Molecular Catalysis
·
2024
·
IF 3.9
Guili Luan,Guihua Yang,Hongyu Wang,Jiaxuan Li,Haojie Sun,Mengyao Sun,Changfei Shi,Shitao Yu,Ji-Jun Zou,Genkuo Nie
(Alkyl-)cyclohexane diols are of high value as industrial reagents and resources, but current producing methods are still unsustainable. Herein, a new method of producing (alkyl-)cyclohexane diols using lignin derived phenols with yield as high as 91.2 % by selective hydrogenolysis is firstly achieved over Nb 2 O 5 and Ni/MCM-41. The hydrogenolysis is completed by designing two-step reactions compositing of selective crack of C(sp 3 )-O bond and selective hydrogenation of benzene ring of lignin derived phenols to achieve a high selectivity. Nb 2 O 5 demonstrates superior activity and long-life time in C(sp 3 )-O bond cleavage compared to commercial solid acids. The robust catalytic performance was thoroughly analyzed through detailed characterization and attributed to the abundant oxygen vacancies produced, which lead more strong L acids and adsorb the methoxy group in lignin derived phenols and at the same time interact with the acid sites to facilitate the cleavage of the C(sp 3 )-O bond. The consequent selective hydrogenation of benzene ring is completed by Ni/MCM-41 easily. More lignin derived phenols are explored in this reaction with (alkyl-)cyclohexane diols universally synthesized. This work provides a new application of lignin derived phenols to synthesize value-added chemicals and makes contribution to sustainable development by biorefineries.
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2026
·
IF 5.1
Guoping Chen,Xingyun Ye,Xuan Zhou,Dongjie Yang,Weifeng Liu,Jinhao Huang
High-purity lignin was extracted using a citric acid-LiBr molten salt system. • Nano-sized lignin colloidal spheres (LCSs) were prepared via solvent/anti-solvent self-assembly. • The Lignin-Pine shows higher photothermal property due to its higher –OH and β-O-4 retention. • The LCSs exhibit better photothermal property due to the ordered aromatic π–π stacking structure. • The Narrowest bandgap of HK (3.269 eV) explains the superior photothermal performance of LCSs-Pine. Lignin has emerged as a promising photothermal material due to its unique conjugated aromatic rings and phenolic hydroxyl groups. Herein, a citric acid–lithium bromide molten salt extraction method was employed to isolate high-purity lignin from pine, fir, poplar and bamboo. Uniform nano-sized lignin colloidal spheres (LCSs) with ordered supramolecular frameworks were subsequently fabricated through solvent/anti-solvent self-assembly driven by intermolecular hydrogen bonds. Such an ordered stacking structure of LCSs strengthens π–π interactions between aromatic moieties, expanding electron delocalization and boosting non-radiative transitions, thereby exceeding pristine lignin in photothermal conversion. LCSs-Pine displays superior photothermal performance due to the higher hydroxyl density (8.06 mmol·g −1 ), regular G-unit distribution and favorable retention of β-O-4 linkages (46.7%) of pine-derived lignin, contributing to its temperature rise from 30 °C to 84 °C within 10 min at 0.1 W·cm −2 . Density functional theory (DFT) simulations confirm that Lignin-Pine containing relatively higher Hibbert ketone (HK) units (49.5%) with the narrowest bandgap (3.269 eV) rationalizes its superior photothermal performance. The samples were characterized by Fourier-transform infrared spectroscopy (FTIR), quantitative 31 P nuclear magnetic resonance (NMR), two-dimensional heteronuclear single quantum coherence (2D-HSQC) NMR, gel permeation chromatography (GPC), scanning electron microscopy (SEM), dynamic light scattering (DLS), and thermogravimetric analysis (TGA). Moreover, the LCSs exhibit excellent photothermal cycling and thermal stability. This work provides a scalable, structure-guided route to convert lignin into efficient photothermal nanomaterials.
