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Lignin-based polymer with high phenolic hydroxyl group content prepared by the alkyl chain bridging method

《化学科学与工程前沿（英文）》 2023年 第17卷 第8期   页码 1075-1084 doi: 10.1007/s11705-022-2272-x

摘要： Inspired by the importance of the phenolic group to the electron transporting property of hole transport materials, phenolic hydroxyl groups were introduced in lignosulfonate (LS) via the alkyl chain bridging method to prepare phenolated-lignosulfonate (PLS). The results showed that the phenolic group was boosted from 0.81 mmol∙g–1 of LS to 1.19 mmol∙g–1 of PLS. The electrochemical property results showed two oxidation peaks in the cyclic voltammogram (CV) curve of PLS, and the oxidation potential of the PLS-modified electrode decreased by 0.5 eV compared with that of LS. This result indicates that PLS is more easily oxidized than LS. Based on the excellent electron transporting property of PLS, PLS was applied as a dopant in poly(3,4-ethylenedioxythiophene) (PEDOT, called PEDOT:PLSs). PLS showed excellent dispersion properties for PEDOT. Moreover, the transmittance measurement results showed that the transmittance of PEDOT:PLSs exceeded 85% in the range of 300–800 nm. The CV results showed that the energy levels of PEDOT:PLSs could be flexibly adjusted by PLS amounts. The results indicate that the phenolic hydroxyl group of lignin can be easily boosted by the alkyl chain bridging method, and phenolated lignin-based polymers may have promising potential as dopants of PEDOT to produce hole transporting materials for different organic photovoltaic devices.

关键词： lignosulfonate     phenolic group     PEDOT:PLS     hole extract layer     energy level    

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Decontamination of Cr(VI) facilitated formation of persistent free radicals on rice husk derived biochar

Kaikai Zhang, Peng Sun, Yanrong Zhang

《环境科学与工程前沿（英文）》 2019年 第13卷 第2期 doi: 10.1007/s11783-019-1106-7

摘要：

PFRs were produced on biochar during Cr(VI) decontamination.

PFRs formation on biochar was owing to the oxidization of phenolic-OH by Cr(VI).

Appearance of excessive oxidant led to the consumption of PFRs on biochar.

Biochar charred at high temperature possessed great performance to Cr(VI) removal.

关键词： Biochar     Persistent free radicals     Phenolic hydroxyl groups     Cr(VI) reduction    

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The catalytic effect of both oxygen-bearing functional group and ash in carbonaceous catalyst on CH 4 -CO 2 reforming

Weidong ZHANG, Yongfa ZHANG,

《化学科学与工程前沿（英文）》 2010年 第4卷 第2期   页码 147-152 doi: 10.1007/s11705-009-0242-1

摘要： A kind of new catalyst—carbonaceous catalyst—for CH-CO reformation has been developed in our laboratory. The effect of both oxygen-bearing functional group such as phenolic hydroxyl, carbonyl, carboxyl, and lactonic, and ash such as FeO, NaCO, and KCO in the carbonaceous catalyst on the CH-CO reforming has been investigated with a fixed-bed reactor. It has been found that the carbonaceous catalyst is an efficient catalyst on CO-CH reforming. With the decrease of oxygen-bearing functional group, the catalytic activity of carbonaceous catalyst decreases quickly. The oxygen-bearing functional groups play a significant role in the carbonaceous-catalyzed CO-CH reforming; the ash components in carbonaceous catalyst also have an important influence on the CO-CH reforming. FeO, NaCO, and KCO in the ash can catalyze the CO-CH reforming reaction; CaO has little effect on CO-CH reforming reaction. CaO can catalyze the gasification between carbonaceous catalyst and CO; AlO and MgO inhibit the CO-CH reforming.

