ACS Omega
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2023
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IF 4.1
Yajie Zuo,Siying Zhu,Yi Liu,Jingjing Zhao,Shiyi Zhang,Chongmin Zhong
Efficient O-alkylation of phenols and carboxylic acids has essential applications in organic synthesis. A mild alkylation method for phenolic and carboxylic OH groups is developed using alkyl halides as alkylation reagents and tetrabutylammonium hydroxide as a base, and lignin monomers can be fully methylated in quantitative yields. Additionally, phenolic and carboxylic OH groups can be alkylated by different alkyl halides in one pot in different solvent systems.
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Biotechnology for Biofuels and Bioproducts
·
2022
·Vol. 15
·期 1
·1-12
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IF 0
Hu Yueli,Zhang Chen,Zou Lihua,Zheng Zhaojuan,Ouyang Jia
Background The conversion of lignin-derived aromatic monomers into valuable chemicals has promising potential to improve the economic competitiveness of biomass biorefineries. Pinosylvin is an attractive pharmaceutical with multiple promising biological activities. Results Herein, Escherichia coli was engineered to convert the lignin-derived standard model monomer cinnamic acid into pinosylvin by introducing two novel enzymes from the wood plant: stilbene synthase from Pinus pinea (PpSTS) and 4-Coumarate-CoA ligase from Populus trichocarpa (Ptr4CL4) . The expression of Ptr4CL4 drastically improved the production of pinosylvin (42.5 ± 1.1 mg/L), achieving values 15.7-fold higher than that of Ptr4CL5 (another 4-Coumarate-CoA ligase from Populus trichocarpa ) in the absence of cerulenin. By adjusting the expression strategy, the optimized engineered strain produced pinosylvin at 153.7 ± 2.2 mg/L with an extremely high yield of 1.20 ± 0.02 mg/mg cinnamic acid in the presence of cerulenin, which is 83.9% ± 1.17 of the theoretical yield. This is the highest reported pinosylvin yield directly from cinnamic acid to date. Conclusion Our work highlights the feasibility of microbial production of pinosylvin from cinnamic acid and paves the way for converting lignin-related aromatics to valuable chemicals.
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JOURNAL OF APPLIED POLYMER SCIENCE
·
2023
·Vol. 140
·期 12
·e53636
·
IF 3
Jituo Chen,Yuxiang Zhang,Feng He,Jun Ying,Shi-Neng Li,Li Peng,Qiang Wu,Zhiqiang Fan,Baiyu Jiang
Preparing bio-based epoxy resins with high performance is crucial to sustainable development. However, seeking renewable and flame-retardant epoxy resins with high mechanical properties are still challenging. Here, we reported a facile way to transform lignin derivatives to intrinsic flame-retardant epoxy resins with satisfactory mechanical properties. Two guaiacol-based novolac epoxy resins (i.e., GTEP/DDM and GPEP/DDM) were prepared as alternatives for petroleum-based DGEBA/DDM. The cured GTEP/DDM product showed a high T g of 209.5°C, a high tensile modulus of 3.13 GPa, and a high LOI of 28.6% with UL-94 V-1 rating, which outperformed DGEBA/DDM system. Specially, GPEP/DDM resin possessed more superior mechanical properties (e.g., tensile strength of 73.9 MPa, and tensile modulus of 5.85 GPa) owing to additional interactions (i.e., π–π interactions and hydrogen bonds), and outstanding anti-flammability (e.g., LOI of 31.2% with UL-94 V-0 rating) due to the endow of phosphorus-containing groups. The mechanical reinforcement and flame-retardant mechanisms were clarified based on structural evolution and performance variation. This work provides an efficient synthesis route to achieve a high-performance thermoset, which is a promising alternative for substituting conventional bisphenol-A epoxy resin for use as fireproof materials.
