;"><span style="font-family:Verdana;"> lignin is isolated from three different agro-industrial waste, sweet sorghum, rice straw and sugarcane bagasse using </span><i><span style="font-family:Verdana;">in-situ</span></i><span style="font-family:Verdana;"> sodium hydroxide-sodium bisulfate methodology. Characterization was performed using fourier transform infrared analysis (FTIR), scan electron microscopy (SEM), thermo gravimetric analysis (TGA). The SEM micrographs showed sponge-like structure except for sugarcane bagasse lignin reveals rock-like structure. The FTIR indicates the presence of hydroxyl, carbonyl and methoxyl groups in the lignin structure. TGA thermograms were relatively same and sugarcane bagasse lignin was found the most thermally stable up to 201<span style="white-space:nowrap;">˚</span>C as compared to both of soda and kraft sugarcane bagasse lignin and its maximal temperature degradation rate DTG</span><sub><span style="font-family:Verdana;">max</span></sub><span style="font-family:Verdana;"> was found at 494<span style="white-space:nowrap;">˚</span>C while 450<span style="white-space:nowrap;">˚</span>C, 464<span style="white-space:nowrap;">˚</span>C in addition to thermal stabilities up to 173<span style="white-space:nowrap;">˚</span>C and 180<span style="white-space:nowrap;">˚</span>C for sweet sorghum and rice straw lignins respectively. All lignins exhibited low percentage of bio-char less than 10% remained unvalotilized at the end of the thermogravimetric analysis at 800<span style="white-space:nowrap;">˚</span>C in nitrogen atmosphere</span></span><span style="line-height:1.5;font-family:Verdana;">,</span><span style="line-height:1.5;font-family:Verdana;"> reveal</span><span style="line-height:1.5;font-family:Verdana;">ing</span><span "="" style="line-height:1.5;"><span style="font-family:Verdana;"> a high conversion yield into volatiles. Moreover, all lignin samples depicted higher cytotoxic potential towards lung cancer cell line (A549), IC</span><sub><span style="font-family:Verdana;">50</span></sub><span style="font-family:Verdana;">: 12</span></span><span "="" style="line-height:1.5;"> </span><span style="line-height:1.5;font-family:Verdana;">-</span><span "="" style="line-height:1.5;"> </span><span "="" style="line-height:1.5;"><span style="font-family:Verdana;">17 μg/ml. These findings suggest that the </span><i><span style="font-family:Verdana;">in-situ</span></i><span style="font-family:Verdana;"> separated lignins would be good candidates for pyrolysis, polymer composites preparations and seem to be promising natural anti-cancer agents despite its main utilization as </span></span><span style="line-height:1.5;font-family:Verdana;">the</span><span style="line-height:1.5;font-family:Verdana;"> caner drug delivery substrates.展开更多
The increasing scarcity of freshwater resources has driven the rapid emergence of solar-driven interfacial evaporators(SDIEs)as a sustainable approach to harvest fresh water by utilizing solar energy.Lignocellulosic b...The increasing scarcity of freshwater resources has driven the rapid emergence of solar-driven interfacial evaporators(SDIEs)as a sustainable approach to harvest fresh water by utilizing solar energy.Lignocellulosic biomass,featuring natural abundance,excellent renewability,unique natural structures,and superior biodegradability compared to the synthetic polymers,is highly attractive for constructing solar steam generators.This review aims to offer an innovative and in-depth insight into designing and optimizing highperformance integrated solar interfacial evaporators derived from renewable lignocellulosic biomass.First,the structural characteristics of lignocellulosic biomass are briefly introduced,serving as photothermal layer or supporting substrates in SDIEs.Secondly,the fabrication methods and processing technologies of lignocellulosic biomass-based evaporators are summarized from the perspective of photothermal layer and supporting substrates.Next,the most recent advances of regulation and optimization strategies are proposed to improve evaporation efficiency.Subsequently,this review summarizes the diverse functionalities of SDIEs,including desalination,power generation,wastewater treatment and antimicrobial,atmospheric water harvesting,and photocatalytic hydrogen production.Finally,the challenges in this field and outlook on the future development are discussed,which are anticipated to provide new opportunities for the advancement of lignocellulosic biomass-based SDIEs.展开更多
Lignin,the most abundant natural aromatic polymer globally,has garnered considerable interest due to its rich and diverse active functional groups and its antioxidant,antimicrobial,and adhesive properties.Recent resea...Lignin,the most abundant natural aromatic polymer globally,has garnered considerable interest due to its rich and diverse active functional groups and its antioxidant,antimicrobial,and adhesive properties.Recent research has significantly improved the performance of lignin-based hydrogels,suggesting their substantial potential in fields such as biomedicine,environmental science,and agriculture.This paper reviews the process of lignin extraction,systematically introduces synthesis strategies for preparing lignin-based hydrogels,and discusses the current state of research on these hydrogels in biomedical and environmental protection fields.It concludes by identifying the existing challenges in lignin hydrogel research and envisioning future prospects and development trends.展开更多
Plant-related organic compound(PROC)may interact with redox-active metals like iron while they are present in soil or aquatic environment,but their effects on the photoreduction of Fe(III)remain largely unexplored.Thi...Plant-related organic compound(PROC)may interact with redox-active metals like iron while they are present in soil or aquatic environment,but their effects on the photoreduction of Fe(III)remain largely unexplored.This study investigates the photochemical behavior of Fe(III)-PROC complexes using alkaline lignin(AL),betaine hydrochloride(BH),and phytic acid(PA)as representative proxies for PROC.The reductive agent AL demonstrated the ability to directly reduce Fe(III)to Fe(II).In contrast,BH,being unable to form strong complexes with Fe(III),was able to quench·OH,thereby resulting in a shift of the redox equilibrium towards Fe(II).PA exhibited a strong binding affinity for Fe(III),effectively inhibiting its photoreduction.Electron paramagnetic resonance(EPR)analysis,utilizing 5,5-dimethyl-1-pyrroline-N-oxide(DMPO)as a spin trap,revealed that the DMPO-OH signal detected in photolyzed Fe(III)-PROC solutions originated from various pathways.Specifically,uncomplexed Fe(III)in AL or BH solutions was shown to oxidize DMPO directly,leading to the formation of a false DMPO-OH adduct.The addition of ethanol to the photolyzed Fe(III)-AL and Fe(III)-BH systems resulted in the generation of the DMPO-CH(CH_(3))OH adduct,thereby confirming the presence of authentic·OH in these systems.The photolysis of the Fe(III)-PA complex may proceed via a photodissociation mechanism,where the resulting loosely bound Fe(III)can oxidize DMPO,followed by a nucleophilic attack from water.This research highlights the multifaceted roles of PROC in facilitating the redox cycling of iron within soil and aquatic ecosystems.展开更多
