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    Volume 41,  2024 Issue 5
      Review and monographs
    • TAN Shenxin, QU Xiaohu, LUO Jiaojiao, FAN Huiling, LIN Jianying, ZHAO Zhihuan

      2024,41(5), DOI:

      Abstract:

      Amino acid metal-organic framework is a kind of material with periodic structure, which is synthesized with the participation of metal ions and amino acids as organic ligands. As a component of protein, amino acids have the advantages of the green environmental protection, good biocompatibility, variety and low price. Introducing them into MOF can endow materials with special flexible structure, rich active sites, special structure and other characteristics, which has aroused great interest of researchers. The review first elaborates the structure-dimensional classification of amino acid MOFs. Secondly, the main synthesis methods of amino acid MOF include solvothermal method, mechanochemical synthesis method, microwave heating auxiliary method. The performance regulation of materials is then further explained. On this basis, the applications of these materials in chiral separation, catalysis, adsorption and other fields are introduced emphatically. Finally, by analyzing the problems of poor material stability, unpredictable structure, the future research of amino acid metal-organic framework materials is prospected.

    • CHENG Shi-jin, PANG Xu-fu, JIANG Gui-quan, PANG Jiu-yin

      2024,41(5), DOI:

      Abstract:

      The commonly used halogenated flame retardants in polyurethane have the problem of releasing corrosive gases and toxic and harmful substances such as hydrogen halide during combustion, which poses a threat to human health. In recent years, halogen-free flame retardants have gradually replaced halogen-free flame retardants for flame retardancy of rigid polyurethane foam with the advantages of halogen-free, low smoke and environmental protection. In this paper, halogen-free flame retardants for rigid polyurethane foam were subdivided in two major directions: additive flame retardants and reactive flame retardants, and in the following sub categories: organic, inorganic, intumescent, nitrogen, phosphorus, silicon, nano, etc. The characteristics, flame retardant mechanism, common flame retardants and flame retardant effects of halogen-free flame retardants for rigid polyurethane foam were summarized. The common universal flame retardant mechanisms of halogen-free flame retardants for polyurethane foam were described. At last, the development hotspots of halogen-free flame retardants for polyurethane foam were prospected.

    • ZHANG Yutong, LIU Yun, DONG Chaohong, ZHANG Xinlei, XU Tingting, LI Xiangrong, ZHANG Kaitao, ZHANG Xin

      2024,41(5), DOI:

      Abstract:

      In recent years, with the continuous improvement of people"s awareness of environmental protection, bio-based materials are receiving more and more attention. As an emerging bio-based nanomaterial, nanocellulose has excellent mechanical properties, surface chemical modifiability and other characteristics, which shows great potential in many application fields. However, nanocellulose is a highly flammable material, which greatly limits their applications. Thus, the construction of flame-retardant nanocellulose materials is beneficial to expanding its application areas. This paper mainly introduces common methods for preparing flame-retardant nanocellulose based materials, including intrinsic flame-retardant nanocellulose materials and flame-retardant nanocellulose-based materials with additives. Several major types of flame-retardant nanocellulose based materials (membranes, aerogels, filament, etc.) and their applications are summarized, and the future development directions of flame retardant modification of nanocellulose are prospected.

    • YIN Junlian, FENG Ranran, ZHANG Yuecheng, ZHAO Jiquan

      2024,41(5), DOI:

      Abstract:

      Selectively oxidative cleavage of vicinal diols to the corresponding aldehydes, ketones and carboxylic acids is an important and basic organic reaction. Traditionally, this process is carried out by using stoichiometric periodate or lead tetraacetate as oxidants, respectively. Obviously, the traditional protocols are contrary to the development concept of green chemical industry in views of both economic and environmental standards. In principle, water is the only by-product in the selective oxidation cleavage of vicinal diols with molecular oxygen as oxidant, and molecular oxygen is cheap?and?easily?available, which affords the oxidative cleavage of vicinal diols of the dual advantages of environmental friendliness and economic feasibility. Therefore, a number of heterogeneous catalysts or catalytic systems with different transition metals as active components have been developed for such reaction after unremitting exploration, Such as Ru, Au, Mn,Co,which provides?groundwork for widespread application in the future. Herein, we summarize the advances of these catalysts and reaction processes by the classifications of precious and non-precious metals, and point out the development direction in this field.

