CATALYSIS TODAY
·
2017
·
IF 4.636
Xuli Zhuang,Xinli Tong,Yongtao Yan,Song Xue,Linhao Yu,Yongdan Li
A highly efficient and selective transformation of lignin-derived vanillin and vanillyl alcohol to prepare methyl vanillate has been developed in the presence of molecular oxygen. A series of supported Au, Pd and Pt catalysts were prepared and employed for the selective oxidation of vanillin. It is found that, in the presence of Au-h/Al 2 O 3 catalyst, a 98.1% conversion of vanillin and 99.9% selectivity of methyl vanillate was obtained in methanol under 0.3 MPa of O 2 at 140 °C for 4 h. Moreover, the oxidative esterifications of isovanillin, syringaldehyde, p -anisaldehyde and 3, 4, 5- trimethoxybenzaldehyde were successfully performed, and 70.2–98.0% yields of methyl aromatic esters are obtained. The recycling experiment showed that the Au-h/Al 2 O 3 still keep a high catalytic activity after being reused five times. Next, the oxidation of vanilly alcohol was studied, and 99.9% conversion and 99.6% selectivity of methyl vanillate was attained at 140 °C for 12 h with the Au-h/Al 2 O 3 as catalyst. Finally, based on the reaction phenomena and experimental results, a possible reaction mechanism for the oxidation of vanillyl alcohol is proposed.
✓ 已验证
产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2016
·Vol. 18
·期 20
·5510-5517
·
IF 8.506
Guang-Yue Xu,Jian-Hua Guo,Yan-Chao Qu,Ying Zhang,Yao Fu,Qing-Xiang Guo
Cyclohexanol and alkyl cyclohexanol are important chemical intermediates. It is meaningful to prepare cyclohexanols from non-fossil-based biomass. Here we report Ru/ZrO2–La(OH)3, a metal-solid base bifunctional catalyst, to show its excellent performance on the partial hydrodeoxygenation of lignin-derived phenols. Guaiacol could be converted to cyclohexanol with a 91.6% yield in water. Alkyl phenols with one or two methoxy groups were converted into alkyl cyclohexanols with yields over 86.9%. The catalyst had good activity of removing a methoxy group and retaining a hydroxyl group. In this catalyst, Zr and La interacted with each other to form a mixed (hydr)oxide, thus making ZrO2–La(OH)3 a stable support. Ru was highly dispersed on the ZrLa support. The pathway from guaiacol to cyclohexanol was investigated and proposed as two parallel ways, demethoxylation followed by hydrogenation (I), the saturation of the aromatic ring through hydrogenation and then demethoxylation through direct hydrogenolysis (II).
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2016
·
IF 7.145
Liming Zhang,Tingting You,Tian Zhou,Xia Zhou,Feng Xu
The advent of bioethanol production has generated abundant lignin-derived byproducts which contain proteins and polysaccharides. These byproducts are inapplicable for direct material applications. In this study, lignin-derived byproducts were used for the first time as carbon precursors to construct an interconnected hierarchical porous nitrogen-doped carbon (HPNC) via hydrothermal treatment and activation. The obtained HPNC exhibited favorable features for supercapacitor applications, such as hierarchical bowl-like pore structures, a large specific surface area of 2218 m2 g–1, a high electronic conductivity of 4.8 S cm–1, and a nitrogen doping content of 3.4%. HPNC-based supercapacitors in a 6 M KOH aqueous electrolyte exhibited high-rate performance with a high specific capacitance of 312 F g–1 at 1 A g–1 and 81% retention at 80 A g–1 as well as an excellent cyclic life of 98% initial capacitance after 20 000 cycles at 10 A g–1. Moreover, HPNC-based supercapacitors in the ionic liquid electrolyte of EMI-BF4 displayed an enhanced energy density of 44.7 Wh kg–1 (remaining 74% of max value) at an ultrahigh power density of 73.1 kW kg–1. The proposed strategy may facilitate lignin utilization and lead to a green bioethanol production process.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Catalysis
·
2016
·
IF 9.307
Nengchao Luo,Min Wang,Hongji Li,Jian Zhang,Huifang Liu,Feng Wang
One of the challenges of depolymerizing lignin to valuable aromatics lies in the selective cleavage of the abundant C–O bonds of β-O-4 linkages. Herein we report a photocatalytic oxidation–hydrogenolysis tandem method for cleaving C–O bonds of β-O-4 alcohols. The Pd/ZnIn2S4 catalyst is used in the aerobic oxidation of α-C–OH of β-O-4 alcohols to α-C═O with 455 nm light, and then a TiO2–NaOAc system is employed for cleaving C–O bonds neighboring the α-C═O bonds through a hydrogenolysis reaction by switching to 365 nm light. Interestingly, the oxidation–hydrogenolysis tandem reaction can be conducted in one pot to offer ketones and phenols (up to 90% selectivity) via a dual light wavelength switching (DLWS) strategy. EPR and metal loading experiments elucidate that Ti3+ in TiO2 is formed in situ and is responsible for the photocatalytic hydrogenolysis through electron transfer from Ti3+ to the β-O-4 ketones.
