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2020 Volume 37 Issue 12
2020, 37(12): 1343-1356
doi: 10.11944/j.issn.1000-0518.2020.12.200146
Abstract:
Dimethyl sulfoxide (DMSO), known as a "universal solvent", is not only used routinely in chemistry, medicine, cosmetics and other fields, but also has its own applications in the field of organic electronics. Poly(3, 4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS), as a conductive polymer materials with excellent water dispersion, has the advantages of excellent machinability, miscibility, biological compatibility, film-forming property and commercial scale production, and is widely used in antistatic coating, organic solar cells, biological sensors, and other areas of the new materials and green energy. DMSO plays an important role in regulating the properties of PEDOT:PSS films, such as morphology, conductivity, thermoelectricity, power function, interface contact, mechanics, and self-healing. Based on the research results of our team, other domestic and foreign scholars in this field, this paper systematically reviewed the effect and mechanism of DMSO on PEDOT and its derivative:PSS (PEDOTs:PSS), and discussed the problems and challenges in the application.
Dimethyl sulfoxide (DMSO), known as a "universal solvent", is not only used routinely in chemistry, medicine, cosmetics and other fields, but also has its own applications in the field of organic electronics. Poly(3, 4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS), as a conductive polymer materials with excellent water dispersion, has the advantages of excellent machinability, miscibility, biological compatibility, film-forming property and commercial scale production, and is widely used in antistatic coating, organic solar cells, biological sensors, and other areas of the new materials and green energy. DMSO plays an important role in regulating the properties of PEDOT:PSS films, such as morphology, conductivity, thermoelectricity, power function, interface contact, mechanics, and self-healing. Based on the research results of our team, other domestic and foreign scholars in this field, this paper systematically reviewed the effect and mechanism of DMSO on PEDOT and its derivative:PSS (PEDOTs:PSS), and discussed the problems and challenges in the application.
2020, 37(12): 1357-1363
doi: 10.11944/j.issn.1000-0518.2020.12.200173
Abstract:
The recycling of carbon fiber/resin composites (CFRC) is critical for the sustainable development of carbon fiber industry and has received intensive attention from both the academy and industry. Recycling CFRC via supercritical fluid (SCF) is an effective and clean technique to recycle carbon fibers without damaging the properties of the carbon fibers. This article reviews the recent progress of the recycling of CFRC via SCF. The influence of the SCF system, reaction condition, and catalyst on recycling of carbon fibers are systematically discussed. Finally, the future development of the recycling of CFRC via SCF is also discussed in this article.
The recycling of carbon fiber/resin composites (CFRC) is critical for the sustainable development of carbon fiber industry and has received intensive attention from both the academy and industry. Recycling CFRC via supercritical fluid (SCF) is an effective and clean technique to recycle carbon fibers without damaging the properties of the carbon fibers. This article reviews the recent progress of the recycling of CFRC via SCF. The influence of the SCF system, reaction condition, and catalyst on recycling of carbon fibers are systematically discussed. Finally, the future development of the recycling of CFRC via SCF is also discussed in this article.
2020, 37(12): 1364-1373
doi: 10.11944/j.issn.1000-0518.2020.12.200180
Abstract:
Surface enhanced Raman scattering (SERS) is a molecular detection spectroscopy technique. With the help of the SERS substrate, trace molecules in complex systems such as biology and chemistry can be analyzed. Among them, the electrospun nanofiber SERS substrate has the characteristics of high specific surface area, air permeability, water permeability, flexibility, foldability and bending. In the application scenarios of extracting and detecting trace molecules in complex systems, its surface structure has unmatched by other rigid SERS substrates. However, the development of electrospun nanofiber SERS substrates is limited by the preparation method, which has the problems of low detection sensitivity and complicated preparation process. Therefore, the current research work mainly focuses on the development of new preparation methods and processes. This article reviews several common preparation methods for SERS substrates of electrospun nano-gold-silver composite fibers, including direct mixed spinning, chemical adsorption, electrostatic adsorption, physical deposition, and in-situ chemical reduction, and summarizes the application of electrospinning nanofiber SERS substrate in the extraction, filtration and concentration of molecules to be tested in complex systems, and finally the prospect of the development of electrospun nano-composite fiber SERS substrate.
