CN100575251C - The preparation method of carbon nanotube supported magnetic ferroferric oxide nano-particles - Google Patents
The preparation method of carbon nanotube supported magnetic ferroferric oxide nano-particles Download PDFInfo
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- CN100575251C CN100575251C CN200710049525A CN200710049525A CN100575251C CN 100575251 C CN100575251 C CN 100575251C CN 200710049525 A CN200710049525 A CN 200710049525A CN 200710049525 A CN200710049525 A CN 200710049525A CN 100575251 C CN100575251 C CN 100575251C
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Abstract
The invention discloses a kind of preparation method of carbon nanotube supported magnetic ferroferric oxide nano-particles.It is characterized in that carbon nanotube is joined in the nitric acid high iron solution, stir, ultra-sonic oscillation are handled, and then add certain water-soluble polymer aqueous solution, stir, continuing ultra-sonic oscillation handles, filter, drying is ground, calcination certain hour in inert atmosphere at a certain temperature further obtains carbon nanotube supported magnetic ferroferric oxide nano-particles after the milled processed at last.This preparation method is efficient, with low cost, technology is simple, is suitable for suitability for industrialized production.Gained carbon nanotube supported magnetic ferroferric oxide nano-particles charge capacity height, Stability Analysis of Structures, evenly, good dispersity, and and carbon nanotube between stronger bonding force is arranged.Can be widely used in magnetic target material, various catalyzer, electromagnetic shielding absorbing material, electrode material for super capacitor and other relevant field of functional materials.
Description
Technical field
The present invention relates to carbon nanomaterial processing and applied technical field, specifically is the preparation method of carbon nanotube supported magnetic ferroferric oxide nano-particles.
Technical background
Carbon nanotube (CNT) is the most representative nano material with particular electrical, magnetic, optical property, and its excellent physics, chemistry and mechanical property have obtained global scientist and researchist's extensive concern and carried out a large amount of research.Carbon nanotube has special tubular structure, has bigger specific surface area, can manage the material that inside and outside deposition has specific function at it, common as catalyzer, electrochemical energy conversion, transmitter etc., this makes the application of carbon nanotube obtain further expansion, therefore, the research of this respect also is the focus that people competitively study always, such as, the patent contents of applying at home such as CN 1481932A, CN1424149A, CN 1806914A and CN 1778470A all are the research about this respect in recent years.From bibliographical information in recent years, depositing used method at carbon nanotube mainly contains: electroless plating method, chemical precipitation method, dipping-pyrolysis method etc., wherein dipping-pyrolysis method is compared preceding two kinds and is had with low cost, advantage of simple technology, therefore be widely used, but the subject matter that exists in this method reality is that charge capacity is lower, the bonding force of settled layer and carbon nanotube a little less than, in the process of practical application, break away from easily with carbon nanotube, such as at ultra-sonic dispersion, under the processing conditionss such as high-speed stirring, therefore can not bring into play expected effect, this is a serious problem, and this problem is equally also in the preceding two kinds of methods of ubiquity.
Nano ferriferrous oxide is one of a kind of nano-functional material that is widely used owing to have special physicals and chemical stability, and it has excellent magnetism, extensively is used as magnetic recording material and magnetic target material; It also has excellent catalytic activity simultaneously, is a kind of important catalyst at chemical field, more is considered at chemical sensor simultaneously, and there is very big application potential in the electrode material for super capacitor field; It also is one of absorbing material that is widely used in addition.
With carbon nanotube supported magnetic ferroferric oxide nano-particles is a kind of functional composite material that application potential is arranged very much, and utilize the excellent carbon nanotube supported magnetic ferroferric oxide nano-particles of dipping-pyrolysis method preparation must solve following two problems: how (1) improves charge capacity; (2) how to improve bonding force between Z 250 and the carbon nanotube.
Summary of the invention
The object of the present invention is to provide that a kind of technology is simple, with low cost, bonding force is strong between deposited particles and the carbon nanotube, charge capacity is high, be applicable to the preparation method of the carbon nanotube supported magnetic ferroferric oxide nano-particles of suitability for industrialized production.
The preparation method of carbon nanotube supported magnetic ferroferric oxide nano-particles of the present invention is to utilize a kind of water-soluble polymer, adopts the nitrate pyrolysis method to deposit magnetic ferroferric oxide nano-particles on carbon nanotube, and its technology comprises the steps:
1, add carbon nanotube in the nitric acid high iron solution, stirring, ultra-sonic oscillation are handled;
2, the aqueous solution that in the mixed solution that the first step obtains, adds a kind of water-soluble polymer, stirring, ultra-sonic oscillation are handled;
3, the mixed solution that second step was obtained left standstill 2 hours to 48 hours;
4, above-mentioned mixed solution filtration, oven dry, grinding are obtained pressed powder;
5, above-mentioned pressed powder in inert atmosphere, 300 ℃～800 ℃ the heating 10 minutes to 24 hours, promptly obtain carbon nanotube supported magnetic ferroferric oxide nano-particles.
