ACS Catalysis
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2019
·
IF 12.221
Hongji Li,Anon Bunrit,Jianmin Lu,Zhuyan Gao,Nengchao Luo,Huifang Liu,Feng Wang
Depolymerization of lignin meets the difficulty in cleaving the robust aryl ether bond. Herein, through installing an internal nucleophile in the β-O-4′ linkage, the selective cleavage of aryl ether was realized by the intramolecular substitution on aryl rings affording non-phenolic arylamine products. In particular, nitrogen-modified lignin models and lignin samples were employed to generate the iminyl radical under photocatalytic reduction, which acted as the internal nucleophile inducing aryl migration from O to the N atom. The following hydrolysis released primary arylamines and α-hydroxy ketones. Mechanism studies including electron spin resonance (ESR), fluorescence quenching experiments, and density functional theory (DFT) calculations proved the aryl migration pathway. This method enables access to non-phenolic arylamine products from lignin conversion.
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JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
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2023
·
IF 6
Runzhen Lai,Jun Hu,Yahui Sun,Ping Lu
Activated carbons (AC) were prepared from the three major components (cellulose, xylan , and lignin) of lignocellulosic biomass by H 3 PO 4 activation. Physicochemical characterizations reveal that as compared with AC from lignin (AC-L), AC from carbohydrates, especially AC from xylan (AC-X), have higher-developed porous structure, more disordered carbon, and more active O-containing and P-containing functional groups. The adsorption of methylene blue (MB) on all ACs followed Langmuir isotherm and pseudo-second-order kinetic models . Primarily due to its superior porosity, AC-X possessed the highest adsorption capacity for MB of 666 mg/g. AC from cellulose (AC-C) and AC-L followed with the adsorption capacities of 498 mg/g and 395 mg/g. The adsorption of MB was endothermic and AC-X had the highest feasibility and spontaneity. AC-X also exhibited superior adsorption capacities for the adsorption of typical heavy metals, although the superiority is much weaker as compared with that for MB. This research suggests the positive impact of carbohydrates, especially hemicellulose , in the precursors of the ACs on their adsorption performances.
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ACS Sustainable Chemistry & Engineering
·
2019
·
IF 6.97
Wei Yang,Munan Fang,Hao Xu,Hui Wang,Shengji Wu,Jie Zhou,Shouxin Zhu
To clarify the interactions between holocellulose and lignin, the hydrolysis behaviors of sawdust, holocellulose, lignin, and holocellulose–lignin mixture (HLM) in subcritical water were investigated in the present study, where HLM acted as a model of sawdust without covalent linkages between holocellulose and lignin. Holocellulose in sawdust showed negligible effects on lignin at low reaction temperatures, whereas it might promote the hydrolysis of lignin at higher reaction temperatures. In contrast, the hydrolysis of holocellulose in sawdust was inhibited by lignin due to the high bond dissociation energies of covalent linkages between them. The destruction of covalent linkages mainly occurred at the reaction temperatures of 273–315 °C, due to the high activation energy at this temperature range. However, they could barely be destroyed at the reaction temperatures of 192–273 °C. The lignin inhibited the ring scission and glycosidic bond cleavage of holocellulose, resulting in lower yields of total carbohydrates and furan derivates than those of HLM. In addition, it also suppressed the decomposition of holocellulose hydrolysate to levoglucosenone and aromatic-linked chars. The above results could provide the basis for developing models for predicting product distribution during the hydrolysis of biomass.
