CATALYSIS LETTERS
·
2026
·Vol. 156
·期 6
·160
·
IF 2.5
Wu Yuchen,Luo Xue,Deng Zeyu,Zhou Hualan,Wang Shengkang,Wang Xuesong
Conventional fossil fuels represent non-renewable energy resources that contribute significantly to environmental pollution, primarily through the emission of black carbon (BC). Given the urgent need to develop sustainable energy alternatives and utilize waste resources, this study reports the synthesis of a defective yet stable sponge-like catalyst through the anchoring of ruthenium (Ru) nanoparticles on a hybrid substrate composed of BC and carbonized Metal-Organic Framework-303 (MOF-303). Systematic optimization of the BC/MOF-303 mass ratio and sintering temperature yielded a catalyst exhibiting exceptional performance in the heterogeneous phase hydrodeoxygenation (HDO) of vanillin (VAN) to 2-methoxy-4-methylphenol (MMP) under mild conditions (1 MPa H 2 , 220 °C, 1.5 h). The optimized catalyst achieved complete VAN conversion with an MMP selectivity of 92%. Furthermore, the catalyst demonstrated remarkable reusability, maintaining high activity over five consecutive reaction cycles, and exhibited broad applicability to various lignin-derived compounds as well as raw lignin. Structural characterization revealed that the integration of BC and MOF-303 formed a defective substrate characterized by a well-developed porous architecture and abundant active sites. Notably, the nitrogen-containing moieties within MOF-303 facilitated the formation of Ru-N chelates, which enhanced the adsorption and polarization of C = O bonds, thereby promoting the HDO reaction pathway. This work not only provides a viable strategy for designing sustainable and efficient lignin conversion catalysts but also advances the valorization of industrial waste materials. Graphical The alternative text for this image may have been generated using AI.
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高影响因子
RARE METALS
·
2026
·Vol. 45
·期 9
·e70566
·
IF 12.1
Tianjin Li,Weimin Zhang,Pingxian Feng,Yu Feng,Zhongwei Wang,Yuying Zhao,Dongliang Hua,Laizhi Sun,Shuangxia Yang,Zhiguo Dong,Lei Chen,Huan Wang
en This link goes to a English section zh This link goes to a Chinese section Lignin hydrogenolysis is a promising route to separable aromatic monomers, yet practical upgrading is still hindered by macromolecular mass-transfer limitations and the aggregation/deactivation of metal sites. Herein, we propose a “dual-confinement” strategy to construct ultrafine Ru nanoclusters supported on lignin-based N-doped hierarchical porous carbon, utilizing lignin itself as the precursor. This architecture synergizes physical confinement via a potassium oxalate-activated hierarchical pore network, with chemical confinement through in situ nitrogen doping that anchors Ru species. The resulting catalyst exhibits exceptional performance, achieving 99.8% conversion of model compounds and a remarkable 40.6 wt% yield of aromatic monomers from isolated birch lignin under mild conditions. The exceptional catalytic performance originates from synergistic dual-confinement effects, in which hierarchical porosity enables efficient mass transfer of lignin substrates, whereas N-doping provides robust chemical anchoring of the ultrafine Ru active sites. Density functional theory calculations further elucidate that electronic modulation at the Ru–N interface significantly lowers the activation energy for C–O bond cleavage. This work demonstrates a high-efficiency depolymerization protocol and establishes a theoretical framework for designing robust dual-confined catalysts in macromolecular biomass conversion. 摘要 en This link goes to a English section zh This link goes to a Chinese section 木质素氢解是制备可分离芳香单体的重要途径,然而其实际转化升级仍受制于大分子传质阻力以及金属活性位点团聚与失活等问题。针对上述瓶颈,本研究提出一种“双重限域”策略,以木质素自身为前驱体,构建了负载于木质素基氮掺杂分级多孔碳上的超细Ru纳米团簇。该体系通过草酸钾活化构筑的分级孔网络实现物理限域,并借助原位氮掺杂对Ru物种的锚定实现化学限域,二者协同强化了活性位点的稳定性与可及性。所制备催化剂展现出优异的催化性能,温和条件下对模型化合物的转化率达99.8%,桦木木质素获得高达40.6 wt%的芳香单体产率。上述卓越性能源于双重限域的协同效应:分级孔隙结构促进了木质素大分子底物的高效传质,氮掺杂位点则为超细Ru活性中心提供了牢固的化学锚定。密度泛函理论 (DFT)计算进一步表明,Ru–N界面处的电子调控显著降低了C–O键断裂的活化能。本研究提供了一种高效的木质素解聚方案,并为大分子生物质转化中限域催化剂的设计奠定了理论基础。