    • FENG Zhen-hua, QIU Xiang-yun, ZHANG Tao, DAI Zuo-qiang, GUO Xiang-xin

      2024,41(5), DOI:

      Abstract:

      With the widespread use of liquid lithium batteries, thermal runaway phenomenon occurs from time to time, and their thermal safety has become an urgent issue to be solved. The all-solid-state lithium battery shows great potential for application with its excellent safety. The paper briefly introduces the basic concept and structure of all-solid-state lithium batteries, focuses on the latest research progress of oxide, sulfide and polymer solid electrolytes, and summarizes the differences in the thermal safety of these three types of all-solid-state lithium batteries, including the thermal safety at the level of the solid electrolyte material, the level of the interface between the solid electrolyte and the mixing of the active material or the lithium metal cathode, and the thermal safety at the level of the full-cell battery. In addition, the influence of lithium dendrite phenomenon on the safety of all-solid-state lithium batteries is still not negligible. At present, there are many studies on the thermal safety at the material and interface levels, but fewer studies at the full-cell level, and most of them are focused on small-capacity batteries, so the thermal safety at the full-cell battery level still needs to be further investigated. Finally, it is pointed out that the future commercialization of high-safety all-solid-state lithium batteries should focus on solving the key interface problems and lithium dendrite problems in all-solid-state lithium batteries.

    • Functional materials
    • Yu Xueyan, wang xiaojun, Chen Zhengtao, Kang Sibo, Zhang Huaqing, Liu Shuhui, Cong Weiwei, Zhang Kai, Gui Tai-jiang and

      2024,41(5), DOI:

      Abstract:

      We have developed an anti-fouling coating with excellent flexibility suitable for the surface of elastomer substrates.The first a flexible silyl ester acrylate resin with self polishing property was synthesized, further increasing the flexibility of the matrix resin by adding low molecular weight toughness resin for external plasticization. A flexible self polishing anti-fouling coating was prepared using acrylic silane ester resin and a tough mixed resin Experimental results shown that the glass transition temperature of the resin was -20℃, it had good physical and mechanical properties. Further increase the flexibility of the matrix resin by adding low molecular weight toughness resin. Experimental results shown that the ratio was 7:3, the defects of the blend resin were the smallest compared with other ratios, and the compatibility of the resin was the best. A flexible self polishing antifouling coating was prepared by using acrylic silicone resin and toughness mixed resin. The flexibility of the antifouling coating was Grade 1, the adhesion on the surface of elastomer substratewas 4.0MPa, After 60 days of testing, the water absorption of the coating is between 1.1% and 1.2%, within a reasonable range. The shallow water immersion test for 36 months had good antifouling effect.

    • CAO Yan, GAO Junkai, XIA Mengsheng, XU Pengtao, HAN Zhi, CHEN Yan

      2024,41(5), DOI:

      Abstract:

      In order to develop green and environmentally friendly hydrogel membranes for oil-water separation, this study extracted cellulose from waste poplar wood and employed a synergistic assembly strategy to construct a green cellulose-based hydrogel (CLH) membrane for oil-water separation. Lithium chloride (LiCl) was introduced as an active water-absorbing unit into the cellulose framework, and then polyvinyl alcohol (PVA) was used to encapsulate LiCl particles on the cellulose framework to prepare the CLH hydrogel. The preparation process was environmentally friendly and simple. The prepared CLH hydrogel membrane exhibited a laminar structure, overcoming the compressibility limitation of traditional hydrogels. Under the influence of gravity, the CLH hydrogel membrane achieved efficient separation of oil-water mixtures and oil-in-water emulsions. Moreover, the CLH hydrogel membrane demonstrated good stability, durability, and recyclability during the separation process. In short, the collaborative assembly strategy can not only effectively solve the problem of cellulose resource waste caused by waste wood production, but also can provide a new method for oil-water separation.

    • ZHANG Meng, XIANG Yanli, ZHANG Lei, FANG Jianbo, REN Qiang, WANG Chenyi

      2024,41(5), DOI:

      Abstract:

      Imidazoline quaternary ammonium salt corrosion inhibitor was synthesized from oleic acid, diethylenetriamine and benzyl chloride. The structure of quaternary ammonium salt was characterized by FT-IR, 1H-NMR. The ions were exchanged into the Na-montmorillonite (DK0) layer to prepare the corrosion inhibitor modified organic montmorillonite. The structure, composition and release properties of QACDK0 were characterized by XRD, TGA and UV-Vis. The results showed that the insertion of quaternary ammonium salt inhibitor increased the spacing of montmorillonite layers from 12.8 ? to 39.8 ?, and the load of inhibitor in montmorillonite was about 39.0 wt%. In order to study the effect of different nano-clay particles on the corrosion resistance of water-based epoxy coating, epoxy resin/montmorillonite composite emulsions were prepared by phase inverse method with the incorporation of QACDK0, DK0 and commercially available common organic montmorillonite blended with epoxy resin E-51. DLS and Zeta potential were used to characterize the stability of epoxy emulsion. The Zeta potential of imidazoline quaternary ammonium salt corrosion inhibitor modified montmorillonite/epoxy emulsion was -27.8 mV, indicating the highest stability. Electrochemical impedance spectroscopy (EIS) test demonstrated that after 30 days of immersion in corrosive medium, the impedance modulus of the anticorrosive coatings prepared based on QACDK0 remained the highest, with a high impedance value of 2.29×108 Ohm.cm2, indicating that the release of quaternary ammonium salt corrosion inhibitor made the coatings have better active anticorrosive properties. In the test of neutral salt spray resistance, the grey coating containing pigment corresponding to QACDK0 salt spray resistance time, which verified that the coating has good salt spray resistance performance. In addition, the coating surface is flat and compact, which was beneficial to good barrier performance.

