CN101092749A - Method for synthesizing controlable template of Nano polyaniline tube - Google Patents
Method for synthesizing controlable template of Nano polyaniline tube Download PDFInfo
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- CN101092749A CN101092749A CN200710022910.XA CN200710022910A CN101092749A CN 101092749 A CN101092749 A CN 101092749A CN 200710022910 A CN200710022910 A CN 200710022910A CN 101092749 A CN101092749 A CN 101092749A
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002071 nanotube Substances 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005457 ice water Substances 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 239000002070 nanowire Substances 0.000 claims abstract description 7
- 239000003929 acidic solution Substances 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000002121 nanofiber Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- 239000012265 solid product Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 17
- 229920000547 conjugated polymer Polymers 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005287 template synthesis Methods 0.000 claims description 8
- HVCXHPPDIVVWOJ-UHFFFAOYSA-N [K].[Mn] Chemical compound [K].[Mn] HVCXHPPDIVVWOJ-UHFFFAOYSA-N 0.000 claims description 7
- 230000002269 spontaneous effect Effects 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 4
- 239000011260 aqueous acid Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 6
- 238000001035 drying Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 229910006648 β-MnO2 Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 239000003990 capacitor Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000012377 drug delivery Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019082 Osmanthus Nutrition 0.000 description 1
- 241000333181 Osmanthus Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
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Abstract
This invention discloses a method for controllable templated synthesis of polyaniline nanotubes. The method comprises: utilizing highly oxidative metal oxide nanowires or nanotubes, such as cryptomelane-type MnO2 nanofibers or beta-MnO2 nanotubes as the template, mixing with aniline monomer in an acidic solution in an ice water bath under stirring, reacting for 4-8 h to obtain a dark green solid product, filtering, washing with deionized water and ethanol to remove residual ions and oligomers on the surface, an drying to obtain polyaniline nanotubes. The ratio of MnO2 template to aniline monomer is 40-50 mg/0.08-0.1 mL. Aniline monomer is adequately stirrer in the acidic solution, and then rapidly transferred into an aqueous solution dispersed with the MnO2 template, where aniline monomer is polymerized in an ice water bath under stirring.
Description
Technical field:
The present invention relates to a kind of controllable synthesis method of Optical Properties of Novel Conjugated nanotube, present method is mainly utilized the metal oxide (MnO with oxidisability
2Deng) nano wire or nanotube template polymerization aniline monomer generation polyaniline under sour environment.
Background technology:
The nano tube structure of conjugated polymers has very big potentiality in the application of device, especially with transistor, aspect such as transmitter and secondary cell is comparatively outstanding, and polyaniline is as a kind of important conjugated conductive polymer, it has stable physicochemical property, controlled redox state and electric conductivity advantages of higher, thereby is applied to all many-sides such as solar cell, electromagnetic shielding material, antistatic material, electrode materials, high capacity capacitor material, thermoelectric material, triode, sensor material and gas separation material by people.Referring to A.G.MacDiarmid, Chem.Int.Ed.2001,40,2581-2590; 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; E Rodri osmanthus is JW Lin Desai now, antistatic fibers and preparation method thereof, Chinese patent, notification number 1145720; Wang Wanxi, solid polymer high-energy battery, Chinese patent, publication number 1156911; The beam road, superhigh-capacitance capacitor with composite carbon nanotube and manufacture method thereof, Chinese patent, publication number 1388540; 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.