Lignin is a significant secondary metabolite produced through the phenylpropanoid pathway.As a vital component of the plant cell wall,lignin affects various fruit characteristics,including size,seed quantity,and firmn...Lignin is a significant secondary metabolite produced through the phenylpropanoid pathway.As a vital component of the plant cell wall,lignin affects various fruit characteristics,including size,seed quantity,and firmness.In this study,we conducted comprehensive identification and phylogenetic analysis of 265 Caffeic acid O-methyltransferase(COMT)genes across ten different plant species,including Vaccinium corymbosum and four other Vaccinium species.The results reveal that VcCOMT38 is a promising structural gene for the biosynthesis of lignin in blueberry.An in vitro enzymatic assay of VcCOMT38 demonstrated that it is a special enzyme in the lignin biosynthesis pathway and prefers to use caffeic acid as a substrate over 5-hydroxyferulic acid.Transient overexpression and silencing of VcCOMT38 in Vaccinium corymbosum‘Northland’fruits demonstrated that VcCOMT38 participates in lignin biosynthesis and contributes to both an increased number of immature seeds and enhanced fruit firmness.The heterologous overexpression of VcCOMT38 in Nicotiana benthamiana revealed that this gene could increase the lignin content and the syringyl/guaiacyl(S/G)ratio,which determines the maximum monomer yield during lignin depolymerization.These results highlight VcCOMT38 as a crucial gene in lignin biosynthesis and its potential for improving lignin production in industry through genetically modified woody plants.展开更多
Lodging is a major constraint limiting oil flax production efficiency in northern China.Crop lodging susceptibility is closely related to stem lignin content,and the regulatory mechanisms by which nitrogen and potassi...Lodging is a major constraint limiting oil flax production efficiency in northern China.Crop lodging susceptibility is closely related to stem lignin content,and the regulatory mechanisms by which nitrogen and potassium fertilization interactively influence lignin biosynthesis in oil flax stems require further investigation.Therefore,this study aimed to enhance lodging resistance and increase grain yield in oil flax.We examined the interactive effects of different nitrogen (75,150,and 225 kg N ha^(–1)) and potassium (60 and 90 kg K_(2)O ha^(–1)) fertilizer rates on lignin metabolism,lodging resistance,and grain yield during the 2022 and 2023 growing seasons.Results indicated that nitrogen and potassium fertilizer levels and their interactions promoted lignin accumulation,improved lodging resistance,and increased grain yield.Compared to the control (CK),the75–150 kg N ha^(–1) combined with 60 kg K_(2)O ha^(–1) treatments significantly enhanced the activities of key lignin-synthesizing enzymes (tyrosine ammonia-lyase (TAL),phenylalanine ammonia-lyase (PAL),cinnamyl alcohol dehydrogenase (CAD),and peroxidase (POD)) and upregulated the expression of 4CL1 and F5H3 genes,leading to a 29.63–43.30%increase in lignin content,improved stem bending strength and lodging resistance index,and a 23.27–32.34%increase in grain yield.Correlation analysis revealed that nitrogen and potassium fertilizers positively regulated enzyme activities and gene expression related to lignin biosynthesis,thereby facilitating lignin accumulation and enhancing stem mechanical strength and lodging resistance.Positive correlations were observed among lignin-related enzyme activities,gene expression,lodging resistance traits,and grain yield.In summary,the application of 75–150 kg N ha^(–1) in conjunction with 60 kg K_(2)O ha^(–1)promoted lignin biosynthesis and accumulation,enhanced lodging resistance,and increased grain yield in oil flax grown in the dryland farming region of central Gansu,China.Furthermore,this treatment provides a technical basis for cultivating stress-tolerant and high-yield oil flax in arid regions.展开更多
With the rapid development of flexible wearable electronics,the demand for stretchable energy storage devices has surged.In this work,a novel gradient-layered architecture was design based on single-pore hollow lignin...With the rapid development of flexible wearable electronics,the demand for stretchable energy storage devices has surged.In this work,a novel gradient-layered architecture was design based on single-pore hollow lignin nanospheres(HLNPs)-intercalated two-dimensional transition metal carbide(Ti_(3)C_(2)T_(x) MXene)for fabricating highly stretchable and durable supercapacitors.By depositing and inserting HLNPs in the MXene layers with a bottom-up decreasing gradient,a multilayered porous MXene structure with smooth ion channels was constructed by reducing the overstacking of MXene lamella.Moreover,the micro-chamber architecture of thin-walled lignin nanospheres effectively extended the contact area between lignin and MXene to improve ion and electron accessibility,thus better utilizing the pseudocapacitive property of lignin.All these strategies effectively enhanced the capacitive performance of the electrodes.In addition,HLNPs,which acted as a protective phase for MXene layer,enhanced mechanical properties of the wrinkled stretchable electrodes by releasing stress through slip and deformation during the stretch-release cycling and greatly improved the structural integrity and capacitive stability of the electrodes.Flexible electrodes and symmetric flexible all-solid-state supercapacitors capable of enduring 600%uniaxial tensile strain were developed with high specific capacitances of 1273 mF cm^(−2)(241 F g^(−1))and 514 mF cm^(−2)(95 F g^(−1)),respectively.Moreover,their capacitances were well preserved after 1000 times of 600%stretch-release cycling.This study showcased new possibilities of incorporating biobased lignin nanospheres in energy storage devices to fabricate stretchable devices leveraging synergies among various two-dimensional nanomaterials.展开更多
This review is composed of three main parts each of which is written by well-known top specialists that have been,in a way or other,also the main participants of the majority of the developments reported.Thus,after a ...This review is composed of three main parts each of which is written by well-known top specialists that have been,in a way or other,also the main participants of the majority of the developments reported.Thus,after a general part covering the grand lines and more in-depth views of more recent tannin,lignin,carbohydrate and soy bioadhesives,somemix of the other bio raw materials with soy protein and soy flour and some other differently sourced bioadhesives for wood,this review presents a more in-depth part on starch-based wood adhesives and a more indepth part covering plant protein-based adhesives.It must be kept in mind that the review is focused on completely or almost completely biosourced adhesives,the fashionable adhesives derived from mixes of biosourced materials with synthetic resins having been intentionally excluded.This choice was made as the latter constitute only an intermediate interval,possibly temporary if even for a somewhat long times,towards a final full bioeconomy of scale in this field.This review also focuses on more recent results,mainly obtained in the last 10–20 years,thus on adhesive formulations really innovative and sometimes even non-traditional.In all these fields there is still a lot of possibility of innovation for relevant formulation as this field is still in rapid growth.展开更多