    • ZHENG Xian-hong, TANG Jin-hao, DING Bin-bin, XIA Wen, LI Changlong, WANG Wei

      2024,41(5), DOI:

      Abstract:

      Inspired by the dyeing processes, a highly elastic and conductive transition metal carbide/nitride (MXene) modified rib knitting fabric was prepared via a scalable roll-to-roll technology. Characterizations on the structure and performance of composite fabrics were conducted through SEM, resistance measurement, sensing performance testing. The results show that MXene modified rib knitting fabric has good elasticity and elastic recovery, and the MXene loading in the composite fabric increased with roll-to-roll cycles. On the contrary, the electrical resistance decreased with roll-to-roll cycles, and the minimum sheet resistance can be low as 38.3 Ω/?. The strain sensing performance test of the composite fabrics show that the MXene modified rib knitting fabric exhibit anisotropic strain sensing performance, and the strain sensing performance in course direction was better than that in the wale direction. In addition, the maximum gauge factor and sensing range were 72.8 and 0~160%, respectively, which were higher than those in wale direction (gauge factor: 4.4, sensing range: 0~24%). More importantly, the MXene modified rib knitting fabric exhibited superior sensing performance than the majority of reported woven and knitted fabric-based strain sensors, and can be used as a wearable flexible strain sensor to monitor various movements of the human body, demonstrating great potential in the field of intelligent wearable applications.

    • HAN Chunran, YUE Zhenge, YU Shiyou, WANG Xin, LI Chenchen, ZHANG Siyao

      2024,41(5), DOI:

      Abstract:

      Based on the catalytic oxidation effect of nickel-manganese oxide complex against corbic acid, an electrochemical sensor for rapid detection of ascorbic acid was constructed by modifying glassy carbon electrode with nickel-manganese oxide complex. Ni - Mn - based oxide composites were prepared by one - step hydrothermal method. Electron microscopy (SEM), EDS, X-ray diffraction (XRD) and Fourier infrared spectroscopy (FT-IR) were used to characterize the morphology, elemental composition ratio and structure of the materials.The structure shows that the material is a spherical structure with voids on the surface. All the diffraction peaks can be indexed as Mn2O3(JCPDS No. 41-1442) ,NiMnO3 (JCPDS No. 48-1330) , and Mn-O and NI-O functional groups exist. According to the response of electric signal, the sensitive and rapid detection of anticorbic acid is realized. The composite material was modified on the electrode surface by drip coating method. The electrochemical behavior of ascorbic acid on the nickel-manganese oxide composite electrode was measured by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Finally, the drop coating amount was determined to be 10μL under the condition of acetic acid buffer solution pH=4. The peak oxidation current of ascorbic acid has a linear relationship with the concentration from 0.4 to 7600 μmol/L. The linear equation is Ip= 0.0039x (mmol/L)+11.643, and the detection limit is 0.023 μmol/L. The sensor has been applied to the determination of ascorbic acid in fruit drinks. The recovery rate of the sensor is 95.5% ~ 103.12%, indicating that it has a good application prospect in food analysis and biochemical analysis.

    • XU Sikuan, ZHANG Hongmei, QI Pengfei, CAO Zhangjun, XING Yanjun

      2024,41(5), DOI:

      Abstract:

      A series thermoreversible hydrogel CS-Ag were prepared by the supermolecule complexation of chitosan with silver ion. The CS-Ag systems are in the semi-transparent and stable flowable sol state at room temperature, and become the gel state at temperature above 50 °C in 2 min and recover to flowable sol state when temperature was below 50 °C. This phase transition process could be repeated at least 5 times and shows a good stability. The structure and chemical state of the hydrogel were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and X-ray energy spectrometer (EDS). The thermoreversible hydrogel CS-Ag with same gelation temperature could be prepared by adjusting the AgNO3 amount and the pH value simultaneously. The different supramolecular interactions of the -NH2 group of chitosan in the hydrogel system at different temperatures were proposed to dominate the reversible thermo-responsive process of CS-Ag hydrogel. CS-Ag-19 hydrogel showed good antibacterial, and injectable and thermos-gelation performance, and it had potential application as hydrogel antibacterial dressing.