The nano tube structure of conjugated polymers can form by self-organization, also can be synthetic by the auxiliary way of template.Self-assembling method mainly is to come synthesized polyaniline nanotube [Z.Wei, M.X.Wan Adv.Mater.2002,14,1314.] by the colloid that forms nanostructure, this method to the controllability of product pattern a little less than, and productive rate is not high; Traditional template auxiliary law mainly contains track etching [M.Kanungo, A.Kumar, A.Q.Contractor, Anal.Chem.2003,75,5673.], the how empty aluminum oxide of anode [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.] and silica or polystyrene sphere etc.; Method than self-assembly, template is stronger to the controllability of product, but in traditional template, usually these templates do not participate in reaction, and the template utilization ratio is low, and in order to obtain purified product, reaction must separate template after finishing with final product, and this step general operation difficulty is relatively usually easily destroyed the orderly mesoscopic structure that aniline forms after by the masterplate polymerization, or changes the chemical structure of polyaniline.Therefore,, be necessary to seek the nanotopography that a cover can effectively be controlled product, can simplify purification of products again, and then play the method for the final pattern effect of protection product along with the raising of people to the nanotechnology requirement.
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 synthetic [13] that do not relate to monodimension nanometer materials such as polyaniline nano pipe and nano wire are oxygenant chemical oxidization method compositing conducting polyaniline Chinese patent publication number 1446839 with Manganse Dioxide.Chinese patent publication number 1667021 utilizes under the thermal and hydric environment mineral acid of different concns to mix and controls the microscopic appearance of polyaniline, but does not relate to synthetic that template can the controlled polyaniline nano pipe of spontaneous dissolved equally.
Summary of the invention:
The objective of the invention is: what propose that a kind of template can the controlled conjugated polymers nanotube of spontaneous dissolved one-dimentional structure material is synthetic.Especially synthesizing of controlled polyaniline nano pipe.
Technical scheme of the present invention is: the controlled template synthesis method of polyaniline nano pipe, the latent potassium manganese type MnO that will have oxidisability
2Nanofiber or β-MnO
2Nanotube synthesizes with the aniline monomer hybrid reaction under acidic solution as template; And reaction obtains the deep green solid product after 4-8 hour under ice-water bath and stirring environment; Product cleans to remove surperficial survivor ion and oligopolymer and oven dry promptly through deionized water and ethanol through after filtering again.MnO
2The ratio of the weight of template and aniline monomer be 40-50mg than 0.08-0.1ml., or mol ratio is controlled at 0.5-2.0.
Aniline monomer fully stirs under acidic solution, and this solution is shifted the MnO that into is scattered here and there
2In the aqueous solution of masterplate, and under ice-water bath and stirring environment, react.
The present invention controls synthesizing quadrate conjugated polymers nanotube with the template of tetragonal system nanofibrous structures; The conjugated polymers nanotube of the synthetic double-walled construction of nano tubular structure template control.
The present invention mainly provides a kind of template synthesis method that the conjugated polymers product is had strong nanotopography controllability: (template size must be in the nanometer scale range scale can to get suitable metal oxide nano-wire/nanotube template with oxidisability, commonly used is tens to the hundreds of nanometer, yardstick is crossed conference influences the product pattern) be dispersed in the suitable aqueous acid back and add the conjugated polymers monomer fast, should make the conjugated polymers monomer excessive slightly in the entire reaction course to guarantee carrying out fully of reaction, with MnO
2Template and aniline monomer are example, and especially its mol ratio preferably should be controlled at below 1.31 to guarantee aniline monomer excessively, and entire reaction stirring reaction after 6 hours in ice water bath environment filters and can obtain final product with deionized water and dehydrated alcohol cleaning.
Choose suitable aqueous acid (comprising mineral acid or organic acid soln), make it can not dissolution of metals oxide template itself, but can dissolve the reduzate behind the template reaction, melt to realize the spontaneous of template.For example for MnO
2Template can be used 1moldm
-3Sulfuric acid reacts, MnO before the reaction
2Template is insoluble to this concentration sulfuric acid, reaction back MnO
2The reduzate of template dissolves in sulfuric acid and forms Mn
2+The selection of inappropriate acid can't be synthesized and be expected the conjugated polymers product of nanotopography.