Electrochemical conversion of lignin for the production of high-value heterocyclic aromatic compounds has great potential.We demonstrate the targeted synthesis and cation modulation of NiCo_(2)O_(4)spinel nanoboxes,sy...Electrochemical conversion of lignin for the production of high-value heterocyclic aromatic compounds has great potential.We demonstrate the targeted synthesis and cation modulation of NiCo_(2)O_(4)spinel nanoboxes,synthesized via cation exchange and calcination oxidation.These catalysts exhibit excellent efficacy in the electrocatalytic conversion of lignin model compounds,specifically 2-phenoxy-1-phenylethanol,into nitrogen-containing aromatics,achieving high conversion rates and selectivities.These catalysts were synthesized via a cation exchange and calcination oxidation process,using Prussian blue nanocubes as precursors.The porous architecture and polymetallic composition of the NiCo_(2)O_(4)spinel demonstrated superior performance in electrocatalytic oxidative coupling,achieving a 99.2 wt%conversion rate of the 2-phenoxy-1-phenylethanol with selectivities of 37.5 wt%for quinoline derivatives and 31.5 wt%for phenol.Key innovations include the development of a sustainable one-pot synthesis method for quinoline derivatives,the elucidation of a multistage reaction pathway involving CAO bond cleavage,hydroxyaldol condensation,and CAN bond formation,and a deeper mechanistic understanding derived from DFT simulations.This work establishes a new strategy for lignin valorization,offering a sustainable route to produce high-value nitrogen-containing aromatics from renewable biomass under mild conditions,without the need for additional reagents.展开更多
Ni-based catalysts are widely applied in the hydrodeoxygenation of lignin derivatives via C-O cleavage for the production of cycloalkanes.However,they often have difficulty in achieving high activity under mild condit...Ni-based catalysts are widely applied in the hydrodeoxygenation of lignin derivatives via C-O cleavage for the production of cycloalkanes.However,they often have difficulty in achieving high activity under mild conditions and exhibit relatively poor stability,and rare studies focus on the cleavage of the stubborn interunit C-C linkages.To address this issue,we developed a Ni@AlPO_(4)/Al_(2)O_(3)catalyst in which the surface of Ni nanoparticles was decorated by AlPO_(4)species,demonstrating excellent catalytic activity and stability in the C-C and C-O cleavages.In the hydrodeoxygenation of guaiacol,this catalyst afforded99.1%conversion and 92.9%yield of cyclohexane under 1 MPa H_(2)at 230℃ for 2 h.More important,this catalyst maintained unchanged performance even after 6 runs with the conversion controlled at about50%,Mecha nistic investigations revealed that the moderate surface coverage of AlPO_(4)on Ni with the formation of Ni^(δ+)-AlPO_(4)interface significantly facilitated the conversion of methoxycyclohexanol and cyclohexanol to cyclohexane,whereas,excess coverage would also block the access to Ni site.Moreover,Ni@AlPO_(4)/Al_(2)O_(3)demonstrated broad applicability in the C-O cleavage of various typical lignin monomers and dimers into cycloalkanes.To our delight,this catalyst also displayed pretty good activity even in the simultaneous cleavage of C-C linkages and C-O bonds for the lignin-derived C-C dimers,achieving cycloalkanes as final products.As a consequence,a 27.1 wt%yield of monocycloalkanes was obtained in the depolymerization of poplar lignin with both C-C and C-O cleavages.展开更多
Many strategies have been proposed to produce arenes from lignin as liquid fuel additives.However,the development of these methods is limited by the low yield of products,low atom utilization,and inefficient lignin de...Many strategies have been proposed to produce arenes from lignin as liquid fuel additives.However,the development of these methods is limited by the low yield of products,low atom utilization,and inefficient lignin depolymerization.Herein,we develop an energy-efficient synthetic method for the production of high-carbon-number arenes from sustainable lignin with a total yield of 23.1 wt%.Particularly,high carbon number arenes are obtained by fully utilizing the formaldehyde stabilizing additive and the methoxy group in lignin.The process begins with the reductive depolymerization of formaldehyde-stabilized lignin,followed by transmethylation between lignin monomers over Au/Nb_(2)O_(5) catalyst,and the Ru/Nb2O5-catalyzed hydrodeoxygenation.This work demonstrates the potential of value-added arenes production directly from lignin.展开更多
Carbon fibers(CFs)with notable comprehensive properties,such as light weight,high specific strength,and stiffness,have garnered considerable interest in both academic and industrial fields due to their diverse and adv...Carbon fibers(CFs)with notable comprehensive properties,such as light weight,high specific strength,and stiffness,have garnered considerable interest in both academic and industrial fields due to their diverse and advanced applications.However,the commonly utilized precursors,such as polyacrylonitrile and pitch,exhibit a lack of environmental sustainability,and their costs are heavily reliant on fluctuating petroleum prices.To meet the substantial market demand for CFs,significant efforts have been made to develop cost-effective and sustainable CFs derived from biomass.Lignin,the most abundant polyphenolic compound in nature,is emerging as a promising precursor which is well-suited for the production of CFs due to its renewable nature,low cost,high carbon content,and aromatic structures.Nevertheless,the majority of lignin raw materials are currently derived from pulping and biorefining industrial by-products,which are diverse and heterogeneous in nature,restricting the industrialization of lignin-derived CFs.This review classifies fossil-derived and biomass-derived CFs,starting from the sources and chemical structures of raw lignin,and outlines the preparation methods linked to the performance of lignin-derived CFs.A comprehensive discussion is presented on the relationship between the structural characteristics of lignin,spinning preparation,and structure-morphology-property of ligninderived CFs.Additionally,the potential applications of these materials in various domains,including energy,catalysis,composites,and other advanced products,are also described with the objective of spotlighting the unique merits of lignin.Finally,the current challenges faced and future prospects for the advancement of lignin-derived CFs are proposed.展开更多
Carbon quantum dots are a new type of fluorescent nanomaterials with broad applications in drug delivery,bioimaging,solar cells,and photocatalysis due to their unique biocompatibility,optical properties and easy funct...Carbon quantum dots are a new type of fluorescent nanomaterials with broad applications in drug delivery,bioimaging,solar cells,and photocatalysis due to their unique biocompatibility,optical properties and easy functionalization.In the meantime,because of its high carbon content,renewable nature,and environmental friendliness,lignin has drawn the attention of researchers as a desirable raw material for creating carbon quantum dots.Here we review the synthesis of carbon quantum dots from lignin,focusing on synthetic methods,properties,and applications in energy,and photocatalysis.Later,we propose some new development prospects from preparation methods,luminescence mechanism research,application,and commercial cost of lignin carbon quantum dots.Finally,based on this,the development prospects of this field are prospected and summarized.展开更多
