Journal of Materials Chemistry A
·
2023
·Vol. 11
·期 6
·2595-2617
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IF 11.9
Ruijin Li,Danlian Huang,Lei Lei,Sha Chen,Yashi Chen,Guangfu Wang,Li Du,Wei Zhou,Jiaxi Tao,Haojie Chen
Considering the two limitations of the biocompatibility of metal–organic-frameworks (MOFs) and the low utilization of lignin biomass, herein, we review the interaction between lignin macromolecules and MOFs to promote their high-end applications and sustainability. Firstly, lignin and lignin derivatives can coordinate with metal ions to form bio-based MOFs due to their biocompatibility and surface-rich functional groups, which solves the difficulty of applying the original MOFs in biomedicine and other fields. We introduce the structure, coordination process, and advantages of applying bio-based MOFs in detail and discuss the problem that powdered MOFs are easily blocked and difficult to be separated and recovered. Secondly, MOFs can be used as catalysts to facilitate the conversion of lignin to liquid fuels and fine chemicals, thereby alleviating the energy shortage. We discuss the mechanism and products from the redox depolymerization of lignin using MOFs and their derivatives. The opportunities and challenges encountered in bio-based MOFs and selective cleavage of lignin are discussed based on several perspectives. It is hoped that this study can provide good theoretical guidance for the synthesis of bio-based MOFs and the conversion of lignin.
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CHEMOSPHERE
·
2023
·
IF 8.8
Zhengzhong Zhou,Lili Xu,Xue Zhu,Qian Wang,Xiaoshan Meng,Taoli Huhe
In this study, a photocatalytic biochar-TiO 2 (C–Ti) composite was prepared using lignin as carbon precursor, and blended with PVDF polymer to fabricate PVDF/C–Ti MMMs via non-solvent induced phase inversion. The prepared membrane demonstrates both 1.5 times higher initial and recovered fluxes than the similarly prepared PVDF/TiO 2 membrane, suggesting the C–Ti composite can help maintain higher photodegradation efficiency and better anti-fouling performance. In addition, the comparison of PVDF/C–Ti membrane against pristine PVDF membrane show that the reversible fouling and photodegradation reversible fouling of BSA increased from 10.1% to 6.4%–35.1% and 26.6%, respectively. And the FRR of PVDF/C–Ti membrane was 62.12%, 1.8 times that of PVDF membrane. The PVDF/C–Ti membrane was also applied for lignin separation, where the rejection to sodium lignin sulfonate was maintained at about 75%, and the flux recovery ratio after UV irradiation reached 90%. The demonstrated the advantages of PVDF/C–Ti membrane in photocatalytic degradation and antifouling performance.
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ACS Applied Polymer Materials
·
2023
·
IF 5
Zhiwei Yang,Weiyi Su,Jing Fang,Yong Qian,Hao Li
Mulch film and slow-release fertilizers are widely used in agriculture and horticulture, and it has become a trend to use degradable materials for the preparation of mulch films using slow-release materials. However, most degradable materials have poor performance or relatively high cost. In this study, three types of degradable materials, namely, poly(vinyl alcohol) (PVA), corn starch (CS), and alkali lignin (AL), were used as degradable materials to obtain a mulch film with a slow-release fertilizer function (MSRF). MSRF had excellent performance when 10% AL was added. The properties consisted of elongation at break (180.14%), water vapor permeability (203.8 g m–2 day–1), water resistance (its morphology remained good for 50 days), water absorption (300%), and urea release efficiency (cumulative release of 70.63% in 30 days). Rapid plant growth trials demonstrated that the MSRF had excellent functionality and that the MSRF could reduce the amount of fertilizer applied by about 70%. These excellent performances were due to the combination of chemical cross-linking (chemical bonding) between AL and PVA/CS molecular chains, the hydrogen bonding between the AL, PVA, and CS molecules, and the aggregation properties of AL. This provided a green and efficient strategy for the preparation and application of dual functions of mulching and the slow release of fertilizer.