The pattern of final product is by the surface tissue decision of the template that adopts, and step is separated final product and template specially.With MnO
2Template and aniline monomer are example, different MnO
2Template (nano wire or nanotube-shaped) can form single wall or double-walled polyaniline nano tubular construction, the statistical average diameter of polyaniline nano pipe, thickness of pipe can be by certain formula prediction, and can adjust the size of polyaniline nano pipe by the geometric parameter of regulating template, finally realize the controlledly synthesis of p-poly-phenyl amine nanotube.This controllable synthesis method has been simplified experimental procedure, ensured product quality, being expected to obtain in the field of the strong nanometer microscopic appearance controllability of needs potential uses, the for example miniature drug delivery system or the advanced subject such as accurate control of organic nano conduit also can be applicable to electrode materials, the high capacity capacitor material, triode, sensor material, gas separation material, electromagnetic shielding material and antistatic material.
In the polyreaction of the present invention, the metal oxide template is used as the oxygenant of this reaction simultaneously.After reaction is finished, template can be spontaneous remove, obtain special nanostructure conjugated polymers product, its microscopic appearance can accurately duplicate the surface tissue of metal oxide template, form the single wall or the conjugated polymers nanotube of double-walled, and can control the size of conjugated polymers product microtexture (as length by the geometric parameter (as length, diameter etc.) of regulating the metal oxide template, caliber, wall thickness etc.).The nano tubular structure conjugated polymers is expected to obtain potential in the field of the strong nanometer microscopic appearance controllability of needs and uses, the for example miniature drug delivery system or the advanced subject such as accurate control of organic nano conduit, also can be applicable to electrode materials, the high capacity capacitor material, triode, sensor material, gas separation material, electromagnetic shielding material and antistatic material.
Description of drawings
Fig. 1 is the latent potassium manganese type MnO of Electronic Speculum figure: Fig. 1 (a)
2SEM Electronic Speculum figure; Fig. 1 (b) is with latent potassium manganese type MnO
2Be template synthetic polyaniline nano pipe, upper left corner illustration has shown TEM result; Sample is corresponding to the sample a in the table 1.
Fig. 2 is that the TEM photo of template is β-MnO
2The TEM photo of template;
Fig. 3 is with Fig. 2 template synthetic polyaniline double-layer nanometer pipe
Embodiment:
Utilize MnO
2The typical method of masterplate synthesized polyaniline nanotube is as follows: at first will conceal potassium manganese type MnO
2Nanofiber or β-MnO
2The nanotube ultra-sonic dispersion is put into ice water bath environment and constantly slowly stirring then in the deionized water of 30ml; Meanwhile, we press 1: 6.15 dilution proportion with the vitriol oil of 2.8ml, and behind the cool to room temperature, slowly add the aniline monomer of 96 μ l, and fully stir, and at last this solution are shifted the MnO that advances to be scattered here and there rapidly
2In the 30ml aqueous solution of masterplate, and reaction obtains the deep green solid product after 6 hours under ice-water bath and stirring environment.After product filters through micropore filter paper (Millipore, type GN, 0.20 μ m filter), clean repeatedly to remove the survivor ion and the oligopolymer on surface through deionized water and ethanol, last products therefrom will be dried (12 hours) under 60 ℃ of vacuum environments again.
Reaction soln system of the present invention is simpler, and its preparation is reacted the later stage and purified simply easily, and step that need not be special is separated template.
After reaction is finished, obtain cyan suspension, filter the washing back and observe down at transmission electron microscope (TEM) or scanning electron microscope (SEM).If adopt latent potassium manganese type MnO
2Nanofiber is as template, and then reaction product mostly is square polyaniline nano pipe, and thickness of pipe can be passed through formula d
c=0.44D
0, external diameter can pass through formula D
2c=2d
c+ D
0=1.88D
0Estimation (D in the formula
0Be latent potassium manganese type MnO
2The diameter of nanofiber); If adopt β-MnO
2Nanotube is as template, and then reaction product mostly is the polyaniline nano pipe of double-walled construction.The analytical results of infrared spectra, UV spectrum, ultimate analysis shows that product is the polyaniline of doping attitude.