Lignin has been proved to be a promising precursor for producing carbon foam.The thermal and chemistry properties of lignin during its thermal conversion make it quite unique comparing with other precursors,and the co...Lignin has been proved to be a promising precursor for producing carbon foam.The thermal and chemistry properties of lignin during its thermal conversion make it quite unique comparing with other precursors,and the conversion parameters can clearly affect the properties of the derived products.Therefore,this study systematically investigated the effects of key carbonization parameters on the properties of the resulting carbon foam materials.The findings demonstrate that the performance of the self-shaping lignin-derived carbon foam is simultaneously influenced by the factors that carbonization temperature,heating rate,and carbonization duration.Specifically,the carbonization temperature and carbonization duration have a significant impact on the mechanical performance,where higher temperatures and long carbonization time improve compressive strength and specific strength.Moreover,the data revealed that elevated temperatures,rapid heating rates,and shortened carbonization periods collectively promoted the development of higher porosities and larger pore diameters within the carbon foam structure.Conversely,lower carbonization temperatures,slower heating rates,and extended carbonization durations facilitated the formation of microporous in the carbon foam.This study provides a scientific foundation for optimizing the production of lignin-derived carbon foam with tailored properties and performance characteristics.展开更多
As the most abundant aromatic bio-based polymer,lignin has great potential as a sustainable feedstock for building crosslinked thermoset polymers as bio-based adhesives.However,the potential of hardwood kraft lignin(H...As the most abundant aromatic bio-based polymer,lignin has great potential as a sustainable feedstock for building crosslinked thermoset polymers as bio-based adhesives.However,the potential of hardwood kraft lignin(HKL)is limited due to its poor crosslinking reactivity.Hence,for the first time,the present study reports the facile oxidation of HKL involving a redox reaction with silver-ammonia complexes([(AgNH3)2]+),primarily focusing on oxidation to produce reactive quinones and promote C-C linkages during reaction.This study aims to increases reactivity of oxidized HKL for effective crosslinking with monoethanolamine(MEA)for the development of bio-based wood adhesives.The characterization,including 13C-nuclear magnetic resonance(NMR)and Fourier transform infrared(FT-IR)spectroscopy,confirms the oxidation reaction,such as the formation of quinones(C=O)and subsequent crosslinking between the oxidized HKL molecules and MEA.Additionally,gel permeation chromatography(GPC)confirms the C-C and C-O linkages with increased molecular weight after oxidation,and is supported by differential scanning calorimetry(DSC)which shows the exothermic reaction due to the crosslinking of the oxidized HKL molecules via condensation to form C-C and C-O linkages.The crosslinked HKL/MEA-based adhesives underwent mild reaction and achieved a maximum dry shear strength of 0.77 MPa,which exceeds the standard requirement of 0.6 MPa.These findings demonstrate not only a one-pot oxidation for improving the reactivity of HKL using silver complexes,but also its facile crosslinking with MEA for sustainable bio-based wood adhesives.展开更多
文摘In order to manufacture environmentally friendly particle boards and enhance local resources, the lignins of Sorghum bicolor and Andropogon gayanus characterized using RMN 13C and MALDI TOF have the same structures. They contents Guaiacyl (G), Syringyl (S), p-hydroxyphenylpropane (H) and functional groups of phenols, flavonoids and secondary alcohols. The total phenol content determinated using Folin-Ciocalteu reagent is respectively 20.97 and 15.42 mg eqgallic acid/g of extract. The power of their adhesives is different. The Internal Bond (IB) of particleboards manufactured with these adhesives are respectively 0.37 MPa and 0.41 MPa. These lignins can be used as antioxydants.
基金Supported by the National Natural Science Foundation of China （20876078, 21176124）, the National High Technology Research and Development Program of China （2011AA02A207）, the National Basic Research Program of China （2009CB724700）, the Key Program of the National Natural Science Foundation of China （20936002）, and the Independent Innovation Project of Jiangsu Province （CX（11）2051）.
文摘Lignins were isolated and purified from alkali treated prehydrolysate of corn stover. The paper presents the structural features of lignins in a series purification processes. Fourier transform infrared spectroscopy, ultraviolet-vis spectroscopy and proton nuclear magnetic resonance spectroscopy were used to analyze the chemical structure. Thermogravimetric analysis was applied to follow the thermal degradation, and wet chemical method was used to determine the sugar content. The results showed that the crude lignin from the prehydrolysate of corn stover was a heterogeneous material of syringyl, guaiacyl and p-hydroxyphenyl units, containing associated polysaccharides, lipids, and melted salts. Some of the crude lignin was chemically linked to hemicelluloses （mainly xylan）. The lipids in crude lignin were probably composed of saturated and/or unsaturated long carbon chains, fatty acids, tdterpenols, waxes, and derivatives of aromatic. The sugar content of purified lignin was less than 2.11%, mainly composed of guaiacyl units. DTGmax of purified lignin was 359 ℃. The majority of the hydroxyl groups were phenolic hydroxyl groups. The main type of linkages in purified lignin was β-O-4. Other types of linkages included β-5, β-β and α-O-4.
基金National Natural Science Foundation of China(31871549,32001579,31830067and 31171177)National Key Research and Development Program of China(2016YFD0100506)+2 种基金Special Financial Aid to Post-doctor Research Fellow of Chongqing(Xm T2018057)“111”Project(B12006)Young Eagles Program of Chongqing Municipal Commission of Education(CY200215)。
文摘Brassica crops,which are of worldwide importance,provide various oil,vegetable and ornamental products,as well as feedstocks for animal husbandry and biofuel industry.Cinnamoyl-Co A reductase(CCR)is the entry point to the lignin pathway and a crucial locus in manipulation of associated traits,but CCRassociated metabolism and traits in Brassica crops have remained largely unstudied except in Arabidopsis thaliana.We report the identification of 16 CCR genes from Brassica napus and its parental species B.rapa and B.oleracea.The Bn CCR1 and Bn CCR2 subfamilies displayed divergent organ-specificity and participation in the yellow-seed trait.Their functions were dissected via overexpression of representative paralogs in B.napus.Bn CCR1 was expressed preferentially in G-and H-lignin biosynthesis and vascular development,while Bn CCR2 was expressed in S-lignin biosynthesis and interfascicular fiber development.Bn CCR1 showed stronger effects on lignification-related development,lodging resistance,phenylpropanoid flux control,and seed coat pigmentation,whereas Bn CCR2 showed a stronger effect on sinapate biosynthesis.Bn CCR1 upregulation delayed bolting and flowering time,while Bn CCR2 upregulation weakened the leaf vascular system in consequence of suppressed G-lignin accumulation.Bn CCR1 and Bn CCR2 were closely but almost oppositely linked with glucosinolate metabolism via inter-pathway crosstalk.We conclude that Bn CCR1 and Bn CCR2 subfamilies offer great but differing potential for manipulating traits associated with phenylpropanoids and glucosinolates.This study reveals the CCR1–CCR2 divergence in Brassicaceae and offers a resource for rapeseed breeding for lodging resistance,yellowseed traits,and glucosinolate traits.