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
·
2022
·Vol. 23
·期 15
·8743
·
IF 6.208
Baojuan Deng,Yadan Luo,Meijiao Peng,Tao Li,Jianwei Su,Yang Wang,Xuelian Xia,Chengqi Feng,Shuangquan Yao
As a green and efficient component separation technology, organic acid pretreatment has been widely studied in biomass refining. In particular, the efficient separation of lignin byp-toluenesulfonic acid (p-TsOH) pretreatment has been achieved. In this study, the mechanism of the atmospheric separation of bagasse lignin withp-TsOH was investigated. The separation kinetics of lignin was analyzed. A non-simple linear relationship was found between the separation yield of lignin and the concentration ofp-TsOH, the temperature and the stirring speed. The shrinking nucleus model for the separation of lignin was established based on the introduction of mass transfer and diffusion factors. A general model of the total delignification rate was obtained. The results showed that the process of lignin separation occurred into two phases, i.e., a fast stage and a slow stage. The results provide a theoretical basis for the efficient separation of lignin byp-TsOH pretreatment.Keywords:p-toluenesulfonic;lignin;mechanism;kinetics;shrinking nucleus model
✓ 已验证
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2022
·
IF 8.025
Wangda Qu,Zizhu Zhao,Chen Liang,Pengyu Hu,Zhongyi Ma
To achieve lignin valorization, we reported a simple method to direct covert lignin into carbon foam materials in this work. Unlike multiple steps required to fabricate traditional carbon foams from most of other precursors (often non-renewable), the approach herein required solely heating for carbon production. We found that the intrinsic features of lignin render the formation of lignin block meanwhile generate the porous structure under the invented heating course. Three key factors including glass transition temperature , crosslinking ability, and thermal stability of lignin were identified to determine the successful fabrication of lignin foam (i.e., precursor of carbon foam). Upon tuning the heating profile or fractionating the lignin, lignin foam with different morphologies and properties were obtained. After carbonization, the selected lignin-derived carbon foams possessed well porous structures with bulk densities of 0.52 or 0.62 g cm −3 , superior integrity with strength properties of around 10 MPa, BET surface areas of 143.29 or 325.86 m 2 g −1 , and many other attractive properties. This work is expected to stimulate further seek of lignin valorization in carbon foam production.
✓ 已验证
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2020
·Vol. 8
·期 45
·24065-24074
·
IF 11.301
Weisheng Yang,Xiu Wang,Liang Jiao,Huiyang Bian,Yongzheng Qiao,Hongqi Dai
Lignin, a renewable and low-cost biopolymer, has been widely reported as an energy-storage material. The energy-storage capability of lignin primarily originates from the redox of its internal quinone group. Hence, effective optimization of the lignin structure is of great significance for increasing the quinone group content, which is vital for improving the energy-storage performance of lignin-based electrode materials. Herein, synthetic polymers (SPs) with an extremely high quinone group content were prepared using lignin-derived aromatic monomers (LDAMs) as precursors. The chemical structure of the SP samples was analyzed using 13C and 31P NMR, and the results showed that their quinone content was as high as 5.49–6.75 mmol g−1, which is 6–7 times higher than that of commercial kraft lignin (KL). The RGO/SP composite was prepared using ultrasound-assisted self-assembly, and as expected, the SP coupled with reduced graphene oxide acquired a high specific capacitance of 352–465 F g−1, which is 1.4–1.9 times higher than that of RGO/KL. In addition, the RGO/SP electrodes showed an excellent rate performance of 265–365 F g−1 at 10 A g−1. Overall, our strategy provides a possibility for the preparation of high-performance lignin-based energy-storage materials.
✓ 已验证
DOI
高影响因子
Journal of Cleaner Production
·
2020
·
IF 7.246
Ning Ding,Huai Liu,Yong Sun,Xing Tang,Tingzhou Lei,Feng Xu,Xianhai Zeng,Lu Lin
Non-phenol structure in lignin is difficult to be degraded under alkaline conditions, thus limiting the delignification efficacy in many pretreatment technologies . Intriguingly, the non-phenol structures can be degraded into low-molecular-weight products in cooking with active oxygen and solid alkali process. Herein, model compounds were adopted to investigate the degradation mechanism of lignin non-phenol structure under same conditions. Two pathways of converting the non-phenol structure to degradable structures are found: 1) After the C α -C β bond cleavage at the lignin side chain, the benzoic structure intermediates are degraded; 2) After hydrolysis of the aryl-ether bond, the phenol structure intermediates are then degraded. Moreover, the degradation of the phenol structure intermediates will further promote the hydrolysis of the ether bonds, thus resulting in the improvement in the delignification process. This work describes a novel pathway in lignin oxidation degradation and helps to understand the chemistry of lignin degradation process in related alkaline oxidation pretreatment technologies .