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JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
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2016
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IF 3.652
Yalun Hu,Isaac Nartey Oduro,Yong Huang,Yunming Fang
The structural characteristics and pyrolysis behaviors of two holocelluloses obtained from lignin-first biorefinery with Ru/C or Raney Ni as catalysts were studied in this paper. The infrared spectra of the remaining solid from the lignin-first biorefinery show that both lignin and a portion of hemicellulose were decomposed. Compared with Ru/C, Raney Ni was more effective for delignification and gave a holocellulose with higher degree of crystallinity, based on both the ratio of infrared bands (1372 cm −1 /2900 cm −1 ) and XRD analysis. The pyrolyses of holocelluloses were performed in fixed-bed and free-falling reactors, and the resulting char yields from both reactors were significantly higher than those of the parent biomass and commercial cellulose. This resulted from the cleavage of cellulose chain during the lignin-first biorefinery. Raney Ni related biorefinery cleaved cellulose chain to a higher degree.
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ANALYST
·
2021
·Vol. 146
·期 24
·7573-7582
·
IF 4.616
Xiaoyong Zhao,Huiwen Wang,Yilong Liu,Ruohan Ou,Yaqin Liu,Xian Li,Yuanjiang Pan
Driven by the interest in metabolomic studies and the progress of imaging techniques, small molecule analysis is booming, while it remains challenging to be realized by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). Herein, lignin, the second most abundant biomass in nature, was applied as a dual-ion-mode MALDI matrix for the first time to analyze small molecules. The low ionization efficiency and strong optical absorption properties make lignin a potential MALDI matrix in small molecule analysis. A total of 30 different small molecules were identified qualitatively and six kinds of representative molecules were detected quantitatively with a good linear response (R2 > 0.995). To verify the accuracy of our quantitative method in MALDI, myricitrin, a major bioactive component in Chinese bayberry, was analyzed in different cultivars and tissues. The myricitrin content in real samples detected by MALDI was highly consistent (R2 > 0.999) with that detected by high-performance liquid chromatography, thus indicating the applicability of the lignin matrix. Further characterization by ultraviolet and nuclear magnetic resonance spectroscopy was carried out to explain the possible mechanism of lignin as a matrix and provide more theories for a rational matrix design.
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JOURNAL OF APPLIED POLYMER SCIENCE
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2019
·Vol. 136
·期 21
·47482
·
IF 2.188
Dandan Bao,Yuntao Xie,Shenglin Ma,Zhibing Wu,Ji-Gang Piao
Lignin is considered one of the main biorenewable polymers from natural resources. Each year, a large amount of lignin is generated as a waste byproduct of the pulping process in the paper industry. However, it is seldom treated as a value-added material because of its undefined structure, the diverse methods of isolation and processing, and the origin of the material; these greatly hinder its application. Therefore, it is of great significance to explore new potential applications of this readily available yet underappreciated natural product. In this study, we developed a preparation method of lignin-based microstructures or nanostructures via self-assembly. We created various self-assembled nanostructures, including nanocubes, nanorods, nano-octahedrons, nanobranches, and other morphologies, by choosing different types of simple inorganic acids at various pHs. Some of these nanostructures have never been reported. These structures were fully characterized with scanning electron microscopy, ultraviolet–visible spectroscopy, and dynamic light scattering. All of them were uniform and stable. They displayed little or no cytotoxicity to cells in vitro at concentrations up to 1024 μg/mL. We hope the results of this study provide some insight for the future development of new applications of lignin-based materials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136 , 47482.
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FUEL
·
2020
·
IF 5.578
Sijia Chen,Hao Cheng,Shubin Wu
In this paper, kraft lignin (KL) was fractionated by organic solvent method, and different lignin fractions were characterized by Gel permeation chromatography (GPC) and 1 H– 13 C HSQC NMR. The active functional groups content was analyzed by 31 P NMR and headspace gas chromatography (HS-GC). The results showed that fractionation could efficiently separate different molecular weight lignin fractions and the linkage bonds of lignin fractions F1 to F3 changed as follows: non-condensed linkages ( β -O-4) and condensed linkages ( β -5 and β - β ) both decreased. Moreover, some active functional groups such as phenolic hydroxyl groups and methoxy groups increased by fractionation. The thermochemical properties and volatiles formation rule of fractionized kraft lignin during pyrolysis were studied by thermogravimetric (TG), kinetics analysis, in situ Fourier-transform infrared spectroscopy (FT-IR) and U-type tube closed system pyrolysis experiment. The result showed that low-molecule lignin fractions were easier to depolymerize than that with high-molecule. Low-molecule lignin fractions had better selectivity of S-type monomer products while high-molecule fractions had better selectivity of G-type monomer products, and pyrolysis conducted at a relatively higher temperature was beneficial to the generation of G-type monomer products.