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Pingxian Feng,Huan Wang,Peipei Huang,Lijie Zhong,Shiyu Gan,Wei Wang,Li Niu
Lignin-derived carbon electrode materials for supercapacitors can be prepared from industrial lignin with a high carbon content and a rich benzene ring structure. However, the capacitive performance is significantly affected by the nanoporous structure of the lignin-derived carbon. In this study, three nitrogen-doped nanoporous carbons were prepared using alkali lignin as a carbon source to examine the effect of different nanopore distributions on the electrochemical performance. Carbon activated by ZnC 2 O 4 (PLC-Zn) had a hierarchical porous structure composed of nanosheets, endowing it with a combined ability to store charge and transfer ions. The specific capacitance of PLC-Zn reached a maximum of 254F/g at 0.5 A/g, surpassing that obtained by the microporous-dominated carbon activated by K 2 CO 3 (PLC-K) and mesoporous-dominated carbon obtained by SiO 2 template method (PLC-Si). This study provides theoretical guidance for the preparation of excellent lignin-derived carbon electrode materials.
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ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Liangliang Zhu,Ben Dang,Kairui Zhang,Jun Zhang,Mei Zheng,Ning Zhang,Guanben Du,Zhijun Chen,Rongbo Zheng
Bioplastics (BPs) prepared from lignocellulose are an excellent replacement for petrochemical-plastics (PCPs) due to their renewability and biodegradability. The presence of residual/added/regenerated lignin reduced the water sensitivity; however, these BPs possessed a deep color and low transmittance and were prone to photodegradation. Herein, we developed a UV- and water-insensitive, colorless, transparent, and sustainable wood-derived BP (W-BP) by pressing delignified wood (DW) with 0.21% lignin and abundant hydrophobic crystal plane (200) of cellulose. The DW was obtained by the pretreatment of the wood sample with NaOH/Na2SO3 followed by H2O2 steam conditioning. The abundant hydrophobic crystal plane (200) of cellulose in DW was demonstrated by a large ratio of the crystal plane (200) to (110), the presence of two-dimensional (2D) nanosheets of defibrated cellulose, and a low moisture uptake of 8.7% of the freeze-dried DW. The aged W-BP with a thickness of about 50 μm displayed good photostability with a ΔE* value of 2.3 and a transparency of 84% transmittance at 550 nm. Additionally, W-BP also possessed water stability with a wet tensile strength of 74 MPa and a low water uptake of 28.3%. These values exceeded those of lignocellulosic BPs and some commercial PCPs. The W-BP could replace transparent PCPs and provide indirectly experimental support to the lignin–cellulose interaction.
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RENEWABLE ENERGY
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2022
·
IF 8.634
Lingyan Zhu,Xudong Liu,Yuan Wu,Qifan Wang,Haotian Wang,Dongbing Li
Lignin-based activated carbons (LAC) were produced using thermochemical pretreatment and chemical activation with KOH. Fast pyrolysis at 550 °C in a CO 2 /N 2 atmosphere resulted in lignin char (LC) with a more developed porous structure than slow pyrolysis. The effect of activation conditions (KOH usage, temperature, and duration) on surface/physicochemical properties and electrochemical characteristics of the resulting LAC was fully studied. Using fast pyrolysis lignin char as a precursor and optimized activation conditions ( w KOH : w LC = 2, 800 °C, and 2 h), the resulting LAC featured a large surface area of 2149.5 m 2 g −1 , a total pore volume of 0.88 m 3 g −1 , and high capacitance of 300 F g −1 at 0.5 A g −1 in a 6 mol L −1 KOH electrolyte. The LAC-based symmetric supercapacitor could offer superior energy density (19.15 W h kg −1 at 250 W kg −1 power density) and a stable lifetime (98.2% of original capacity after 10,000 charge-discharge cycles). The excellent capacitor performance of LAC was attributed to its microporous-mesoporous structure developed from fast pyrolysis and subsequent chemical activation.
