CN101481500B - Preparation of conductive polymer / carbon nano-tube composite mesoporous nano-tube - Google Patents
Preparation of conductive polymer / carbon nano-tube composite mesoporous nano-tube Download PDFInfo
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- CN101481500B CN101481500B CN2009100247056A CN200910024705A CN101481500B CN 101481500 B CN101481500 B CN 101481500B CN 2009100247056 A CN2009100247056 A CN 2009100247056A CN 200910024705 A CN200910024705 A CN 200910024705A CN 101481500 B CN101481500 B CN 101481500B
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Abstract
The invention relates to a method for preparing a conductive macromolecular carbon nano tube/ compound mesoporous nano tube, which comprises the following steps: (1) firstly growing an MnO2 layer on the carbon nano tube, mixing the carbon nano tube and water solution of potassium permanganate of 0.01 to 1 meters, guiding the mixture to react for 1 to 20 hours at a temperature of between 50 and 100 DEG C, and separating the mixture through a filtration method to obtain a compound nano structure MnO2.CNTs of the carbon nano tube coated with manganese dioxide; (2) dispersing the MnO2.CNTs raw material into a solvent, dissolving conductive macromolecular monomer in a solvent of protonic acid, and reacting for 10 minutes to 72 hours, wherein the range of pH value is between 0 and 6.5, the reaction temperature ranges from 0 to 100 DEG C, the organic acid is dodecylbenzene sulfonic acid or perfluorooctane sulfonated, the inorganic acid is sulfuric acid or hydrochloric acid, and the conductive macromolecule is polyaniline, polypyrrole or polythiophene; and (3) guiding an MnO2 template to react, and removing the template spontaneously after the reaction is finished.
Description
One, technical field:
The present invention relates to a kind of preparation method of conducting polymer/carbon nano-tube composite mesoporous nano-tube.
Two, background technology:
The conducting polymer nanostructure has very big potentiality in the application of device, especially with transistor [1], transmitter [2] and secondary cell aspects such as [3] are comparatively outstanding, conducting polymer has stable physicochemical property, controlled redox state and electric conductivity advantages of higher [4], the matrix material of conducting polymer and carbon nanotube have specific conductivity high advantage such as specific surface area is big, thereby at solar cell, electromagnetic shielding material [5], antistatic material [6], electrode materials [7], high capacity capacitor material [8], thermoelectric material [9], triode, numerous areas such as sensor material and gas separation material has wide practical use.Traditional conducting polymer/carbon nanotube composite nanostructure all is directly conducting polymer to be covered on the carbon nanotube, the purpose of present patent application is the hollow two-layer compound nanotube of the conducting polymer/carbon nanotube of the mesoporous hollow of preparation, this type of nanotube has big ratio effective surface area, good conductivity, in fields such as gas and biochemical sensors the potential application prospect is arranged.
Relating to conducting polymer synthetic method also can be referring to the open CN1415645 of Chinese patent, the preparation method of soluble conductive polyaniline, disclose a kind of preparation method of soluble conductive polyaniline, its key step is that polyaniline in eigenstate and macromole function protonic acid are carried out hot doping in water and solubility promoter composition mixed solvent.It is oxygenant chemical oxidization method compositing conducting polyaniline that Chinese patent discloses 1446839 usefulness Manganse Dioxide, the sour water suspension that aniline monomer is added and contain Manganse Dioxide carries out oxidizing reaction, its invention compositing conducting polyaniline is simple, the residual quantity of Manganse Dioxide is very low in the product, but does not relate to the preparation of conducting polymer/carbon nano-tube composite mesoporous nano-tube.Chinese patent discloses 1667021 and utilizes under the thermal and hydric environment mineral acid of different concns to mix to control the microscopic appearance of polyaniline, but does not relate to the synthetic of conducting polymer/carbon nano-tube composite mesoporous nano-tube equally.
[1]A.N.Aleshin，Adv.Mater.2006，18，17.
[2]M.Kanungo，A.Kumar，A.Q.Contractor，Anal.Chem.2003，758，5673.
[3]F.Y.Cheng，W.Tang，C.S.Li，J.Chen，H.K.Liu，P.W?.Shen，S.X.Dou，Chem.-Eur.J.2006，12，3082.
[4]A.G.MacDiarmid，Synthetic?metals：A?Novel?role?for?organic?polymers，Angew.Chem.Int.Ed.2001，40，2581-2590
[5] Wan Meixiang, Li Junchao, Li Suzhen, a kind of conductive high-polymer microwave absorbent and method for making thereof, Chinese patent, publication number 1110786, notification number 1040043
[6] E Rodri osmanthus JW Lin Desai now, antistatic fibers and preparation method thereof, Chinese patent, notification number 1145720
[7] Wang Wanxi, solid polymer high-energy battery, Chinese patent, publication number 1156911
[8] beam road, superhigh-capacitance capacitor with composite carbon nanotube and manufacture method thereof, Chinese patent, publication number 1388540
[9] Zhang Zuxun, Zhang Shengtang, Hao Jixiang can directly change the heat energy in the environment into the polyaniline composition of electric energy and use its metal sandwich spare, Chinese patent, [publication number] 1254728
[10]Z.Wei，M.X.Wan?Adv.Mater.2002，14，1314.