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BIORESOURCE TECHNOLOGY
·
2025
·
IF 9
Xinyue Xu,Ying Xu,Jialong Wen,Tongqi Yuan
Lignin contains aromatic rings, phenolic hydroxyl, and methoxy groups that confer promising potential for sunscreen applications. However, traditional extraction methods often lead to structural condensation, thus limiting the functional utilization of lignin. Herein, we propose a strategy for simultaneous lignin extraction and in-situ modification using tannic acid (TA) as both a functionalizing agent and a phenolic modifier. This approach enables efficient lignin isolation under mild conditions, while preserving reactive sites and enhancing multifunctional performance. Under optimized conditions (100 °C, 30 min), the pretreatment achieved a delignification efficiency of 89.1 %. The resulting TA-modified lignin (TA-Lig) exhibited excellent UV-blocking performance, antioxidant activity, tyrosinase inhibition, and favorable biocompatibility. Notably, incorporating 5 wt% TA-Lig into a commercial sunscreen (SPF 15) markedly enhanced the SPF to 145.3. This work demonstrates a sustainable extraction–modification strategy that yields multifunctional bio-based ingredients with strong potential for cosmetic applications.
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PubMed
高影响因子
JOURNAL OF POWER SOURCES
·
2025
·
IF 7.9
Peiyuan Zhang,Biao Zhang,Ting Yu,Hui Wu,Kai Liu,Lihui Chen,Xiaxing Zhou
The development of hydrogels with high mechanical strength, ionic conductivity and electrochemical activity is crucial for advancing flexible supercapacitors. In this study, zinc oxide nanoparticles (ZnO NPs), recognized for their high chemical activity and conductivity, were incorporated into dual-network hydrogel based on poly (acrylic acid- co -acrylamide) (P (AA- co -AM)) matrix to improve its properties. By optimizing the ratio of AA to AM and adjusting the amounts of AlCl 3 and ZnO NPs, the -COO - groups in AA and the -CONH 2 in AM form a hydrogen bond network. This network effectively integrated the -SO 3 - groups of lignosulfonate (LS) with Zn 2+ , and Al 3+ ions, establishing a multi-pathway ion transport system that served as a dual conductive channel. Leveraging the nanoscale effect, the transport of Zn 2+ and Al 3+ connection framework enhanced the tensile strength from 140.48 kPa to 420.16 kPa by three times. The optimized flexible supercapacitor exhibited a specific capacitance of 99.63 F g −1 , accompanied by exemplary flexibility, with capacitance retention rate of 80.63 % and nearly 100 % coulomb efficiency. This strategy offers a new framework for designing hydrogel electrolytes with high mechanical strength and ionic conductivity, suitable for use in high-performance energy storage devices.
