CN1304282C - Method for uniformly coating inorganic nanoparticles on carbon nanotube surface by anti-microemulsion method - Google Patents
Method for uniformly coating inorganic nanoparticles on carbon nanotube surface by anti-microemulsion method Download PDFInfo
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- CN1304282C CN1304282C CNB2004100990224A CN200410099022A CN1304282C CN 1304282 C CN1304282 C CN 1304282C CN B2004100990224 A CNB2004100990224 A CN B2004100990224A CN 200410099022 A CN200410099022 A CN 200410099022A CN 1304282 C CN1304282 C CN 1304282C
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Abstract
The present invention provides a method for uniformly covering inorganic nanometer granules on the surface of a carbon nanometer tube. The present invention is mainly characterized in that a carbon nanometer tube and inorganic nanometer granules are combined together by a non-covalent bond, so various intrinsic physical and chemical properties of the carbon nanometer tube can be protected to the maximum. The precipitation reaction of the inorganic nanometer granules is limited in microemulsion drops of the nanometer grade, the dimension of the granules is small, and the aggregation degree is low. In addition, the method can also be used for covering two kinds of or various inorganic nanometer granules on a carbon nanometer tube.
Description
Technical field
The present invention relates to anti-microemulsion method in the method for carbon nano tube surface uniformly coating inorganic nanoparticles, the carbon nanotube of the surface modification for preparing is expected to be applied in various functional and structural material.Belong to field of nanometer material technology.
Background technology
Carbon nanotube (CNTs) is that Sumio Iijima at first reports a kind of have brand-new performance, the ideal quasi-one-dimensional nanometer material.There is stronger sp between its lamella
2Bonding and short C-C interatomic distance have suppressed impurity and generation of defects, axially have higher intensity.It is reported that the Young's modulus of carbon nanotube is identical with diamond, theoretical strength can reach 1.0TPa, is 100 times of steel, and has toughness preferably.Its density only is 1/7th of steel, anti-strong acid, highly basic, and not oxidation substantially below the 973K in air is expected to become the advanced composite materials ideal and strengthens body.In addition, carbon nanotube also has a lot of unusual physical and chemical performances, as the metal of uniqueness or semi-conductor electroconductibility, hydrogen storage ability, adsorptive power and stronger microwave absorption capacity etc.The early 1990s is considered to a kind of new function material and structured material of excellent performance once the very big attention of finding promptly to be subjected to physics, chemistry and material educational circles and new high-tech industry department.
Because the carbon nano tube surface defective is few, lack active group, makes its solubleness in all kinds of SOLVENTS medium all very low, its huge specific surface area and big length-to-diameter ratio often form between carbon nanotube and twine in addition.Carbon nanotube can not and body material between form stronger interface combination, influenced the performance of its excellent properties.Therefore, people strive to find that the whole bag of tricks carries out modification to carbon nanotube or the surface coats.Utilize the hydrolysis of tetraethoxy as T.Seeger, coated on multi-walled carbon nano-tubes (MWNTs) surface one deck SiO2 (T.Seeger et al.Chem.Commum.2002,34-35.).S.Banerjee at first carries out acidification with Single Walled Carbon Nanotube (SWNTs) surface, produces a plurality of carboxylic groups on the CNTs surface, utilizes carboxylic group and aminating TiO
2Intergranular reaction has obtained TiO
2The SWNTs that particle coats (S.Banerjee et al. Nano Lett.2002,2 (3), 195-200, J.Am.Chem.Soc., 2003,125,10342-10350).A.Zettl passes through SnCl
4Hydrolysis reaction coated SnO on the surface of SWNTs
2Particle (A.Zettl et al.Nano lett., 2003,3 (5), 681-683).But up to now, also there is not a kind of blanket method to be used for the coating of inorganic oxide nanoparticles on carbon nanotube.Therefore, develop new experimental technique to improving the interface bond strength of carbon nanotube and various inorganic materials, the application of expanding carbon nanotube is significant.