✓ 已验证
产品关联
DOI
高影响因子
Journal of Physical Chemistry C
·
2017
·
IF 4.536
Guodian Zhu,Meilu Lin,Di Fan,Wenshan Ning,Xinping Ouyang,Yong Qian,Xueqing Qiu
The effect of benzylic alcohol (Cα—OH) pretreatments on microwave-assisted cleavage of Cα—Cβ bonds in lignin model compounds was investigated by combining experimental results with density functional theory (DFT) calculations at the M06-2X/6-311++G(d,p) level. The oxidization of Cα—OH to benzylic ketone (Cα═O) facilitated the cleavage of the Cα—Cβ bond due to a greater decomposition rate constant and a lower barrier for the decomposition-determining step. The reduction of Cα—OH to benzylic hydrogen (Cα—H) resulted in no Cα—Cβ bond being cleaved. Since the Cα—OH quickly reacted with methanol solvent, the etherification of Cα—OH to benzylic ether (Cα—OCH3) had no effect on the Cα—Cβ bond cleavage. The aromatic aldehyde would be obtained from the model compounds containing Cα—OH or Cα—OCH3, while the model compound containing Cα═O would produce aromatic ester. The research also revealed that the microwave-assisted cleavage of Cα—Cβ bonds followed a first-order kinetic and radical reaction mechanism.
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Shan Jiang,Qian Zhang,Xizi Lin,Wenjun Liu,Songbai Qiu,Riyang Shu
Hydrodeoxygenation (HDO) is an effective method for upgrading lignin-derived phenolic compounds into high-quality liquid fuels, and the support rational design of HDO catalysts is critical for boosting reaction efficiency. In this study, a series of Ni/Al 2 O 3 -C catalysts with different ratio of Al 2 O 3 and carbon components were proposed for the HDO of lignin-derived phenolic compounds. Ni/Al 2 O 3 -C-0.25 catalyst is screened for a superior HDO efficacy compared to the other catalysts, in which guaiacol can be completely converted at 220 °C, with 99.9 % cyclohexane selectivity produced at 4 h. Various characterizations for the catalysts were carried out, including BET, XRD, TEM, XPS and NH 3 -TPD. According to the characterization results, Ni/Al 2 O 3 -C-0.25 catalyst presents little dense Al 2 O 3 fiber structure, which favors the Ni metal dispersion and possesses the smallest Ni metal particle size (10.9 nm). This leads to the outstanding catalytic hydrogenation activity. Moreover, the specific interaction between Al 2 O 3 and carbon in Ni/Al 2 O 3 -C-0.25 catalyst results in the moderate acid property, which promotes the deoxygenation process of the intermediate products, as evidenced by the effective cleavage of C-O bond and the enhanced selectivity of cyclohexane products. The adaptation of Ni/Al 2 O 3 -C-0.25 catalyst to lignin-oil upgrade was also investigated, with a rise of hydrocarbon content from 6.1% to 47.5%. These results indicate that the catalysts with this composite support had the potential to upgrade lignin-derived phenolic compounds to superior grade hydrocarbon liquid fuels.
