CN101469141A - Method for preparing multi-wall carbon nano-tube composite material - Google Patents
Method for preparing multi-wall carbon nano-tube composite material Download PDFInfo
- Publication number
- CN101469141A CN101469141A CNA2007103085923A CN200710308592A CN101469141A CN 101469141 A CN101469141 A CN 101469141A CN A2007103085923 A CNA2007103085923 A CN A2007103085923A CN 200710308592 A CN200710308592 A CN 200710308592A CN 101469141 A CN101469141 A CN 101469141A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- ionic liquid
- composite material
- carbon nano
- charged ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing multi-wall carbon nanotube/polymeric type ionic liquid composite material with controllable hydrophilic and hydrophobic properties. The method comprises: an ionic liquid containing a metacrylic acid ester functional group has polymerization reaction on the surface of a carbon nanotube to form the carbon nanotube coated with polyelectrolyte; hydrophilic and hydrophobic anions are utilized to modulate the dispersibility of the carbon nanotube/polymeric type ionic liquid composite material in an organic solvent and water, thereby realizing the reversible change of the hydrophilic and hydrophobic properties. The preparation process and the preparation method are simple and feasible. The carbon nanotube/polymeric type ionic liquid composite material with the controllable hydrophilic and hydrophobic properties can be applied in the field of catalysis, electrochemistry, novel sensors and intelligent materials.
Description
Technical field
The present invention relates to the preparation method of the controlled multi-walled carbon nano-tubes of a kind of hydrophilicity and hydrophobicity/aggretion type ionic liquid composite material, particularly aggretion type ionic liquid high molecule bonding is realized the method for functionalization reversing process to carbon nano tube surface.
Background technology
Carbon nanotube since being found in 1991, because excellent electric property of its intrinsic and mechanical property just become the research focus of sciemtifec and technical spheres such as physics, chemistry, biology gradually.Desirable CNT (carbon nano-tube) can be regarded seamless, the hollow tube body that graphite flake layer that carbon atom forms is rolled into as.Because distinctive immanent structure, carbon nanotube are expected to as nano electron device, nano semiconductor material, support of the catalyst, sensor material etc.Carbon nanotube is considered to one of the most rising nano material of 21 century.
Carbon nanotube relatively perfectly structure itself has caused its further difficulty increase of processing.Very important one side is exactly to show insoluble in water and other many organic solvents.The shortage of insoluble and surface functional group causes carbon nanotube application in a lot of fields to be restricted.Therefore the chemically modified carbon nanotube obtains researchist's concern gradually.
Ionic liquid at room temperature has excellent physics and chemical property, has good consistency with many materials.If ionic liquid is bonded to the surface of carbon nanotube, will greatly enriches the function of carbon nanotube.Aggretion type ionic liquid decorative layer possesses the characteristic of macromolecular material, makes the matrix material that obtains have satisfactory stability.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of carbon nano-tube/poly mould assembly ionic liquid composite material.
The ionic liquid monomer that the present invention will contain methacrylate functional forms carbon nano-tube/poly mould assembly ionic liquid composite material behind the multi-walled carbon nano-tubes surface aggregate, utilize the anionresin of matrix material ion liquid section to come the reversibility of controlling carbon nanotube/aggretion type ionic liquid hydrophilicity and hydrophobicity to change.