Summary of the invention
The objective of the invention is to provides a kind of non covalent bond combination that utilizes with the micro emulsion method, coats the method for various inorganic nanoparticles in carbon nano tube surface.Water-in-oil microemulsion (being inverse micellar solution) is thermodynamically stable transparent liquid.In inverse micellar solution, the surfactant micelle that small water droplet is dispersed in the oil-continuous phase surrounds, and dispersed phase size is very little, is generally several nanometers, chemical reaction in fine droplet inside or water-oil interface take place.Utilize micro emulsion to be reflected at the method that carbon nano tube surface coats various inorganic nanoparticles and have easy, practical characteristics, to improving the dispersiveness of carbon nanotube in various inorganic matrix media, improve both interface bond strengths, and then give full play to various specific physical and the chemical property that carbon nanotube has and have pervasive meaning.
Of the present invention with the method for anti-microemulsion method at the carbon nano tube surface uniformly coating inorganic nanoparticles, it is characterized in that described method comprises that the preparation, inorganic nanoparticles of the dispersion of carbon nanotube in the aqueous solution, anti-micro emulsion phase are at the coating of carbon nano tube surface, sedimentary washing, calcination process
Concrete grammar is:
(a) be to be dispersion agent with Sodium dodecylbenzene sulfonate (NaDDBS) with the dispersion of carbon nanotube in the aqueous solution, the mass concentration of dispersion agent is 0.1%～2%, and the concentration of carbon nanotube is 5～35mg/ml;
(b) oil phase of anti-micro emulsion phase is TritonX-100 and hexanaphthene, and both dissolve each other with 10: 90～30: 70 mass ratio;
(c) carbon nano-tube solution that step (a) is made dropwise is added drop-wise in the described organic oil phase of step (b) and obtains stable anti-microemulsion system;
(d) be raw material with metal acetate salt, the concentration of described nitrate solution is 0.1～0.45M, under agitation condition, at first acetate solution dropwise is added drop-wise in the described microemulsion system of step (c), and then will dropwise splash into as the ammonia soln of precipitation agent in the anti-microemulsion system, generate the inorganic nanoparticles precipitation;
(e) described temperature of reaction is 30～50 ℃, and sedimentation time is 0.5～3 hour, and dropwise adding concentration is rare NH of 0.4～1.0M
4OH solution is until pH=9.With washing with alcohol, oven dry;
(f) described sedimentary calcining temperature is 350～550 ℃, 0.5～2 hour time, thus prepare the inorganic nanoparticles enveloped carbon nanometer tube.
Described metal acetate salt be a kind of in zinc acetate, magnesium acetate, the neutralized verdigris, two or more, form the coating of a kind of, two or more component in carbon nano tube surface.
The inorganic nano zinc oxide particle diameter of prepared enveloped carbon nanometer tube is 5～50nm.
The inorganic nano magnesium oxide particle diameter of prepared enveloped carbon nanometer tube is 20～70nm.
The concentration of described ammoniacal liquor is 0.5～1.0M,
Described acetate joins microemulsion system under 400～1000 rev/mins of rotating speeds stir.
Described washing with alcohol number of times 2～6 times, bake out temperature are 60～120 ℃, and the time is 1～12 hour,
The grain size of the inorganic nanoparticles of the enveloped carbon nanometer tube of the present invention's preparation is 5～70 nanometers.
The preparation method of nano oxide powder enveloped carbon nanometer tube provided by the invention has following characteristics:
(1) microemulsion method provides a kind of and has adhered to the method for inorganic oxide nanoparticles in carbon nano tube surface by the non covalent bond effect, can keep the electroconductibility and the mechanical property of carbon nanotube to greatest extent.
(2) water droplet couples together carbon nanotube and inorganic nanoparticles, and they are limited in the microemulsion, and the mixture of generation is reunited few, coats evenly.
(3) present method can be expanded and be used for other metallic cations in the adhering to of carbon tube-surface, and if can appropriately select experiment condition, can realize the coating of two or more component in carbon nano tube surface.