    • ZHAO Mingyao, ZHANG Yongjie, SU Junjun, PAN Hongfei, CHEN Zhijian

      2024,41(5), DOI:

      Abstract:

      Azadipyrromethene (ADP) dyes have been applied widely in various fields due to their outstanding optical properties. An amphiphilic Cu(II)-ADP dye Ⅰ was designed and synthesized by the coordination of one ADP ligand containing two hydrophobic dodecyloxy chains and one ADP ligand containing two hydrophilic poly ethylene glycol chains with Cu(II). The dye Ⅰ was characterized by 1H NMR, MS, and elemental analysis. UV-Vis absorption spectroscopic studies indicated that the dye Ⅰ self-assembled into J-type aggregates in ethanol/water with bathochromic shift of 89 nm. Further AFM and TEM studies indicated a two-dimensional nanosheets of the aggregates. SAXS experiments indicated a bilayer structure of the J-aggregates of dye Ⅰ.

    • ZHANG Yu-feng, PEI Hao-nan, FAN Xiao-qing, ZHOU Jie, LIU Teng-long, XUE Dong-xu

      2024,41(5), DOI:

      Abstract:

      The study aimed to synthesize a novel indium-based organic framework material with potential applications in clean energy, particularly in methane storage for vehicular transportation. The researchers utilized In(NO3)3.4H2O and H3BTB, acetic acid as template agents, and employed a solvothermal method to achieve material synthesis. The resulting material exhibited a high specific surface area of 2487 m2 g-1 and permanent porous structure, with a pore volume of 1.07 cm3 g-1. And demonstrated a methane working capacity of 397 cm3 g-1 (0.29 g g-1) at 273 K and 80 bar. These results indicate the potential application of this material for methane storage. The innovation of this study lies in the successful synthesis of indium-based MOF material with excellent methane adsorption performance, providing a new direction for the development of high-performance gas adsorption materials. Therefore, this paper presents a new perspective for the advancement of clean energy technology. Additionally, the material also exhibits good repeatability, providing strong support for its long-term sustainability in practical applications.

    • Surfactants
    • LIU Yun-yu, YANG Lun, JI Yong-xin

      2024,41(5), DOI:

      Abstract:

      Synthesis of thiol silicone oil using octamethylcyclotetrasiloxane and mercaptopropyl methyl dimethoxy silane as raw materials; synthesis of organosilicon based RAFT reagents using thiol based silicone oil; The polyether modified silicone defoamer is synthesized by the reaction of silicone based RAFT reagent with methyl terminated allyl group polyethers (EO and PO) through reversible addition breaking chain transfer polymerization. The optimal process conditions were as follows: the equivalent molecular weight of silicone based RAFT reagent was 2000, m (EO)∶ m (PO)=1∶4, m (organosilicon based RAFT reagent): m (ether)=1∶1.15, the reaction temperature was 75 ℃, the reaction time was 8 h, the amount of initiator was 2% of the mass of methyl terminated allyl group polyether, and the yield was 91.8%.The structure of polyether modified silicone defoamer was characterized by FTIR, NMR and GPC, and it was used in coatings and lotion to determine the defoaming and inhibiting properties.

    • Modernization technology of traditional Chinese medicines
    • WANG Junlong, SHI Wenpan, JIANG Shenqi, LI Wenwen, CHEN Yu

      2024,41(5), DOI:

      Abstract:

      In order to obtain the best extraction process of flavonoids (TF) and antioxidant activity, hypoglycemic activity, explore the influence of five extraction process on the TF extraction(Ultrasound-assisted extraction, acid extraction, enzymatic extraction, hot water extraction, hot alcohol extraction), optimized the extraction process through single factor experiment and response surface experiment; determination and analysis of the distribution and contents of seven major flavonoid glycosides by HPLC;and further study the correlation between TF and in vitro antioxidant activity (DPPH clearance ability, ABTS radical clearance ability, hydroxyl radical scavenging ability, reducing ability) and in vitro glucose reduction ability of α-glucosidase. The results showed that ultrasound-assisted extraction had the highest TF content, and the response surface was optimized for the best extraction process: temperature 68 ℃, time 23 min, ethanol volume fraction 24 %, liquid ratio 63:1 mL/g. Under this condition, the TF content was 34.85 mg RT/g (Equivalent rutin RT mass per gram of TF compound expressed); the HPLC identified 7 major flavonoids in TF, The most abundant flavonoid compounds in the TF were quercetin-3-O-palmitoyl-7-O-rhamnoside and quercetin with 3.897 mg/g and 2.874 mg/g; TF mass concentration and DPPH clearance capacity, ABTS radical scavenging ability, hydroxyl radical scavenging ability and reducing ability showed significantly positive correlation, and the hypoglycemic capacity of α-glucosidase could reach 92.6 %.