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FUEL
·
2022
·
IF 8.035
Tao Liu,Zhipeng Tian,Weijie Zhang,Bowen Luo,Libin Lei,Chao Wang,Jianping Liu,Riyang Shu,Ying Chen
Selective hydrodeoxygenation (HDO) of phenolic compounds derived from the pyrolysis lignin-oil to desired products is a promising route in the high-value utilization of biomass-derived products. Cyclohexanol, as one of the important chemical materials, is an intermediate of catalytic HDO of guaiacol. Controllable selective HDO is conducted to improve the cyclohexanol selectivity over RuFe bimetallic catalyst prepared by ethylene glycol reduction method in this work. 99.99% guaiacol conversion and 81.35% cyclohexanol selectivity are obtained over optimized 2Ru2.5Fe/Al 2 O 3 -EG catalyst, which is better than those over 2Ru/Al 2 O 3 -EG catalyst. The mild catalyst preparation method gives it a high dispersion and uniform distribution of Ru and Fe species on the support. Various characterizations have proved that the intimate contact between Ru and Fe 2 O 3 species contributes to the improvement of cyclohexanol selectivity. Partial blockage of Ru sites by Fe 2 O 3 species slightly reduces the hydrogen adsorption capacity while the addition of Fe helps enhancing the hydrogenolysis of C-OMe bond. The reciprocal effect facilitates the removal of methoxyl groups and hinders the dehydroxylation of cyclohexanol to cyclohexane. Besides, other phenolic compounds and pyrolysis lignin-oil as substrates also show good selective HDO reactivity to corresponding alkyl cyclohexanols, implying potential application in the transformation from lignin-oil to high-value products.
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ACS Sustainable Chemistry & Engineering
·
2023
·
IF 8.4
Sican Zhou,Kaifeng Huang,Xiwei Xu,Binbo Wang,Weiqiong Zhang,Yi Su,Kezhen Hu,Chuanzhi Zhang,Jin Zhu,Gengsheng Weng,Songqi Ma
Developing thermosets from lignin has huge significance due to the abundant renewable resources and rigid polyaromatic structure of lignin; nevertheless, it is still a challenge to develop fully biobased thermosets with high performance. Herein, lignin was modified with glycidol and further reacted with maleic anhydride to produce multicarboxyl lignin (MGL) which possessed improved solubility in green solvents such as ethanol and increased reactivity toward the epoxy group. Fully biobased epoxy thermosets were prepared from MGL, citric acid (CA), and epoxidized soybean oil (ESO) with the assistance of ethanol. The thermosets exhibited superior thermal and mechanical properties and degradability. This study provides a straightforward countermove to achieve rigid and flexible thermosets from lignin and other abundant renewable bioresources and also provides a promising sustainable alternative to conventional epoxy thermosets.
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
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2023
·
IF 8.2
Ling Zheng,Farzad Seidi,Weibing Wu,Yuanfeng Pan,Huining Xiao
An effective way of improving the efficiency of agrochemicals and improving crop yield and quality is by slow or sustained release , which is conducive to environmental protection. Meanwhile, the excessive amount of heavy metal ions in soil can create toxicity in plants. Here, we prepared lignin-based dual-functional hydrogels containing conjugated agrochemical and heavy metal ligands through free-radical copolymerization. The content of the agrochemicals (including plant growth regulator 3-indoleacetic acid (IAC) and herbicide 2,4-dichlorophenoxyacetic acid (DCP)) in the hydrogels were tuned by changing the hydrogel composition. The conjugated agrochemicals could slowly release through the gradual cleavage of the ester bond. As a result of the release of the DCP herbicide, the growth of lettuce was effectively regulated, thus confirming the feasibility and effectiveness of this system in application. At the same time, due to the presence of metal chelating groups (such as COOH, phenolic OH, and tertiary amine) the hydrogels could act as adsorbents or stabilizers towards heavy metal ions for improving the soil remediation and preventing the adsorption of these toxic metals by plant roots. Specifically, Cu(II) and Pb(II) could be adsorbed >380 and 60 mg/g, respectively.
