CN102086302A - Preparing method for molybdenum oxide - polyaniline composite nanowire and nanotube - Google Patents
Preparing method for molybdenum oxide - polyaniline composite nanowire and nanotube Download PDFInfo
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- CN102086302A CN102086302A CN2009101997488A CN200910199748A CN102086302A CN 102086302 A CN102086302 A CN 102086302A CN 2009101997488 A CN2009101997488 A CN 2009101997488A CN 200910199748 A CN200910199748 A CN 200910199748A CN 102086302 A CN102086302 A CN 102086302A
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Abstract
The invention belongs to the nano-material technical field, and relates to a preparing method for molybdenum oxide - polyaniline composite nanowire and nanotube. Molybdena - aniline hybrid nano wire precursor is obtained by using molybdate as the source of molybdenum and interacting with aniline,,and the molybdenum oxide - polyaniline composite nanowire and nanotube are obtained by respectively adjusting system pH value under the initiation of oxidizing agent. The nanowire and the nanotube prepared by the method of the invention have the characteristics of a composite construction of nanometer scale, controllable physical and chemical features, large specific surface area, uniform one-dimensional morphology and controllable thickness and length. The prepared composite molybdenum oxide - polyaniline composite nanowire and nanotube have important application value in many fields such as designing of advanced catalyst, electrocatalysis, electrochemical super capacitor, electrode material, sensor, thermoelectric material, the synthesis and application of advanced optics, electrical material and magnetism material.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of method for preparing molybdenum oxide-polyaniline composite nano-line and nanotube.
Background technology
The compound research on nanoscale of inorganic materials and conductive polymer polymkeric substance is noticeable day by day, studies show that, both are compound can to combine its good physical and chemical performance, mutually improves, and makes the more easy to control and modulation of performance of mixture.Prior art discloses polyaniline and has had surface of good stability, thermostability and electroconductibility, and it is widely used in electrochemical capacitor, battery, transmitter, the corrosion inhibitor.Molybdenum oxide has peculiar electrochemical properties, electrocatalysis characteristic etc.Compound that molybdenum oxide and polyaniline material is compound on nanoscale by organic and inorganic, undoubtedly will be in conjunction with both good physical and chemical performances, and derive numerous special physicochemical property, strengthen its application (Y.P.Li in various fields such as lithium ion battery, ultracapacitor, fuel cell, gas sensors, Y.X.Xiang, X.W.Dong, J.Q.Xu, F.Ruan, Q.Y.Pan, J.Solid State Chem.2009,182,2041; K.Shao, S.P.Liao, H.M.Luo, M.L.Wang, J.Solid StateElectrochem, 2007,11,1279; C.J.Song, M Khanfar, J.Appl.Electrochem, 2006,36,339; T.Itoh, I.Matsubara, W.Shin, N.Izu, M.Nishibori, Sens.ActuatorsB, 2008,128,512.).For example molybdenum oxide-polyaniline mixture nano material embodies higher capacity and good cyclicity in anode material for lithium-ion batteries.Hybrid unidimensional nanotopography is owing to have high outer surface area, good assembling performance, thereby improved molybdenum oxide-above-mentioned character of polyaniline hybridized thing.
At present, about the molybdenum oxide-research of polyaniline mixture mainly concentrates on the research of molybdenum oxide and polyaniline composite film, main synthetic method has ion-exchange polymerization, original position interpolation, independently adorns method and electrochemical deposition method (K.Shao, Y.Ma, Z.H.Chen, Chem Letters, 2002,322; J.Wang, IchiroMatsubara, Thin Solid Films, 2006,514,329; K.Shao, S.P.Liao, J.ColloidInterface Sci, 2008,320,445; Zhitomirsky I, Adv Colloid Interface Sci, 2002,97,279.).What aforesaid method obtained all is molybdenum oxide-polyaniline composite films, and complex operation, and the ion-exchange forerunner is difficult to preparation and preservation, synthesis condition limit harsh.
Therefore, for the physico-chemical property that promotes this composite nano materials with in the application in fields such as electrochemistry, sensing, embedded photoluminescent material, simultaneously for meeting scale operation, the synthetic method of seek new convenience, easily controlling becomes this area researchist's focus.
Summary of the invention
Molybdenum oxide-polyaniline the composite nano-line, the nanotube that provide a kind of method simple and easy to control, economical rationality to enrich with preparation property are provided for overcoming the deficiencies in the prior art.