Preparation method of the present invention may further comprise the steps:
Step (a): with exsiccant multi-walled carbon nano-tubes ultra-sonic dispersion in the mixing solutions of concentrated nitric acid/vitriol oil, under 40 ℃ of conditions with the ultrasonication of 40~100KHz, with the filter membrane suction filtration, be neutral with a large amount of deionized water wash to filtrate, obtain the carboxylated carbon nanotube in surface, carbon nanotube and an amount of lithium aluminium hydride that carboxyl is rich on surface after the vacuum-drying are scattered in the toluene, and stirring reaction under 20~40 ℃ of conditions obtains the carbon nanotube of surface hydroxylation;
Step (b): the carbon nanotube of the surface hydroxylation that step (a) is obtained and trimethoxy are scattered in the toluene the benzyl chlorophenyl silane coupling agent; Stirring and refluxing under 40~80 ℃ of conditions obtains the carbon nanotube that benzyl chloride is rich on the surface;
Step (c): the carbon nanotube and cuprous chloride, the pentamethyl--diethyl triamine that the surface are rich in benzyl chloride are scattered in the methyl alcohol, the degassing is handled, adding negatively charged ion under argon shield is the ionic liquid monomer of the methacrylate type of chlorion, at room temperature reaction back stopped reaction; In reaction system, add a large amount of tetrahydrofuran (THF)s, suction filtration, repetitive scrubbing for several times, to guarantee that some homopolymer that generate in unreacted monomer and catalyzer and the reaction are thoroughly removed, product vacuum-drying, obtain polymethacrylate type poly ion liquid grafted and have water-soluble carbon nanometer tube, wherein the negatively charged ion of polyelectrolyte decorative layer is a chlorion;
Step (d): the carbon nanotube that the aggretion type ionic liquid that step (c) obtains is modified demonstrates wetting ability, adopt the hydrophobic anion and the chlorion exchange of high density, then demonstrate hydrophobicity through the carbon nano-tube/poly ionic liquid composite material after the ion-exchange.The hydrophobicity product is handled with the anionic aqueous solution of the wetting ability that contains high density, can be made matrix material change wetting ability again into.
The used silane coupling agent of step of the present invention (b) is that trimethoxy is to benzyl chlorophenyl silane.
The ion liquid positively charged ion that contains the methacrylic acid functional group that step of the present invention (c) adopts is 1-methyl-3-(2-methylacryoyloxyethyl) imidazoles, 1-ethyl-3-(2-methylacryoyloxyethyl) imidazoles, 1-butyl-3-(2-methylacryoyloxyethyl) imidazoles, a kind of in 1-hexyl-3-(2-methylacryoyloxyethyl) imidazoles.
Hydrophobic anion in the step of the present invention (d) is the aqueous solution of hexafluoro-phosphate radical, trifluoroacetic acid root, the amino negatively charged ion of trifluoromethane sulfonic acid root, two (trifluoromethyl sulphonyl) etc., the wetting ability negatively charged ion is the aqueous solution of chlorion, bromide anion, and the concentration of the described aqueous solution is 0.5~1.0mol/L.
The monomeric preparation of the said polymerisable ionic liquid of the present invention is achieved in that
Adding imidazoles and bromo alkane back flow reaction obtain alkyl imidazole in the ethanolic soln of sodium ethylate.Drip chloroethanol under protection of nitrogen gas in alkyl imidazole, reaction obtains ionic liquid alkyl hydroxyethyl imidazole salt muriate after refluxing.Utilize the reaction of methacrylic chloride and ionic liquid alkyl hydroxyethyl imidazole salt muriate can obtain the ionic liquid monomer.Its cationic structure can be expressed as:
Produce the ionic liquid reference that contains methacrylate functional:
Branco?C.,Rosa?J.N.,Ramos?J.J.M.,Afonso?C.A.M..Preparation?andcharacterization?of?new?room?temperature?ionic?liquids.Chem.Eur.J.2002,8(16):3671-3677
Ding?S.,Maciej?R.,Shen?Y..Ionic?liquid?catalyst?for?biphasic?atom?transferradical?polymerization?of?methyl?methacrylate.Macromolecules.2005,38:5921-5928.
The present invention utilizes polymerisable ionic liquid that carbon nanotube is carried out chemically modified, for the consistency of improving carbon nanotube and multiple organic solvent provides new approach.The present invention will contain the ionic liquid of methacrylate based functional group at the carbon nano tube surface polymerization reaction take place, form the polyelectrolyte coated carbon nanotube, utilize close and distant water negatively charged ion to come the dispersiveness of modulation carbon nano-tube/poly ionic liquid composite material in organic solvent and water, thereby the reversibility that realizes hydrophilicity and hydrophobicity change.Preparation process is with method is simple.The controlled carbon nano-tube/poly ionic liquid composite material of hydrophilicity and hydrophobicity is expected to be applied in catalytic field, electrochemistry, novel sensor and intelligent material.
Embodiment
Now be illustrated for example in order to understand the present invention better.