[11]M.Kanungo，A.Kumar，A.Q.Contractor，Anal.Chem.2003，75，5673.
[12]M.Yang，J.Ma，C.L.Zhang，Z.Z.Yang，Y.F.Lu，Angew.Chem.2005，117，6885；Angew.Chem.Int.?Ed.2005，44，6727.
Three, summary of the invention:
The objective of the invention is to propose a kind of preparation method of conducting polymer/carbon nano-tube composite mesoporous nano-tube.Especially earlier by solution reaction one deck MnO that on carbon nanotube, grows
2Layer, the in-situ chemical template method is with MnO then
2Layer is transformed into hollow conducting polymer nanotube and forms conducting polymer/carbon nano-tube composite mesoporous nano-tube structure.
Technical scheme of the present invention is the preparation method of conducting polymer/carbon nano-tube composite mesoporous nano-tube, (1) MnO
2The preparation of @CNTs, i.e. growth one deck MnO on carbon nanotube
2Layer, carbon nanotube (comprising that single wall, both arms are or/and multi-walled carbon nano-tubes) and 0.01M～1M potassium permanganate solution are mixed, under 50～100 ℃ of temperature condition, reacted 1～20 hour, separate, obtain being coated with the carbon nanotube composite nanostructure (MnO of Manganse Dioxide by filtration method
2@CNTs).
(2) preparation of conducting polymer/carbon nano-tube composite mesoporous nano-tube is with MnO
2The @CNTs raw material is dispersed in the solvent (solvent comprises water or/and ionic liquid etc.), and conductive high polymer monomer is dissolved in the protonic acid solvent of (comprising organic acid or mineral acid) (solvent comprises water or/and ionic liquid etc.), reacts 10 minutes～72 hours; PH value scope is between 0～6.5, and temperature of reaction is in 0 ℃～100 ℃ scopes, and organic acid can be selected as Witco 1298 Soft Acid, perfluorooctane sulfonate etc., or mineral acid such as sulfuric acid, hydrochloric acid etc.The nano-tube composite mesoporous structure of conducting polymer such as polyaniline, polypyrrole, polythiophene class and carbon nanotube can be by the preparation of this kind method.
(3), MnO
2Template itself participates in reaction, and can spontaneous removing after reaction is finished.
(4), the synthetic conducting polymer has duplicated MnO accurately
2The micro-nano structure of masterplate has formed hollow conducting polymer/carbon nano-tube composite mesoporous nano-tube.
The present invention relates to the preparation of conducting polymer/carbon nano-tube composite mesoporous nano-tube, by forming the metal oxide (MnO that one deck has oxidisability earlier at the carbon nanotube outer wall
2Deng) as template layer, then be that template polymerization conductive high polymer monomer under sour environment generates hollow conducting polymer nanotube, the reaction finish after MnO
2What template was spontaneous removes, and forms the conducting polymer/carbon nano-tube composite mesoporous nano-tube with mesopore orbit structure.Conducting polymer/carbon nano-tube composite mesoporous nano-tube is expected to have concurrently at needs the field acquisition potential application of nanometer microscopic appearance and excellent conductivity, for example fields such as ultracapacitor, heavy metal containing wastewater treatment, lithium ion battery, transmitter, gas separation material, electromagnetic shielding material and antistatic material.
The invention has the beneficial effects as follows: the reaction soln system is simpler, and its preparation is reacted the later stage and purified simply easily, and step that need not be special is separated template, and synthetic method is fit to production in enormous quantities.
Four, description of drawings
Fig. 1: the preparation of conducting polymer/carbon nano-tube composite mesoporous nano-tube, wherein a is the carbon nanotube electromicroscopic photograph; B is MnO
2The coated carbon nanotube photo; The nano-tube composite mesoporous photo of Dao Diangaofenzijubenan @CNTs that c forms for the reaction back; D is the microtexture photo that the transmission electron microscope photo of the nano-tube composite mesoporous ultrathin section(ing) of Ju Benan @CNTs has disclosed its double-layer hollow tube wall; E is that primary first-order equation can be prepared the above nano-tube composite mesoporous photo of 10g; F is for by forming composite mesoporous structure, the dispersiveness of carbon nanotube in the water photo that can be enhanced.Scale length: 100nm.
Fig. 2: other conducting polymer/carbon nano-tube composite mesoporous nano-tubes: wherein a is a Ju Bika @CNTs photo, and b is a Ju Saifen @CNTs photo.
Five, embodiment:
The nano-tube composite mesoporous exemplary steps of compositing conducting macromolecule/carbon nano-tube is as follows:
1, with carbon nanotube (comprising single wall, both arms and multi-walled carbon nano-tubes) and potassium permanganate solution (0.01M～1M) mix, reacted 1～20 hour under 50～100 ℃ of situations, precipitation is disperseed and is separated by filtration method, obtains being coated with the carbon nanotube composite nanostructure of Manganse Dioxide.Potassium permanganate solution is more than five times of carbon nanotube quality, and the present embodiment potassium permanganate solution is 25 times of carbon nanotube quality, and 70 ℃ were reacted 6 hours down.