The present invention proposes a kind of method of regulating synthetic molybdenum oxide-polyaniline composite nano-line and nanotube, molybdenum oxide and polyaniline is compound at nanoscale, and assembling forms one-dimensional composite nano line and nanotube.
Particularly, the method for preparing molybdenum oxide-polyaniline composite nano-line and nanotube of the present invention, it is characterized in that, with molybdate as the molybdenum source, by with the interaction of aniline, at first obtain molybdenum oxide-aniline hybridized nanometer line presoma, under the initiation of oxygenant, by the pH value of regulation system, obtain molybdenum oxide-polyaniline composite nano-line or nanotube respectively.
It comprises the steps:
(1) molybdate is dissolved in the distilled water, makes molybdate solution;
(2) aniline is injected above-mentioned solution;
(3) dropwise add mineral acid, occur to white precipitate;
(4) above-mentioned reaction be placed in the oil bath react, molybdenum oxide-aniline hybridized nanometer line presoma product;
(5) with the molybdenum oxide-aniline hybridized nanometer line presoma product washing, suction filtration, the oven dry that obtain;
(6) above-mentioned presoma product is dissolved in polyelectrolyte solution, centrifugal back adds distilled water or directly is dissolved in the distilled water solvent;
(7) add polymerization starter ammonium persulphate or Iron(III) chloride hexahydrate;
(8) mineral acid is regulated above-mentioned pH value of solution value, room temperature reaction, and different pH condition makes molybdenum oxide-polyaniline composite Nano product.
In the step of the present invention (1), molybdate is selected from ammonium molybdate, Sodium orthomolybdate or potassium molybdate, and described molybdate solution calculates with molybdenum atom, and its volumetric molar concentration is 0.01～3.0mol/L.
In the step of the present invention (2), the mol ratio 12.0～1.0 of aniline and molybdenum atom.
In the step of the present invention (3), mineral acid is selected from hydrochloric acid, nitric acid or sulfuric acid, and pH value of solution 4～5 when white precipitate occurred.
In the step of the present invention (4), 30～60 ℃ of oil bath temperatures, 4～24 hours reaction times.
In the step of the present invention (5), product is with absolute ethanol washing number time, and bake out temperature is a room temperature to 80 ℃.
In the step of the present invention (6), polyelectrolyte is selected from sodium polystyrene sulfonate (PSS) or sodium apolate (PVS).
In the step of the present invention (7), the mol ratio of described ammonium persulphate and molybdenum atom is 0.4～1; The mol ratio of described Iron(III) chloride hexahydrate and molybdenum atom is 1～10.
In the step of the present invention (8), described mineral acid is selected from hydrochloric acid or sulfuric acid, and the reaction times is 6～24 hours;
When the pH value is 1～2, prepare molybdenum oxide-polyaniline composite nano-line; The pH value is 3～5 o'clock, prepares molybdenum oxide-polyaniline composite nano tube.
Among the present invention, preferred reaction conditions is:
(1) described molybdate is Ammonium Molybdate Tetrahydrate ((NH
4)
6Mo
7O
244H
2O), purity 99.99%;
(2) aniline is analytical pure;
(3) concentration of molybdate solution is 0.4～1.0mol/L (calculating with molybdenum atom), and the mol ratio of organic amine and molybdenum atom is 2.0～4.0; Mineral acid is a hydrochloric acid, and concentration is 0.5～2.5mol/L;
(3) solvent adds distilled water for adding sodium polystyrene sulfonate (PSS) after centrifugal again.
(5) initiator is an ammonium persulphate, and the mol ratio of ammonium persulphate and molybdenum atom is 0.4～1.
(6) different-shape product optimal ph: the preferred pH of molybdenum oxide-polyaniline composite nano-line is 1.0; The preferred pH of molybdenum oxide-polyaniline composite nano tube is 3.0.
The nano wire of the inventive method preparation, the composite structure that nanotube has nanoscale, regulatable physico-chemical property, big specific surface area, one dimension pattern and the thickness and the regulatable characteristic of length of homogeneous, the compound molybdenum oxide-polyaniline nano-line that makes, nanotube have important use to be worth in the numerous areas such as synthetic and application of advanced catalyst design, electrocatalysis, electric chemical super capacitor, electrode materials, transmitter, thermoelectric material and advanced optics, electricity and magnetics material.
The inventive method productive rate is up to more than 95%.Preparation condition is simple and easy to control, and the processing condition cost is low, the preparation efficiency height, and quality product and yield rate height have good application and industrialization prospect.