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MICROPOROUS AND MESOPOROUS MATERIALS
·
2015
·
IF 3.453
Xiaoyun Chen,Dong-Hau Kuo,Dongfang Lu,Yongxuan Hou,Yen-Rong Kuo
Mesoporous TiO 2 was synthesized by a hydrolysis precipitation method with the utilization of the biological renewable resource of lignin as template and TiCl 4 as reactant. The photocatalytic activity of TiO 2 was investigated by the degradation of phenol under UV light irradiation. The microstructure, crystallinity , powder characteristic, and chemical bonding of the catalyst were analyzed. The 500 °C-calcined TiO 2 had average crystallite size of about 11.1 nm and a mesoporous structure with specific area of 165.8 m 2 /g and pore volume of 0.312 cm 3 /g. The results showed that TiO 2 synthesized with lignin template exhibited high photocatalytic activity, which can be attributed to the electronegativity and the network skeleton of lignin to uniformly distribute the TiO 2 precursor for forming TiO 2 mesoporous particles. The mechanism for the improved photodegradation of the lignin-assisted TiO 2 was proposed.
研究领域:
材料科学
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环境化学
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纳米技术
·
光催化
·
绿色化学
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高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Qingqing Zhang,Yi-Chun Chu,Zhulan Liu,Mei Hong,Weiwei Fang,Xin-Ping Wu,Xue-Qing Gong,Zupeng Chen
Photocatalytic lignin depolymerization emerges as a sustainable and cost-competitive strategy to produce low-molecular-weight aromatic chemicals from renewable resources. Significant efforts have been devoted to engineering C−C bond cleavage photocatalysts with diverse compositional and morphologic characteristics in the past decade. We herein present a facile photocatalytic strategy of promoting C−C bond cleavage in lignin models to achieve high-yield aromatic monomers over triazine-heptazine-based carbon nitride heterojunctions, exceeding the triazine- or heptazine-based counterparts. Mechanistic investigations reveal that the photo-excited electron and hole synergistically trigger the C−C bond cleavage. A combination of experimental results and theoretical calculations confirms that the improved photocatalytic performance is primarily attributed to the accelerated charge carriers separation and migration induced by the built-in electric field at the heterojunction interface, and the facilitated C β -radical generation. These findings highlight the effectiveness of interfacial engineering of intramolecular heterostructures towards the rational promotion of photocatalytic cleavage of C−C bond in lignin models.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Qiuxia Zou,Hongshen He,Jie Xie,Shibo Han,Weijie Lin,Ajoy Kanti Mondal,Fang Huang
In this study, Sn modified molecular sieves with Lewis (L) acid center and Al modified molecular sieves with Brönsted (B) acid center were prepared by post-synthesis method. They were applied to the catalytic pyrolysis of Kraft lignin for the preparation of bio-oil. The acid properties of acid modified zeolites were systematically investigated by XRD, SEM, EDS and Py-FT-IR, and the bio-oil is analyzed by heteronuclear single quantum coherent nuclear magnetic resonance (HSQC-NMR). By separating L acid and B acid from zeolite molecular sieves, the conformational relationships between these two acids on the oxygen-containing functional groups in Kraft lignin bio-oil are investigated separately. The results show that acid modified molecular sieves’ L acid and B acid can effectively improve the cleavage of aromatic C-O bonds including methoxy and ether bonds. The L acid of Sn modified molecular sieve tends to break the O-C 4 bond and the natural methoxy bond, while the B acid of Al modified molecular sieve generates aliphatic hydrocarbon intermediates and phenolic compounds by breaking the C β -O bond and rearranging the methoxy bond. By chemical characterization of the acid modified molecular sieves and the bio-oil, the conformational relationship between the L acid and B acid of zeolite molecular sieves on the deoxygenation efficiency of Kraft lignin pyrolysis bio-oil is established.