关键词： oxygen-bearing functional     carboxyl     phenolic hydroxyl     CH-CO reformation     CO-CH reforming    

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Immobilization of laccase on organic–inorganic nanocomposites and its application in the removal of phenolic

《化学科学与工程前沿（英文）》 2023年 第17卷 第7期   页码 867-879 doi: 10.1007/s11705-022-2277-5

摘要： Polydopamine-functionalized nanosilica was synthesized using an inexpensive and easily obtainable raw material, mild reaction conditions, and simple operation. Subsequently, a flexible spacer arm was introduced by using dialdehyde starch as a cross-linking agent to bind with laccase. A high loading amount (77.8 mg∙g‒1) and activity retention (75.5%) could be achieved under the optimum immobilization conditions. Thermodynamic parameters showed that the immobilized laccase had a lower thermal deactivation rate constant and longer half-life. The enhancement of thermodynamic parameters indicated that the immobilized laccase had better thermal stability than free laccase. The residual activity of immobilized laccase remained at about 50.0% after 30 days, which was 4.0 times that of free laccase. Immobilized laccase demonstrated excellent removal of phenolic pollutants (2,4-dichlorophenol, bisphenol A, phenol, and 4-chlorophenol) and perfect reusability with 70% removal efficiency retention for 2,4-dichlorophenol after seven cycles. These results suggested that immobilized laccase possessed great reusability, improved thermal stability, and excellent storage stability. Organic–inorganic nanomaterials have a good application prospect for laccase immobilization, and the immobilized laccase of this work may provide a practical application for the removal of phenolic pollutants.

关键词： polydopamine     pollutant removal     thermodynamic     phenolic pollutants     immobilized laccase    

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A pulsed switching peroxi-coagulation process to control hydroxyl radical production and to enhance 2,4

Yaobin Lu, Songli He, Dantong Wang, Siyuan Luo, Aiping Liu, Haiping Luo, Guangli Liu, Renduo Zhang

《环境科学与工程前沿（英文）》 2018年 第12卷 第5期 doi: 10.1007/s11783-018-1070-7

摘要：

• A new pulsed switching peroxi-coagulation (PSPC) system was developed.

• The ECT for 2,4-D removal in the PSPC was lower than that in the EF.

• The iron consumption for 2,4-D removal in the PSPC was lower than that in the PC.

关键词： Pulsed switching peroxi-coagulation system     Energy consumption     Hydroxyl radical production     2     4- Dichlorophenoxyacetic acid    

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Electrospun porous carbon nanofibers derived from bio-based phenolic resins as free-standing electrodes

《化学科学与工程前沿（英文）》 2023年 第17卷 第5期   页码 504-515 doi: 10.1007/s11705-022-2260-1

摘要： Phenolic resins were employed to prepare electrospun porous carbon nanofibers with a high specific surface area as free-standing electrodes for high-performance supercapacitors. However, the sustainable development of conventional phenolic resin has been challenged by petroleum-based phenol and formaldehyde. Lignin with abundant phenolic hydroxyl groups is the main non-petroleum resource that can provide renewable aromatic compounds. Hence, lignin, phenol, and furfural were used to synthesize bio-based phenolic resins, and the activated carbon nanofibers were obtained by electrospinning and one-step carbonization activation. Fourier transform infrared and differential scanning calorimetry were used to characterize the structural and thermal properties. The results reveal that the apparent activation energy of the curing reaction is 89.21 kJ·mol–1 and the reaction order is 0.78. The activated carbon nanofibers show a uniform diameter, specific surface area up to 1100 m2·g–1, and total pore volume of 0.62 cm3·g–1. The electrode demonstrates a specific capacitance of 238 F·g–1 (0.1 A·g–1) and good rate capability. The symmetric supercapacitor yields a high energy density of 26.39 W·h·kg–1 at 100 W·kg–1 and an excellent capacitance retention of 98% after 10000 cycles. These results confirm that the activated carbon nanofiber from bio-based phenolic resins can be applied as electrode material for high-performance supercapacitors.