Description of drawings
Fig. 1 is scanning electron microscope (SEM) figure of molybdenum oxide-polyaniline composite nano-line A.
Fig. 2 is transmission electron microscope (TEM) figure of product A.
Fig. 3 is infrared (IR) figure of product A.
Fig. 4 is thermogravimetric (TGA) figure of product A.
Fig. 5 is x-ray photoelectron power spectrum (XPS) figure of product A.
Fig. 6 is scanning electron microscope (SEM) figure of product B.
Fig. 7 is transmission electron microscope (TEM) figure of product B.
Fig. 8 is transmission electron microscope (TEM) figure of product B.
Fig. 9 is infrared (IR) figure of product B.
Figure 10 is thermogravimetric (TGA) figure of product B.
Figure 11 is x-ray photoelectron power spectrum (XPS) figure of product B.
Figure 12 is scanning electron microscope (SEM) figure of product B.
Embodiment
With 1.24g (NH
4)
6Mo
7O
244H
2O is dissolved in the 20mL distilled water, injects 1.67g aniline, and (pH 4 ~ 5) appear in hydrochloric acid to the white precipitate that dropwise adds 1.0mol/L then.Be transferred among 50 ℃ the oil bath, reacted 6 hours, will obtain the product washing with alcohol for several times and suction filtration, 50 ℃ of dryings, product is called precursor.0.355g precursor is dissolved in 10mLPSS, centrifugal back adds distilled water, and 0.5mol/L hydrochloric acid regulation system pH is 1.0, adds the 0.143g ammonium persulphate, and reaction is 12 hours under the room temperature, obtains molybdenum oxide-polyaniline composite nano-line A.
Method with embodiment 1 experimentizes, and changes wherein ammonium molybdate into Sodium orthomolybdate, makes nanowire product A
1
Embodiment 3
Method with embodiment 1 experimentizes, and changes wherein ammonium molybdate concentration into 0.01mol/L (calculating with molybdenum atom), makes nanowire product A
2
Embodiment 4
Method with embodiment 1 experimentizes, and changes wherein ammonium molybdate concentration into 3.0mol/L (calculating with molybdenum atom), makes nanowire product A
3
Embodiment 5
Method with embodiment 1 experimentizes, and changes wherein the organic amine and the mol ratio of molybdenum atom into 12.0, makes nanowire product A
4
Embodiment 6
Method with embodiment 1 experimentizes, and changes wherein the organic amine and the mol ratio of molybdenum atom into 1.0, makes nanowire product A
5
Embodiment 7
Method with embodiment 1 experimentizes, and does not wherein add PSS, and distilled water is directly added precursor, makes nanowire product A
6
Embodiment 8
Method with embodiment 1 experimentizes, and changes wherein PSS into PVS, makes nanowire product A
7
Embodiment 9
Method with embodiment 1 experimentizes, and is 2.0 with 0.5mol/L hydrochloric acid regulation system pH wherein, makes nanowire product A
8
Embodiment 10
Method with embodiment 1 experimentizes, and wherein, changes the mol ratio of precursor and Ammonium Persulfate 98.5 into 1, makes nanowire product A
9
Embodiment 11
With 1.24g (NH
4)
6Mo
7O
244H
2O is dissolved in the 20mL distilled water, injects 1.67g aniline, and (pH 4 ~ 5) appear in hydrochloric acid to the white precipitate that dropwise adds 1.0mol/L then.Be transferred among 50 ℃ the oil bath, reacted 6 hours, will obtain product for several times and suction filtration with washing with alcohol, 50 ℃ of dryings, product is called precursor.0.355g precursor is dissolved in 10mLPSS, centrifugal back adds distilled water, adds the 0.143g ammonium persulphate, and 1.0mol/L hydrochloric acid regulation system pH is 3.0, and reaction is 12 hours under the room temperature, obtains molybdenum oxide-polyaniline and can get the nanotube product B.
Embodiment 12
Method with embodiment 11 experimentizes, and does not wherein add PSS, and distilled water is directly added precursor, makes the nanotube product B
1
Embodiment 13
Method with embodiment 11 experimentizes, and wherein regulation system pH is 4-5, makes the nanotube product B
2
Embodiment 14
Method with embodiment 11 experimentizes, and wherein the mol ratio with precursor and Ammonium Persulfate 98.5 changes 1 into, makes the nanotube product B
3
Embodiment 15
Method with embodiment 11 experimentizes, and wherein initiator is changed to Iron(III) chloride hexahydrate, and the mol ratio of Iron(III) chloride hexahydrate and molybdenum atom is 6, makes the nanotube product B
4
Embodiment 16
Method with embodiment 11 experimentizes, and is 0.5 with 0.5mol/L hydrochloric acid regulation system pH wherein, makes product C.