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ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Mengzhen Yan,Junqi Cai,Zhiqiang Fang,Huan Wang,Xueqing Qiu,Weifeng Liu
Hydrogels with excellent mechanical properties and high conductivity are key materials for the development of flexible electronic devices, smart soft robots, and so forth. However, the preparation of high-performance conductive hydrogels remains a challenge. Enlightened by the strengthening mechanism of skeletal muscles, a green muscle-like conductive hydrogel was prepared through a repeated mechanical training process. Using cellulose nanofibrils (CNFs) as the fiber reinforcing source, partial depolymerized enzyme hydrolyzed lignin as the interfacial binding agent, and Ag+ as the conducting medium in a polyvinyl alcohol (PVA) matrix, the prepared composite hydrogel exhibited anisotropic high strength, high toughness, and excellent conductivity. Through the introduction of double physical enhancement networks and the adoption of a mechanical training method that mimics the muscle strengthening principle, the enhancement effect of CNFs was maximally demonstrated in the PVA composite hydrogel. Meanwhile, this study also provides a new and effective reference for the preparation of high-performance green hydrogels.
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FUEL PROCESSING TECHNOLOGY
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2022
·
IF 8.129
Lei Wang,Mengdi Liang,Yang Fang,Jun Yin,Jungang Jiang,Yifan Zhang,Haiping Yang
Understanding the pyrolysis mechanism of native lignin is essential for improving the conversion efficiency of fast pyrolysis technology. However, due to the complex and various nature of lignin interunit linkages, the pyrolysis mechanism of lignin has not been clearly revealed so far, especially for native lignin. In this work, two types of guaiacyl-dehydrogenation polymers (G-DHPs) were synthesized using two different methods in vitro , namely endwise polymerization (G-DHPs-endwise) and bulk polymerization (G-DHPs-bulk), which were used as native lignin models. The chemical structures of the synthesized G-DHPs along with natural G-lignin ( i.e., milled wood lignin, MWL) were analyzed by using 2D HSQC NMR, and their pyrolysis characteristics were investigated by using a fixed bed reactor . In comparison with G-DHPs-bulk, G-DHPs-endwise had more similar structure and pyrolysis characteristics with that of MWL, which suggested that G-DHPs-endwise was a more suitable model for G-type lignin. Further mechanical study revealed that the pyrolysis of G-DHPs-endwise underwent an end-breaking pathway, by which the branched carbon of the coniferyl alcohol structure ends were cleaved at the early stage to depolymerize into guaiacol . This study can thus enhance the understanding of the thermal depolymerization of native lignin and provide the evidence for revealing pyrolysis mechanism.
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CARBOHYDRATE POLYMERS
·
2022
·
IF 10.723
Xin Wang,Jinzhi Han,Shuyu Pang,Jiao Li,Jinwei Zhao,Chengrong Qin,Shuangquan Yao,Yang Liu,Chen Liang
Effectively breaking down its anti-depolymerization barrier is key to the conversion and utilization of biomass resources . The anti-depolymerization barrier is mainly composed of a lignin-carbohydrate complex (LCC), which hinder the high-value utilization of biomass. In an alkaline environment, phenyl glycosidic bonds in LCC exist stably. Therefore, it is of great significance for the structural analysis of LCC in alkaline environment. In this study, LCC rich in carbohydrates was extracted from alkaline hemicellulose by using the xylanase-macroporous resin method, the effects of enzyme dosage and treatment time on LCC enrichment were discussed. The results showed that the LC bond of LCC samples was dominated by phenyl glucoside bond, the composition of lignin showed the rule of S > H > G. This method could fulfill the requirements of lignin enrichment and structural integrity. This provides a new method for solving the problems of LCC signal masking and low detection sensitivity.