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2024
·
IF 5.6
Penghui Wang,Junran Pang,Hua Zhang,Huiyun Liao,Dangan Xiong,Longjie Zhu,Dong Xue,Min You,Yukun Liu,Jiang Li,Shuang Li,Xiaoyan Tan,Zheng Yao,Bo Chi,Junzhang Wu
In order to encourage effective recycling of tobacco resources in the industry and successfully enhance the quality of reconstituted cut stems (GS30). This study investigates the thermal, structural, and material composition of GS30. It was found that compared with high-quality tobacco leaves and cut stems, the contents of important macromolecules including cellulose, hemicellulose and lignin in GS30 were 21.74 ± 1.14 %, 3.66 ± 0.56 %, and 1.69 ± 0.46 % respectively. Its content is smaller than that of blank cut stems but similar to high-quality tobacco leaves. The important macromolecular structures were further analyzed for their surface morphology and crystal structure using FTIR, XRD, SAXS, and SEM. After analyzing the thermal cracking behavior of GS30 through PY-GC-MS, it was found that GS30 has four weight loss stages and thermal cracking releases near 30 types of aroma substances, showing obvious advantages in releasing aromatic gases. This demonstrates that the structure of GS30 obtained from secondary processing of discarded tobacco leaves is loose and easy to burn and decompose, which can effectively reduce the release of cigarette tar.
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Shiyao Song,Xingfeng Qiu,Shaoqing Huang,Huixuan Tian,Ruihan Pu,Jingyi Huang,Jiayin Su,Yan-Lai Tang,Libin Huang,Xuequn Luo,Weiling He,Qingfeng Ni,Weijing Zhang
The clinical application of tyrosine kinase inhibitors (TKIs) is rapidly growing and has emerged as a cornerstone in the treatment of both solid tumors and hematologic malignancies. However, resistance to TKI targets and disease progression remain inevitable. Nanocarrier-mediated delivery has emerged as a promising strategy to overcome the limitations of the TKI application. We utilized the facile modification of lignin polyhydroxyl groups to synthesize cystine-grafted lignin–copper coordinated nanoparticles for TKI delivery via the Mannich reaction. The materials exhibited a stable, uniform morphology and effectively encapsulated and delivered a variety of TKI inhibitors. Moreover, we optimized the fabrication process and found that the material could release the encapsulated drug in response to both pH and GSH. These nanoparticles significantly enhanced the therapeutic activity of TKIs both in vitro and in vivo through cuproptosis while demonstrating good biosafety. We propose a novel strategy for the targeted delivery of TKI inhibitors by combining cuproptosis with modified lignin. This approach not only offers new strategies for the clinical application of TKIs but also provides novel insights and inspiration for the modified use of lignin.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CATALYSIS TODAY
·
2024
·
IF 5.2
Yushuai Sang,Mingze Yang,Hong Chen,Yongdan Li
Catalytic lignin solvolysis (CLS) holds promise for efficient lignin utilization, yielding small molecules with minimal or no char formation. However, the role of different active sites of catalyst in CLS are rarely discussed. Here, Ni catalysts on different supports, i.e., SiO 2 , Al 2 O 3 , MgO, and ZrO 2 , were prepared with the aim of manipulating the relative importance of metal and acid-base functionalities to investigate the role of different active sites in the enzymatic hydrolysis of lignin (EHL) ethanolysis. The main ether linkage, i.e., β-O-4, in EHL is cleaved without the participation of a catalyst. Metal sites suppress repolymerization through hydrogenating active intermediates, while acid and base sites facilitate the conversion of phenolic monomers into complex alkylated and etherified products and also promote repolymerization reactions. Among the catalysts, Ni/SiO 2 demonstrated the highest hydrogenation activity and yielded the most monomers (24.7 wt %) at 280 °C for 6 h under 2 MPa H 2 in ethanol. These findings shed light on the catalytic mechanisms in CLS, offering valuable insights for future catalyst design.