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高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2023
·
IF 8.2
Yuan Zhu,Tian-Xiao Yang,Ben-Kun Qi,Hang Li,Qing-Sheng Zhao,Bing Zhao
Deep eutectic solvents (DESs) have been extensively applied to pretreat lignocellulose; however, comparative research on acidic and alkaline DES pretreatment is relatively lacking. Herein, pretreatment of grapevine agricultural by-products with seven DESs were compared in terms of removal of lignin and hemicellulose and component analysis of the pretreated residues. Among the tested DESs, both acidic choline chloride-lactic (CHCl-LA), and alkaline potassium carbonate-ethylene glycol (K 2 CO 3 -EG) were effective in delignification . Thereafter, the CHCl-LA and K 2 CO 3 -EG extracted lignin was compared by analyzing their physicochemical structure changes and antioxidant properties. The results showed that the thermal stability , molecular weight, and phenol hydroxyl percentage of CHCl-LA lignin were inferior to K 2 CO 3 -EG lignin. It was found that the high antioxidant activity of K 2 CO 3 -EG lignin was mainly attributed to the abundant phenol hydroxyl, guaiacyl (G), and para-hydroxy-phenyl (H). By comparing acidic and alkaline DES pretreatments and their lignin nuances in biorefining, novel insights are derived for the scheduling and selection of DES for lignocellulosic pretreatment.
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PubMed
高影响因子
WOOD SCIENCE AND TECHNOLOGY
·
2023
·Vol. 57
·期 3
·583-603
·
IF 3.4
Yu Fanjun,You Ziyuan,Ma Yushen,Liu Haoyang,Wang Yonggui,Xiao Zefang,Xie Yanjun
A novel, environmentally friendly, biomass-based modification technique utilizing carboxymethylation-activated alkali lignin (CAAL) and glutaraldehyde (GA) is proposed to enhance the physical and mechanical properties of poplar and fir wood. Water-soluble CAAL was prepared by modifying alkali lignin (AL) with sodium chloroacetate following low-temperature activation under a NaOH/urea system. AL is a biomass-based material from industrial by-products. As such, it does not rely on fossil resources nor emit volatile compounds that might limit its range of application. The successful preparation of CAAL was demonstrated by Fourier transform infrared spectroscopy (FTIR), 1 H nuclear magnetic resonance spectroscopy (NMR), and 13 C NMR, and the changes in structure were analyzed by 2D-heteronuclear singular quantum correlation (2D-HSQC), 31 P NMR, and gel permeation chromatography (GPC). The following characteristics of the modified wood samples were investigated in detail: weight percent gain (WPG), bulking, anti-swelling efficiency (ASE), water absorption rate (WAR), leachability of the modifier, microstructure, and mechanical properties. Water immersion results demonstrated that the CAAL/GA hybrid modifier enhanced ASE to 41.3% and 31.5% for fir and poplar, respectively, at a concentration of 15 wt.%. Furthermore, the WAR of fir was reduced by nearly three times to 30.7%, compared to that of a control sample treated solely with GA. GA-treated samples showed high brittleness, whereas both poplar and fir showed enhanced modulus of rupture and elasticity following treatment with the CAAL/GA hybrid modifier.