关键词： lignin     bio-based phenolic resins     electrospinning     activated carbon nanofibers     supercapacitors    

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Rapid method for on-site determination of phenolic contaminants in water using a disposable biosensor

Yuanting LI, Dawei LI, Wei SONG, Meng LI, Jie ZOU, Yitao LONG

《环境科学与工程前沿（英文）》 2012年 第6卷 第6期   页码 831-838 doi: 10.1007/s11783-012-0393-z

摘要： A disposable biosensor was fabricated using single-walled carbon nanotubes, gold nanoparticles and tyrosinase (SWCNTs-AuNPs-Tyr) modified screen-printed electrodes. The prepared biosensor was applied to the rapid determination of phenolic contaminants within 15 minutes. The SWCNTs-AuNPs-Tyr bionanocomposite sensing layer was characterized with scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry methods. The characterization results revealed that SWCNTs could lead to a high loading of tyrosinase (Tyr) with the large surface area and the porous morphology, while AuNPs could retain the bioactivity of Tyr and enhance the sensitivity. The detection conditions, including working potential, pH of supporting electrolyte and the amount of Tyr were optimumed. As an example, the biosensor for catechol determination displayed a linear range of 8.0 × 10 to 2.0 × 10 mol·L with a detection limit of 4.5 × 10 mol·L (S/ = 3). This method has a rapid response time within 10 s, and shows excellent repeatability and stability. Moreover, the resulting biosensor could be disposable, low-cost, reliable and easy to carry. This kind of new Tyr biosensor provides great potential for rapid, on-site and cost-effective analysis of phenolic contaminants in environmental water samples.

关键词： on-site determination     tyrosinase biosensor     phenolic contaminants     single-walled carbon nanotubes     gold nanoparticles     screen-printed electrodes    

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Hydroxyl radical-involved cancer therapy via Fenton reactions

《化学科学与工程前沿（英文）》 2022年 第16卷 第3期   页码 345-363 doi: 10.1007/s11705-021-2077-3

摘要： The tumor microenvironment features over-expressed hydrogen peroxide (H2O2). Thus, versatile therapeutic strategies based on H2O2 as a reaction substrate to generate hydroxyl radical (•OH) have been used as a prospective therapeutic method to boost anticancer efficiency. However, the limited Fenton catalysts and insufficient endogenous H2O2 content in tumor sites greatly hinder •OH production, failing to achieve the desired therapeutic effect. Therefore, supplying Fenton catalysts and elevating H2O2 levels into cancer cells are effective strategies to improve •OH generation. These therapeutic strategies are systematically discussed in this review. Furthermore, the challenges and future developments of hydroxyl radical-involved cancer therapy are discussed to improve therapeutic efficacy.

关键词： hydroxyl radical     Fenton catalyst     hydrogen peroxide     cancer therapy    

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Characterization of electrode fouling during electrochemical oxidation of phenolic pollutant

Xuefeng Liu, Shijie You, Fang Ma, Hao Zhou

《环境科学与工程前沿（英文）》 2021年 第15卷 第4期 doi: 10.1007/s11783-020-1345-7

摘要： Abstract • Electrode fouling is characterized by non-destructive characterization. • Electrode fouling is highly dependent on electrochemical process. • Active chlorine can prevent the formation of polymeric fouling film. Electrode fouling is a problem that commonly occurs during electro-oxidation water purification. This study focused on identifying the fouling behavior of Pt electrode associated with the formation of polymeric layer during electro-oxidation of phenol. The in situ electrochemical measurements and non-destructive observation of the electrode morphology were reported. The results demonstrated that the electrode fouling was highly dependent on thermodynamic process of electrode that was controlled by anode potential. At anode potential lower than 1.0 V vs SHE, the direct electro-oxidation caused the electrode fouling by the formation of polymeric film. The fouling layer decreased the electrochemically active surface area from 8.38 cm2 to 1.57 cm2, indicated by the formation of polymeric film with thickness of 2.3 mm, increase in mass growing at a rate of 3.26 μg/cm2/min. The degree to which the anode was fouled was independent of anion in the electrolyte. In comparison, at anode potential higher than 2.7 V vs SHE, the anions (e.g., chloride) could exert a major influence to the behavior of electrode fouling. The presence of chloride was shown to mitigate the fouling of electrode significantly through preventing the formation of polymeric film by active chlorine (e.g., Cl• and Cl2) produced from anodic oxidation of chloride. Since chloride is the most abundant anionic species existing in both natural and engineered water system, this study not only offers a deep insight into the mechanism of electrode fouling, but also suggests strategies for anti-fouling in the presence of chloride in electro-oxidation process.