✓ 已验证
产品关联
DOI
高影响因子
CONSTRUCTION AND BUILDING MATERIALS
·
2025
·
IF 8
Bianyang He,Shiheng Wan,Xuemei Li,Chuyue Xu,Yixin Li,Jianying Yu,Bo Xiong,Yafang Tang,Lei Zhu
Lignin (LG) is utilized to strengthen the photooxidative aging resistance of bitumen due to its ability to absorb ultraviolet (UV) radiation and scavenge free radicals. However, the anti-aging performance of LG is constrained by a dilemma: at low dosages, the functional structures are insufficient; while at high dosages, uneven dispersion occurs within the bituminous matrix. Herein, we demonstrate a strategy to functionalize LG for improving bituminous photooxidative aging resistance through synergistically introducing benzene rings and adjusting intramolecular polarity. Specifically, 4,4′-diphenylmethane diisocyanate (MDI) functionalized LG (MFLG) was synthesized via covalent bonding between hydroxyl and isocyanate groups, and its structural properties were analyzed using multiple characterization techniques. The results revealed that the introduction of benzene rings enhanced the particle size, hydrophobic, thermal stability, and UV absorption capacity of LG. Meanwhile, bitumen modified with MFLG (MFLG-MB) demonstrated superior resistance to photooxidative aging compared to LG modified bitumen (LG-MB) and pristine bitumen (PB). Furthermore, molecular simulations (MS) elucidated the anti-aging mechanism. The incorporation of MDI improved the dispersion of LG within the bituminous matrix, as evidenced by binding energy calculations, which was beneficial for anti-aging protection of bitumen. Snapshots, electrostatic potential, and dipole moment values further demonstrated that MFLG exhibited stronger intramolecular polarity and higher affinity for asphaltenes compared to LG. These properties underscored MFLG's critical role in inhibiting asphaltene gelation for enhancing the photooxidative aging resistance significantly. This finding highlights a novel strategy to improve the anti-aging effectiveness of LG in bitumen by increasing aromatic groups and optimizing intramolecular polarity.
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2025
·
IF 8.5
Sheng Dai,Xueyan Zang,Xuehan Zhang,Meiduo Ren,Hua Qiu,Kunlin Chen
The increasing emphasis on green and sustainable development has propelled the integration of lignin into polymer matrices as a promising trend. Lignin, a highly reactive biomass material endowed with hydrophilic functional groups, presents significant potential in polymer applications. However, its intrinsic dark coloration poses a considerable challenge to its polyurethanes (PU) use. In this study, lignin was chemically modified through sulfonation, introducing an abundance of sulfonic acid groups that not only enhanced its hydrophilicity but also markedly reduced its color intensity. Additionally, 2-methacryloyloxyethyl phosphorylcholine diol (MPC-diol) was employed as a chain extender in conjunction with sulfonated lignin (SL) to further augment the hydrophilicity of the resulting PU. The incorporation of both anionic and cationic species within the polymer side chains facilitated improved polymer chain interactions. The synergistic combination of polycaprolactone (PCL) soft segments and SL end-capped segments enabled the formation of multiple hydrogen bonds and disulfide linkages, culminating in waterborne polyurethanes (WPU) characterized by superior mechanical properties and self-healing capabilities. The application of these light-colored, SL-based polycarbonate waterborne polyurethane (PCPUSL) coatings to fabrics significantly enhanced their biocompatibility and antimicrobial properties. This development represents a green, sustainable, and highly flexible WPU coating with exceptional self-healing properties and promising potential for diverse applications.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2024
·
IF 7.7
Xuan Li,Yixin Yun,Yitong Wang,Wanbin Zhu,Quan Bu,Yaxun Fan,Hongliang Wang
Inexpensive biomass materials hold great potential for the development of green delivery systems aimed at improving the extremely low utilization efficiency of pesticides. However, current systems face challenges in achieving both high encapsulation rates and drug loading capacities. This study introduces a novel method using chitosan (CS) and sodium lignosulfonate (SL) to co-assemble with avermectin (AVM), a widely used hydrophobic pesticide, forming AVM-CS-SL micro-nano capsules. Engineered under optimized conditions of pH 5 and 40 °C, the capsules exhibit an AVM encapsulation efficiency of 84.27 % and a loading capacity of 90 %. The AVM-CS-SL capsules demonstrate multifunctional attributes that enhance pesticide application. The capsules, with an average diameter of 356 nm, facilitate stable embedding in leaf grooves and enable effective adhesion to leaf surfaces, thereby improving their resistance to wash-off by rain compared to conventional formulations. Their core-shell structure protects AVM from photodegradation, ensuring long-term stability and efficacy. The capsules also exhibit enhanced bioactivity, with higher mortality rates in Plutella xylostella larvae and low genotoxicity to Vicia faba plants. These findings highlight the strategy of developing multifunctional delivery systems by the co-assembled carrier materials with active ingredients, offering an effective solution for the sustainable development of society and environment.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）