    • Catalysis,separation and purification technology
    • FANG Zi-yu, ZHANG Wei, WANG Jin-ding, CHONG Si-ying, ZHANG Yajing, WANG kang-jun

      2024,41(5), DOI:

      Abstract:

      Ni/SiO2 catalyst was prepared by coprecipitation method, with nickel nitrate as nickel source and acid/alkaline silica sol as silica source. The catalytic performance for 2-methylfuran (2-MF) gas phase hydrogenation to 2-methyltetrahydrofuran (2-MTHF) of the catalyst was evaluated in a fixed bed reactor.The catalysts were characterized by XRD, N2 isothermal adsorption and desorption, H2-TPR, NH3-TPD, XPS, FT-IR and TEM, in order to investigate the effect of acidity and alkalinity of silica sol on the catalytic performance. The results showed that the Ni/SiO2 catalyst prepared with acidic silica sol possessed more amount of weak acid sites and medium strong acid sites, larger specific surface area and average pore size, which was beneficial for the improvement of catalyst activity and 2-MTHF selectivity. The catalyst is stable in 200 hours at reaction temperature of 90 ℃, 2 MPa, WHSV=4.4 h?1, with a 2-MTHF yield of 95.5%.

    • HE Zizi, LI Junrong, LI Fangbin, HE Beihai, QIAN Liying

      2024,41(5), DOI:

      Abstract:

      : Using bagasse as raw material, the xylose-rich pre-hydrolyzed sugar solution was obtained by pre-hydrolysis under high temperature and low acid concentration (0.176% H2SO4), and then furfural was obtained by further deep acidolysis, and the separation of furfural was realized by the highly efficient extraction from the aqueous phase with a mixture of organic solvents. The pre-hydrolysis of bagasse, the deep acid hydrolysis and the organic solvent extraction of furfural were investigated; morphology and structure of bagasse and pre-hydrolysis residue were characterized by FT-IR, XRD, SEM and TGA; and quantitatively detection of the xylose in the pre-hydrolysis process and the furfural in the deep acid hydrolysis process was conducted by an UV spectrophotometer. The results showed that the highest xylose concentration (41.72 g/L) was obtained in the pre-hydrolyzed solution at 160 °C, liquid-solid ratio of 6:1, and mass percentage of concentrated sulfuric acid to bagasse (oven dry) as 0.176%. The pre-hydrolyzed solution was directly deep acidified at 170 °C for 90 min, the concentration of furfural in the solution could reach up to 15.91 g/L, with the highest molar yield of furfural as 59.60%. Extraction of furfural from aqueous solution was carried out by mixing organic solvents in the ratio of v(1,2-dichloroethane):v(n-butanol) = 9:1, and the extraction rate of furfural was up to 93.53% when the volume ratio of the extracting phase was v(organic phase):v(aqueous phase) = 2:1.

    • Drug and cosmetic materials
    • WAN Kaibo, CHEN Diansong, MA Ling, WANG Jing

      2024,41(5), DOI:

      Abstract:

      Sapindus mukorossi Gaertn extracting solution as a natural active raw material to care products, in order to promote the application of Sapindus mukorossi Gaertn extracting solution in daily chemical industry, the water extraction was purified by microbial fermentation method. Lactobacillus plantarum was selected as the suitable fermentation strain based on sugar consumption and saponin purity, Sapindus mukorossi fermented liquid (SF) was prepared. The anti-acne effect of SF was studied from the three major causes of acne: sebum, inflammation and overgrowth of pathogenic bacteria. The results showed that 20 μg/mL SF reduced the lipid binding rate of SZ95 cells by 26.4%; the levels of NO, TNF-α, IL-6 and ROS in RAW 264.7 cells induced by lipolyaccharide (LPS) were decreased by 52.3, 57.5, 56.2 and 35.9%, respectively; The MIC of SF to Propionibacterium acnes, Malassezia furfur and Staphylococcus aureus were 3.125, 12 .5 and 6.25 g/L, respectively, by double dilution method. Through the human efficacy evaluation, the facial acne situation was significantly improved.