The stereoscan photograph of the said products (SEM) all absorbs on Philips XL30D6716 instrument, and lens photo (TEM) absorbs on JEOL JEM-2010 instrument.
Fig. 1 has shown the stereoscan photograph of molybdenum oxide-polyaniline composite nano-line A that embodiment 1 makes, demonstrates product A and has the one dimension linear structure.
It is composite Nano wire structure that Fig. 2 (lens photo) further illustrates product A.
Product A to gained characterizes (as shown in Figure 3) with IR (Nicolet 360FT-IR spectrometer), and wave number is 1579.2,1497.7,1303.5,1239.9,1143.6 and 864.2cm
-1The peak be the characteristic peak of polyaniline, wave number is 944.21,902.4,739.3 and 682.3cm
-1The vibration peak of corresponding oxidation state molybdenum shows that this material is the organic inorganic hybridization mixture that is made of the polyaniline molybdenum oxide.
Weightlessness between the thermogravimetric analysis of product A (Perkin-Elmer TGA7) (as shown in Figure 4), room temperature to 100 ℃ mainly be since the weightlessness between the removing of the deionized water of absorption, 300 ℃ to 410 ℃ mainly due to the decomposition of polyaniline.
The x-ray photoelectron power spectrum XPS of product A (Perkin-Elmer PHI5000c XPS) characterizes (as shown in Figure 5), shows that Mo is a sexavalence in the product.
The SEM photo (as shown in Figure 6) of product B proves that embodiment 11 makes is molybdenum oxide-polyaniline composite nano tube, and size is even.
The TEM photo of product B (shown in Fig. 7 and 8) further demonstrates the tubular structure of product of nano.
The IR collection of illustrative plates (as shown in Figure 9) of B proves that the nanotube product shown in Fig. 7 and 8 is similarly polyaniline-molybdenum oxide mixture.
Weightlessness between the thermogravimetric analysis of product B (as shown in figure 10) room temperature to 100 ℃ mainly is owing to the decomposition of the weightlessness between the removing of adsorption deionizing water, 260 ℃ to 430 ℃ mainly due to polyaniline.
With XPS the sign (as shown in figure 11) of product B is shown that Mo is similarly sexavalence in the product.
Figure 12 demonstrates the product S EM figure that embodiment 16 methods obtain, show when reaction system pH is 0.5, what obtain is not molybdenum oxide-polyaniline composite nano-line or nanotube pattern, further specifies in the inventive method the conditional request to different-shape product pH value.
Molybdenum oxide-polyaniline nano-line that the present invention makes, nanotube have novel composite structure, big outer surface area and the one dimension pattern of homogeneous, the good physico-chemical property that embodies in fields such as electrode materials, ultracapacitor, catalysis, sensings based on molybdenum oxide and polyaniline simultaneously, described aluminum oxide-polyaniline composite nano-line and nanotube will be applied to as, the synthetic field of nano-device design and assembling, electrode materials, lithium ion battery, ultracapacitor, fuel cell, gas sensor and advanced optics, electricity and magnetics material.
Claims (13)
1. method for preparing molybdenum oxide-polyaniline composite nano-line and nanotube, it is characterized in that, with molybdate as the molybdenum source, by with the interaction of aniline, obtain molybdenum oxide-aniline hybridized nanometer line presoma, under the initiation of oxygenant,, make molybdenum oxide-polyaniline composite nano-line or nanotube respectively by the pH value of regulation system; It comprises the steps:
(1) molybdate is dissolved in the distilled water, makes molybdate solution;
(2) aniline is injected above-mentioned solution;
(3) dropwise add mineral acid, occur to white precipitate;
(4) above-mentioned reaction be placed in the oil bath react, molybdenum oxide-aniline hybridized nanometer line presoma product;
(5) with the molybdenum oxide-aniline hybridized nanometer line presoma product washing, suction filtration, the oven dry that obtain;
(6) the presoma product with above-mentioned (5) is dissolved in polyelectrolyte solution, and centrifugal back adds distilled water or directly is dissolved in the distilled water solvent;
(7) add polymerization starter;
(8) use mineral acid to regulate above-mentioned pH value of solution value, room temperature reaction, different pH condition makes molybdenum oxide-polyaniline composite Nano product.