✓ 已验证
DOI
高影响因子
EUROPEAN POLYMER JOURNAL
·
2021
·
IF 4.598
Jia Zeng,Dongqiao Zhang,Weifeng Liu,Jinhao Huang,Dongjie Yang,Xueqing Qiu,Shenhui Li
High efficiency lignin-grafted cationic polyacrylamide multifunctional flocculant (CL-CPAs) was synthesized via “grafting to” strategy using carboxymethylated lignin (CL), acrylamide (AM) and methylacryloyloxyethyltrimethyl ammonium chloride (DMC) as raw materials. The synthesized CL-CPAs showed high flocculation efficiency. Only a small dosage between 3.6 and 4.2 mg‧L −1 of CL-CPAs and a short flocculation time of 1–2 min were needed for sedimentation of kaolin suspension. Meanwhile, the carboxyl groups on the modified lignin endowed CL-CPAs with good copper ion capture function through complexation and electrostatic interaction. In addition, simultaneous flocculation of kaolin suspension and removal of copper ion was achieved for CL-CPAs attributing to the charge neutralization, bridging, and electrostatic complexation. The synthesized carboxymethylated lignin-based flocculants are cheap, environmentally friendly and technically feasible, showing broad prospects in wastewater treatment.
✓ 已验证
DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2022
·
IF 6.633
Weili Ma,Guangyong Liu,Qian Wang,Ju Liu,Xiaoqing Yuan,Jiayu Xin,Sufan Wang,Hongyan He
The valuable exploitation of lignin depends mainly on the conversion strategy of lignin, of which the conversion of lignin into valuable aromatic molecules is a critical approach. In this study, three lignin model compounds, veratrylglycerol-β-guaiacyl ether (VG), 4-phenoxyphenol (PP), 4-ethoxyphenol (EP), are comparatively degraded by electrochemical oxidation in an aprotic ionic liquid (IL), [Bmim][OTf], and two protic ILs, [PrSO 3 Hmim][OTf] and [BSO 3 Hmim][HSO 4 ]. The protic ILs are more favorable for the degradation of lignin-derived substrates compared to aprotic ILs. Oxygen reduction reaction (ORR) in the O 2 atmosphere generates reactive oxygen species (ROSs) that play an indirect oxidation effect on substrates, which is stronger for the protic ILs. In addition, the different types of ILs allow modulating the distribution of degradation products. Combined with the identification of products and CV curves, the microscopic mechanisms of the degradation process for lignin model compounds are further elucidated.
✓ 已验证
DOI
高影响因子
Energy & Environmental Science
·
2013
·Vol. 6
·期 3
·994-1007
·
IF 11.653
Qi Song,Feng Wang,Jiaying Cai,Yehong Wang,Junjie Zhang,Weiqiang Yu,Jie Xu
Valorization of native birch wood lignin into monomeric phenols over nickel-based catalysts has been studied. High chemoselectivity to aromatic products was achieved by using Ni-based catalysts and common alcohols as solvents. The results show that lignin can be selectively cleaved into propylguaiacol and propylsyringol with total selectivity >90% at a lignin conversion of about 50%. Alcohols, such as methanol, ethanol and ethylene glycol, are suitable solvents for lignin conversion. Analyses with MALDI-TOF and NMR show that birch lignin is first fragmented into smaller lignin species consisting of several benzene rings with a molecular weight of m/z ca. 1100 to ca. 1600 via alcoholysis reaction. The second step involves the hydrogenolysis of the fragments into phenols. The presence of gaseous H2 has no effect on lignin conversion, indicating that alcohols provide active hydrogen species, which is further confirmed by isotopic tracing experiments. Catalysts are recycled by magnetic separation and can be reused four times without losing activity. The mechanistic insights from this work could be helpful in understanding native lignin conversion and the formation of monomeric phenolics via reductive depolymerization.
