COMPOSITES PART B-ENGINEERING
·
2020
·
IF 7.635
Jingkai Liu,Jinyue Dai,Shuaipeng Wang,Yunyan Peng,Lijun Cao,Xiaoqing Liu
With the purpose to obtain an eco-friendly flame retardant for epoxy resin, a facile method for the synthesis of a bio-based epoxy monomer containing DOPO units (DGEBDB) from lignin-derived vanillin and guaiacol, was presented in this work. During the synthesis process, guaiacol acted as both reactant and solvent. And it could be recycled in situ and re-used as the fresh one. In order to evaluate the flame retardancy of DGEBDB, it was mixed with diglycidyl ether of bisphenol A (DGEBA) and cured with 4,4-diaminodiphenylmethane (DDM). Results showed that, DGEBDB demonstrated a good compatibility with DGEBA, and the mechanical properties of cured resins were obviously improved with the addition of DGEBDB. As expected, the limiting oxygen index (LOI) of cured resin reached 30.2% with the content of phosphorus only 0.67 wt%, in which the weight ratio between DGEBDB and DGEBA was 1:9 (B1D9/DDM). When the weight ratio of DGEBDB to DGEBA was further increased to 2:8 for the B2D8/DDM system, the UL-94 V-0 grade was achieved. Meanwhile, the mechanism of DGEBDB in improving the flame retardancy of cured resin was discussed and revealed. This easily available and eco-friendly DGEBDB was proved to be a highly efficient reactive flame retardant for epoxy resin.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2018
·
IF 6.759
Kairui Liu,Peifang Yan,Hong Jiang,Zhi Xia,Zhanwei Xu,Shi Bai,Z. Conrad Zhang
Selective hydrocleavage of aromatic C O bond while preserving the aromatic ring is a desired catalytic process in hydrodeoxygenation (HDO) of biomass derived aromatic oxygenates to high value biochemicals. Guaiacol with typical methoxy and phenolic hydroxyl groups is a representative aromatic di-oxygenates of lignin fragments. Sub-nanometer sized silver, a poor hydrogenation metal catalyst, was found to initiate H 2 dissociation and H spillover onto anatase TiO 2 (TiO 2 -A) surface. The spillover hydrogen enhanced the partial reduction of TiO 2 -A surface at a substantially lowered temperature as compared to the reduction of TiO 2 -A by molecular H 2 . The reduction of TiO 2 -A surface by spillover hydrogen was enhanced at Ag loading as low as 0.01 wt% on TiO 2 -A. The ratio of spillover H to Ag was as high as 675 at Ag loading of 0.01 wt% and the ratio decreased with increasing Ag loading. We found that the yield of phenolic products was linearly correlated with the amount of spillover hydrogen that created oxygen vacancy (Ov) through partial reduction of TiO 2 -A surface. Methanol was formed as the main side-product, indicating that the direct hydrocleavage of aromatic C-OCH 3 in guaiacol is favored over that of aromatic C-OH on the created site.
研究领域:
催化化学
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生物质能
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材料科学
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产品关联
DOI
高影响因子
RSC Advances
·
2019
·Vol. 9
·期 5
·2764-2771
·
IF 3.049
Fuhang Mai,Kai Cui,Zhe Wen,Kai Wu,Fei Yan,Mengmeng Chen,Hong Chen,Yongdan Li
The conversion of guaiacol is examined at 300 °C in supercritical ethanol over a H2WO4 catalyst. Guaiacol is consumed completely, meanwhile, 16.7% aromatic ethers and 80.0% alkylphenols are obtained. Interestingly, tert-butylphenols are produced mainly with a high selectivity of 71.8%, and the overall selectivity of 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-4-ethylphenol is as high as 63.7%. The experimental results indicate that catechol and 2-ethoxyphenol are the intermediates. Meanwhile, the WO3 sites play an important role in the conversion of guaiacol and the Brønsted acid sites on H2WO4 enhance the conversion and favour a high selectivity of the tert-butylphenols. The recycling tests show that the carbon deposition on the catalyst surface, the dehydration and partial reduction of the catalyst itself are responsible for the decay of the H2WO4 catalyst. Finally, the possible reaction pathways proposed involve the transetherification process and the alkylation process during guaiacol conversion.