Described nitric acid high iron solution volumetric molar concentration is 2～0.1mol/L.
Described carbon nanotube is multi-walled carbon nano-tubes or Single Walled Carbon Nanotube.
The aqueous solution of described water-soluble polymer is any in polyacrylamide, polyacrylic acid, polymethyl acrylic acid, polyvinyl alcohol, polyoxyethylene glycol, polyoxyethylene, Polyvinylpyrolidone (PVP), the Walocel MT 20.000PV, and mass percent concentration is 10～0.1%.
Described water solvent is any in deionized water or the distilled water.
Described rare gas element is any in nitrogen or the argon gas.
Utilize the carbon nanotube supported magnetic ferroferric oxide particle of the inventive method preparation, its electronic scanning Electronic Speculum (SEM) shows, on carbon nanotube, deposited the Z 250 particle more equably, its median size is about 15nm, ferriferrous oxide nano-particle has stronger bonding force by the ablation layer and the carbon nanotube of water-soluble polymer, can not break away from carbon nanotube in ultra-sonic dispersion and high-speed stirring process.Its differential scanning calorimetric (DSC) test shows that the use water-soluble polymer can significantly improve the charge capacity to magnetic ferroferric oxide.Its X-ray diffraction curve (XRD) shows that the purity of the carbon nanotube supported magnetic ferroferric oxide particle of preparation is higher.
The invention has the advantages that:
Gained carbon nanotube supported magnetic ferroferric oxide nano-particles charge capacity height of the present invention, Stability Analysis of Structures, evenly, good dispersity, and and carbon nanotube between stronger bonding force is arranged.Preparation technology of the present invention has efficiently, environmental protection, advantage of simple technology, this carbon nanotube supported magnetic ferroferric oxide nano-particles can be widely used in magnetic target material, various catalyzer, aspect and other relevant field of functional materials such as electromagnetic shielding absorbing material, electrode material for super capacitor.
Description of drawings:
Fig. 1 is a carbon nanotube supported magnetic ferroferric oxide nano-particles SEM photo, process ultra-sonic dispersion and high-speed stirring during sample preparation.
Fig. 2 is the dsc analysis curve of the described pressed powder of step 4, the peak of marking 1 be the decomposition peak of the iron nitrate that floods in the pressed powder, peak 2 is the decomposition of water-soluble polymer.
Fig. 3 is the XRD curve of carbon nanotube supported magnetic ferroferric oxide nano-particles.
Embodiment
The present invention will be further described below in conjunction with embodiment:
1, is to add 10 gram multi-walled carbon nano-tubes in the 2.0mol/L nitric acid high iron solution at 100 ml concns, stirred 1 hour, ultra-sonic oscillation processing 1 hour;
2, adding 20 gram mass per-cents in the mixed solution that the first step obtains is 10% polyacrylamide solution, stirs 1 hour, ultra-sonic oscillation processing 1 hour;
3, the mixed solution that second step was obtained left standstill 8 hours;
4, above-mentioned mixed solution filtration, oven dry, grinding are obtained pressed powder;
5, above-mentioned pressed powder in nitrogen atmosphere, 400 ℃ the heating 30 minutes.
1, is to add 10 gram multi-walled carbon nano-tubes in the 1.0mol/L nitric acid high iron solution at 100 ml concns, stirred 1 hour, ultra-sonic oscillation processing 1 hour;
2, adding 10 gram mass per-cents in the mixed solution that the first step obtains is 4% the polyacrylic acid aqueous solution, stirs 1 hour, ultra-sonic oscillation processing 1 hour;
3, the mixed solution that second step was obtained left standstill 10 hours;
4, above-mentioned mixed solution filtration, oven dry, grinding are obtained pressed powder;
5, above-mentioned pressed powder in nitrogen gas, 300 ℃ the heating 1 hour.
Embodiment 3
1, is to add 10 gram multi-walled carbon nano-tubes in the 1.0mol/L nitric acid high iron solution at 100 ml concns, stirred 1 hour, ultra-sonic oscillation processing 1 hour;
2, adding 50 gram mass per-cents in the mixed solution that the first step obtains is 5% polymethyl aqueous acid, stirs 1 hour, ultra-sonic oscillation processing 1 hour;
3, the mixed solution that second step was obtained left standstill 24 hours;
4, above-mentioned mixed solution filtration, oven dry, grinding are obtained pressed powder;
5, above-mentioned pressed powder in nitrogen atmosphere, 700 ℃ the heating 10 hours.