Surface enhanced Raman scattering (SERS) is a molecular detection spectroscopy technique. With the help of the SERS substrate, trace molecules in complex systems such as biology and chemistry can be analyzed. Among them, the electrospun nanofiber SERS substrate has the characteristics of high specific surface area, air permeability, water permeability, flexibility, foldability and bending. In the application scenarios of extracting and detecting trace molecules in complex systems, its surface structure has unmatched by other rigid SERS substrates. However, the development of electrospun nanofiber SERS substrates is limited by the preparation method, which has the problems of low detection sensitivity and complicated preparation process. Therefore, the current research work mainly focuses on the development of new preparation methods and processes. This article reviews several common preparation methods for SERS substrates of electrospun nano-gold-silver composite fibers, including direct mixed spinning, chemical adsorption, electrostatic adsorption, physical deposition, and in-situ chemical reduction, and summarizes the application of electrospinning nanofiber SERS substrate in the extraction, filtration and concentration of molecules to be tested in complex systems, and finally the prospect of the development of electrospun nano-composite fiber SERS substrate.
2020, 37(12): 1374-1383
doi: 10.11944/j.issn.1000-0518.2020.12.200163
Abstract:
With excellent electrical conductivity, mechanical properties and large specific surface areas, graphene is a new material with great potentials. However, graphene is prone to stacking because of the intermolecular forces and π-π interaction between sheets. Constructing a three-dimensional hollow microsphere structure not only effectively prevents the agglomeration of graphene sheets, ensures a large specific surface area and excellent properties, but also has unique advantages of regular structures and adjustable sizes. This article describes the preparation methods of graphene hollow microspheres reported in recent years. It is mainly arranged and analyzed according to two major categories:template method and templateless method, and the template method is divided into two categories:hard template method and soft template method. Introductions and examples of various technologies applied in the preparation of graphene hollow microspheres are presented. The review concludes with the analyses and summaries of the hard template method, soft template method and templateless method respectively, as well as a discussion of future perspectives.
With excellent electrical conductivity, mechanical properties and large specific surface areas, graphene is a new material with great potentials. However, graphene is prone to stacking because of the intermolecular forces and π-π interaction between sheets. Constructing a three-dimensional hollow microsphere structure not only effectively prevents the agglomeration of graphene sheets, ensures a large specific surface area and excellent properties, but also has unique advantages of regular structures and adjustable sizes. This article describes the preparation methods of graphene hollow microspheres reported in recent years. It is mainly arranged and analyzed according to two major categories:template method and templateless method, and the template method is divided into two categories:hard template method and soft template method. Introductions and examples of various technologies applied in the preparation of graphene hollow microspheres are presented. The review concludes with the analyses and summaries of the hard template method, soft template method and templateless method respectively, as well as a discussion of future perspectives.
2020, 37(12): 1384-1402
doi: 10.11944/j.issn.1000-0518.2020.12.200190
Abstract:
Lithium/sodium ion batteries with low cost, long life, high safety, high performance and easy massive fabrication have become very effective secondary energy storage devices. For lithium/sodium batteries, the electrode materials have crucial influence on their performance and cycling life. Metal sulfides are regarded as potential anode materials for lithium/sodium ion batteries because of their high specific capacity and low potential. Metal sulfides show drawbacks, such as shuttle effect and volume change, resulting in structural deformation, together with decayed capacity and reduced stability. This review summarizes the research progress on the modification and properties of metal sulphide anode materials. Designing controlled complex structure and composite anodes enhances electronic conductivity and minimizes the effect caused by volume change, and thereby further to achieve better electrochemical performance. The structure-function relationship of metal sulphide materials is discussed and their positive prospects are proposed.
Lithium/sodium ion batteries with low cost, long life, high safety, high performance and easy massive fabrication have become very effective secondary energy storage devices. For lithium/sodium batteries, the electrode materials have crucial influence on their performance and cycling life. Metal sulfides are regarded as potential anode materials for lithium/sodium ion batteries because of their high specific capacity and low potential. Metal sulfides show drawbacks, such as shuttle effect and volume change, resulting in structural deformation, together with decayed capacity and reduced stability. This review summarizes the research progress on the modification and properties of metal sulphide anode materials. Designing controlled complex structure and composite anodes enhances electronic conductivity and minimizes the effect caused by volume change, and thereby further to achieve better electrochemical performance. The structure-function relationship of metal sulphide materials is discussed and their positive prospects are proposed.