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INDUSTRIAL CROPS AND PRODUCTS
·
2022
·
IF 6.449
Xin Zhao,Zeyu Zhang,Jinyin Pang,Ling Su
Formaldehyde attacks the ortho phenolic hydroxyl groups on the p-hydroxyphenyl and guaiac-based structures in the lignin, shedding the hydrogen atom on the ortho-position carbon and grafting hydroxymethyl group to obtain the hydroxymethylated modified lignin (HMKL). The infrared spectroscopy , hydrogen NMR spectroscopy, thermogravimetric (TG), and derivative thermogravimetric (DTG) analysis show that the hydroxymethylation modification of alkali lignin is successful. Then, lignin nanoparticles (LNPs) are prepared by the acid precipitation self-assembly method in ethylene glycol solution of hydroxymethylated modified lignin. The particle size and shape of lignin nanoparticles are determined by scanning electron microscopy and dynamic light scattering (DLS) analysis. In the liquefaction agent prepared from polyethylene glycol 400 and glycerol, the graft polyol is liquefied under methanesulfonic acid . The Fourier transform infrared spectroscopy , hydrogen NMR, and thermogravimetric analysis indicate the successful formation of nano-lignin polyols. In addition, epoxy resin is synthesized by two-step epoxidation of nano-lignin polyols including ring-opening and closed-loop epoxidation in an alkaline environment. The prepared epoxy resin from nano-lignin polyol exhibits excellent performance and wide application prospects. The optimum process conditions are the mass fraction of LNP-P is 19.98 %, the amount of catalyst (NaOH) is 20.10 %, the reaction time is 6.99 h, the solid content of the epoxy resin is 57.05 %, the viscosity is 615.58 mPa.s, the tensile strength is 44.80 MPa, the elastic modulus is 2.77 GPa.
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POLYMER BULLETIN
·
2022
·Vol. 80
·期 5
·5553-5571
·
IF 2.843
Shi Mengqing,Wang Xiwen,Yang Jin
A series of lignin-based biological waterborne polyurethanes (LBWPU) with excellent properties were synthesized by prepolymerization with different contents of sodium lignosulfonate aqueous solution (NaLS) as dispersant. Biological isocyanate (1, 5-pentamethylene diisocyanate), biological polyether polyol (H-2000) and castor oil were used as the main reaction materials to prepare waterborne polyurethane with biological content up to 70%, which had excellent storage stability. The effects of different contents of NaLS on the thermo-mechanical properties, mechanical properties and thermal stability of polyurethane films were studied. With the increase in NaLS content, the mechanical properties, storage modulus and water resistance of LBWPU films were significantly enhanced. Meanwhile, the limiting oxygen index of the prepared LBWPU could reach 24.7% after blending with the flame retardant, showing good flame retardancy. In this work, the water-based polyurethane materials with high bio-base content could be used as a film-forming agent in the field of leather finishing agent, which has an important influence on improving the flame retardant of leather. Graphical abstract
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INDUSTRIAL CROPS AND PRODUCTS
·
2022
·
IF 6.449
Haitao Yu,Zhimin Xue,Ruifen Shi,Fengyi Zhou,Tiancheng Mu
Deep eutectic solvents (DESs) composed by carboxylic acids and quaternary ammonium salts are potential candidate for lignocellulose dissolution and pretreatment . To both explore the most efficient DESs for lignocellulose dissolution and pretreatment as well as unveil the process mechanism, DESs composed by carboxylic acids as the hydrogen bond donors (HBDs) and quaternary ammonium salts as the hydrogen bond acceptors (HBAs) were prepared and further applied for kraft lignin (KL) dissolution as well as poplar and pine pretreatment. We found DES composed by lactic acid (LA) and allyltrimethylammonium chloride (ATMAC) with mole ratio of 2:1 is high-efficient for the dissolution of KL. In addition, 70% poplar lignin and 82% pine lignin could be removed at 120 ℃ for 6 h with a solid-to-liquid ratio of 1:10. Furthermore, the -OH and -COOH groups in HBDs of DESs provided active protons to cleave ether bonds and part of carbon-carbon bonds during lignin dissolution and extraction. Additionally, the KL solubility and the Kamlet-Taft (K-T) parameters (α and π * ) of the DESs showed good positive correlation. These findings give a deep insight into the dissolution mechanism of KL and pretreatment of lignocellulose, which is helpful for designing robust DESs for dissolution and pretreatment of lignocellulose.
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