关键词： Electro-oxidation     Electrode fouling     Polymeric film     Chloride ions    

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Kinetics and mechanism of nitrobenzene degradation by hydroxyl radicals-based ozonation process enhanced

Weizhou Jiao, Shengjuan Shao, Peizhen Yang, Kechang Gao, Youzhi Liu

《化学科学与工程前沿（英文）》 2021年 第15卷 第5期   页码 1197-1205 doi: 10.1007/s11705-020-1998-6

摘要： This study investigated the indirect oxidation of nitrobenzene (NB) by hydroxyl radicals (·OH) in a rotating packed bed (RPB) using competitive kinetics method with -nitrochlorobenzene as a reference compound. The rate constants of NB with ·OH are calculated to be between (1.465±0.113) × 10 L/(mol·s) and (2.497±0.192) × 10 L/(mol·s). The experimental data are fitted by the modified Arrhenius equation, where the activation energy is 4877.74 J/mol, the order of NB concentration, rotation speed, and initial pH is 0.2425, 0.1400 and 0.0167, respectively. The ozonation process of NB could be enhanced by RPB, which is especially effective for highly concentrated NB-containing wastewater under alkaline conditions. The high gravity technology can accelerate ozone mass transfer and self-decomposition of ozone to produce more ·OH, resulting in an increase in the indirect oxidation rate of NB by ·OH and consequently effective degradation of NB in wastewater.

关键词： high gravity technology     hydroxyl radicals     nitrobenzene     reaction kinetics    

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Phenolic rigid organic filler/isotactic polypropylene composites. II. Tensile properties

QI Dongming, SHAO Jianzhong, WU Minghua, NITTA Kohhei

《化学科学与工程前沿（英文）》 2008年 第2卷 第4期   页码 396-401 doi: 10.1007/s11705-008-0077-1

摘要： A novel phenolic rigid organic filler (KT) was used to modify isotactic polypropylene (iPP). The influence of KT particles on the tensile properties of PP/KT microcomposites was studied by uniaxial tensile test and the morphological structures of the stretched specimens were observed by scanning electron microscopy (SEM) and polarized optical microscopy (POM). We found that the Young’s modulus of PP/KT specimens increased with filler content, while the yield and break of the specimens are related to the filler particles size. The yield stress, the breaking stress and the ultimate elongation of PP/KT specimens were close to those of unfilled iPP specimens when the maximal filler particles size is less than a critical value, which is 7 ?m at a crosshead speed of 10 mm/min and 3 ?m at 200 mm/min, close to that of glass bead but far more than those of other rigid inorganic filler particles. The interfacial interaction was further estimated from yield stress, indicating that KT particles have a moderate interfacial interaction with iPP matrix. Thus, the incorporation of small KT particles can reinforce iPP matrix and simultaneously cause few detrimental effects on the other excellent tensile properties of iPP matrix, due to their organic nature, higher specific area, solid true-spherical shape and the homogenous dispersion of the ROF particles in microcomposites.