研究领域:
化学工程
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催化
·
有机化学
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产品关联
DOI
PubMed
高影响因子
Scientific Reports
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2016
·Vol. 6
·期 1
·1-10
·
IF 5.228
Zhang Huiyan,Wang Yun,Shao Shanshan,Xiao Rui
Lignin is the most difficult to be converted and most easy coking component in biomass catalytic pyrolysis to high-value liquid fuels and chemicals. Catalytic conversion of guaiacol as a lignin model compound was conducted in a fixed-bed reactor over ZSM-5 to investigate its conversion and coking behaviors. The effects of temperature, weight hourly space velocity (WHSV) and partial pressure on product distribution were studied. The results show the maximum aromatic carbon yield of 28.55% was obtained at temperature of 650 °C, WHSV of 8 h −1 and partial pressure of 2.38 kPa, while the coke carbon yield was 19.55%. The reaction pathway was speculated to be removing methoxy group to form phenols with further aromatization to form aromatics. The amount of coke increased with increasing reaction time. The surface area and acidity of catalysts declined as coke formed on the acid sites and blocked the pore channels, which led to the decrease of aromatic yields. Finally, a kinetic model of guaiacol catalytic conversion considering coke deposition was built based on the above reaction pathway to properly predict product distribution. The experimental and model predicting data agreed well. The correlation coefficient of all equations were all higher than 0.90.
研究领域:
生物质能
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催化化学
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产品关联
DOI
PubMed
高影响因子
ChemCatChem
·
2017
·Vol. 10
·期 6
·1376-1384
·
IF 4.803
Zhaoxia Zheng,Zhicheng Luo,Chen Zhao
Graphical Taking the cross : Morphologically cross-shaped HZSM-5 loaded Ru nanoparticles demonstrate high activity (rate: 7.8 g g −1 h −1 ) in the selective hydrogenolysis of guaiacol to benzene in water with a nearly quantitative yield accompanied with high durability. Hydrogenolysis of C−O bonds is an important tool for synthesis of valuable fuels and chemicals from biomass. In this contribution, we report that morphologically cross-shaped HZSM-5-loaded Ru nanoparticles have demonstrated high activity in the selective hydrogenolysis of guaiacol to benzene in water with 97 % yield and a rate of 7.8 g g −1 h −1 accompanied with high durability. N 2 sorption analysis showed that Ru/HZSM-5 (cross-shaped) had a large mesoporous surface area and pore volume for loading small and uniform Ru nanoparticles, as confirmed by TEM images. The stronger interaction of Ru and cross-shaped HZSM-5 was simultaneously confirmed by a higher hydrogen reduction temperature of RuO 2 on calcined Ru/HZSM-5, a blueshift of Ru δ+ -(CO) n , Ru δ+ -(CO), and Ru 0 -(CO) species in the IR spectra of adsorbed CO, and a higher Ru 3d 5/2 binding energy in X-ray photoelectron spectroscopy measurements. The reaction constant in guaiacol hydrogenolysis to phenol over cross-shaped Ru/HZSM-5 (0.051 min −1 ) was 3–4 times higher than that on spherical and cuboid Ru/HZSM-5 (0.012–0.029 min −1 ) at identical conditions, attributed to the remarkable hydrogenolysis catalytic capability of Ru nanoparticles on cross-shaped HZSM-5. In addition, adsorption of guaiacol and hydrogen was more substantial on cross-shaped Ru/HZSM-5, as evidenced by of IR and mass spectroscopy, respectively. The higher adsorption of guaiacol is attributed to the abundant Lewis acid sites on cross-shaped Ru/HZSM-5, as the Al−OH enriched Lewis acid sites favor the adsorption of oxygen-containing guaiacol. The higher rate constant in the primary step, together with the adsorbed high concentrated reactant and hydrogen (with nearly first-order reaction kinetics) on cross-shaped Ru/HZSM-5, facilitates the overall tandem reaction, leading to an excellent hydrogenolysis catalyst working at hydrothermal conditions for biomass conversion.
研究领域:
催化化学
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能源化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS TODAY
·
2026
·
IF 5.1
Nan Yang,Yaru Xue,Zehui Ma,Furang Li,Li Dong,Xiaoxuan Yin,Junhao Liu,Fei Wang,Jianye Fu,Xinmei Liu,Yuchao Lyu
The hydrodeoxygenation (HDO) of lignin-derived guaiacol offers an alternative to fossil-based routes for cyclohexanol production. However, the guaiacol HDO involves multiple parallel and sequential reactions, making the control of reaction pathways particularly challenging. In this work, Co-Zn-based HDO catalysts were synthesized using layered double hydroxide (LDH) as a precursor. The Co particle size decreases and electron density increases, while oxygen vacancy (Ov) concentration rises compared to monometallic Co, yielding higher activity and cyclohexanol selectivity. Most importantly, kinetic study reveals that electron density of Co plays a determining role in governing the HDO pathway. The guaiacol hydrogenation mainly follows two pathways over the Co-based catalyst: guaiacol → phenol → cyclohexanol (Pathway Ⅰ) and guaiacol → phenol → cyclohexanone → cyclohexanol (Pathway Ⅱ). Electron rich Co facilitates C aryl -OCH 3 bond cleavage of guaiacol to form phenol. It also selectively enhances adsorption and hydrogenation of aromatic ring while keeps the hydroxyl group intact as confirmed by the DFT calculations, favoring conversion of phenol to cyclohexanol (Pathway Ⅰ) rather than cyclohexanone (Pathway Ⅱ). These findings provide theoretical guidance for the rational catalyst design and regulation of reaction pathways in guaiacol hydrodeoxygenation.