Description of drawings
The anti-microemulsion method of Fig. 1 is at the schematic flow sheet of carbon nano tube surface coated inorganic oxide nano particles
Fig. 2 calcines preceding Zn (OH)
2The TEM photo of presoma enveloped carbon nanometer tube
Fig. 3 calcines preceding Zn (OH)
2The EDS Spectrum of presoma enveloped carbon nanometer tube
The TEM photo (a) of Fig. 4 ZnO nano particle enveloped carbon nanometer tube and electron-diffraction diagram (b)
The TEM photo (a) of Fig. 5 MgO nano particle enveloped carbon nanometer tube and electron-diffraction diagram (b)
Embodiment
Further specify embodiment and effect with following indefiniteness embodiment:
Embodiment 1
According to schematic flow sheet shown in Figure 1, earlier carbon nanotube is dispersed in the solution of making 14.5mg/ml in Sodium dodecylbenzene sulfonate (NaDDBS) aqueous solution, NaDDBS concentration is 0.5%.Tensio-active agent is Triton X-100, and itself and hexanaphthene are dissolved each other in 30: 70 ratio, and this solution stirs 30min down at 40 ℃.Then, the stable carbon nano-tube solution of above-mentioned preparation dropwise added lentamente and continue stir, the ultimate density of carbon nanotube is in 15mL hexanaphthene/Triton X-114 solution the 35mg carbon nanotube to be arranged.Subsequently, 0.25M Zn (CH
3COO)
2Solution splashes in the above-mentioned microemulsion system.Mixture was stirred 2 hours down at 40 ℃.At last, dropwise add rare NH
3H
2O solution reaches 9 until the pH value.Add 50mL ethanol and continue and stirred 30 minutes.Settling washing with alcohol 3 times, centrifugal, drying, 450 ℃ of calcining 20min obtain products.Fig. 2 is Zn (OH)
2The TEM photo of enveloped carbon nanometer tube, coated pellet is hollow shape as can be seen, and diameter is 10-20nm.Its EDS Spectrum contains element Zn, O and a spot of C as shown in Figure 3, and the confirmation hollow particle is Zn (OH)
2, and contain a small amount of organism.Throw out obtains the carbon nanotube of ZnO parcel through 450 ℃ of calcining 20min.Fig. 4 has provided its TEM photo and SAED diffractogram.As can be seen from Figure 4, the particle size of ZnO is 5nm, evenly is wrapped in the skin of carbon nanotube.
Preparation 0.15M Mg (CH
3COO)
2Solution obtains the carbon nanotube that nano magnesia wraps up by embodiment 1 described step.Fig. 5 provides the TEM photo and the electron-diffraction diagram of MgO nano particle enveloped carbon nanometer tube, and the MgO particle size is 30-40nm, evenly is wrapped on the outer wall of carbon nanotube.
Embodiment 3
Compound concentration is the Mg (CH of 0.45M
3COO)
2And Zn (CH
3COO)
2Complex phase solution obtains the carbon nanotube of MgO and the compound parcel of ZnO by embodiment 1 described step.
Embodiment 4
Compound concentration is the Mg (CH of 0.45M
3COO)
2, Zn (CH
3COO)
2, Cu (CH
3COO)
2Complex phase solution obtains the carbon nanotube of MgO and ZnO, the compound parcel of CuO by embodiment 1 described step.
Claims (8)
1, a kind of with the method for anti-microemulsion method at the carbon nano tube surface uniformly coating inorganic nanoparticles, it is characterized in that preparation, inorganic nanoparticles that described method comprises the dispersion of carbon nanotube in the aqueous solution, anti-micro emulsion phase at the coating of carbon nano tube surface, sedimentary washing, calcination process, concrete grammar is:
(a) with the dispersion of carbon nanotube in the aqueous solution, be dispersion agent with the Sodium dodecylbenzene sulfonate, the mass concentration of dispersion agent is 0.1%～2%, the concentration of carbon nanotube is 5～35mg/ml;
(b) oil phase of anti-micro emulsion phase is TritonX-100 and hexanaphthene, and both dissolve each other with 10: 90～30: 70 mass ratio;
(c) carbon nano-tube solution that step (a) is made dropwise is added drop-wise in the described organic oil phase of step (b) and obtains stable anti-microemulsion system;
(d) be raw material with metal acetate salt, the concentration of described acetate solution is 0.1～0.45M, under agitation condition, at first acetate solution dropwise is added drop-wise in the described microemulsion system of step (c), and then will dropwise splash into as the ammonia soln of precipitation agent in the anti-microemulsion system, generate the inorganic nanoparticles precipitation;
(e) described temperature of reaction is 30～50 ℃, and sedimentation time is 0.5～3 hour, and dropwise adding concentration is rare NH of 0.4～1.0M
4OH solution is until pH=9, with washing with alcohol, oven dry;
(f) described sedimentary calcining temperature is 350～550 ℃, 0.5～2 hour time, thus prepare the inorganic nanoparticles enveloped carbon nanometer tube.