基金Major State Basic Research Projects of China(973-2010CB732204)Specific Programs in Graduate Science and Technology Innovation of Beijing Forestry University(BLYJ201110)
文摘In order to efficiently explore and use woody biomass,six lignin fractions were isolated from dewaxed Caragana sinica via successive extraction with organic solvents and alkaline solutions.The lignin structures were characterized by Fourier transform infrared spectroscopy(FT-IR) and 1D and 2D Nuclear Magnetic Resonance(NMR).FT-IR spectra revealed that the "core" of the lignin structure did not significantly change during the treatment under the conditions given.The results of 1H and 13C NMR demonstrated that the lignin fraction L2,isolated with 70% ethanol containing 1% NaOH,was mainly composed of β-O-4 ether bonds together with G and S units and trace p-hydroxyphenyl unit.Based on the 2D HSQC NMR spectrum,the ethanol organosolv lignin fraction L1,extracted with 70% ethanol,presents a predominance of β-O-4′ aryl ether linkages(61% of total side chains),and a low abundance of condensed carbon-carbon linked structures(such as ββ′,β-1′,and β-5′) and a lower S/G ratio.Furthermore,a small percentage(ca.9%) of the linkage side chain was found to be acylated at the γ-carbon.
基金Supported by the National Science and Technology Supporting Plan Through Contract(2015BAD15B06)the National Natural Science Foundation of China(51276166)+1 种基金the National Basic Research Program of China(2013CB228101)Guangdong Province Key Laboratory of Efficient and Clean Energy Utilization(2013A061401005)
文摘Pyrolytic lignin, the water-insoluble fraction in bio-oil, often shows a high content and has strong intermolecular interactions with other compounds in bio-oil. In order to obtain pure pyrolytic lignin and facilitate the utilization of aqueous phase obtained from water extraction of bio-oil, methanol–water extraction method was employed to further separate the bio-oil water-insoluble phase in this paper. Different technologies, including Fourier transform infrared spectroscopy, gel permeation chromatography, and nuclear magnetic resonance, were adopted to characterize the structures of pyrolytic lignins with different activities obtained through this method. Both the heating value and the polymerization degree of high-molecular-weight pyrolytic lignin were higher than those of low-molecular-weight pyrolytic lignin. The molecular weight distribution of high-molecular-weight pyrolytic lignin was relatively wider, among which the contents of dimers to pentamers all accounted for 12% –18%,while the low-molecular-weight pyrolytic lignin mainly consisted of trimers(75.38%). The pyrolytic lignins had similar basic structures, both of which contained syringyl and guaiacyl units, whereas the low-molecular-weight pyrolytic lignin had more abundant syringyl units, reactive carbonyl groups and hydroxyl groups. Meanwhile,thermogravimetric study revealed that the final char residue yield of low-molecular-weight pyrolytic lignin was lower than that of high-molecular-weight pyrolytic lignin.
文摘<span style="line-height:1.5;font-family:Verdana;">In the present work</span><span style="line-height:1.5;font-family:Verdana;">,</span><span "="" style="line-height:1.5;"><span style="font-family:Verdana;"> lignin is isolated from three different agro-industrial waste, sweet sorghum, rice straw and sugarcane bagasse using </span><i><span style="font-family:Verdana;">in-situ</span></i><span style="font-family:Verdana;"> sodium hydroxide-sodium bisulfate methodology. Characterization was performed using fourier transform infrared analysis (FTIR), scan electron microscopy (SEM), thermo gravimetric analysis (TGA). The SEM micrographs showed sponge-like structure except for sugarcane bagasse lignin reveals rock-like structure. The FTIR indicates the presence of hydroxyl, carbonyl and methoxyl groups in the lignin structure. TGA thermograms were relatively same and sugarcane bagasse lignin was found the most thermally stable up to 201<span style="white-space:nowrap;">˚</span>C as compared to both of soda and kraft sugarcane bagasse lignin and its maximal temperature degradation rate DTG</span><sub><span style="font-family:Verdana;">max</span></sub><span style="font-family:Verdana;"> was found at 494<span style="white-space:nowrap;">˚</span>C while 450<span style="white-space:nowrap;">˚</span>C, 464<span style="white-space:nowrap;">˚</span>C in addition to thermal stabilities up to 173<span style="white-space:nowrap;">˚</span>C and 180<span style="white-space:nowrap;">˚</span>C for sweet sorghum and rice straw lignins respectively. All lignins exhibited low percentage of bio-char less than 10% remained unvalotilized at the end of the thermogravimetric analysis at 800<span style="white-space:nowrap;">˚</span>C in nitrogen atmosphere</span></span><span style="line-height:1.5;font-family:Verdana;">,</span><span style="line-height:1.5;font-family:Verdana;"> reveal</span><span style="line-height:1.5;font-family:Verdana;">ing</span><span "="" style="line-height:1.5;"><span style="font-family:Verdana;"> a high conversion yield into volatiles. Moreover, all lignin samples depicted higher cytotoxic potential towards lung cancer cell line (A549), IC</span><sub><span style="font-family:Verdana;">50</span></sub><span style="font-family:Verdana;">: 12</span></span><span "="" style="line-height:1.5;"> </span><span style="line-height:1.5;font-family:Verdana;">-</span><span "="" style="line-height:1.5;"> </span><span "="" style="line-height:1.5;"><span style="font-family:Verdana;">17 μg/ml. These findings suggest that the </span><i><span style="font-family:Verdana;">in-situ</span></i><span style="font-family:Verdana;"> separated lignins would be good candidates for pyrolysis, polymer composites preparations and seem to be promising natural anti-cancer agents despite its main utilization as </span></span><span style="line-height:1.5;font-family:Verdana;">the</span><span style="line-height:1.5;font-family:Verdana;"> caner drug delivery substrates.