| MnO 2The nano wire masterplate | The PAni nanotube | |||||||||
| Sample | Synthesis temperature [℃] | m M[g] | D 0[nm] | m p[g] | D 2[nm] | D 1[nm] | d[nm] | A exp＝S p/S m | d c[nm] | D 2c[nm] |
| a | 120 | 0.8000 | 120 | 0.8501 | 211 | 112 | 49.5 | 2.22 | 52.8(7％) | 225.6(7％) |
| b | 180 | 0.8000 | 108 | 0.8505 | 192 | 103 | 44.5 | 2.25 | 47.5(7％) | 203.0(6％) |
| c | 240 | 0.8000 | 45 | 0.8495 | 76 | 38 | 19.0 | 2.14 | 19.8(4％) | 84.6(11％) |
Table 1:MnO
2The parameter mapping table of masterplate and PAni nanotube.M wherein
MRepresentative participates in the MnO of reaction
2Total mass; D
0Represent MnO
2The diameter of fiber; m
pRepresent the ultimate production of PAni; D
1Caliber in the representative; D
2Represent outer tube diameter; D represents the average tube wall thickness; A
ExpSectional area ratio (S
p: polyaniline sectional area, S
m: MnO
2The fibre section is long-pending); d
cThe thickness of pipe (the per-cent representation theory in the bracket and the deviation of experimental data) of representation theory expection; D
2cThe tube wall external diameter (the per-cent representation theory in the bracket and the deviation of experimental data) of representation theory expection.
d
c＝0.5D
0[(1+A
mechanism)
0.5-1]＝0.44D
0；D
2c＝2d
c+D
0＝1.88D
0。
Claims (5)
1, the controlled template synthesis method of polyaniline nano pipe is characterized in that metal oxide nano-wire or the promptly latent potassium manganese type MnO of nanotube that will have than strong oxidizing property
2Nanofiber or β-MnO
2Nanotube synthesizes with the aniline monomer hybrid reaction under acidic solution as template; And reaction obtains the deep green solid product after 4-8 hour under ice-water bath and stirring environment; Product cleans to remove surperficial survivor ion and oligopolymer and oven dry promptly through deionized water and ethanol through after filtering again; MnO
2The weight of template is that 40-50mg compares 0.08-0.1ml. with the ratio of aniline monomer.
2, by the controlled template synthesis method of the described polyaniline nano pipe of claim 1, it is characterized in that aniline monomer fully stirs under acidic solution, this solution is shifted the MnO that advances to be scattered here and there fast
2In the aqueous solution of masterplate, and under ice-water bath and stirring environment, react.
3,, it is characterized in that metal oxide template control synthesizing quadrate conjugated polymers nanotube with the tetragonal system nanofibrous structures by the controlled template synthesis method of the described polyaniline nano pipe of claim 1; The conjugated polymers nanotube of the synthetic double-walled construction of nano tubular structure metal oxide template control.
4, by the controlled template synthesis method of the described polyaniline nano pipe of claim 1, it is characterized in that choosing suitable aqueous acid, make it can not dissolution of metals oxide template itself, but the reduzate behind the dissolving template reaction melt to realize the spontaneous of template.