Embodiment 1:
In single neck round-bottomed flask of 100mL, the multi-walled carbon nano-tubes 2.0g that will adopt chemical Vapor deposition process (CVD) to make is dispersed in the mixed acid solution of 60ml concentrated nitric acid/vitriol oil, handles 8h with the 40KHz power ultrasonic under 35 ℃ of conditions.With Φ 0.2 μ m tetrafluoroethylene millipore filtration suction filtration, wash to the apparent neutrality of filtrate with the deionized water repeated multiple times, behind vacuum-drying 72h under 40 ℃ of conditions, obtain the carboxylated carbon nanotube in surface.Carbon nanotube that 0.10g after vacuum-drying surface is carboxylated and 0.8g lithium aluminium hydride ultra-sonic dispersion are in toluene, and stirring reaction 72h under 20~40 ℃ of conditions obtains the about 0.08g of carbon nanotube of surface hydroxylation; To the benzyl chlorophenyl silane coupling agent, ultra-sonic dispersion is in toluene with the carbon nanotube of 0.08g surface hydroxylation and 0.03g trimethoxy.Stirring and refluxing 24h under 40~80 ℃ of conditions obtains the about 0.09g of carbon nanotube that benzyl chloride is rich on the surface.
In the three neck round-bottomed flasks of 25mL, add the carbon nanotube 0.08g that benzyl chloride is rich on the surface; the about 0.05g of cuprous chloride; pentamethyl--diethyl triamine 0.1g; with its ultra-sonic dispersion in methyl alcohol; the degassing is handled the back and add ionic liquid monomer 1-methyl-3-(2-methylacryoyloxyethyl) imidazoles that contains methacrylate functional, stopped reaction behind the 72h gradually under nitrogen protection.In reaction system, add a large amount of tetrahydrofuran (THF)s, suction filtration, repetitive scrubbing 3 times, to guarantee that some homopolymer that generate in unreacted monomer and catalyzer and the reaction are thoroughly removed, product vacuum-drying is spent the night, obtain polymethacrylate type poly ion liquid grafted water-soluble carbon nanometer tube, wherein the negatively charged ion of polyelectrolyte decorative layer is a chlorion.
The carbon nano-tube/poly ionic liquid composite material ultra-sonic dispersion that above-mentioned steps is obtained is in water, to wherein adding the phosphofluoric acid aqueous ammonium that concentration is 1.0mol/L, then matrix material changes hydrophobicity into by wetting ability, and this moment, matrix material can be scattered in non-polar solvents such as methylene dichloride.The sodium chloride aqueous solution that in the non-polar solvent that is dispersed with matrix material, adds 1.0mol/L, constantly concussion, matrix material is transferred to aqueous phase again from organic phase, illustrate that matrix material is transformed into hydroaropic substance once more.
Embodiment 2:
Utilization obtains the carbon nanotube that benzyl chloride is rich on the surface with the method among the embodiment 1.
In the three neck round-bottomed flasks of 25mL, add the carbon nanotube 0.08g that benzyl chloride is rich on the surface; the about 0.05g of cuprous chloride; pentamethyl--diethyl triamine 0.1g; with its ultra-sonic dispersion in methyl alcohol; the degassing is handled the back and add ionic liquid monomer 1-butyl-3-(2-methylacryoyloxyethyl) imidazoles that contains methacrylate functional, stopped reaction behind the 72h gradually under nitrogen protection.In reaction system, add a large amount of tetrahydrofuran (THF)s, suction filtration, repetitive scrubbing 3 times, to guarantee that some homopolymer that generate in unreacted monomer and catalyzer and the reaction are thoroughly removed, product vacuum-drying is spent the night, obtain polymethacrylate type poly ion liquid grafted water-soluble carbon nanometer tube, wherein the negatively charged ion of polyelectrolyte decorative layer is a chlorion.
The carbon nano-tube/poly ionic liquid composite material ultra-sonic dispersion that above-mentioned steps is obtained is in water, to wherein adding the trifluoromethyl sulfonate aqueous solution that concentration is 1.0mol/L, then matrix material changes hydrophobicity into by wetting ability, and this moment, matrix material can be scattered in non-polar solvents such as methylene dichloride.The aqueous sodium bromide that in the non-polar solvent that is dispersed with matrix material, adds 1.0mol/L, constantly concussion, matrix material is transferred to aqueous phase again from organic phase, illustrate that matrix material changes hydroaropic substance once more into.