2020, 37(12): 1403-1410
doi: 10.11944/j.issn.1000-0518.2020.12.200185
Abstract:
The liquid crystal alignment layer plays a critical role in the liquid crystal display. In order to prepare liquid crystal alignment layer with excellent properties, three kinds of 3, 5-diaminobiphenyls with different terminal groups were synthesized by Suzuki coupling reaction, and three polyimides were prepared by polymerization of the three diamines with 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride. The structures of monomers and polymers were characterized by proton nuclear magnetic resonance (1H NMR) spectroscopy. The solubility, thermal stability and properties of the polymers as liquid crystal alignment layer were studied. The resulting polyimides show good solubility and thermal stability. After rubbing, the polyimide with methoxy as terminal group can align the liquid crystal molecules parallel to the rubbing direction. On the contrary, the polyimides with phenoxycarbonyl and biphenoxycarbonyl as terminal groups align the liquid crystal molecules perpendicular to the rubbing direction. This kind of soluble polyimide liquid crystal alignment film will simplify the preparation process and present great application value in flexible display devices.
The liquid crystal alignment layer plays a critical role in the liquid crystal display. In order to prepare liquid crystal alignment layer with excellent properties, three kinds of 3, 5-diaminobiphenyls with different terminal groups were synthesized by Suzuki coupling reaction, and three polyimides were prepared by polymerization of the three diamines with 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride. The structures of monomers and polymers were characterized by proton nuclear magnetic resonance (1H NMR) spectroscopy. The solubility, thermal stability and properties of the polymers as liquid crystal alignment layer were studied. The resulting polyimides show good solubility and thermal stability. After rubbing, the polyimide with methoxy as terminal group can align the liquid crystal molecules parallel to the rubbing direction. On the contrary, the polyimides with phenoxycarbonyl and biphenoxycarbonyl as terminal groups align the liquid crystal molecules perpendicular to the rubbing direction. This kind of soluble polyimide liquid crystal alignment film will simplify the preparation process and present great application value in flexible display devices.
2020, 37(12): 1411-1419
doi: 10.11944/j.issn.1000-0518.2020.12.200133
Abstract:
A high content of the electroactive β phase in polyvinylidene fluoride (PVDF) is one of the prerequisites for achieving excellent piezoresponse and sensing in flexible sensors and wearable electronic devices. Herein, three types of nanoparticles of ZnO, Ag, and their composite (Ag-ZnO) were successfully synthesized by hydrothermal method and compounded with PVDF. The morphological, crystallization and piezoelectric properties of PVDF composites were systematically characterized. The synergistic effect of Ag-ZnO nanoparticles promotes crystallization and piezoelectric properties of PVDF. What's more, after stretching, the amount of β phase of all the PVDF films is further improved, the highest β phase content is 70.0% for stretched PVDF/Ag-ZnO nanoparticles, and the best piezoelectric coefficient (d33) is 31.0 pC/N.
A high content of the electroactive β phase in polyvinylidene fluoride (PVDF) is one of the prerequisites for achieving excellent piezoresponse and sensing in flexible sensors and wearable electronic devices. Herein, three types of nanoparticles of ZnO, Ag, and their composite (Ag-ZnO) were successfully synthesized by hydrothermal method and compounded with PVDF. The morphological, crystallization and piezoelectric properties of PVDF composites were systematically characterized. The synergistic effect of Ag-ZnO nanoparticles promotes crystallization and piezoelectric properties of PVDF. What's more, after stretching, the amount of β phase of all the PVDF films is further improved, the highest β phase content is 70.0% for stretched PVDF/Ag-ZnO nanoparticles, and the best piezoelectric coefficient (d33) is 31.0 pC/N.