Embodiment 4
1, is to add 10 gram multi-walled carbon nano-tubes in the 0.5mol/L nitric acid high iron solution at 100 ml concns, stirred 1 hour, ultra-sonic oscillation processing 1 hour;
2, adding 30 gram mass per-cents in the mixed solution that the first step obtains is 2% polyvinyl alcohol water solution, stirs 1 hour, ultra-sonic oscillation processing 1 hour;
3, the mixed solution that second step was obtained left standstill 1 hour;
4, above-mentioned mixed solution filtration, oven dry, grinding are obtained pressed powder;
5, above-mentioned pressed powder in nitrogen atmosphere, 800 ℃ the heating 5 minutes.
Embodiment 5
1, is to add 10 gram Single Walled Carbon Nanotube in the 1.5mol/L nitric acid high iron solution at 100 ml concns, stirred 1 hour, ultra-sonic oscillation processing 1 hour;
2, adding 20 gram mass per-cents in the mixed solution that the first step obtains is 7% the polyoxyethylene glycol aqueous solution, stirs 1 hour, ultra-sonic oscillation processing 1 hour;
3, the mixed solution that second step was obtained left standstill 24 hours;
4, above-mentioned mixed solution filtration, oven dry, grinding are obtained pressed powder;
5, above-mentioned pressed powder in nitrogen atmosphere, 550 ℃ the heating 24 hours.
Embodiment 6
1, is to add 10 gram Single Walled Carbon Nanotube in the 1.0mol/L nitric acid high iron solution at 100 ml concns, stirred 1 hour, ultra-sonic oscillation processing 1 hour;
2, adding 20 gram mass per-cents in the mixed solution that the first step obtains is 8% polyoxyethylene aqueous solution, stirs 1 hour, ultra-sonic oscillation processing 1 hour;
3, the mixed solution that second step was obtained left standstill 12 hours;
4, above-mentioned mixed solution filtration, oven dry, grinding are obtained pressed powder;
5, above-mentioned pressed powder in nitrogen gas, 400 ℃ the heating 12 hours.
Embodiment 7
1, is to add 10 gram Single Walled Carbon Nanotube in the 0.1mol/L nitric acid high iron solution at 100 ml concns, stirred 1 hour, ultra-sonic oscillation processing 1 hour;
2, adding 50 gram mass per-cents in the mixed solution that the first step obtains is 5% the Polyvinylpyrolidone (PVP) aqueous solution, stirs 1 hour, ultra-sonic oscillation processing 1 hour;
3, the mixed solution that second step was obtained left standstill 48 hours;
4, above-mentioned mixed solution filtration, oven dry, grinding are obtained pressed powder;
5, above-mentioned pressed powder in nitrogen gas, 300 ℃ the heating 24 hours.
Embodiment 8
1, is to add 10 gram Single Walled Carbon Nanotube in the 0.5mol/L nitric acid high iron solution at 100 ml concns, stirred 1 hour, ultra-sonic oscillation processing 1 hour;
2, adding 20 gram mass per-cents in the mixed solution that the first step obtains is 10% the Walocel MT 20.000PV aqueous solution, stirs 1 hour, ultra-sonic oscillation processing 1 hour;
3, the mixed solution that second step was obtained left standstill 48 hours;
4, above-mentioned mixed solution filtration, oven dry, grinding are obtained pressed powder;
5, above-mentioned pressed powder in nitrogen gas, 600 ℃ the heating 30 minutes.
Claims (4)
1. the preparation method of a carbon nanotube supported magnetic ferroferric oxide nano-particles is characterized in that comprising the steps:
(1), in the nitric acid high iron solution, adds carbon nanotube, stirring, ultra-sonic oscillation processing;
(2), in the mixed solution that (1) obtains, add a kind of aqueous solution of water-soluble polymer, stir, ultra-sonic oscillation handle;
(3), the mixed solution that (2) are obtained left standstill 2 hours to 48 hours;
(4), above-mentioned mixed solution filtration, oven dry, grinding are obtained pressed powder;
(5), above-mentioned pressed powder in rare gas element, 300 ℃～800 ℃ the heating 10 minutes to 24 hours, promptly obtain carbon nanotube supported magnetic ferroferric oxide nano-particles;
The aqueous solution of described water-soluble polymer is any aqueous solution in polyacrylamide, polyacrylic acid, polymethyl acrylic acid, polyvinyl alcohol, polyoxyethylene glycol, polyoxyethylene, Polyvinylpyrolidone (PVP), the Walocel MT 20.000PV, and mass percent concentration is 10～0.1%.
2. the preparation method of carbon nanotube supported magnetic ferroferric oxide nano-particles as claimed in claim 1, it is characterized in that: the described nitric acid high iron solution of step (1) volumetric molar concentration is 2～0.1mol/L.
3. the preparation method of carbon nanotube supported magnetic ferroferric oxide nano-particles as claimed in claim 1, it is characterized in that: the described carbon nanotube of step (1) is multi-walled carbon nano-tubes or Single Walled Carbon Nanotube.
4. the preparation method of carbon nanotube supported magnetic ferroferric oxide nano-particles as claimed in claim 1 is characterized in that: the described rare gas element of step (5) is any in nitrogen or the argon gas.
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