    • Electro-organic chemistry and industry
    • Yunsong Ran, Yi Chen, Yangsong Liu, Zhenqiang Zhao, Xianguo Ma

      2024,41(5), DOI:

      Abstract:

      Environmentally friendly polymer electrolyte membrane was prepared by emulsion polymerization via interpenetrating network technology. The physicochemical property of the prepared polymer membrances were characterized by Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), mechanical strength measurements, thermal analysis, electrochemical impedance spectroscopy (EIS) and charge-discharge test. The results showed that the as-prepared polymer membrane M2 exhibited a mechanical strength of 7.53 MPa and elongation of 90.4%, uptake electrolyte 150%, thermal shrinkage 4% with ionic conductivity of 0.98 mS/cm at 25 ℃ when the mass ratio of m(AMPS):m(BA):m(AA):m(AN) was 1:3:2:2, demonstrating the best mechanical and electrochemical properties. The polymer electrolyte membrane has good compatibility and universality with the anode and cathode materials current mainstream used in lithium-ion batteries. The LiCoO2 as cathode active material had an initial discharge capacity of 141.3 mA.h/g, while the graphite as cathode active material possessed an initial discharge capacity of 347.1 mA.h/g, and their corresponding discharge capacity retention were 94.8% and 85.0% after 100 cycles at 0.1 C rate. The battery delivered a discharge capacity of 119.8 mA.h/g and 239 mA.h/g based on the LiCoO2 and graphite in the cathode at 2.0 C rate, indicating that the prepared material exhibited excellent electrochemical performances.

    • TU Qian, WANG Jinglu, ZHENG Yinyin, LIN Baoying, ZHANG Qiang, LIU Shanpei, CHEN Liangzhe

      2024,41(5), DOI:

      Abstract:

      Vanadic oxide (V2O5) served as the raw material, and the vanadium trioxide (V3O7?H2O) nanorod is prepared via a one-step solvothermal method. The V3O7?H2O nanorods are used as electrode materials to explore the influence of screen-printing technology on the electrochemical performance of electrodes. Then, screen-printing technology is used to prepare electrodes, followed by the assembling of the coin supercapacitor. The results of morphology and structure characterized by SEM, EDS, XPS and FT-IR find that V3O7?H2O nanorods have been successfully synthesized. In the electrochemical performance test, the specific capacitance of the screen-printed electrode can reach 268.0 F/g (the current density is 0.3 A/g), and the specific capacitance retention is still 85.9% after 5000 charge/discharge cycles, which is superior to the smear electrode specific capacity (246.0 F/g) and specific capacitance retention (68.0%). The reason can be attributed to the regular arrangement of ink structure of screen printing. Moreover, the coin supercapacitors can exhibit excellent electrochemical performance with specific capacitance and capacitance retention of 134.2 F/g (0.5 A/g current density) and 91.2% (after 5000 charge/discharge cycles). When the power density is 413.0 W/kg, the energy density is as high as 22.0 W h/kg. In this study, which can provide a reference for further research of printed energy storage devices.

    • Water treatment technology and environmental protection
    • GUO Kai, WANG Jia-qi, LI Ya-nan, WU Yaning

      2024,41(5), DOI:

      Abstract:

      Coal gasification slag (CGS), a kind of solid waste generated during the production of coal gasification, was used as persulfate (PS) activator to effectively remove phenanthrene (PHE), a typical polycyclic aromatic hydrocarbon difficult to eliminate from aquatic environment. The microstructure and elemental composition of CGS were characterized by SEM-EDS and XPS. The types of free radicals were determined through free radical quenching experiments and EPR experiments. The effects of CGS and PS dosages, initial pH value and coexisting substances on PHE removal in the CGS/PS system were investigated, the oxidation mechanism was explored, and the degradation pathways were predicted. ECOSAR software was used to evaluate the toxicity of PHE and its products. The results showed that 11.9% of Fe was identified in CGS, indicating that CGS was an effective PS activator. The degradation efficiency of PHE reached 95.34% after 60 minutes of reaction, with the initial conditions of PHE dosages of 1 mg/L, pH value of 3, CGS dosages of 0.7g/L and PS dosages of 1mmol/L, and the utilization rate of PS reached 29.18%. The degradation process of PHE conformed to pseudo first-order reaction kinetics,and the sulfate radical (SO4?-) and hydroxyl radical(HO?)were produced. SO4?- was found to play a dominating role during the oxidation, and HCO3- and NO3- inhibited the reaction significantly. PHE was decomposed into long-chain acids and esters through decarbonylation, hydroxylation and decarbonization, and finally converted into CO2 and H2O. The ECOSAR model evaluation found that the toxicity of intermediate products is generally lower than that of PHE.

    • FAN Liping, WEN Yuexiao

      2024,41(5), DOI:

      Abstract:

      In order to improve the wastewater treatment effect and power generation performance of microbial fuel cell (MFC), a kind of carbon felt (CF) anode modified by sodium alginate and polyquaternium 11 (SA-PQ-11/CF) was prepared. A microbial fuel cell (MFC) experimental system was constructed using pharmaceutical wastewater and molasses wastewater as anode solutions and carbon felt as cathode, respectively, and its performance was characterized by scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and chemical oxygen demand (COD). The results showed that the SA-PQ-11/CF anode had a larger specific surface area, and the solution resistance and charge transfer resistance of MFC were also significantly reduced. When the anolyte was pharmaceutical wastewater, the steady-state output voltage and the COD removal rate of MFC using SA-PQ-11/CF anode were about 0.22 V and 62%, respectively, which were 100% and 130% higher than those using CF. When the anolyte was molasses wastewater, the steady-state voltage and COD of MFC using SA-PQ-11/CF anode were 0.15 V and 43%, respectively, which were 275% and 95% higher than those using CF anode. The anode modification based on SA-PQ-11 can effectively improve the wastewater treatment efficiency and power generation capacity of MFC.