基金supported by grants from National Natural Science Foundation of China(224708046,22508229,22278049)Young Elite Scientists Sponsorship Program by CAST(2022QNRC001)+1 种基金Xingliao Talent Program-Young Top Talent(XLYC2403126)Liaoning Provincial Basic Scientific Research Project for Higher Education(LJ212510152013)。
文摘The increasing scarcity of freshwater resources has driven the rapid emergence of solar-driven interfacial evaporators(SDIEs)as a sustainable approach to harvest fresh water by utilizing solar energy.Lignocellulosic biomass,featuring natural abundance,excellent renewability,unique natural structures,and superior biodegradability compared to the synthetic polymers,is highly attractive for constructing solar steam generators.This review aims to offer an innovative and in-depth insight into designing and optimizing highperformance integrated solar interfacial evaporators derived from renewable lignocellulosic biomass.First,the structural characteristics of lignocellulosic biomass are briefly introduced,serving as photothermal layer or supporting substrates in SDIEs.Secondly,the fabrication methods and processing technologies of lignocellulosic biomass-based evaporators are summarized from the perspective of photothermal layer and supporting substrates.Next,the most recent advances of regulation and optimization strategies are proposed to improve evaporation efficiency.Subsequently,this review summarizes the diverse functionalities of SDIEs,including desalination,power generation,wastewater treatment and antimicrobial,atmospheric water harvesting,and photocatalytic hydrogen production.Finally,the challenges in this field and outlook on the future development are discussed,which are anticipated to provide new opportunities for the advancement of lignocellulosic biomass-based SDIEs.
基金supported by the National Natural Science Foundation of China(21706052,22278114)Natural Science Foundation of Henan Province(242300421575).
文摘Lignin,the most abundant natural aromatic polymer globally,has garnered considerable interest due to its rich and diverse active functional groups and its antioxidant,antimicrobial,and adhesive properties.Recent research has significantly improved the performance of lignin-based hydrogels,suggesting their substantial potential in fields such as biomedicine,environmental science,and agriculture.This paper reviews the process of lignin extraction,systematically introduces synthesis strategies for preparing lignin-based hydrogels,and discusses the current state of research on these hydrogels in biomedical and environmental protection fields.It concludes by identifying the existing challenges in lignin hydrogel research and envisioning future prospects and development trends.
基金supported by the Natural Science Foundation of Shanghai(No.24ZR1419600).
文摘Plant-related organic compound(PROC)may interact with redox-active metals like iron while they are present in soil or aquatic environment,but their effects on the photoreduction of Fe(III)remain largely unexplored.This study investigates the photochemical behavior of Fe(III)-PROC complexes using alkaline lignin(AL),betaine hydrochloride(BH),and phytic acid(PA)as representative proxies for PROC.The reductive agent AL demonstrated the ability to directly reduce Fe(III)to Fe(II).In contrast,BH,being unable to form strong complexes with Fe(III),was able to quench·OH,thereby resulting in a shift of the redox equilibrium towards Fe(II).PA exhibited a strong binding affinity for Fe(III),effectively inhibiting its photoreduction.Electron paramagnetic resonance(EPR)analysis,utilizing 5,5-dimethyl-1-pyrroline-N-oxide(DMPO)as a spin trap,revealed that the DMPO-OH signal detected in photolyzed Fe(III)-PROC solutions originated from various pathways.Specifically,uncomplexed Fe(III)in AL or BH solutions was shown to oxidize DMPO directly,leading to the formation of a false DMPO-OH adduct.The addition of ethanol to the photolyzed Fe(III)-AL and Fe(III)-BH systems resulted in the generation of the DMPO-CH(CH_(3))OH adduct,thereby confirming the presence of authentic·OH in these systems.The photolysis of the Fe(III)-PA complex may proceed via a photodissociation mechanism,where the resulting loosely bound Fe(III)can oxidize DMPO,followed by a nucleophilic attack from water.This research highlights the multifaceted roles of PROC in facilitating the redox cycling of iron within soil and aquatic ecosystems.
文摘Lignin is a significant secondary metabolite produced through the phenylpropanoid pathway.As a vital component of the plant cell wall,lignin affects various fruit characteristics,including size,seed quantity,and firmness.In this study,we conducted comprehensive identification and phylogenetic analysis of 265 Caffeic acid O-methyltransferase(COMT)genes across ten different plant species,including Vaccinium corymbosum and four other Vaccinium species.The results reveal that VcCOMT38 is a promising structural gene for the biosynthesis of lignin in blueberry.An in vitro enzymatic assay of VcCOMT38 demonstrated that it is a special enzyme in the lignin biosynthesis pathway and prefers to use caffeic acid as a substrate over 5-hydroxyferulic acid.Transient overexpression and silencing of VcCOMT38 in Vaccinium corymbosum‘Northland’fruits demonstrated that VcCOMT38 participates in lignin biosynthesis and contributes to both an increased number of immature seeds and enhanced fruit firmness.The heterologous overexpression of VcCOMT38 in Nicotiana benthamiana revealed that this gene could increase the lignin content and the syringyl/guaiacyl(S/G)ratio,which determines the maximum monomer yield during lignin depolymerization.These results highlight VcCOMT38 as a crucial gene in lignin biosynthesis and its potential for improving lignin production in industry through genetically modified woody plants.
基金funded by the National Natural Science Foundation of China (31760363)the Earmarked Fund for CARS (CARS-14-1-16)+1 种基金the Gansu Education Science and Technology Innovation Industry Support Program,China (2021CYZC-38)the Gansu Provincial Key Laboratory of Arid Land Crop Science,Gansu Agricultural University,China (GSCS-2020-Z6)。
文摘Lodging is a major constraint limiting oil flax production efficiency in northern China.Crop lodging susceptibility is closely related to stem lignin content,and the regulatory mechanisms by which nitrogen and potassium fertilization interactively influence lignin biosynthesis in oil flax stems require further investigation.Therefore,this study aimed to enhance lodging resistance and increase grain yield in oil flax.We examined the interactive effects of different nitrogen (75,150,and 225 kg N ha^(–1)) and potassium (60 and 90 kg K_(2)O ha^(–1)) fertilizer rates on lignin metabolism,lodging resistance,and grain yield during the 2022 and 2023 growing seasons.Results indicated that nitrogen and potassium fertilizer levels and their interactions promoted lignin accumulation,improved lodging resistance,and increased grain yield.Compared to the control (CK),the75–150 kg N ha^(–1) combined with 60 kg K_(2)O ha^(–1) treatments significantly enhanced the activities of key lignin-synthesizing enzymes (tyrosine ammonia-lyase (TAL),phenylalanine ammonia-lyase (PAL),cinnamyl alcohol dehydrogenase (CAD),and peroxidase (POD)) and upregulated the expression of 4CL1 and F5H3 genes,leading to a 29.63–43.30%increase in lignin content,improved stem bending strength and lodging resistance index,and a 23.27–32.34%increase in grain yield.Correlation analysis revealed that nitrogen and potassium fertilizers positively regulated enzyme activities and gene expression related to lignin biosynthesis,thereby facilitating lignin accumulation and enhancing stem mechanical strength and lodging resistance.Positive correlations were observed among lignin-related enzyme activities,gene expression,lodging resistance traits,and grain yield.In summary,the application of 75–150 kg N ha^(–1) in conjunction with 60 kg K_(2)O ha^(–1)promoted lignin biosynthesis and accumulation,enhanced lodging resistance,and increased grain yield in oil flax grown in the dryland farming region of central Gansu,China.Furthermore,this treatment provides a technical basis for cultivating stress-tolerant and high-yield oil flax in arid regions.
