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lignin-based carbon fibers: Formation, modification and potential applications

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Green Energy & Environment 2022年第4期7卷 578-605页

作者： Shichao Wang Jixing Bai Mugaanire Tendo Innocent Qianqian Wang Hengxue Xiang Jianguo Tang Meifang Zhu Institute of Hybrid materials College of Materials Science and EngineeringQingdao UniversityQingdao266071China State Key laboratory for Modification of Chemical Fibers and Polymer materials College of Materials Science and EngineeringDonghua UniversityShanghai201620China

As an aromatic polymer in nature, lignin has recently attracted gross attention because of its advantages of high carbon content, low cost and bio-renewability. However, most lignin is directly burnt for power generation to satisfy the energy demand of the pulp mills. As a result, only a handful of isolated lignin is used as a raw material. Thus, increasing value addition on lignin to expand its scope of applications is currently a challenge demanding immediate attention. Many efforts have been made in the valorization of lignin, including the preparation of precursors for carbon fibers. However, its complex structure and diversity significantly restrict the spinnability of lignin. In this review, we provide elaborate knowledge on the preparation of lignin-based carbon fibers ranging from the relationships among chemical structures, formation conditions and properties of fibers, to their potential applications. Specifically, control procedures for different spinning methods of lignin, including melt spinning, solution spinning and electrospinning, together with stabilization and carbonization are deeply discussed to provide an overall understanding towards the formation of lignin-based carbon fibers. We also offer perspectives on the challenges and new directions for future development of lignin-based carbon fibers.

关键词： lignin-based carbon fiber Melt spinning Solution spinning Electrospinning

Synthesis and characterization of water-soluble PEGylated lignin-based polymers by macromolecular azo coupling reaction

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Chinese Chemical Letters 2018年第1期29卷 143-146页

作者： Jilei Wang Shang Li Ruiqi Liang Bing Wu Yaning He Department of Chemical Engineering Key Laboratory of Advanced Materials (MOE) Tsinghua University

Water-soluble PEG grafted lignin-based polymers （AL-azo-PEG） were efficiently synthesized by macromolecular azo coupling reaction between alkali lignin and PEG based macromolecular diazonium salts in alkaline water. This one-step PEGylation method showed many advantages such as high efficiency, controllable grafting radio, extremely mild conditions and without organic solvents. The prepared AL-azo-PEG polymers were well characterized by using various spectroscopic methods including UV-vis, FTIR and 1H NMR spectra. Experimental results showed that the synthesized polymers had good solubility both in water over a wide pH range （pH 2-12） and in the majority of organic solvents, which helped to easily fabricate self-assembly colloidal particles and nanofibers by vapor diffusion method and electrospinning method, respectively, The azobenzene linkages generated by the macromolecular azo coupling reaction also brought photo-responsive properties to the prepared polymers.

关键词： lignin-based polymersWater-solubleMacromolecular azo coupling reactionColloid particlesNanofibers

Bio-renewable polymers based on lignin-derived phenol monomers:Synthesis,applications,and perspectives

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SusMat 2022年第5期2卷 535-568页

作者： Weijun Yang Hui Ding Debora Puglia Jose M Kenny Tianxi Liu Jiaqi Guo Qingwen Wang Rongxian Ou Pengwu Xu Piming Ma Pieter Jan Lemstra The Key laboratory of Synthetic and Biological Colloids Ministry of EducationJiangnan UniversityWuxiChina Civil and Environmental Engineering Department Materials Engineering CenterPerugia UniversityUdR INSTMTerniItaly Jiangsu Co-Innovation Center for Efficient Processing and Utilization of Forest Resources and Joint International Research Lab of Lignocellulosic Functional materials Nanjing Forestry UniversityNanjingChina Key laboratory for Bio-based materials and Energy of Ministry of Education College of Materials and EnergySouth China Agricultural UniversityGuangzhouChina PlemPolco B.V. De Zicht 115502 HVVeldhovenThe Netherlands