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
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2025
·
IF 8.5
Daoming Chen,Han Xu,Lifeng Li,Tao Ruan,Xinping Ouyang,Xueqing Qiu
The hydrodemethoxylation (HDMO) of lignin-derived monophenolics to alkylphenols is a crucial step for the conversion of lignin bio-oil into chemicals. A new FeNi 3 alloy catalyst was firstly prepared by being reduced in-suit from Fe, Ni oxides precursor. The FeNi 3 /FeNi 8 O 9.25 catalyst prepared using optimal 12:88 of molar ratio of iron nitrate to nickel nitrate showed good catalytic activity and selectivity to HDMO of lignin-derived monophenolics. In the HDMO process of lignin-derived 4-propylguaiacol, FeNi 3 /FeNi 8 O 9.25 contributed to a 94.53 % of conversion and a 90.67 % of demethoxylation selectivity under 0.4 MPa H 2 at 280 °C for 2 h. Compared with the Ni/Ni 1 O catalyst, the FeNi 3 /FeNi 8 O 9.25 catalyst increased by 6.19 times and 2.35 times of the specific surface area and total acid amount, respectively. FeNi 3 (111) possessed lower adsorption energy to substrate and changed adsorption configuration of the benzene ring in tilted mode. Consequently, prepared catalyst facilitated the removal of methoxy group, as well as suppressing hydrogenation saturation of the benzene ring. Moreover, FeNi 3 /FeNi 8 O 9.25 catalyst exhibited versatile capacity of HDMO to different lignin-derived monophenolics and high stability. This work offers a new strategy for constructing non-noble metallic alloy catalyst for highly selective HDMO reactions.
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INDUSTRIAL CROPS AND PRODUCTS
·
2024
·
IF 5.6
Pengfei Lian,Shuangjie Liu,Zihao Ma,Xing Wang,Ying Han
Effective oxidative depolymerization of lignin to phenolic monomers and oligomers is a crucial step in the economic feasibility of biorefinery. To date, most studies on the processing technical of lignin have focused on intermittent treatment, with little attention paid to microreactor. In this research, a novel and efficient process technical of oxidative depolymerization lignin via a continuous manufacturing platform was developed, in which the lignin alkaline solution is the disperse phase and the hydrogen peroxide is the continuous phase (oxidants, 8 wt%). The results show that different products can be obtained through varying the reaction conditions of lignin depolymerization. Under the optimized condition, 93.03 wt% conversion of raw lignin and 22.37 wt% yield of monomer was obtained. Besides, comparative characterizations on the samples of raw lignin and depolymerization products by GC-MS-FID and HSQC NMR analysis illustrated that 84.26 wt% of monomers (the sum of yield of 18.85 wt%) is phenolic compounds, with syringaldehyde (yield of 4.22 wt% and selectivity of 18.86 wt%) and vanillin (yield of 3.49 wt% and selectivity of 15.60 wt%) are the main products and the high yields attributed to the efficient cleavage of C-O linkages (mainly β-O-4 linkages) of lignin. Moreover, GPC and elemental analyses show that the light oil product with an oxygen content of 41.28% was mainly composed of dimers and trimers. This work demonstrating that continuous-flow oxidative depolymerization was an effective strategy on lignin processing technical and will be an interesting field of research on lignin comprehensive utilization.
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INDUSTRIAL CROPS AND PRODUCTS
·
2023
·
IF 5.9
Wenchao Li,Bin Xu,Mingfang Xu,Yue Wu,Zhihua Liu,Bingzhi Li,Cheng Zhong,Shiru Jia
In this study, a novel mild and recyclable ethylenediamine (EDA) pretreatment method was developed. This pretreatment process efficiently eliminated lignin and facilitated the recovery of pretreatment reagents. Under optimized conditions at 70 °C, more than half of lignin was removed from the corn stover (CS). Consequently, the enzymatic hydrolysis of glucose and xylose achieved yields of 82.1% and 50.4%, respectively. Notably, the recovered EDA was efficiently reused and maintained comparable pretreatment efficiency even after five rounds of recovery. The pretreated CS was effectively used for bacterial cellulose fermentation without requiring additional detoxification steps. Furthermore, the analysis of EDA lignin (EL) revealed the presence of numerous amino groups introduced into the lignin structure. Subsequently, EL was used in the polyurethane (PU) foam preparation. The results revealed that EL-based PU foam featured higher compressive strength, density, thermal stability, and adsorption capacity for dyes and heavy metal ions compared with alkali lignin-based PU foam.
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