Embodiment 3:
Utilization obtains the carbon nano-tube/poly ionic liquid composite material with the method among the embodiment 2.
The carbon nano-tube/poly ionic liquid composite material is carried out anionresin earlier, obtain the matrix material that hydrophobic negatively charged ion is a hexafluoro-phosphate radical, with this product ultra-sonic dispersion in methylene dichloride, to wherein adding the aqueous sodium bromide that concentration is 1.0mol/L, concussion, carbon nanotube changes aqueous phase over to by organic phase, illustrates that hydrophobic composites changes hydroaropic substance into.Adding concentration to aqueous phase is the trifluoroacetic acid sodium water solution of 1.0mol/L, and then matrix material changes in the organic phase once more, illustrates that matrix material can change lyophobic dust once more into.
Claims (4)
1, a kind of preparation method of multi-wall carbon nano-tube composite material is characterized in that may further comprise the steps:
Step (a): with exsiccant multi-walled carbon nano-tubes ultra-sonic dispersion in the mixing solutions of concentrated nitric acid/vitriol oil, under 40 ℃ of conditions with the ultrasonication of 40~100KHz, with the filter membrane suction filtration, be neutral with a large amount of deionized water wash to filtrate, obtain the carboxylated carbon nanotube in surface, carbon nanotube and an amount of lithium aluminium hydride that carboxyl is rich on surface after the vacuum-drying are scattered in the toluene, and stirring reaction under 20~40 ℃ of conditions obtains the carbon nanotube of surface hydroxylation;
Step (b): the carbon nanotube of the surface hydroxylation that step (a) is obtained and trimethoxy are scattered in the toluene the benzyl chlorophenyl silane coupling agent; Stirring and refluxing under 40~80 ℃ of conditions obtains the carbon nanotube that benzyl chloride is rich on the surface;
Step (c): the carbon nanotube and cuprous chloride, the pentamethyl--diethyl triamine that the surface are rich in benzyl chloride are scattered in the methyl alcohol, the degassing is handled, adding negatively charged ion under argon shield is the ionic liquid monomer of the methacrylate type of chlorion, at room temperature reaction back stopped reaction; In reaction system, add a large amount of tetrahydrofuran (THF)s, suction filtration, the repetitive scrubbing several, product vacuum-drying obtains polymethacrylate type poly ion liquid grafted and has water-soluble carbon nanometer tube, and wherein the negatively charged ion of polyelectrolyte decorative layer is a chlorion;
Step (d): the carbon nanotube that the aggretion type ionic liquid that step (c) obtains is modified demonstrates wetting ability, adopt the hydrophobic anion and the chlorion exchange of high density, then demonstrate hydrophobicity through the carbon nano-tube/poly ionic liquid composite material after the ion-exchange; The hydrophobicity product is handled with the anionic aqueous solution of the wetting ability that contains high density, can be made matrix material change wetting ability again into.
2, the method for claim 1 is characterized in that the used silane coupling agent of step (b) is that trimethoxy is to benzyl chlorophenyl silane.
3, the method for claim 1, it is characterized in that the ion liquid positively charged ion that contains the methacrylic acid functional group that step (c) adopts is 1-methyl-3-(2-methylacryoyloxyethyl) imidazoles, 1-ethyl-3-(2-methylacryoyloxyethyl) imidazoles, 1-butyl-3-(2-methylacryoyloxyethyl) imidazoles, a kind of in 1-hexyl-3-(2-methylacryoyloxyethyl) imidazoles.