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Jie Dong,Weihua Xu,Shaobo Liu,Youzi Gong,Ting Yang,Li Du,Qiang Chen,Xiaofei Tan,Yunguo Liu
The conversion of biomass wastes to highly efficient biochar-based catalysts has attracted more and more attention because it meets the environmental protection concept of waste recycling. In this work, a novel magnetic catalyst (CoFe 2 O 4 @BC) was developed by using alkaline lignin, the dominant by-products of papermaking industry, as feedstock for biochar. More importantly, PAA (CH 3 C(=O) OOH) was successfully activated by CoFe 2 O 4 @BC nanoparticles for sulfamethoxazole (SMX) elimination. The catalytic activity of CoFe 2 O 4 @BC on PAA activation was systematically studied. When PAA was 825 μM and CoFe 2 O 4 @BC was 100 mg/L, 10 mg/L SMX could be completely degraded. The cycle of Co 3+ /Co 2+ of CoFe 2 O 4 @BC prompted the generation of acetyl(per)oxyl groups (CH 3 C(O)O• and CH 3 C(O)OO•), which were believed to be the dominant reactive substances for SMX degradation. The degradation of SMX was promoted under near-neutral pH conditions, and was inhibited when humic acid and HCO 3 − were added, while the Cl − showed a negligible influence. According to the analysis of oxidation products, three main transformation pathways of SMX were illustrated. The remarkable stability and magnetic separability of CoFe 2 O 4 @BC make it have a wider application prospect in the treatment of various wastewater.
✓ 已验证
DOI
高影响因子
Phytopathology Research
·
2024
·Vol. 6
·期 1
·1-15
·
IF 3.2
Li Xiufang,Liu Zongling,Wu Haoming,Yu Zhuoxin,Meng Jiaorong,Zhao Haiyun,Deng Xingli,Su Yizu,Chen Baoshan,Li Ru
Sugarcane ( Saccharum spp.) is a major sucrose and bioenergy crop in the world. The fungal pathogen Sporisorium scitamineum causes sugarcane smut, a devastating disease that destroys stalks and reduces sugar content in sugarcane. This disease can be controlled most effectively by applying smut-resistant sugarcane varieties. Previous studies have shown that Dirigent (DIR ) genes are involved in the synthesis of the lignin precursor pinoresinol, which plays a crucial role in plant resistance to biotic stresses. However, the immune response of the DIR homologs in sugarcane ( ScDIR ) has not been reported yet. In this study, we found that the lignin content of smut-resistant sugarcane varieties (ZZ1, ZZ6, and ZZ9) was significantly higher than that of smut-susceptible varieties (GT42, ROC22, and FN41), and the lignin content of sugarcane increased after smut infection. The smut-resistant and smut-susceptible clones derived from the same genetic population (ROC25 × YZ89-7) showed similar patterns. Quantitative real-time PCR assays revealed that among the 64 DIR genes in sugarcane, ScDIR5 , ScDIR7 , ScDIR11 , and ScDIR40 showed elevated expression after S. scitamineum infection. In vitro coupling reactions showed that the four corresponding ScDIR proteins could mediate the coupling of coniferyl alcohol and its conversion into the lignin precursor pinoresinol. Overexpression of the four ScDIR genes in Nicotiana benthamiana enhanced disease resistance to the fungal pathogens Sclerotium rolfsii , Rhizoctonia solani , and Botrytis cinerea . Moreover, transgenic sugarcane overexpressing these ScDIR genes showed enhanced resistance to smut disease. Taken together, our findings provide evidence that sugarcane ScDIR genes can improve the resistance of plants to fungal pathogens and highlight their potentials in sugarcane breeding for disease resistance.
✓ 已验证
DOI
高影响因子
JOURNAL OF THERMOPLASTIC COMPOSITE MATERIALS
·
2024
·
IF 3.6
Shihui Wang,Yanling Hao,Qixiang He,Qiqi Gao
In this work, firstly, the optimal performance ratio of potato starch and polyvinyl alcohol (PVA) was selected, and then the sustainable high-grade food packaging film was developed by adding different amounts (0, 5, 10, 15, 20, and 25 wt% based on the starch mass) of functional additive lignin into the starch - PVA film matrix. Starch - PVA based films with different amounts of lignin were studied from the aspects of morphology, physical and chemical properties, barrier properties, mechanical properties and antioxidant properties. Mechanical tests showed that lignin significantly improved the tensile strength (TS) of the film and effectively blocked the passage of water vapor. Lignin, starch and PVA were linked by hydrogen bond to form polymer network structure, which improved the interfacial compatibility between polymers. The interaction between polymer molecules and the distribution of lignin particles were confirmed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The high content of phenolic hydroxyl in lignin undergoes proton coupled electron transfer mechanism, which endows the composite film with high antioxidant activity, which is proved by DPPH radical scavenging activity experiment. At the same time, it also gives the film excellent UV barrier and antibacterial properties. The introduction of lignin in this study provides a valuable way for the preparation of multifunctional composite films using biomass as raw materials, and has a potential application prospect in food packaging.
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）