关键词： maximal     uniaxial tensile     unfilled     excellent tensile     influence    

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Phenolic compounds removal by wet air oxidation based processes

Linbi Zhou, Hongbin Cao, Claude Descorme, Yongbing Xie

《环境科学与工程前沿（英文）》 2018年 第12卷 第1期 doi: 10.1007/s11783-017-0970-2

摘要： Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) are efficient processes to degrade organic pollutants in water. In this paper, we especially reviewed the WAO and CWAO processes for phenolic compounds degradation. It provides a comprehensive introduction to the CWAO processes that could be beneficial to the scientists entering this field of research. The influence of different reaction parameters, such as temperature, oxygen pressure, pH, stirring speed are analyzed in detail; Homogenous catalysts and heterogeneous catalysts including carbon materials, transitional metal oxides and noble metals are extensively discussed, among which Cu based catalysts and Ru catalysts were shown to be the most active. Three different kinds of the reactor implemented for the CWAO (autoclave, packed bed and membrane reactors) are illustrated and compared. To enhance the degradation efficiency and reduce the cost of the CWAO process, biological degradation can be combined to develop an integrated technology.

关键词： Wet air oxidation     Catalytic wet air oxidation     Phenolic compounds     Heterogeneous catalysts     Mechanism    

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Performance and synergistic effect of phenolic and thio antioxidants in ABS graft copolymers

Gongsheng LI, Xuhong GUO, Wang NA, Diancheng HAO, Mingyao ZHANG, Huixuan ZHANG, Jun XU

《化学科学与工程前沿（英文）》 2011年 第5卷 第1期   页码 26-34 doi: 10.1007/s11705-010-0531-8

摘要： The synergistic effect of phenolic and thio antioxidants on the stabilization of acrylonitrile-butadiene-styrene (ABS) graft copolymers has been studied. Three commercial antioxidants Irganox245, Irganox1076 and dilauryl thiodipropionate (DLTP) were selected. Formulations based on hindered phenols and secondary antioxidant DLTP were prepared. Stabilization was monitored in terms of changes in the functional groups (oxidation products), tensile properties and yellowness index. Differential scanning calorimetry (DSC) and thermogravimetry (TG) were also used to assess the stability. The results indicated that the combination of Irganox245 and DLTP showed much better stabilization effect than the individual components due to the strong synergistic effect. Only weak synergism could be observed in the formulation that contained Irganox1076 and DLTP. Irganox1076 and Irgnox1076/DLTP exhibited similar behaviors between antioxidants with the highest and lowest efficiencies.

关键词： antioxidant     ABS graft copolymers     synergistic effect    

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Impact and inhibitory mechanism of phenolic compounds on the formation of toxic Maillard reaction products

Jing TENG, Xiaoqian HU, Ningping TAO, Mingfu WANG

《农业科学与工程前沿（英文）》 2018年 第5卷 第3期   页码 321-329 doi: 10.15302/J-FASE-2017182

摘要：

As one of the dominant reactions occurring during thermal treatment of food, the Maillard reaction not only leads to the formation of aroma, browning color and taste compounds, but also contributes to the formation of some unpleasant toxic substances including acrylamide, heterocyclic amines and advanced glycation end products. Polyphenols, one of the most abundant antioxidants in the human diet, are contained in different kinds of foods. In this review, some recent studies on the impact of dietary polyphenols on the formation of acrylamide, heterocyclic amines and advanced glycation end products formed during the Maillard reaction are summarized, including the research work conducted with both chemical model systems and real food model systems; the possible inhibitory mechanisms of different polyphenols are also summarized and discussed in this review. Basically we found that some dietary polyphenols not only scavenge free radicals, but also react with reactive carbonyl species, thus lowering the formation of toxic Maillard reaction products. This review provides a useful theoretical foundation for the application of polyphenols in food safety, and suggests some directions for further study of natural products as inhibitors against the formation of toxic substances in thermally processed food.