4, the method for claim 1, it is characterized in that the hydrophobic anion in the step (d) is the aqueous solution of hexafluoro-phosphate radical, trifluoroacetic acid root, the amino negatively charged ion of trifluoromethane sulfonic acid root, two (trifluoromethyl sulphonyl) etc., the wetting ability negatively charged ion is the aqueous solution of chlorion, bromide anion, and the concentration of the described aqueous solution is 0.5~1.0mol/L.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNA2007103085923A CN101469141A (en) | 2007-12-28 | 2007-12-28 | Method for preparing multi-wall carbon nano-tube composite material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNA2007103085923A CN101469141A (en) | 2007-12-28 | 2007-12-28 | Method for preparing multi-wall carbon nano-tube composite material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN101469141A true CN101469141A (en) | 2009-07-01 |
Family
ID=40826954
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA2007103085923A Pending CN101469141A (en) | 2007-12-28 | 2007-12-28 | Method for preparing multi-wall carbon nano-tube composite material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101469141A (en) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102060286A (en) * | 2010-11-12 | 2011-05-18 | 哈尔滨工业大学 | Energy consumption nano-fluid material and preparation method thereof |
CN102146222A (en) * | 2011-01-20 | 2011-08-10 | 哈尔滨工业大学 | Fluorosilane series carbon nanotube-based nanofluid energy dissipation materials and preparation method thereof |
CN101724933B (en) * | 2009-11-05 | 2011-08-31 | 南京大学 | Preparation method of viscose fibers for loading multi-wall carbon nanotubes |
CN102786693A (en) * | 2012-08-31 | 2012-11-21 | 哈尔滨理工大学 | Polysilane/multi-walled carbon nanotube composite material and preparation method thereof |
CN102796266A (en) * | 2012-09-13 | 2012-11-28 | 哈尔滨理工大学 | Multiwall carbon nanotube-polysilane composite material and preparation method thereof |
CN103214881A (en) * | 2013-04-15 | 2013-07-24 | 苏州大学 | Ionic liquid grafted modified carbon black and preparation method thereof |
CN103894160A (en) * | 2014-04-17 | 2014-07-02 | 上海锅炉厂有限公司 | Carbon dioxide solid absorbent as well as preparation method thereof |
CN104479170A (en) * | 2014-11-25 | 2015-04-01 | 上海交通大学 | Method for preparing composite material through ionic liquid modified carbon nano tube |
CN104577127A (en) * | 2015-01-08 | 2015-04-29 | 辽宁大学 | Borate functionalized carbonyl carbon sphere and preparation method and application thereof |
CN104892866A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院大连化学物理研究所 | Ionic liquid polymer grafted magnetic carbon nanotube and preparation method thereof |
CN105175837A (en) * | 2015-10-14 | 2015-12-23 | 上海交通大学 | Neoprene/carboxylated multiwalled carbon nanotube composite material modified by carboxylated imidazole ionic liquid and preparing method |
CN108285138A (en) * | 2018-05-08 | 2018-07-17 | 西南石油大学 | A kind of preparation method of anionic polymer modified multiwalled carbon nanotube |
CN108470630A (en) * | 2018-04-28 | 2018-08-31 | 东南大学 | A kind of intelligence ultracapacitor combination electrode material and its preparation method and application |
CN109928696A (en) * | 2019-03-11 | 2019-06-25 | 江苏华友装饰工程有限公司 | Preparation method of freeze-thaw resistant cement hollow brick |
CN110511556A (en) * | 2019-08-30 | 2019-11-29 | 合肥工业大学 | A kind of porous light polyurethane electromagnetic shielding composite material and preparation method thereof of electromagnetism collaboration enhancing |
CN112857118A (en) * | 2021-01-08 | 2021-05-28 | 厦门大学 | Method and device for regulating and controlling hydrophilicity and hydrophobicity of surface of carbon nanotube array based on external electric field/plasma for enhancing phase change heat exchange |
CN114232012A (en) * | 2021-09-29 | 2022-03-25 | 中国科学院金属研究所 | Ionic liquid modified nano carbon material catalyst and preparation method and application thereof |
CN115322628A (en) * | 2022-06-30 | 2022-11-11 | 安徽登王化工有限公司 | High-wear-resistance fluorocarbon powder coating and preparation method thereof |