2. method according to claim 1 is characterized in that, molybdate is selected from ammonium molybdate, Sodium orthomolybdate or potassium molybdate in the described step (1); Described molybdate solution calculates with molybdenum atom, and its volumetric molar concentration is 0.01～3.0mol/L.
3. method according to claim 1 is characterized in that, in described step (2) solution, the mol ratio of aniline and molybdenum atom is 12.0～1.0.
4. method according to claim 1 is characterized in that, the mineral acid in the described step (3) is selected from hydrochloric acid, nitric acid or sulfuric acid, and pH value of solution 4～5 when described white precipitate occurred.
5. method according to claim 1 is characterized in that, the oil bath temperature in the described step (4) is 30～60 ℃, and the reaction times is 4～24 hours.
6. method according to claim 1 is characterized in that, the molybdenum oxide in the described step (5)-aniline hybridized nanometer line presoma product is with absolute ethanol washing number time, suction filtration, and oven dry, temperature is a room temperature to 80 ℃.
7. method according to claim 1 is characterized in that, the polyelectrolyte in the described step (6) is selected from sodium polystyrene sulfonate or sodium apolate.
8. method according to claim 1 is characterized in that, the initiator in the described step (7) is ammonium persulphate or Iron(III) chloride hexahydrate.
9. method according to claim 8 is characterized in that, the mol ratio of described ammonium persulphate and molybdenum atom is 0.4～1.
10. method according to claim 8 is characterized in that, the mol ratio of described Iron(III) chloride hexahydrate and molybdenum atom is 1～10.
11. method according to claim 1 is characterized in that, the mineral acid in the described step (8) is hydrochloric acid or sulfuric acid.
12., it is characterized in that the room temperature reaction time in the described step (8) is 6～24 hours according to claim 1 or 11 described methods.
13. method according to claim 1 is characterized in that, in the described step (8), when the pH value was 1～2, product was molybdenum oxide-polyaniline composite nano-line, and when the pH value was 3～5, product was molybdenum oxide-polyaniline composite nano tube.
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Cited By (5)
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| CN103613759A (en) * | 2013-12-06 | 2014-03-05 | 东华大学 | Preparation method of MoO3/polyaniline coaxial nano heterojunction |
| CN106065180A (en) * | 2016-06-08 | 2016-11-02 | 东华大学 | A kind of preparation method of molybdenum trioxide polypyrrole polyaniline trielement composite material |
| CN109427981A (en) * | 2017-08-28 | 2019-03-05 | Tcl集团股份有限公司 | QLED device and preparation method thereof |
| CN113750987A (en) * | 2021-09-16 | 2021-12-07 | 南京信息工程大学 | Quadrature phase MoO3Electrocatalyst and preparation method and application thereof |
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| US4604427A (en) * | 1984-12-24 | 1986-08-05 | W. R. Grace & Co. | Method of forming electrically conductive polymer blends |
| CN101245187B (en) * | 2008-01-08 | 2010-06-30 | 上海大学 | Process for preparing molybdenum trioxide/polyaniline laminated composite material |
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| CN103613759A (en) * | 2013-12-06 | 2014-03-05 | 东华大学 | Preparation method of MoO3/polyaniline coaxial nano heterojunction |
| CN103613759B (en) * | 2013-12-06 | 2015-10-28 | 东华大学 | A kind of MoO 3the preparation method of/polyaniline co-axial nano heterojunction |
| CN106065180A (en) * | 2016-06-08 | 2016-11-02 | 东华大学 | A kind of preparation method of molybdenum trioxide polypyrrole polyaniline trielement composite material |
| CN106065180B (en) * | 2016-06-08 | 2018-02-16 | 东华大学 | A kind of preparation method of molybdenum trioxide polypyrrole polyaniline trielement composite material |
| CN109427981A (en) * | 2017-08-28 | 2019-03-05 | Tcl集团股份有限公司 | QLED device and preparation method thereof |
| CN113750987A (en) * | 2021-09-16 | 2021-12-07 | 南京信息工程大学 | Quadrature phase MoO3Electrocatalyst and preparation method and application thereof |
| CN115160564A (en) * | 2022-07-19 | 2022-10-11 | 湖北大学 | Molybdenum oxide composite polyaniline nanofiber paper and preparation method thereof |
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