基金supported by Natural Science and Engineering Research Council of Canada(RGPIN-2017-06737)Canada Research Chairs program,the National Key Research and Development Program of China(2017YFD0601005,2022YFD0904201)+1 种基金the National Natural Science Foundation of China(51203075)the China Scholarship Council(Grant No.CSC202208320361).
文摘With the rapid development of flexible wearable electronics,the demand for stretchable energy storage devices has surged.In this work,a novel gradient-layered architecture was design based on single-pore hollow lignin nanospheres(HLNPs)-intercalated two-dimensional transition metal carbide(Ti_(3)C_(2)T_(x) MXene)for fabricating highly stretchable and durable supercapacitors.By depositing and inserting HLNPs in the MXene layers with a bottom-up decreasing gradient,a multilayered porous MXene structure with smooth ion channels was constructed by reducing the overstacking of MXene lamella.Moreover,the micro-chamber architecture of thin-walled lignin nanospheres effectively extended the contact area between lignin and MXene to improve ion and electron accessibility,thus better utilizing the pseudocapacitive property of lignin.All these strategies effectively enhanced the capacitive performance of the electrodes.In addition,HLNPs,which acted as a protective phase for MXene layer,enhanced mechanical properties of the wrinkled stretchable electrodes by releasing stress through slip and deformation during the stretch-release cycling and greatly improved the structural integrity and capacitive stability of the electrodes.Flexible electrodes and symmetric flexible all-solid-state supercapacitors capable of enduring 600%uniaxial tensile strain were developed with high specific capacitances of 1273 mF cm^(−2)(241 F g^(−1))and 514 mF cm^(−2)(95 F g^(−1)),respectively.Moreover,their capacitances were well preserved after 1000 times of 600%stretch-release cycling.This study showcased new possibilities of incorporating biobased lignin nanospheres in energy storage devices to fabricate stretchable devices leveraging synergies among various two-dimensional nanomaterials.
文摘This review is composed of three main parts each of which is written by well-known top specialists that have been,in a way or other,also the main participants of the majority of the developments reported.Thus,after a general part covering the grand lines and more in-depth views of more recent tannin,lignin,carbohydrate and soy bioadhesives,somemix of the other bio raw materials with soy protein and soy flour and some other differently sourced bioadhesives for wood,this review presents a more in-depth part on starch-based wood adhesives and a more indepth part covering plant protein-based adhesives.It must be kept in mind that the review is focused on completely or almost completely biosourced adhesives,the fashionable adhesives derived from mixes of biosourced materials with synthetic resins having been intentionally excluded.This choice was made as the latter constitute only an intermediate interval,possibly temporary if even for a somewhat long times,towards a final full bioeconomy of scale in this field.This review also focuses on more recent results,mainly obtained in the last 10–20 years,thus on adhesive formulations really innovative and sometimes even non-traditional.In all these fields there is still a lot of possibility of innovation for relevant formulation as this field is still in rapid growth.
基金National Natural Science Foundation of China (U23A6005 and 22078069)Project funded by China Postdoctoral Science Foundation (GZB20230172 and 2023M740748)。
文摘Electrochemical conversion of lignin for the production of high-value heterocyclic aromatic compounds has great potential.We demonstrate the targeted synthesis and cation modulation of NiCo_(2)O_(4)spinel nanoboxes,synthesized via cation exchange and calcination oxidation.These catalysts exhibit excellent efficacy in the electrocatalytic conversion of lignin model compounds,specifically 2-phenoxy-1-phenylethanol,into nitrogen-containing aromatics,achieving high conversion rates and selectivities.These catalysts were synthesized via a cation exchange and calcination oxidation process,using Prussian blue nanocubes as precursors.The porous architecture and polymetallic composition of the NiCo_(2)O_(4)spinel demonstrated superior performance in electrocatalytic oxidative coupling,achieving a 99.2 wt%conversion rate of the 2-phenoxy-1-phenylethanol with selectivities of 37.5 wt%for quinoline derivatives and 31.5 wt%for phenol.Key innovations include the development of a sustainable one-pot synthesis method for quinoline derivatives,the elucidation of a multistage reaction pathway involving CAO bond cleavage,hydroxyaldol condensation,and CAN bond formation,and a deeper mechanistic understanding derived from DFT simulations.This work establishes a new strategy for lignin valorization,offering a sustainable route to produce high-value nitrogen-containing aromatics from renewable biomass under mild conditions,without the need for additional reagents.
基金supported by National Natural Science Foundation of China(22178258,22308254)China Postdoctoral Science Foundation(2023M742593,2024T170642)+1 种基金Independent Innova-tion Fund of Tianjin University(2024XQM-0021)the Open Fund of the Key Laboratory of Functional Molecular Solids(FMS2023006)。
文摘Ni-based catalysts are widely applied in the hydrodeoxygenation of lignin derivatives via C-O cleavage for the production of cycloalkanes.However,they often have difficulty in achieving high activity under mild conditions and exhibit relatively poor stability,and rare studies focus on the cleavage of the stubborn interunit C-C linkages.To address this issue,we developed a Ni@AlPO_(4)/Al_(2)O_(3)catalyst in which the surface of Ni nanoparticles was decorated by AlPO_(4)species,demonstrating excellent catalytic activity and stability in the C-C and C-O cleavages.In the hydrodeoxygenation of guaiacol,this catalyst afforded99.1%conversion and 92.9%yield of cyclohexane under 1 MPa H_(2)at 230℃ for 2 h.More important,this catalyst maintained unchanged performance even after 6 runs with the conversion controlled at about50%,Mecha nistic investigations revealed that the moderate surface coverage of AlPO_(4)on Ni with the formation of Ni^(δ+)-AlPO_(4)interface significantly facilitated the conversion of methoxycyclohexanol and cyclohexanol to cyclohexane,whereas,excess coverage would also block the access to Ni site.Moreover,Ni@AlPO_(4)/Al_(2)O_(3)demonstrated broad applicability in the C-O cleavage of various typical lignin monomers and dimers into cycloalkanes.To our delight,this catalyst also displayed pretty good activity even in the simultaneous cleavage of C-C linkages and C-O bonds for the lignin-derived C-C dimers,achieving cycloalkanes as final products.As a consequence,a 27.1 wt%yield of monocycloalkanes was obtained in the depolymerization of poplar lignin with both C-C and C-O cleavages.