CN116314881A (en) * | 2022-12-29 | 2023-06-23 | 苏州擎动动力科技有限公司 | Anode catalyst layer, preparation method thereof, membrane electrode and fuel cell |
-
2007
- 2007-12-28 CN CNA2007103085923A patent/CN101469141A/en active Pending
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101724933B (en) * | 2009-11-05 | 2011-08-31 | 南京大学 | Preparation method of viscose fibers for loading multi-wall carbon nanotubes |
CN102060286B (en) * | 2010-11-12 | 2012-07-25 | 哈尔滨工业大学 | Energy consumption nano-fluid material and preparation method thereof |
CN102060286A (en) * | 2010-11-12 | 2011-05-18 | 哈尔滨工业大学 | Energy consumption nano-fluid material and preparation method thereof |
CN102146222A (en) * | 2011-01-20 | 2011-08-10 | 哈尔滨工业大学 | Fluorosilane series carbon nanotube-based nanofluid energy dissipation materials and preparation method thereof |
CN102146222B (en) * | 2011-01-20 | 2013-01-16 | 哈尔滨工业大学 | Fluorosilane series carbon nanotube-based nanofluid energy dissipation materials and preparation method thereof |
CN102786693A (en) * | 2012-08-31 | 2012-11-21 | 哈尔滨理工大学 | Polysilane/multi-walled carbon nanotube composite material and preparation method thereof |
CN102786693B (en) * | 2012-08-31 | 2014-04-02 | 哈尔滨理工大学 | Polysilane/multi-walled carbon nanotube composite material and preparation method thereof |
CN102796266A (en) * | 2012-09-13 | 2012-11-28 | 哈尔滨理工大学 | Multiwall carbon nanotube-polysilane composite material and preparation method thereof |
CN102796266B (en) * | 2012-09-13 | 2014-08-27 | 哈尔滨理工大学 | Multiwall carbon nanotube-polysilane composite material and preparation method thereof |
CN103214881A (en) * | 2013-04-15 | 2013-07-24 | 苏州大学 | Ionic liquid grafted modified carbon black and preparation method thereof |
CN104892866A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院大连化学物理研究所 | Ionic liquid polymer grafted magnetic carbon nanotube and preparation method thereof |
CN104892866B (en) * | 2014-03-05 | 2017-07-07 | 中国科学院大连化学物理研究所 | A kind of magnetic carbon nano-tube of polymeric ionic liquid grafting and preparation method thereof |
CN103894160B (en) * | 2014-04-17 | 2015-11-18 | 上海锅炉厂有限公司 | A kind of carbon dioxide solid absorbent and preparation method thereof |
CN103894160A (en) * | 2014-04-17 | 2014-07-02 | 上海锅炉厂有限公司 | Carbon dioxide solid absorbent as well as preparation method thereof |
CN104479170A (en) * | 2014-11-25 | 2015-04-01 | 上海交通大学 | Method for preparing composite material through ionic liquid modified carbon nano tube |
CN104577127A (en) * | 2015-01-08 | 2015-04-29 | 辽宁大学 | Borate functionalized carbonyl carbon sphere and preparation method and application thereof |
CN104577127B (en) * | 2015-01-08 | 2017-02-22 | 辽宁大学 | Borate functionalized carbonyl carbon sphere and preparation method and application thereof |
CN105175837A (en) * | 2015-10-14 | 2015-12-23 | 上海交通大学 | Neoprene/carboxylated multiwalled carbon nanotube composite material modified by carboxylated imidazole ionic liquid and preparing method |
CN108470630A (en) * | 2018-04-28 | 2018-08-31 | 东南大学 | A kind of intelligence ultracapacitor combination electrode material and its preparation method and application |
CN108285138A (en) * | 2018-05-08 | 2018-07-17 | 西南石油大学 | A kind of preparation method of anionic polymer modified multiwalled carbon nanotube |
CN109928696A (en) * | 2019-03-11 | 2019-06-25 | 江苏华友装饰工程有限公司 | Preparation method of freeze-thaw resistant cement hollow brick |
CN110511556A (en) * | 2019-08-30 | 2019-11-29 | 合肥工业大学 | A kind of porous light polyurethane electromagnetic shielding composite material and preparation method thereof of electromagnetism collaboration enhancing |
CN110511556B (en) * | 2019-08-30 | 2021-05-04 | 合肥工业大学 | Electromagnetic synergistic enhanced porous light polyurethane electromagnetic shielding composite material and preparation method thereof |
CN112857118A (en) * | 2021-01-08 | 2021-05-28 | 厦门大学 | Method and device for regulating and controlling hydrophilicity and hydrophobicity of surface of carbon nanotube array based on external electric field/plasma for enhancing phase change heat exchange |