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INDUSTRIAL CROPS AND PRODUCTS
·
2023
·
IF 5.9
Zhongqiu Fan,Xingye An,Zhengbai Cheng,Haibing Cao,Junwei Li,Liqin Liu,Hongbin Liu
The main non-wood lignocellulose resource, wheat straw, has been utilized in bio-mechanical pulping process for paper industry to alleviate feedstock shortages, reduce environmental pollution, and lower carbon emissions as well. However, the wheat straw-based bio-mechanical pulping effluent (BMPE) could cause water pollution and resource waste if not properly handled. The efficient extraction of lignin biomass from BMPE is still a great challenge. The novelty of this study is to propose a facile process for efficient extraction of lignin with high yield, high purity and controllable morphology from wheat straw based BMPE via a commercialized technique, LignoForce™ process, which has been industrially applied in lignin extraction from wood based Kraft pulping black liquor. Considering the unique attributes of wheat straw (non-wood) based BMPE, we successfully improved the LignoForce™ technology for high efficient lignin extraction. The extracted lignin from BMPE was characterized for its chemical properties, ash content, monosaccharide composition, controllable morphology, particle size/distribution, and molecule weight/distribution at varying oxygen dosages and oxidation temperatures. The resultant lignin particles possess comparable regular spherical morphology with controllable particle size/ distribution. Additionally, the yield and ash content of the lignin extracted from BMPE and chemical-mechanical pulping effluent (CMPE) of wheat straw were compared and analyzed to evaluate the feasibility of the improved LignoForce™ technology utilized in non-wood BMPE with high extraction efficiency. The study found that the practical successive LignoForce™ treatments, including oxidation process (O 2 ), CO 2 , and H 2 SO 4 acidification procedures, showed great potential in obtaining high-yield and high-quality acid-precipitated lignin with controllable morphology from the non-wood (wheat straw) based BMPE.
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高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2022
·
IF 8.025
Xin Jin,Xiaowen Li,Xuan Liu,Liuping Du,Ling Su,Yanli Ma,Shixue Ren
Lignin is the most abundant biomass source of aromatic hydrocarbons but, at present, is not effectively utilized. The development of simple and efficient methods for producing lignin-based polymers to replace petroleum-based products is an important strategy for promoting environmentally friendly and sustainable materials and controlling carbon emissions. In this work, lignin-based, light-driven shape memory polymers (ELIDs) with improved mechanical properties have been prepared from enzymatic hydrolysis lignin, itaconic acid and 1,12-dodecanediol, without any chemical modification of the lignin. The polymers contain large proportions of lignin (20–40 wt%, designated ELID20 to ELID40) and their mechanical properties are dependent on the lignin content. Maximum tensile strength (46.9 MPa) was achieved with ELID30, maximum elongation at break (93.7 %) was achieved with ELID20 and highest fracture energy (10.75 J cm −3 ) was achieved with ELID25. These excellent mechanical properties are accompanied by good thermal stability and a wide range of glass transition temperatures (21.2–157.3 °C), supporting a broad range of applications. The shape fixation rate (R f ) and shape recovery rate (R r ) were highest for ELID30 (98.7 % and 97.4 %, respectively). Under 1 sun simulated solar irradiation, ELID20 reached a temperature exceeding the glass transition temperature in 15 s and, under 3 sun simulated solar irradiation, ELID30 reached a temperature of 130 °C and shape recovered in 60 s. The excellent mechanical properties and good light-driven shape memory of ELIDs provide inspiration for the development and utilization of lignin-based polymers.