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产品关联
DOI
高影响因子
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
·
2026
·
IF 6.7
Hao Zhao,Chongbo Cheng,Pengfei Li,Fengjie Bian,Dekui Shen,Xiaoxiang Jiang
The selective hydrodeoxygenation (HDO) of lignin-derived phenolics such as guaiacol into high-value chemicals under mild conditions presents a persistent challenge in biomass valorization. In this work, a series of Ni x -Fe y /Al 2 O 3 catalysts were synthesized by a sol-gel method and evaluated for the HDO of guaiacol. Characterization (XRD, XPS, H 2 -TPR, NH 3 -TPD, etc.) revealed that the Ni x -Fe y /Al 2 O 3 catalysts possess enhanced textural properties, improved metal dispersion, and tailored surface acidity, collectively contributing to their high activity and selectivity. The introduction of Fe promotes the formation of a Ni 3 Fe alloy and defect-rich FeO x species. Under mild conditions (180 °C, 2 MPa H 2 ), Ni 5 /Al 2 O 3 achieved full guaiacol conversion with > 85% selectivity to 1,2-cyclohexanediol. By introducing Fe and increasing the temperature to 260 °C (2 MPa H 2 ), the Ni 5 -Fe 1 /Al 2 O 3 catalyst shifted the reaction pathway toward deeper deoxygenation, yielding cyclohexane with over 78% selectivity. This tunable selectivity originates from a synergistic mechanism in which metallic Ni/Ni 3 Fe sites facilitate hydrogenation and hydrogenolysis, while acid sites and FeO x -derived oxygen vacancies promote the dehydration of diol intermediates, especially at higher temperatures. This study provides a design-oriented bimetallic strategy for the targeted valorization of lignin into distinct high-value chemicals.
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产品关联
DOI
高影响因子
INORGANIC CHEMISTRY COMMUNICATIONS
·
2026
·
IF 5.9
Huaiyue Tong,Weiping Tang,Fei Ge,Xiaohui Yang,Minghao Zhou
Catalytic hydrodeoxygenation (HDO) is a pivotal strategy for upgrading lignin-derived oxygen-rich compounds into value-added chemicals. Developing high-performance non-precious metal inorganic catalysts with precisely controllable active sites remains a core challenge in this field. Herein, we reported a facile one-pot hydrothermal-calcination reduction method to construct carbon-confined Co-CoO x dual-site catalysts (Co x @Sa y -T) using salicylic acid as a bifunctional organic ligand and in-situ carbon source. The optimized Co 5 @Sa 5 –550 catalyst exhibited outstanding performance in the transfer HDO of guaiacol to cyclohexanol, achieving 99.3% guaiacol conversion and 93.5% cyclohexanol selectivity under mild conditions (180 °C, 2 MPa N 2 , 4 h) with isopropanol as the hydrogen donor, eliminating the need for external H2. Comprehensive structural characterizations demonstrated that the superior catalytic activity originates from the synergistic effect of uniformly dispersed Co-CoO x sites. Metallic Co centers catalyzed isopropanol dehydrogenation to generate active hydrogen species, while CoO x species acted as moderate Lewis acid sites to facilitate methoxy group adsorption and C O bond cleavage. This work provided a controllable and scalable strategy for designing efficient non-precious metal inorganic catalysts for biomass valorization.
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DOI
高影响因子
ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY
·
2025
·
IF 6.1
Xianhua Zhang,Runfa Wu,Fasheng Liu,Min Huang,Xiaoyan Huang,Nannan Wang,Qianqian Huang,Minhong Zhang,Xinjun Liao,Huiqiang Lu,Lan Liao
The combustion of biomass (e.g., wood, agricultural residues) and coal releases significant amounts of guaiacol (GUA) and its derivatives, major constituents of PM2.5 that threaten human health and ecosystems. GUA can rapidly enter the Earth's water circulation system through atmospheric deposition. However, its potential threat to aquatic organism and humans remains poorly understood. Using zebrafish—a model organism with high genetic homology to humans, transparent embryos, and rapid development—we investigated GUA’s ecological effects. Zebrafish embryos were exposed to 0.08–0.24 mM GUA from 12 to 120 h post-fertilization (hpf). GUA induced craniofacial malformations, behavioral abnormalities (reduced locomotion, impaired stimuli response), and oxidative stress via reactive oxygen species (ROS) accumulation. Disrupted migration, proliferation, and differentiation of cranial neural crest cells (NCCs) were observed, alongside altered Wnt signaling pathway gene expression. Both astaxanthin (AST, an ROS scavenger) and C59 (a Wnt inhibitor) could mitigate craniofacial defects. These findings demonstrate that GUA reduces antioxidant capacity, impairs NCCs function, and disrupts Wnt signaling, leading to craniofacial deformities. This study highlights GUA’s ecological and health risks, providing insights into its toxic mechanisms.