CN114232012A (en) * | 2021-09-29 | 2022-03-25 | 中国科学院金属研究所 | Ionic liquid modified nano carbon material catalyst and preparation method and application thereof |
CN114232012B (en) * | 2021-09-29 | 2024-03-01 | 中国科学院金属研究所 | Ionic liquid modified nano carbon material catalyst and preparation method and application thereof |
CN115322628A (en) * | 2022-06-30 | 2022-11-11 | 安徽登王化工有限公司 | High-wear-resistance fluorocarbon powder coating and preparation method thereof |
CN115322628B (en) * | 2022-06-30 | 2023-04-11 | 安徽登王化工有限公司 | High-wear-resistance fluorocarbon powder coating and preparation method thereof |
CN116314881A (en) * | 2022-12-29 | 2023-06-23 | 苏州擎动动力科技有限公司 | Anode catalyst layer, preparation method thereof, membrane electrode and fuel cell |
CN116314881B (en) * | 2022-12-29 | 2024-01-26 | 苏州擎动动力科技有限公司 | Anode catalyst layer, preparation method thereof, membrane electrode and fuel cell |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101469141A (en) | Method for preparing multi-wall carbon nano-tube composite material | |
Yang et al. | Timesaving, high-efficiency approaches to fabricate aramid nanofibers | |
Ren et al. | Voltage-gated ions sieving through 2D MXene Ti3C2T x membranes | |
Xin et al. | Silicone-coated MXene/cellulose nanofiber aerogel films with photothermal and joule heating performances for electromagnetic interference shielding | |
Moussa et al. | Self-assembly and cross-linking of conducting polymers into 3D hydrogel electrodes for supercapacitor applications | |
Devadas et al. | Effect of carbon dots on conducting polymers for energy storage applications | |
Sarker et al. | Layer-by-layer self-assembled multilayer films composed of graphene/polyaniline bilayers: high-energy electrode materials for supercapacitors | |
Zhao et al. | High-quality boron nitride nanosheets and their bioinspired thermally conductive papers | |
CN101177252A (en) | Method for preparing carbon nanometer pipe | |
EP3050846A1 (en) | Graphene composite powder material and preparation method therefor | |
CN101469145B (en) | Process for preparing attapulgite based composite material | |
Zhang et al. | Formation of superhydrophobic microspheres of poly (vinylidene fluoride–hexafluoropropylene)/graphene composite via gelation | |
CN103146231B (en) | Method for preparing core-shell type carbon nano-tube filling by coating carbon nano-tube through polyionic liquid | |
Wang et al. | Precisely controlled vertical alignment in mesostructured carbon thin films for efficient electrochemical sensing | |
CN104672445A (en) | Method for preparing multiwalled carbon nanotube/polyaniline nano composite material | |
Goto et al. | Creation of coating surfaces possessing superhydrophobic and superoleophobic characteristics with fluoroalkyl end-capped vinyltrimethoxysilane oligomeric nanocomposites having biphenylene segments | |
Gao et al. | Noncovalent microcontact printing for grafting patterned polymer brushes on graphene films | |
Zhang et al. | Zwitterionic polymer modified porous carbon for high-performance and antifouling capacitive desalination | |
WO2016209630A1 (en) | Process for modification of carbon surfaces | |
Zhong et al. | Fabrication of shape-controllable polyaniline micro/nanostructures on organic polymer surfaces: obtaining spherical particles, wires, and ribbons | |
Kim et al. | Janus graphene oxide-doped, lamellar composite membranes with strong aqueous stability | |
CN107759809A (en) | A kind of preparation method of stretchable organic/inorganic composite aquogel | |
Que et al. | Photoredox-mediated ATRP: a facile method for modification of graphite fluoride and graphene fluoride without deoxygenation | |
Liu et al. | Tunable hierarchically structured meso-macroporous carbon spheres from a solvent-mediated polymerization-induced self-assembly | |
Zhu et al. | “Sandwich-like” electrospinning fiber-based molecularly imprinted membrane constructed with electrospun polyethyleneimine as the multifunction interlayer for the selective separation of shikimic acid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090701 |