2020, 37(12): 1420-1425
doi: 10.11944/j.issn.1000-0518.2020.12.200090
Abstract:
Eleven coumarin compounds with aromatic amide skeletons were synthesized. The antioxidant activities of the synthesized compounds were investigated by quenching 1, 1-diphenyl-2-picrylhydrazyl radical (DPPH), 2, 2'-azinobis(3-ethylbenzothiazoline-6-sulphonate) ammonium salt cationic radical (ABTS+·) and hydroxyl radicals. The results show that the scavenging ability of compound 2b to DPPH radicals and hydroxyl radicals is beyond or close to that of the control vitamin C, while the antioxidant activity of derivatives 2a, 2b and 2c is better than that of the parent. Therefore, acylation is a promising way to improve the antioxidant capacity of 3-amino-7, 8-dimethoxycoumarin, especially the scavenging capacity of hydroxyl radicals.
Eleven coumarin compounds with aromatic amide skeletons were synthesized. The antioxidant activities of the synthesized compounds were investigated by quenching 1, 1-diphenyl-2-picrylhydrazyl radical (DPPH), 2, 2'-azinobis(3-ethylbenzothiazoline-6-sulphonate) ammonium salt cationic radical (ABTS+·) and hydroxyl radicals. The results show that the scavenging ability of compound 2b to DPPH radicals and hydroxyl radicals is beyond or close to that of the control vitamin C, while the antioxidant activity of derivatives 2a, 2b and 2c is better than that of the parent. Therefore, acylation is a promising way to improve the antioxidant capacity of 3-amino-7, 8-dimethoxycoumarin, especially the scavenging capacity of hydroxyl radicals.
2020, 37(12): 1426-1431
doi: 10.11944/j.issn.1000-0518.2020.12.200177
Abstract:
To further explore an efficient structural modification strategy, a fragment-based drug design, for improving the antitumor activity of fluoroquinolones, twelve novel 3-arylidene-quinolin-4(1H)-ones as levofloxacin derivatives (3a-3l) were synthesized by a condensation reaction of dihydroquinolin-4(1H)-one with aromatic aldehydes. The measured half inhibition concentration(IC50) values using human hepatocellular carcinoma cell lines (SMMC-7721), human pancreatic cancer cell lines (Capan-1) and human leukemia cell line (HL60) cell lines reveal that the antitumor activities of the synthesized compounds are more potent than that of levofloxacin. Meanwhile, the halophenyl compounds such as fluorophenyl (3i, 3j), chlorophenyl (3k) or bromophenyl compounds (3l) display better activities than the control compounds, especially the IC50 value of chlorophenyl (3k) against SMMC-7721 and Capan-1 cell is comparable to that of doxorubicin. Thus, 3-arylidene-quinolin-4(1H)-one skeleton instead of quinolin-4(1H)-one-3-carboxylic acid is beneficial to improve the antitumor activities of fluoroquinolones. Furthermore, an α, β-unsaturated ketone fragment as a promising candidate pharmacophore for an alternative modified group of fluoroquinolone needs to be developed.
To further explore an efficient structural modification strategy, a fragment-based drug design, for improving the antitumor activity of fluoroquinolones, twelve novel 3-arylidene-quinolin-4(1H)-ones as levofloxacin derivatives (3a-3l) were synthesized by a condensation reaction of dihydroquinolin-4(1H)-one with aromatic aldehydes. The measured half inhibition concentration(IC50) values using human hepatocellular carcinoma cell lines (SMMC-7721), human pancreatic cancer cell lines (Capan-1) and human leukemia cell line (HL60) cell lines reveal that the antitumor activities of the synthesized compounds are more potent than that of levofloxacin. Meanwhile, the halophenyl compounds such as fluorophenyl (3i, 3j), chlorophenyl (3k) or bromophenyl compounds (3l) display better activities than the control compounds, especially the IC50 value of chlorophenyl (3k) against SMMC-7721 and Capan-1 cell is comparable to that of doxorubicin. Thus, 3-arylidene-quinolin-4(1H)-one skeleton instead of quinolin-4(1H)-one-3-carboxylic acid is beneficial to improve the antitumor activities of fluoroquinolones. Furthermore, an α, β-unsaturated ketone fragment as a promising candidate pharmacophore for an alternative modified group of fluoroquinolone needs to be developed.