研究领域:
毒理学
·
发育生物学
·
环境科学
·
分子生物学
·
水生毒理学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Catalysis Science & Technology
·
2025
·
IF 4.2
Chuqiao Song,Wei Cheng,Xiaojie Wu,Shufang Zhao,Ying Tang,Xin Tang,Yao Xu,Lili Lin,Siyu Yao
The one-pot hydrodeoxygenation of lignin-derived (alkyl)-guaiacols to (alkyl)-cyclohexanols with high selectivity is an attractive process for biomass conversion. However, designing catalysts that preferentially cleave etheric CAr–O(R) bonds over hydrogenating aromatic rings under mild conditions remains a significant challenge. In this study, we explore the structure sensitivity of supported Ru catalysts with varying particle sizes (0.6–7.5 nm) and identify the optimal catalyst for selective hydrodeoxygenation. Using a catalyst with 1.5 nm Ru particles, we achieve a ∼95% yield of cyclohexanol from guaiacol under relatively mild conditions (190 °C, 5 bar H2). In situ DRIFTS analysis reveals that the cleavage of CAr–OCH3 bonds occurs preferentially over aromatic ring hydrogenation on the 1.5 nm Ru particles, minimizing side reactions and enhancing cyclohexanol selectivity.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
ENERGY & FUELS
·
2020
·
IF 3.421
Xiangchen Kong,Chao Liu,Yue Han,Ming Lei,Yuyang Fan,Ming Li,Rui Xiao
The development of an economic and sustainable catalytic system was crucial for lignin-based biorefinery. Herein, we reported a low-cost Cu/CuMgAlOx catalyst with promising activity toward lignin hydrodeoxygenation (HDO) through a H2-free method. Supercritical methanol was used as the hydrogen donor, solvent, and reactant simultaneously. Guaiacol was employed as a representative lignin model compound to reveal the HDO mechanism of lignin derivatives. HDOs of guaiacol performed at 250, 275, 300, and 350 °C with durations ranging from 15 to 120 min indicated a high HDO efficiency of the catalytic system. The obtained liquid products were categorized to oxygen-containing unsaturated products (OUPs), oxygen-containing saturated products (OSPs), and cycloalkanes. A kinetic model based on a simplified reaction process containing the three following conversion steps was established: guaiacol transformed to OUPs through the initial HDO, then hydrogenated to OSPs (medium HDO), and eventually turned to cycloalkanes by the deep HDO. The deep HDO was the rate-determining step, and the apparent activation energies of the three steps were all lower than those in the literature. Phenol, 1,2-cyclohexanediol, anisole, and veratrole were the major intermediates, the HDOs of which were programed for pathway verification. Remarkably, catechol (the culprit of condensation) was not produced in this system. Overall, a detailed reaction network of guaiacol HDO was established, and the veil of Cu/CuMgAlOx-catalyzed lignin-derivatives HDO in supercritical methanol was revealed. This work paved the way for the application of Cu/CuMgAlOx catalyst in lignin-derivatives upgrading.
研究领域:
化学工程
·
催化
·
生化工程
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
EUROPEAN POLYMER JOURNAL
·
2020
·
IF 3.862
Rui Yang,Mengchao Han,Boran Hao,Kan Zhang
A novel fully biobased tri-furan functional bis-benzoxazine resin has been synthesized using guaiacol , furfural, furfurylamine and paraformaldehyde as raw materials via a two-step reaction approach. The detailed chemical structure of this newly obtained bis-benzoxazine monomer has been identified by NMR and FT-IR spectroscopies and elemental analysis. In addition, another bio-based benzoxazine monomer has also been synthesized based on the Mannich condensation of guaiacol, furfurylamine and paraformaldehyde for comparison. The polymerization behaviors of benzoxazines are investigated by DSC and in situ FT-IR, and the thermal and fire-related performances of resulting thermosets are investigated by TGA and micro-scale combustion calorimetry (MCC), respectively. Notably, the corresponding polybenzoxazine derived from the newly developed tri-furan functional bis-benzoxazine shows very excellent thermal stability with a T g of 290 °C and a T d10 (the temperature at a weight loss of 10%) of 375 °C in nitrogen atmosphere. Moreover, a non-ignitable polybenzoxazine has also been achieved as shown by the very low heat release capacity (30.4 J g −1 K −1 ) and total heat release value (5.8 kJ/g), making this bio-based thermosetting resin a promising material for high-performance applications.
研究领域:
材料科学
·
有机化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）