    • Papermaking chemicals
    • BAO Kang, JING Yi, WANG Wenlu, ZHANG Qi, HUA Xiangfeng

      2024,41(5), DOI:

      Abstract:

      The solvent-assisted solvent solubilisation method was used for the preparation of maleic rosin ester emulsions, and the optimum process synthesis conditions were determined. The effects of sodium dodecyl sulphate (SDS), alkylphenol polyoxyethylene ether (OP-10) and carboxylated nanofibrillated cellulose (CNF-C) on the particle size and stability of the maleic rosin ester emulsions were comparatively analysed. The process strategy for superhydrophobic paper was constructed using a two-layer coating method, with mechanically pulped nanocellulose and precipitated calcium carbonate PCC as the first coat and maleic rosin ester emulsion as the second coat. It was found that the optimal process conditions for the synthesis of maleic rosin ester were 1:3 ratio of maleic rosin and glycerol; 0.4% dosage of initiator (Azobisisobutyronitrile); 2% dosage of catalyst (nano-ZnO2); and 5 hours reaction at 250 °C. Carboxylated nanocellulose was used as the emulsifier, and the prepared maleic rosin emulsion reached a particle size of 527 nm, which was stable without emulsion breakage and delamination after 90 days of standing at room temperature. The PCC-CNF-MAP-DG coated paper prepared by double-layer coating has a contact angle of 159.1° with water, a cobb value of 2.4 g/m2, and still has super-hydrophobicity after 200 folds, as well as acid- and alkali-resistant, with good chemical stability. The super-hydrophobicity of paper originates from the hold-up of water droplets by air trapped between the two-stage structure, forming a dense hydrophobic layer on the surface of paper fibers.

    • Oil field chemicals and petroleum additives
    • DU Daijun, FANG Zezhou, ZHANG Yangyang, PU Wanfen, ZHANG Hui, ZHU Jianlin, CAO Xiaodong

      2024,41(5), DOI:

      Abstract:

      CO2-responsive monomer N, N-Dimethyl oleic amide propyl tertiary amine (DOAPA) with tertiary amine structure was prepared by using 3-dimethylaminopropylamine and oleic acid as main agents, and was intermixed with organic counter ions to construct CO2-responsive worm-like micelle (CO2-TWMS). The response of the system was characterized by the changes of conductivity, chemical structure and micro-morphology before and after contact with CO2. The anti-channeling performance and mechanism of the system were revealed by combining the changes of surface activity of the system and the changes of pressure and recovery efficiency in the process of CO2 displacement in dense matrix/crack medium and CO2-TWMS channeling prevention. The experimental results show that the viscosity of CO2-TWMS system is the highest when the inverse ion is sodium p-toluene sulfonate and the molar ratio of DOAPA is 1:1. CO2 and N2 can stimulate the reversible change of electrical conductivity between 0.9ms/cm and 1.95ms/cm, and induce the transformation of micromorphology between wormlike micelles and spherical micelles. In addition, CO2 can reduce the critical micelle concentration from 1mmol/L to 0.25mmol/L, and the lowest surface tension from 30.2mN/m to 29.1mN/m. The adsorption efficiency and efficacy of the system at the gas-liquid interface are enhanced, which is conducive to the formation of micelles. In the dense matter-fracture medium, CO2 induced wormlike micelle formation, increased the pressure difference during displacement, expanded the CO2 displacement sweep efficiency, and increased the recovery rate by 22.6%.

    • XU Dong, ZHU Wei-ping, LIU Chuan-qing, WANG Yu-bin, WANG Zheng-fan, MENG Ling-peng, WU Ming-yang

      2024,41(5), DOI:

      Abstract:

      The organic boron crosslinking agent JSA-1 was synthesized using boric acid, n-butanol, ethylene glycol, and diethylenetriamine as raw materials using a one-pot method. The crosslinking performance of JSA-1 was systematically evaluated by examining factors such as the mass fraction of guar gum (the percentage of guar gum to the total mass of guar gum base solution), the dosage of JSA-1 (based on the quality of guar gum base solution), and pH. The results show that the higher the mass fraction of guar gum (0.09%~0.4%), the better the crosslinking state, shorter the crosslinking time, higher the apparent viscosity, and stronger the temperature resistance of guar gum fracturing fluid; The larger the dosage of JSA-1 (0.04%~0.4%), the better the crosslinking state, shorter the crosslinking time, and stronger the temperature resistance of guar gum fracturing fluid; The higher the pH (pH=4~14), the longer the crosslinking time and stronger the temperature resistance of guar gum fracturing fluid. JSA-1 has a wide range of applications for pH and guar gum mass fraction. In terms of low-temperature formula, it can effectively crosslink low mass fraction guar gum. When the guar gum base solution with a mass fraction of 0.13% is crosslinked with JSA-1, the apparent viscosity can reach 50 mPa·s at room temperature shear. In terms of high-temperature formula, the fracturing fluid prepared by cross-linking a 0.4% guar gum base solution with JSA-1 has good temperature and shear resistance, and its apparent viscosity can be stably maintained at around 300 mPa·s under 120 ℃ shear conditions.

    • Acrylic series chemicals
    • ZHOU Li-sha, AN Gui-lei, HUANG Bai-tao, WU Ying-kui, CHEN Bo-han, QI Wen

      2024,41(5), DOI:

      Abstract:

      The synthesis of high solid content and low viscosity fluorocarbon resin is one of the important ways to improve the environmental protection of solvent based fluorocarbon anti-corrosion coatings. Polymerizable acrylic hydrogenated rosin ester monomer was prepared by hydrogenating rosin from biomass raw materials, and high solid content and low viscosity bio-based fluorocarbon resin was further prepared using free radical polymerization method. The viscosity reduction mechanism of acrylic hydrogenated rosin ester was analyzed using molecular dynamics simulation method. And the coating performance of bio-based fluorocarbon resin was explored. It is indicated that with the increase of monomer content of acrylic hydrogenated rosin alcohol ester, the viscosity of modified fluorocarbon resin decreases. When the monomer content of acrylic hydrogenated rosin alcohol ester is 18.6%, the solid content of modified fluorocarbon resin is 78.56%; its kinematic viscosity is equivalent to that of fluorocarbon resin modified by tert ethylene carbonate monomer, and far lower than that of modified fluorocarbon resin without large volume side groups; Compared with petroleum resin tert ethylene carbonate, hydrogenated rosin acrylate monomer has larger space volume, lower intermolecular interaction force and lower viscosity; The hardness and adhesion of fluorocarbon coatings modified by acrylic hydrogenated rosin ester are higher than those modified by tert ethylene carbonate, and the chemical corrosion resistance is slightly lower than that of tert ethylene carbonate modified fluorocarbon coatings.

    • Fine chemical intermediates
    • GAO Song, SHAO Xiao-fu, GUO Bo, LI Qian, WANG Pei, CAO Yang

      2024,41(5), DOI:

      Abstract:

      Sertraline is an important selective serotonin reuptake inhibitor (SSRI)-type of antidepressant that has strongly supported the effort against depression worldwide. (4S)-tetralone is the key intermediate in sertraline synthesis whose supply has been limited by the lack of available chiral resolution routes that are operationally simple and environmentally friendly. The Pseudovibrio-ω-Transaminase (P-ω-TA) is a pyridoxal-5’-phosphate (PLP)-dependent transaminase identified in marine sponge Pseudovibrio sp. WM33 that has shown good chiral resolution of (4S)-tetralone, which can convert (1S,4S) -demethylsertraline to (4S) -tetrahydronaphthalone, but direct application of this enzyme suffers from the high cost caused by the complicated preparation, single-use property and poor stability. In this study, we explored immobilization of P-ω-TA using bacteriophage T4 capsid as the carrier through self-assembly for recoverable biocatalysis. By fusing P-ω-TA to the non-essential small outer capsid protein (Soc) of T4, affinity immobilization of the enzyme on the T4 capsid has been achieved with a high copy number. The immobilized P-ω-TA retains the full activity and can be easily recovered by centrifugation for repeated use. In a five-round recover and reuse process, the average recovery of enzyme activity was >93% for each round. It has been demonstrated that immobilized P-ω-TA maintains the (S) -type selective resolution at the chiral center of the substrate and the catalytic ability for (1S,4S)-4-(3,4-dichlorophenyl)-1,2,3,4-tetrahydronaphthalen-1-amine; hydrochloride. Immobilization of P-ω-TA reduces the biocatalysis cost on chiral resolution of (4S)-tetralone, and helps establishing a greener synthetic route for sertraline.

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Organizers:China Haohua (Dalian) Research & Design Institute of Chemical Industry Co., Ltd.
Edited Published:
Editor in Chief:HAN Jianguo
Associate editor:CHEN Qu
Address:201 Huangpu Road, Hi-Tech Zone, Dalian
Phone:86-411-84699773, 84685669
ISSN:1003-5214