In recent decades,the continuous depletion of fossil fuels and the increasingly serious environmental issue have aroused wide attention on the development of biopolymers based on renewable *** is the second most abundant organic bio-based macromolecule second to cellulose,and it can be widely found in ***,various phenol derivatives can be obtained by their depolymerization *** development of bio-renewable polymeric materials originating from lignin-derivative phenol monomers,such as vanillin,syringaldehyde,eugenol,vanillyl alcohol,vanillic acid,and ferulic acid,will not only valorize the bio-sourced materials but also effectively reduce petroleum resource consumption and mitigate the environmental ***,an updated overview of the synthesis processes of these bio-based polymers developed in the past decade,which includes both thermosets and thermoplastics such as epoxy,phenolic,polyimine,polybenzoxazine,polyurethane,and polyesters,are *** addition,the applications of these bio-based polymers and their composites in flame-retarded materials,degradable and reprocessable materials,dielectric materials,optoelectronic materials,as well as smart responsive materials are also intensively *** line with the gradual development of synthesis technologies,we believe that derivatives of lignin will turn into one of the most promising materials to be considered for the preparation of high-performance and functional bio-based polymer materials.

关键词： applications lignin phenol derivatives renewable polymers synthesis

Gradient‑Layered MXene/Hollow lignin Nanospheres Architecture Design for Flexible and Stretchable Supercapacitors

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Nano-Micro Letters 2025年第2期17卷 447-462页

作者： Haonan Zhang Cheng Hao Tongtong Fu Dian Yu Jane Howe Kaiwen Chen Ning Yan Hao Ren Huamin Zhai Jiangsu Provincial Key Lab of Sustainable Pulp and Paper Technology and Biomass materials NanJing Forestry UniversityNanjing 210037People’s Republic of China Department of Chemical Engineering and Applied Chemistry University of Toronto200 College StreetTorontoON M5S 3E5Canada Department of materials Science and Engineering University of Toronto184 College StreetTorontoON M5S 3E4Canada College of materials Science and Engineering Nanjing Forestry UniversityNanjing 210037People’s Republic of China

With the rapid development of flexible wearable electronics,the demand for stretchable energy storage devices has *** 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 *** 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 ***,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 *** these strategies effectively enhanced the capacitive performance of the *** 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 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)),***,their capacitances were well preserved after 1000 times of 600%stretch-release *** study showcased new possibilities of incorporating biobased lignin nanospheres in energy storage devices to fabricate stretchable devices leveraging synergies among various two-dimensional nanomaterials.

关键词： Hollow lignin nanospheres MXene Gradient-layered architecture Wrinkled electrodes Stretchable supercapacitors

Advanced Functional Electromagnetic Shielding materials:A Review based on Micro‑Nano Structure Interface Control of Biomass Cell Walls

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Nano-Micro Letters 2025年第1期17卷 98-134页

作者： Yang Shi Mingjun Wu Shengbo Ge Jianzhang Li Anoud Saud Alshammari Jing Luo Mohammed A.Amin Hua Qiu Jinxuan Jiang Yazeed M.Asiri Runzhou Huang Hua Hou Zeinhom M.El‑Bahy Zhanhu Guo Chong Jia Kaimeng Xu Xiangmeng Chen Co‑Innovation Center of Efficient Processing and Utilization of Forest Resources College of Materials Science and EngineeringNanjing Forestry UniversityNanjing 210037People’s Republic of China State Key laboratory of Efficient Production of Forest Resourced Beijing Forestry UniversityQinghua East Road 35Haidian DistrictBeijing 100083People’s Republic of China Department of Physics Faculty of Sciences‑ArarNorthern Border UniversityArar 91431Saudi Arabia Department of Chemistry College of ScienceTaif UniversityP.O.Box 1109921944 TaifSaudi Arabia Shaanxi Key laboratory of Macromolecular Science and Technology School of Chemistry and Chemical EngineeringNorthwestern Polytechnical UniversityXi’anShaanxi 710072People’s Republic of China Integrated Composites Lab Department of Mechanical and Construction EngineeringNorthumbria UniversityNewcastle Upon Tyne NE18STUK College of materials Science and Engineering Taiyuan University of Science and TechnologyTaiyuan 030024People’s Republic of China Department of Chemistry Faculty of ScienceAl-Azhar UniversityNasr CityCairo 11884Egypt Yunnan Provincial Key laboratory of Wood Adhesives and Glued Products International Joint Research Center for Biomass MaterialsSouthwest Forestry UniversityKunming 650224People’s Republic of China School of Science Henan Agricultural UniversityZhengzhou 450002People’s Republic of China