2020, 37(12): 1432-1440
doi: 10.11944/j.issn.1000-0518.2020.12.200168
Abstract:
A new long-chain alkoxyphenylhydrozone derivative, 1-(2, 4-dinitrophenyl)-2-(4-(tetradecyloxy) benzylidene) hydrazine, was designed and synthesized. The ultraviolet-visible (UV-Vis) spectra and naked-eye recognition property of the receptor R for nine kinds of anions (F-, Cl-, Br-, I-, HSO4-, NO3-, ClO4-, H2PO4-, Ac-) were studied. The results indicate that the receptor R shows high UV-Vis and naked-eye recognition property towards F-, Ac- and H2PO4- in dimethylsulfoxide (DMSO) solution. Single colorimetric recognition of F- is found by UV-Vis analysis and naked-eye recognition in H2O/DMSO (1/9) solution, and the LOD (limit of detection) of receptor R for F- is 7.02×10-7 mol/L. The naked recognition paper of receptor R is prepared, and the Job's plot indicates the formation of complex between receptor R and F- is in 1:1 stoichiometric ratios. The recognition mechanism of receptor R is the "hydrogen-bond" recognition.
A new long-chain alkoxyphenylhydrozone derivative, 1-(2, 4-dinitrophenyl)-2-(4-(tetradecyloxy) benzylidene) hydrazine, was designed and synthesized. The ultraviolet-visible (UV-Vis) spectra and naked-eye recognition property of the receptor R for nine kinds of anions (F-, Cl-, Br-, I-, HSO4-, NO3-, ClO4-, H2PO4-, Ac-) were studied. The results indicate that the receptor R shows high UV-Vis and naked-eye recognition property towards F-, Ac- and H2PO4- in dimethylsulfoxide (DMSO) solution. Single colorimetric recognition of F- is found by UV-Vis analysis and naked-eye recognition in H2O/DMSO (1/9) solution, and the LOD (limit of detection) of receptor R for F- is 7.02×10-7 mol/L. The naked recognition paper of receptor R is prepared, and the Job's plot indicates the formation of complex between receptor R and F- is in 1:1 stoichiometric ratios. The recognition mechanism of receptor R is the "hydrogen-bond" recognition.
2020, 37(12): 1441-1446
doi: 10.11944/j.issn.1000-0518.2020.12.200149
Abstract:
Using polyvinylidene fluoride (PVDF) and diatomite as raw materials, PVDF@diatomite composite fiber membranes were prepared by electrospinning for lithium-ion battery. The electrolyte absorption rate, thermal stability and electrochemical properties of the separators were investigated. The addition of diatomite can effectively improve the electrolyte absorption rate and electrochemical performance of the composite separators. The electrolyte uptake is up to 623.6%. Compared with PVDF and polypropylene (PP) separators, it has excellent cycle and rate performance.
Using polyvinylidene fluoride (PVDF) and diatomite as raw materials, PVDF@diatomite composite fiber membranes were prepared by electrospinning for lithium-ion battery. The electrolyte absorption rate, thermal stability and electrochemical properties of the separators were investigated. The addition of diatomite can effectively improve the electrolyte absorption rate and electrochemical performance of the composite separators. The electrolyte uptake is up to 623.6%. Compared with PVDF and polypropylene (PP) separators, it has excellent cycle and rate performance.
2020, 37(12): 1447-1456
doi: 10.11944/j.issn.1000-0518.2020.12.200097
Abstract:
Chiral nematic mesoporous silicate (CNMS) was prepared by a sol-gel method and sulfonated CNMS-SO3H solid acid catalyst was prepared by an impregnation method. The structure and properties of the catalysts were characterized by BET, powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy analysis (FT-IR), NH3-TPD and Py-FTIR. When the molar ratio of amount of substance of α-pinene to oxalic acid is 1:0.4, the mass ratio of CNMS-SO3H catalyst to turpentine oil is 7:100, the temperature is 100℃ and the time is 8 h, the conversion of α-pinene is 100% and the yield of borneol is 49.89% and the amount of borneol is 4 times of that of isoborneol. The solid acid catalyst has good catalytic activity and stability. After 8 times of reuse, the conversion of α-pinene is over 99%.