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PubMed
高影响因子
Frontiers in Bioengineering and Biotechnology
·
2022
·
IF 6.064
Shao Lupeng,Wang Chao,Liu Yu,Wang Meng,Wang Luyan,Xu Feng
Lignin, an abundant aromatic biopolymer, has the potential to produce various biofuels and chemicals through biorefinery activities and is expected to benefit the future circular economy. Microwave-assisted efficient degradation of lignin in methanol/formic acid over Ru/C catalyst cooperated with metal chloride was investigated, concerning the effect of type and dosage of metal chloride, dosage of Ru/C, reaction temperature, and reaction time on depolymerized product yield and distribution. Results showed that 91.1 wt% yield of bio-oil including 13.4 wt% monomers was obtained under the optimum condition. Yields of guaiacol-type compounds and 2,3-dihydrobenzofuran were promoted in the presence of ZnCl2. Formic acid played two roles: (1) acid-catalyzed cleavage of linkages; (2) acted as an in situ hydrogen donor for hydrodeoxygenation in the presence of Ru/C. A possible mechanism for lignin degradation was proposed. This work will provide a beneficial approach for efficient depolymerization of lignin and controllable product distribution.
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PubMed
高影响因子
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
·
2023
·
IF 6
Geliang Xie,Guoqiang Zhu,Tong Lv,Yifan Kang,Yuhan Chen,Zhen Fang,Lujiang Xu
Co-valorization of biomass and multiple solid wastes is essential to environment protection and energy security. Herein, aromatic-rich biofuel was produced from lignin and waste polyoxymethylene (POM) via catalytic co-pyrolysis process. Commercial and cheap γ-Al 2 O 3 catalyst exhibited good catalytic performance. Series characterizations and bench-top pyrolysis experiments were conducted to illustrate the synergism between raw materials and the mechanism of aromatics formation. The TG analysis and thermodynamics calculation revealed that a remarkably positive synergistic effect existed between lignin and POM, which reduce the activation energies and make the reaction more conducive in terms of thermodynamics. Meanwhile, the yields of biochar and bio-oil increased considerably. Additionally, the operating conditions affected the product distributions significantly. The suitable mixing ratio of lignin to POM was around equal (5:5) with the bio-oil yield increased to 28.3 % and aromatic hydrocarbons selectivity increased to > 95 %. Moreover, POM, the precursor for alkylating reagents and hydrogen donors , could promote the deoxygenation reactions of phenolic intermediates and result into aromatic hydrocarbons. The acid sites of γ-Al 2 O 3 promoted series secondary cracking reactions (alkylation, deoxygenation), and thus improved bio-oil quality. Finally, the stability test showed that commercial γ-Al 2 O 3 catalyst was slightly deactivated after 4 cycles because of coke deposits and acid sites loss.
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高影响因子
Biochar
·
2023
·Vol. 5
·期 1
·1-14
·
IF 12.7
Chen Chao,Sun Kang,Huang Chen,Yang Mengmei,Fan Mengmeng,Wang Ao,Zhang Gaoyue,Li Bei,Jiang Jianchun,Xu Wei,Liu Junli
The structural reconstruction mechanism of lignin and cellulose-derived biochars during direct graphitization under ultra-high temperatures was intensively investigated. It was demonstrated that cellulose-derived char was almost composed of carbon microcrystallites, whereas lignin-derived char reserved some of its skeleton structures, and such structural difference played a vital role in the morphology of formed graphitic layers. The results illustrated that the graphitized lignin-derived sample under 2800 ℃ had graphitic degree of 89.53%, interlayer spacing of 0.3363 nm and electronic conductivity of 104.6 S cm −1 , while cellulose-derived sample had graphitic degree of 76.74%, layer distance of 0.3374 nm, and electronic conductivity of only 48.8 S cm −1 . Combined with the results of structural analysis of the chars derived from lignin and cellulose, it was inferred that the stable and aromatic ring containing skeleton structure in lignin was beneficial to the ring-enlarging reconstruction and the formation of large areas of continuous graphitic layers during graphitizing process, leading to high electronic conductivity. Meanwhile, the interwoven microcrystallites in cellulose-derived char strongly restricted the expanding of continuous lamellar graphitic areas even at such ultra-high temperature, causing the formation of turbostratic structure with numerous structural defects as well, and finally resulting in relatively lower electronic conductivity. This work is expected to provide theoretical guidance for preparing high-performance functional carbon materials from lignocellulosic biomass. Graphical Abstract
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高影响因子
危险品化学品经营许可证（带存储）