2, the preparation of conducting polymer/carbon nano-tube composite mesoporous nano-tube is with MnO
2The @CNTs raw material is dispersed in the solvent (solvent comprises water and ionic liquid etc.), conductive high polymer monomer is dissolved with in the solvent (solvent comprises water and ionic liquid such as 1-butyl-3-methyl imidazolium tetrafluoroborate etc.) of protonic acid (adopting sulfuric acid or Witco 1298 Soft Acid among the embodiment respectively), pH value scope is especially between 1～4 among the embodiment, 10 minutes～72 hours reaction times; Temperature of reaction is in ℃ scope of room temperature～100, and organic acid can be selected perfluorooctane sulfonate etc., and mineral acid selection hydrochloric acid etc. all can obtain roughly the same result.
(3), MnO
2Template itself participates in reaction, and can spontaneous dissolving remove after reaction is finished.
(4), the synthetic conducting polymer has duplicated MnO accurately
2The micro-nano structure of masterplate has formed hollow conducting polymer/carbon nano-tube composite mesoporous nano-tube.
(5), the nano-tube composite mesoporous structure of conducting polymer such as polyaniline, polypyrrole, polythiophene class and carbon nanotube can be by the preparation of this kind method.
Claims (1)
1. the preparation method of conducting polymer/carbon nano-tube composite mesoporous nano-tube is characterized in that (1) growth one deck MnO on carbon nanotube earlier
2Layer: carbon nanotube and 0.01M～1M potassium permanganate solution are mixed, under 50～100 ℃ of temperature condition, reacted 1～20 hour, potassium permanganate solution is more than five times of carbon nanotube quality, separates by filtration method, obtains being coated with the carbon nanotube composite nanostructure MnO of Manganse Dioxide
2@CNTs; (2) preparation of conducting polymer/carbon nano-tube composite mesoporous nano-tube: with described MnO
2The @CNTs raw material is dispersed in the solvent, conductive high polymer monomer is dissolved in the solvent of protonic acid, reacts 10 minutes～72 hours; Temperature of reaction is in ℃ scope of room temperature～100; PH value scope is between 0～6.5, and protonic acid is perfluorooctane sulfonate or hydrochloric acid; Conducting polymer is polyaniline, polypyrrole or polythiophene class; (3) MnO
2Template itself participates in reaction, and can spontaneous removing after reaction is finished.
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| CN102208610B (en) * | 2011-04-18 | 2013-05-22 | 北京工业大学 | Preparation method of carbon coated MnO cathode material |
| CN102408712B (en) * | 2011-09-22 | 2013-01-23 | 扬州大学 | Polyaniline nanofiber/manganese dioxide nanorod composite material and preparation method thereof |
| CN102516539B (en) * | 2011-12-15 | 2013-09-25 | 河海大学 | Method for preparing polypyrrole/ multi-wall carbon nano tube composite material with core-shell structure |
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| CN102924718B (en) * | 2012-11-16 | 2015-02-11 | 清华大学深圳研究生院 | Preparation method of nanostructured polypyrrole |
| CN103137341B (en) * | 2013-02-06 | 2016-08-24 | 燕山大学 | Nano composite electrode material and preparation method thereof |
| CN103936987B (en) * | 2014-05-08 | 2017-01-18 | 扬州大学 | Carbon nanotube composite material and preparation method thereof |
| CN105384159A (en) * | 2015-11-05 | 2016-03-09 | 云南大学 | Usage of manganese dioxide coated carbon particle dielectric materials as electromagnetic wave absorption materials |
| US9851267B1 (en) * | 2016-06-01 | 2017-12-26 | Microsoft Technology Licensing, Llc | Force-sensing element |
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| CN107785553A (en) * | 2017-10-27 | 2018-03-09 | 天津先众新能源科技股份有限公司 | A kind of ternary material processing method with safe closed pore function |
| CN107946575B (en) * | 2017-11-21 | 2020-06-16 | 厦门理工学院 | Preparation method of nitrogen-doped porous carbon-coated mesocarbon microbeads, composite material prepared by method and application of composite material |
| CN110342493B (en) * | 2018-04-03 | 2021-07-30 | 清华大学 | Transition metal oxide/carbon nanotube composite material and preparation method thereof |
| CN108774490B (en) * | 2018-05-31 | 2021-05-11 | 浙江理工大学 | Preparation method of microwave multi-band response multiple mesoporous structure wave absorber |
| CN111584243B (en) * | 2020-04-30 | 2021-12-17 | 郭米娟 | Mn (manganese)3O4-carbon nano tube-polyaniline super capacitor material and preparation method thereof |
| CN111627717B (en) * | 2020-06-08 | 2021-11-26 | 陕西师范大学 | Carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material and preparation method thereof |
| CN113747777B (en) * | 2021-09-08 | 2022-04-08 | 北京伊斯普电子技术有限公司 | Electromagnetic wave shielding material |
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