Chiral nematic mesoporous silicate (CNMS) was prepared by a sol-gel method and sulfonated CNMS-SO3H solid acid catalyst was prepared by an impregnation method. The structure and properties of the catalysts were characterized by BET, powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy analysis (FT-IR), NH3-TPD and Py-FTIR. When the molar ratio of amount of substance of α-pinene to oxalic acid is 1:0.4, the mass ratio of CNMS-SO3H catalyst to turpentine oil is 7:100, the temperature is 100℃ and the time is 8 h, the conversion of α-pinene is 100% and the yield of borneol is 49.89% and the amount of borneol is 4 times of that of isoborneol. The solid acid catalyst has good catalytic activity and stability. After 8 times of reuse, the conversion of α-pinene is over 99%.
2020, 37(12): 1457-1464
doi: 10.11944/j.issn.1000-0518.2020.12.200152
Abstract:
The manganese-cerium mixed iron oxide nanocomposites were synthesized by hydrothermal synthesis method. The surface was wrapped by SiO2 by chemical vapor deposition to prepare the core-shell magnetic material which was then loaded by H2O2 with Keggin structure phosphomolybdic acid (HPMo) to synthesize the HPMo-H2O2/CeFexOy@SiO2 adsorption-oxidative desulfurization catalyst. The catalyst was characterized by SEM, TEM, FT-IR, XRD, 31P MAS-NMR and XPS. The results of SEM, TEM and XPS characterization show that CeFexOy is wrapped by SiO2 to form core-shell nanocomposite material. The Keggin-type structure is retained after being loaded by HPMo-H2O2 and a little peroxophosphomolybdate active species are produced in this process. The active order of different catalysts on the adsorption and oxidation desulfurization presents as the following:HPMo-H2O2/CeFexOy@SiO2>CeFexOy@SiO2>CeFexOy. The introduction of HPMo greatly improves the adsorption activity of organic sulfides, especially its remarkable performance in oxidative desulfurization. The improvement of the performance in oxidative desulfurization is due to the "pseudo-liquid phase" reaction process of polyoxometalate. The dibenzothiophene(DBT) oxidation removal rate reaches 99.4% under such conditions:m(oil):m(catalyst)=35:1, n(H2O2):n(S)=10:1 at 60℃ for 3 h. The prepared magnetic core-shell oxidative-desulfurization catalyst has ideal recycling performance for oxidative removal of DBT. HPMo-H2O2/CeFexOy@SiO2 catalyst becomes a kind of environmental-friendly catalysts with simple preparation method, high catalytic activity and good stability.
The manganese-cerium mixed iron oxide nanocomposites were synthesized by hydrothermal synthesis method. The surface was wrapped by SiO2 by chemical vapor deposition to prepare the core-shell magnetic material which was then loaded by H2O2 with Keggin structure phosphomolybdic acid (HPMo) to synthesize the HPMo-H2O2/CeFexOy@SiO2 adsorption-oxidative desulfurization catalyst. The catalyst was characterized by SEM, TEM, FT-IR, XRD, 31P MAS-NMR and XPS. The results of SEM, TEM and XPS characterization show that CeFexOy is wrapped by SiO2 to form core-shell nanocomposite material. The Keggin-type structure is retained after being loaded by HPMo-H2O2 and a little peroxophosphomolybdate active species are produced in this process. The active order of different catalysts on the adsorption and oxidation desulfurization presents as the following:HPMo-H2O2/CeFexOy@SiO2>CeFexOy@SiO2>CeFexOy. The introduction of HPMo greatly improves the adsorption activity of organic sulfides, especially its remarkable performance in oxidative desulfurization. The improvement of the performance in oxidative desulfurization is due to the "pseudo-liquid phase" reaction process of polyoxometalate. The dibenzothiophene(DBT) oxidation removal rate reaches 99.4% under such conditions:m(oil):m(catalyst)=35:1, n(H2O2):n(S)=10:1 at 60℃ for 3 h. The prepared magnetic core-shell oxidative-desulfurization catalyst has ideal recycling performance for oxidative removal of DBT. HPMo-H2O2/CeFexOy@SiO2 catalyst becomes a kind of environmental-friendly catalysts with simple preparation method, high catalytic activity and good stability.