2, by the method for the described anti-microemulsion method of claim 1 at the carbon nano tube surface uniformly coating inorganic nanoparticles, it is characterized in that described metal acetate salt be a kind of in zinc acetate, magnesium acetate, the neutralized verdigris, two or more, form the coating of a kind of, two or more component in carbon nano tube surface.
3, the method for preparing the inorganic nanoparticles enveloped carbon nanometer tube by the described anti-microemulsion method of claim 2 is characterized in that by zinc acetate being that the inorganic nano zinc oxide particle diameter of the enveloped carbon nanometer tube that raw material generated is 5～50nm.
4, the method for preparing the inorganic nanoparticles enveloped carbon nanometer tube by the described anti-microemulsion method of claim 2 is characterized in that by magnesium acetate being that the inorganic nano magnesium oxide particle diameter of the enveloped carbon nanometer tube that raw material generated is 20～70nm.
5, by the method for the described anti-microemulsion method of claim 1 at the carbon nano tube surface uniformly coating inorganic nanoparticles, the concentration that it is characterized in that described ammoniacal liquor is 0.5～1.0M.
6,, it is characterized in that acetate under 400～1000 rev/mins of rotating speeds stir, joins microemulsion system by the method for the described anti-microemulsion method of claim 1 at the carbon nano tube surface uniformly coating inorganic nanoparticles.
7, by the method for the described anti-microemulsion method of claim 1 at the carbon nano tube surface uniformly coating inorganic nanoparticles, it is characterized in that described washing with alcohol number of times 2～6 times, bake out temperature is 60～120 ℃, and the time is 1～12 hour.
8, by the method for the described anti-microemulsion method of claim 1 at the carbon nano tube surface uniformly coating inorganic nanoparticles, the grain size that it is characterized in that the inorganic nanoparticles of enveloped carbon nanometer tube is 5～70 nanometers.
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| CN105214733B (en) * | 2015-11-02 | 2019-02-15 | 华东理工大学 | Titanium dioxide covalently loads efficient oxygen reduction electro-catalyst of copper complex and preparation method thereof |
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| CN110090567B (en) * | 2019-05-15 | 2021-08-17 | 浙江工商大学 | Carbon nanomaterial @ metal nanoparticle/copolymer mixed matrix pervaporation membrane and preparation method thereof |
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| US5965267A (en) * | 1995-02-17 | 1999-10-12 | Arizona Board Of Regents On Behalf Of The University Of Arizona | Method for producing encapsulated nanoparticles and carbon nanotubes using catalytic disproportionation of carbon monoxide and the nanoencapsulates and nanotubes formed thereby |
| CN1410455A (en) * | 2002-03-14 | 2003-04-16 | 四川大学 | Preparation method of polymer/carbon nano pipe composite emulsion and its in situ emulsion polymerization |
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| US5965267A (en) * | 1995-02-17 | 1999-10-12 | Arizona Board Of Regents On Behalf Of The University Of Arizona | Method for producing encapsulated nanoparticles and carbon nanotubes using catalytic disproportionation of carbon monoxide and the nanoencapsulates and nanotubes formed thereby |
| CN1410455A (en) * | 2002-03-14 | 2003-04-16 | 四川大学 | Preparation method of polymer/carbon nano pipe composite emulsion and its in situ emulsion polymerization |
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