5, by the controlled template synthesis method of the described polyaniline nano pipe of claim 1, it is characterized in that for MnO
2Template can be used 1moldm
-3Sulfuric acid reacts, MnO before the reaction
2Template is insoluble to this concentration sulfuric acid, reaction back MnO
2The reduzate of template dissolves in sulfuric acid and forms Mn
2+
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|---|---|---|---|
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| Publication Number | Publication Date |
|---|---|
| CN101092749A true CN101092749A (en) | 2007-12-26 |
| CN100497761C CN100497761C (en) | 2009-06-10 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376715B (en) * | 2008-09-26 | 2011-03-23 | 南京大学 | Preparation of large area flexible self-supporting polyaniline nanostructured film |
| CN103435819A (en) * | 2013-07-17 | 2013-12-11 | 青岛科技大学 | Method for preparing thread-shaped polyaniline micro-nano tubes with fullerene fiber as template and products of thread-shaped polyaniline micro-nano tubes |
| CN105061732A (en) * | 2015-09-28 | 2015-11-18 | 吉林大学 | Tellurium-containing electric-conducting high-polymer composite nanowire and preparation method thereof |
| CN105206432A (en) * | 2015-09-29 | 2015-12-30 | 南京绿索电子科技有限公司 | Polyaniline nanometer tube array/copper oxide/manganese dioxide composite material electrode and manufacturing method and application thereof |
| CN106653399A (en) * | 2016-12-09 | 2017-05-10 | 南京邮电大学 | Method for preparing ordered polyaniline nanotube array pseudocapacitor electrode through template electro-deposition method, and application |
| CN107959009A (en) * | 2017-11-13 | 2018-04-24 | 中国计量大学 | A kind of carbon coating TiO2The preparation method of nano-tube material |
| CN113823777A (en) * | 2021-08-11 | 2021-12-21 | 中国地质大学（武汉） | Porous nitrogen-doped carbon coaxial coating manganese dioxide nanotube and preparation method and application thereof |
| CN115282784A (en) * | 2022-01-21 | 2022-11-04 | 浙江师范大学 | Modified magnetic nickel/cobalt @ polydopamine microtube and preparation method thereof |
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2007
- 2007-05-25 CN CNB200710022910XA patent/CN100497761C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101376715B (en) * | 2008-09-26 | 2011-03-23 | 南京大学 | Preparation of large area flexible self-supporting polyaniline nanostructured film |
| CN103435819A (en) * | 2013-07-17 | 2013-12-11 | 青岛科技大学 | Method for preparing thread-shaped polyaniline micro-nano tubes with fullerene fiber as template and products of thread-shaped polyaniline micro-nano tubes |
| CN103435819B (en) * | 2013-07-17 | 2015-04-15 | 青岛科技大学 | Method for preparing thread-shaped polyaniline micro-nano tubes with fullerene fiber as template and products of thread-shaped polyaniline micro-nano tubes |
| CN105061732A (en) * | 2015-09-28 | 2015-11-18 | 吉林大学 | Tellurium-containing electric-conducting high-polymer composite nanowire and preparation method thereof |
| CN105206432A (en) * | 2015-09-29 | 2015-12-30 | 南京绿索电子科技有限公司 | Polyaniline nanometer tube array/copper oxide/manganese dioxide composite material electrode and manufacturing method and application thereof |
| CN105206432B (en) * | 2015-09-29 | 2017-11-03 | 南京绿索电子科技有限公司 | Polyaniline nanotube array/cupric oxide/manganese dioxide composite material electrode and its preparation method and application |
| CN106653399A (en) * | 2016-12-09 | 2017-05-10 | 南京邮电大学 | Method for preparing ordered polyaniline nanotube array pseudocapacitor electrode through template electro-deposition method, and application |
| CN107959009A (en) * | 2017-11-13 | 2018-04-24 | 中国计量大学 | A kind of carbon coating TiO2The preparation method of nano-tube material |
| CN113823777A (en) * | 2021-08-11 | 2021-12-21 | 中国地质大学（武汉） | Porous nitrogen-doped carbon coaxial coating manganese dioxide nanotube and preparation method and application thereof |
| CN113823777B (en) * | 2021-08-11 | 2023-05-26 | 中国地质大学（武汉） | Porous nitrogen-doped carbon coaxial coated manganese dioxide nanotube and preparation method and application thereof |
| CN115282784A (en) * | 2022-01-21 | 2022-11-04 | 浙江师范大学 | Modified magnetic nickel/cobalt @ polydopamine microtube and preparation method thereof |
| CN115282784B (en) * | 2022-01-21 | 2023-08-29 | 浙江师范大学 | Modified magnetic nickel/cobalt@polydopamine micro-tube and preparation method thereof |
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| Publication number | Publication date |
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| CN100497761C (en) | 2009-06-10 |
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