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SCIENCE OF THE TOTAL ENVIRONMENT
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2022
·
IF 10.753
Jialong Wu,Xiaozhen Ma,Pitchaimari Gnanasekar,Fan Wang,Jin Zhu,Ning Yan,Jing Chen
Superhydrophobic polyurethane foam is one of the most promising materials for oil-water separation. However, there are only limited studies prepared matrix superhydrophobic foams as adsorbents. In this paper, SiO 2 modified by 1H, 1H, 2H, 2H-perfluorododecyl trichlorosilane (F-SiO 2 ) was added into the lignin-based foam matrix by a one-step foaming technique. The average diameter of F-SiO 2 was about 480 nm with an water contact angle (WCA) of 160.3°. The lignin-based polyurethane foam with F-SiO 2 had a superhydrophobic water contact angle of 151.3°. There is no obvious change in contact angle after 100 cycles of compression or after cutting and abrasion. Scanning electron microscopy (SEM) analysis showed that F-SiO 2 was distributed both on the surface and inside of the foam. The efficiency for oil-water separation reached 99 %. Under the light intensity of 1 kW/m 2 , the surface temperature of the lignin-based foam rose to 77.6 °C. In addition, the foam exhibited self-cleaning properties and degraded within 2 h in an alcoholic alkali solution. Thus, in this study, we developed a novel matrix superhydrophobic lignin-based polyurethane foam with an excellent promise to be used as oil water separation adsorbents in industrial wastewater treatment and oil spill clean-up processes.
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
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2022
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IF 8.025
Jianhua Huang,Haixu Wang,Weifeng Liu,Jinhao Huang,Dongjie Yang,Xueqing Qiu,Liang Zhao,Fengchao Hu,Yuexia Feng
Using cheap and green lignin as a partial substitute for petroleum-based polyols is highly attractive for sustainable development of polyurethane elastomers (LPUes). However, the traditional synthesis process of LPUes inevitably uses toxic solvents that are difficult to remove or carcinogenic. Here, we reported a solvent-free synthesis method to prepare lignin-containing polyurethane elastomers (SF-LPUes) with high strength, high toughness and high elasticity. Most of the hydroxyl groups of lignin reacted with isocyanates to form a strong chemical cross-linking network, while the unreacted ones formed a dynamic hydrogen bond network with polyurethane matrix, contributing to the in-situ formation of lignin nanoparticles to build a nano-micro phase separation structure. Consequently, a dual-crosslinking network structure was formed and endowed SF-LPUes with excellent mechanical properties. Especially, the SF-LPUes prepared from low molecular alkali lignin possessed a tensile strength as high as 38.2 MPa, a maximum elongation at break of 1108 %, and an elastic recovery ratio of up to 98.7 %. Moreover, SF-LPUes showed impressing reprocessing performance and aging resistance. This work provides an industrial application prospect for the synthesis of lignin-containing polyurethane elastomers via a solvent-free synthesis process.
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CHEMICAL ENGINEERING JOURNAL
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2022
·
IF 16.744
Weichen Wang,Tian Sheng,Shanshuai Chen,Zhiyu Xiang,Fangyuan Zhou,Wanbin Zhu,Hongliang Wang
Designing highly active catalysts for selective hydrodeoxygenation (HDO) of lignin-derived oxygenates into well-defined compounds is of great importance for realizing high-value utilization of lignin. Defect engineering in metal–organic frameworks (MOFs) is an emerging concept for tailoring MOF properties, which might be a promising strategy in the synthesis of high-performance catalysts. Herein, we developed a facile synthetic strategy by adding trifluoroacetic acid as the modulator to prepare a bifunctional catalyst (Pd/NH 2 -MIL-53-d) consisting of Pd nanoparticles highly dispersed on defective NH 2 -MIL-53(Al). Characterizations, including TEM, XRD, IR, XPS and NH 3 -TPD, were employed to reveal the morphology and physicochemical properties of the catalysts. Results indicated that the introduction of defects leads to the generation of coordinatively unsaturated metal sites, which can act as anchor points for high-dispersion of Pd nanoparticles and as additional active acid sites for catalytic reactions. 100% conversion of vanillin and other 8 representative derivates of lignin into their decarbonyl products with yields over 99% has been achieved under mild conditions in the water. Density functional theory calculations revealed that the HDO of vanillin into 2-methoxy-4-methylphenol mainly underwent a cascade of hydrogenation-hydrogenolysis routes, and the synergistic interaction between Pd and defective NH 2 -MIL-53(Al) facilitated the novel bifunctional catalyst to exhibit outstanding catalytic performance. No apparent deactivation of the catalyst was noticed after it was reused 5 times. Therefore, engineering of defects in MOFs holds enormous potential in designing novel bifunctional catalysts for lignin valorization.