关键词： advanced glycation end products     acrylamide     food safety     heterocyclic amine     Maillard reaction     polyphenols    

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Dispersion of a novel phenolic rigid organic filler in isotactic polypropylene matrix by solution-mixing

Dongming QI, Xiaoli ZHAO, Zhijie CHEN, Peng HUANG, Jun CAO

《化学科学与工程前沿（英文）》 2012年 第6卷 第4期   页码 395-402 doi: 10.1007/s11705-012-1269-2

摘要： A novel phenolic rigid organic filler (named KD) with a high melting point was dispersed in an isotactic polypropylene (iPP) matrix by solution-mixing and/or melt-mixing. A series of KD/iPP blends was prepared with or without addition of maleic anhydride-grafted polypropylene (MAPP) as a compatibilizer. Influences of MAPP and mixing methods on the filler dispersion were studied using polaried optical microscope (POM), scanning electron microscope (SEM) and tensile test. The filler particles are always inclined to form large irregular aggregates in the iPP matrix due to their significant differences in polarity and solubility in solvent. However, an iPP/MAPP/KD (PMK) blend containing filler particles with a quasi-spherical shape (~97.8 nm in diameter) and narrow particle size distribution (polydispersity index= 1.076) was successfully prepared by incorporating MAPP to reduce the interfacial tension and surface free energy between the dispersion phase and the continuous phase, and adopting a spray-drying method after solution-mixing to suppress the increase of the size of the dispersed phase during the removal of solvent.

关键词： dispersion     rigid organic filler     isotactic polypropylene     mixing    

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标题 作者 时间 类型 操作

Lignin-based polymer with high phenolic hydroxyl group content prepared by the alkyl chain bridging method

期刊论文

Decontamination of Cr(VI) facilitated formation of persistent free radicals on rice husk derived biochar

Kaikai Zhang, Peng Sun, Yanrong Zhang

期刊论文

The catalytic effect of both oxygen-bearing functional group and ash in carbonaceous catalyst on CH 4 -CO 2 reforming

Weidong ZHANG, Yongfa ZHANG,

期刊论文

Immobilization of laccase on organic–inorganic nanocomposites and its application in the removal of phenolic

期刊论文

A pulsed switching peroxi-coagulation process to control hydroxyl radical production and to enhance 2,4

Yaobin Lu, Songli He, Dantong Wang, Siyuan Luo, Aiping Liu, Haiping Luo, Guangli Liu, Renduo Zhang

期刊论文

Electrospun porous carbon nanofibers derived from bio-based phenolic resins as free-standing electrodes

期刊论文

Rapid method for on-site determination of phenolic contaminants in water using a disposable biosensor

Yuanting LI, Dawei LI, Wei SONG, Meng LI, Jie ZOU, Yitao LONG

期刊论文

Hydroxyl radical-involved cancer therapy via Fenton reactions

期刊论文

Characterization of electrode fouling during electrochemical oxidation of phenolic pollutant

Xuefeng Liu, Shijie You, Fang Ma, Hao Zhou

期刊论文

Kinetics and mechanism of nitrobenzene degradation by hydroxyl radicals-based ozonation process enhanced

Weizhou Jiao, Shengjuan Shao, Peizhen Yang, Kechang Gao, Youzhi Liu

期刊论文

Phenolic rigid organic filler/isotactic polypropylene composites. II. Tensile properties

QI Dongming, SHAO Jianzhong, WU Minghua, NITTA Kohhei

期刊论文

Phenolic compounds removal by wet air oxidation based processes

Linbi Zhou, Hongbin Cao, Claude Descorme, Yongbing Xie

期刊论文

Performance and synergistic effect of phenolic and thio antioxidants in ABS graft copolymers

Gongsheng LI, Xuhong GUO, Wang NA, Diancheng HAO, Mingyao ZHANG, Huixuan ZHANG, Jun XU

期刊论文

Impact and inhibitory mechanism of phenolic compounds on the formation of toxic Maillard reaction products

Jing TENG, Xiaoqian HU, Ningping TAO, Mingfu WANG

期刊论文

Dispersion of a novel phenolic rigid organic filler in isotactic polypropylene matrix by solution-mixing

Dongming QI, Xiaoli ZHAO, Zhijie CHEN, Peng HUANG, Jun CAO

期刊论文