Research efforts on electromagnetic interference(EMI)shielding materials have begun to converge on green and sustainable biomass *** materials offer numerous advantages such as being lightweight,porous,and *** to their porous nature,interfacial compatibility,and electrical conductivity,biomass materials hold significant potential as EMI shielding *** concerted efforts on the EMI shielding of biomass materials have been reported,this research area is still relatively new compared to traditional EMI shielding *** particular,a more comprehensive study and summary of the factors influencing biomass EMI shielding materials including the pore structure adjustment,preparation process,and micro-control would be *** preparation methods and characteristics of wood,bamboo,cellulose and lignin in EMI shielding field are critically discussed in this paper,and similar biomass EMI materials are summarized and *** composite methods and fillers of various biomass materials were *** paper also highlights the mechanism of EMI shielding as well as existing prospects and challenges for development trends in this field.

关键词： Biomass materials Electromagnetic interference shielding Micro-nano structure interface control Conductivity

lignin derived porous carbon with favorable mesoporous contributions for highly efficient ionic liquid-based supercapacitors

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Chinese Chemical Letters 2023年第10期34卷 293-297页

作者： Jia Liu Xiu-Wen Mei Feng Peng Beijing Key laboratory of Lignocellulosic Chemistry MOE Engineering Research Center of Forestry Biomass Materials and BioenergyBeijing Forestry UniversityBeijing 100083China

lignin and its derivatives hold great potential in developing high performance porous carbon materials for supercapacitors due to the versatile features of high carbon content, abundant multifunctional groups,low cost, and environmental benefits. Unfortunately, their derived porous carbon generally has the features of unfavorable microporous-dominated morphologies and low specific surface area(SSA) attributed from the highly-branched structure of lignin, which are hardly suitable for the supercapacitors with ionic liquid(IL) electrolyte, leading to poor energy density and rate capability. Herein, porous carbon materials with desirable mesoporous contributions from sodium lignosulphonate are designed via a facile template method. Such rich mesoporisity carbon materials not only possess with three-dimensional interconnected network, large SSA, as well as favorable pore size distribution for accelerated ion and electron mass transfer, but also feature low heteroatom content for high electrochemical stability. Consequently, the optimal electrode exhibits a high capacitance of 166 F/g at 0.5 A/g, superior rate performance(59 Wh/kg at 59 kW/kg), as well as impressive cycle life with good capacitance retention of 93.1% in EMIBF4 electrolytes. The present work opens a new avenue to design porous carbon materials with high mesopore properties from lignin for effective compatibility with IL electrolyte in high-performance supercapacitors.

关键词： lignin Porous carbon Favorable mesoporous contributions Low heteroatom content Supercapacitors

Synthetic Process of Bio-based Phenol Formaldehyde Adhesive Derived from Demethylated Wheat Straw Alkali lignin and Its Curing Behavior

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Journal of Renewable materials 2021年第5期9卷 943-957页

作者： Yan Song Zhixin Wang Xin Zhang Rong Zhang Jinchun Li Faculty of materials Science&Engineering Changzhou UniversityChangzhou213164China Jiangsu Key laboratory of Environmentally Friendly Polymeric materials School of Materials Science and EngineeringChangzhou UniversityChangzhou213164China Organization Department of the Party Committee Changshu Institute of TechnologyChangshu215500China School of Petrochemical Engineering Changzhou UniversityChangzhou213164China