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2022
·
IF 8.025
Linghong Yin,Pengyu Hu,Chen Liang,Jie Wang,Ming Li,Wangda Qu
Lignin is a renewable biomacromolecule that can be used as precursors for carbon materials. In this work, highly flexible lignin-based carbon nanofibers with abundant ultra-micropores are constructed via electrospinning, oxidative stabilization and carbonization. The results indicate that replacing PAN with 80 % lignin is feasible in regulating ultra-micropores. The synthesized L4P1-CNFs possess many attractive properties (e.g., pore size distribution , electrochemical and deionization property) compared with that produced from other non-renewable precursors or more-complexed processes. It shows excellent electrochemical double-layer capacitance in 6 M KOH (233 to 162 F g −1 at 0.5 to 5 A g −1 ) and 1 M NaCl (158 to 82 F g −1 at 0.5 to 5 A g −1 ) electrolytes. Upon assembling into CDI cells, the average salt adsorption rate could reach 1.79 mg g −1 min −1 at 1.2 V and 3.32 mg g −1 min −1 at 2 V in 500 mg L −1 . Benefiting from the excellent flexibility, we innovatively stack four layers of L4P1-CNFs to improve the areal electrosorption capacity to 0.0817 mg cm −2 at 500 mg L −1 , significantly higher than that of traditional carbon-based electrodes. The good desalination property makes lignin-based carbon nanofibers ideal for practical, low-cost capacitive deionization applications.
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ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Yang Cao,Jie Gao,Cheng Zhang,Daniel C.W. Tsang,Jiajun Fan,James H. Clark,Gang Luo,Xiangdong Zhu,Shicheng Zhang
Efficient conversion of renewable lignin into value-added chemicals and biofuel is of great importance for the sustainable development of biorefineries. However, lignin valorization is highly restricted by its structural variation and complexity. In this regard, we have produced a series of lignins extracted from grass, hardwood, and softwood and focused on scrutinizing their structural variability and key characteristics to provide structural insights into fast and selective production of aromatics. As an energy-efficient approach, microwave-assisted hydrothermal liquefaction without introducing an external oxygen was performed to facilitate the base-catalyzed depolymerization of lignin under moderate conditions. The general applicability of this approach was proved on five different lignins. High yields (58.5–78.6%) of low-molecular-weight bio-oil from all lignins were obtained only after 1 min at 220 °C. In particular, a high ratio of cleavable β–O–4 linkage of grass lignin enabled a fast monomer production, while its specific p-coumaric acid moieties allowed a high monomer selectivity to 4-vinylphenol of 66%. A difference in the product distribution was systematically investigated through a comprehensive analysis of lignin characteristics (e.g., interlinkage, S/G/H unit, and molecular weight) and stability studies of main monomeric products. These results revealed the fast degradation of reactive intermediates (aldehydes and S-type products) and how the monomer’s stability/reactivity affects the selective production. Alongside reaction parameters, several critical factors governing the lignin conversion were further identified by calculating the Pearson correlation coefficient between lignin characteristics and the conversion efficiency. The lignin structure–property–degradability relationships and reaction mechanisms are expounded and updated to foster efficient lignin utilization.
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INDUSTRIAL CROPS AND PRODUCTS
·
2022
·
IF 6.449
Zhihui Chen,Shuaibin Zhang,Bochao Yan,Qinjie Cai,Suping Zhang
Phosphoric acid-activated lignin-based solid acid catalysts (PLSA) were prepared from lignosulfonate by phosphoric acid activation, carbonation , and sulfonation. The physicochemical properties of catalysts were determined by SEM, N 2 adsorption-desorption, FT-IR, XRD , XPS and element analysis. Masses of phosphorous-containing group were grafted on catalyst surface during phosphoric acid activation and carbonation to provide sites for subsequent -SO 3 H substitution. PLSA could efficiently convert cellulose residue into levulinic acid. The effects of reaction temperature, residue time, catalyst loading, substrate concentration, solvent and catalyst stability were investigated and optimized. Using PLSA as catalyst, 67.9 mol% LA yield was obtained from 4 g cellulosic residue at 190 ℃ in 150 min in MIBK/H 2 O-NaCl. Overall, this work provides a valuable basis for the application of lignin-based solid acid in biomass valorization.
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