文摘Many strategies have been proposed to produce arenes from lignin as liquid fuel additives.However,the development of these methods is limited by the low yield of products,low atom utilization,and inefficient lignin depolymerization.Herein,we develop an energy-efficient synthetic method for the production of high-carbon-number arenes from sustainable lignin with a total yield of 23.1 wt%.Particularly,high carbon number arenes are obtained by fully utilizing the formaldehyde stabilizing additive and the methoxy group in lignin.The process begins with the reductive depolymerization of formaldehyde-stabilized lignin,followed by transmethylation between lignin monomers over Au/Nb_(2)O_(5) catalyst,and the Ru/Nb2O5-catalyzed hydrodeoxygenation.This work demonstrates the potential of value-added arenes production directly from lignin.
基金National Natural Science Foundation of China,Grant/Award Numbers:32171717,32271814Natural Science Foundation of Tianjin Municipality,Grant/Award Numbers:24JCJQJC00030,22JCYBJC01560,23JCZDJC00630China Postdoctoral Science Foundation,Grant/Award Number:2023M740562。
文摘Carbon fibers(CFs)with notable comprehensive properties,such as light weight,high specific strength,and stiffness,have garnered considerable interest in both academic and industrial fields due to their diverse and advanced applications.However,the commonly utilized precursors,such as polyacrylonitrile and pitch,exhibit a lack of environmental sustainability,and their costs are heavily reliant on fluctuating petroleum prices.To meet the substantial market demand for CFs,significant efforts have been made to develop cost-effective and sustainable CFs derived from biomass.Lignin,the most abundant polyphenolic compound in nature,is emerging as a promising precursor which is well-suited for the production of CFs due to its renewable nature,low cost,high carbon content,and aromatic structures.Nevertheless,the majority of lignin raw materials are currently derived from pulping and biorefining industrial by-products,which are diverse and heterogeneous in nature,restricting the industrialization of lignin-derived CFs.This review classifies fossil-derived and biomass-derived CFs,starting from the sources and chemical structures of raw lignin,and outlines the preparation methods linked to the performance of lignin-derived CFs.A comprehensive discussion is presented on the relationship between the structural characteristics of lignin,spinning preparation,and structure-morphology-property of ligninderived CFs.Additionally,the potential applications of these materials in various domains,including energy,catalysis,composites,and other advanced products,are also described with the objective of spotlighting the unique merits of lignin.Finally,the current challenges faced and future prospects for the advancement of lignin-derived CFs are proposed.
基金Sponsorship Program by CAST(2023QNRC001)University-Industry Collaborative Education Program(220901115200913,220901115201954)+2 种基金Hunan Provincial Natural Science Foundation of China(2022JJ40007)Jiangsu Agricultural Science and Technology Innovation Fund(CX(22)3047)the National Natural Science Foundation of China(32201491)。
文摘Carbon quantum dots are a new type of fluorescent nanomaterials with broad applications in drug delivery,bioimaging,solar cells,and photocatalysis due to their unique biocompatibility,optical properties and easy functionalization.In the meantime,because of its high carbon content,renewable nature,and environmental friendliness,lignin has drawn the attention of researchers as a desirable raw material for creating carbon quantum dots.Here we review the synthesis of carbon quantum dots from lignin,focusing on synthetic methods,properties,and applications in energy,and photocatalysis.Later,we propose some new development prospects from preparation methods,luminescence mechanism research,application,and commercial cost of lignin carbon quantum dots.Finally,based on this,the development prospects of this field are prospected and summarized.
基金funding support from Taishan Scholars Program of Shandong Province(tsqn201909132)National Natural Science Foundation of China(22208183)+1 种基金Startup Foundation from Qingdao Agricultural University(663-1120040,665-1119020)Technology development project from Jinan Shengquan Company(20233702031771)。
文摘Lignin has been proved to be a promising precursor for producing carbon foam.The thermal and chemistry properties of lignin during its thermal conversion make it quite unique comparing with other precursors,and the conversion parameters can clearly affect the properties of the derived products.Therefore,this study systematically investigated the effects of key carbonization parameters on the properties of the resulting carbon foam materials.The findings demonstrate that the performance of the self-shaping lignin-derived carbon foam is simultaneously influenced by the factors that carbonization temperature,heating rate,and carbonization duration.Specifically,the carbonization temperature and carbonization duration have a significant impact on the mechanical performance,where higher temperatures and long carbonization time improve compressive strength and specific strength.Moreover,the data revealed that elevated temperatures,rapid heating rates,and shortened carbonization periods collectively promoted the development of higher porosities and larger pore diameters within the carbon foam structure.Conversely,lower carbonization temperatures,slower heating rates,and extended carbonization durations facilitated the formation of microporous in the carbon foam.This study provides a scientific foundation for optimizing the production of lignin-derived carbon foam with tailored properties and performance characteristics.
基金supported by the National Research Foundation(NRF)of Korea,funded by the Korean Government(MSIT)(Grant No.RS-2023-00240043).
文摘As the most abundant aromatic bio-based polymer,lignin has great potential as a sustainable feedstock for building crosslinked thermoset polymers as bio-based adhesives.However,the potential of hardwood kraft lignin(HKL)is limited due to its poor crosslinking reactivity.Hence,for the first time,the present study reports the facile oxidation of HKL involving a redox reaction with silver-ammonia complexes([(AgNH3)2]+),primarily focusing on oxidation to produce reactive quinones and promote C-C linkages during reaction.This study aims to increases reactivity of oxidized HKL for effective crosslinking with monoethanolamine(MEA)for the development of bio-based wood adhesives.The characterization,including 13C-nuclear magnetic resonance(NMR)and Fourier transform infrared(FT-IR)spectroscopy,confirms the oxidation reaction,such as the formation of quinones(C=O)and subsequent crosslinking between the oxidized HKL molecules and MEA.Additionally,gel permeation chromatography(GPC)confirms the C-C and C-O linkages with increased molecular weight after oxidation,and is supported by differential scanning calorimetry(DSC)which shows the exothermic reaction due to the crosslinking of the oxidized HKL molecules via condensation to form C-C and C-O linkages.The crosslinked HKL/MEA-based adhesives underwent mild reaction and achieved a maximum dry shear strength of 0.77 MPa,which exceeds the standard requirement of 0.6 MPa.These findings demonstrate not only a one-pot oxidation for improving the reactivity of HKL using silver complexes,but also its facile crosslinking with MEA for sustainable bio-based wood adhesives.