lignin is a natural biopolymer with a complex three-dimensional network, commercially obtained from wasteliquid of paper pulp and bioethanol production, and could be a candidate for preparation of environment-friendlybio-based polyphenol material. In the present work, the demethylated wheat straw alkali lignin (D-Lig), preparedby demethylation of wheat straw alkali lignin (Lig) using an in-situ generated Lewis acid, was used to synthesizebio-based phenol formaldehyde resin adhesive (D-LPF) applied in plywood. Effects of synthetic process’s factors,including lignin substitution for phenol, NaOH concentration and molar ratio of formaldehyde to phenol, on thebonding strength and free formaldehyde content of D-LPF were investigated in detail, and the optimum syntheticprocess of D-LPF was obtained as following: lignin substitution for phenol 60%, NaOH concentration 5.0% andmolar ratio of formaldehyde to phenol 2.0, and under the optimum reaction condition, the D-LPF presented lower free formaldehyde content (0.18%) and higher bonding strength (2.19 MPa), which was better than those ofcontaining-lignin phenol formaldehyde resin adhesive (LPF). Additionally, the curing behavior of the adhesivewas studied by differential scanning calorimetry (DSC) combined with gel time. It can be obtained that D-LPFresin adhesive had the shortest gel time, and fastest curing rate, compared with those of PF and L-PF resin adhesives. The curing kinetics data was fitted well by Kissinger model using non-isothermal DSC method, and theaverage activation energy value was 85.3 kJ/mol, slightly higher than that of commercial PF resin, while lowerthan that of LPF (90.2 kJ/mol). Finally, based on the analytical results of high temperature fourier transform infrared spectroscopy (FTIR), a possible curing mechanism of D-LPF was proposed.

关键词： lignin demethylation phenol-formaldehyde resin biobased adhesive synthetic process curing behavior

Nitrogen-doped lignin based carbon microspheres as anode material for high performance sodium ion batteries

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Green Energy & Environment 2021年第2期6卷 220-228页

作者： Linlin Fan Zhiqiang Shi Qingjuan Ren Lei Yan Fuming Zhang Liping Fan Tianjin Key laboratory of Advanced Fibers and Energy Storuage Schoo of Materials Science and EngineeringTiangong UniversityTianjin300387China Schod of Chemical Engineering and Technology Tianjin University Tianjin300072China

Nitrogen-doped lignin-based carbon microspheres are synthesized using 3-aminophenol as a nitrogen source by the hydrothermal *** structural change and the effect on the electrochemical properties are systematically investigated. Nitrogen-doped lignin-based carbon microspheres represent well-developed spherical morphology with many active sites, ultramicroporous(< 0.7 nm) structure, and large interlayer spacing. Consistent with the obtained physical structures and properties, the nitrogen-doped carbon microspheres exhibit fast sodium ion adsorption/intercalation kinetic process and excellent electrochemical performance. For example, a reversible specific capacity of 374 m Ah g^(-1) at 25 m A g^(-1) with high initial coulombic efficiency of 85% and high capacitance retention of 90% after 300 cycles at 100 m A g^(-1) and stable charge/discharge behavior at different current density is obtained. The additional defects and abundant ultramicroporous structure can enhance sloping capacity, and large interlayer spacing is considered to be the reason for improving plateau capacity.

关键词： Sodium ion batteries Anode Carbon microspheres Hydrothermal method lignin

Mo-V-Nb-O-based catalysts for low-temperature selective oxidation of Cα-OH lignin model compounds

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Frontiers of materials Science 2020年第1期14卷 52-61页

作者： Lu-Lu Zhang Kun Hao Rui-Kai Wang Xiu-Qiang Ma Tong Liu Liang Song Qing Yu Zhong-Wei Wang Jian-Min Zeng Rong-Chang Zeng College of materials Science and Engineering Shandong University of Science and Technology579 Qianwangang RoadQingdao266590China College of materials Science and Engineering Qingdao University of Science and Technology53 Zhengzhou RoadQingdao266000China Ministry-Province Jointly-Constructed Cultivation Base for State Key laboratory of Processing for Non-ferrous Metal and Featured materials Guangxi University100 Daxue East RoadNanning530004China

Mo-V-Nb tri-component oxide catalysts were prepared and firstly used for the selective oxidation of Cα-OH lignin *** catalytic performance of the composite oxides was obviously enhanced due to the synergistic effects of Mo and V ***5-xVxO14 phase with a variable Mo/V ratio provided suitable active sites for the oxidative dehydrogenation(ODH)of Cα-OH lignin model *** optimized Mo-V-Nb molar composition was confirmed as Mo0.61V0.31Nb0.08Ox/TiO2,which exhibited the prominent catalytic activity with the turnover frequency of 1.04×10-3 mmol·g(cat)-1·*** at room temperature,the catalysts showed highly-efficient ODH reaction *** active phase for selective oxidation reaction and the inhibiting effect ofα-MoO3 phase were also discussed in the study.

关键词： selective oxidation secondary alcohol lignin model compound room temperature