CN101255544B - Method for preparing nano metal or metal oxide/carbon nano-tube composite material - Google Patents
Method for preparing nano metal or metal oxide/carbon nano-tube composite material Download PDFInfo
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Abstract
The invention relates to a simple practical preparation for metal or metal oxide/carbon nano-tube nano-composite, characterized in: with carbon nano-tube as the matrix, Fe, Co, Ni, Si, Ag, Au, Ti, Zn, Al, Mg, Ta, Pd, Mo, Sn and Pt as well as oxide nano-materials thereof are prepared by any method of radio frequency sputtering deposition, pulsed laser deposition, spraying schizolysis, hot evaporation or hydrothermal method, metal or metal oxide nano-grain or nano-film is formed on the surface of a carbon nano-tube. By this method, carbon nano-tube matrix composite material having multiple forms can be prepared, the process is simple, the cost is low, the carbon nana-tube matrix composite material has special optical property, electrical property, and magnetic property, thus having wide application prospect.
Description
Technical field
The present invention relates to the preparation method of a kind of nano metal or metal oxide/carbon nano-tube composite material, belong to field of nanometer material technology.
Background technology
Because carbon nanotube (CNT) possesses particular structure, special physics and chemical property, since being come to light from 1991, it has just caused people's extensive concern always.Increasingly mature along with the carbon nanotube synthetic technology; The low-cost carbon nanotube of producing in enormous quantities realizes that thus, carbon nanotube and other materials are formed high performance composite; Being important directions and the means that carbon nanotube is able to widespread use, also is one of key content of Chinese scholars research.
The application of carbon nanotube in matrix material mainly concentrates on aspect following two: (1) utilizes performances such as hollow structure and the capillary performance of carbon nanotube, specific surface area are big, conduction that it is improved the physicals (like magnetic, electroconductibility and photoelectron performance etc.) of material as carrier (matrix or template); Can process the unique one-dimensional nano-composite material of structure; Like (Jitianu A such as nanometer quantum wire, nano electron device, sensing device, tunnel diode, new catalyst and electrode materialss; Cacciaguerra T, Benoit R, etal.Carbon.2004; 42,1147); (2) utilize the excellent mechanical property of carbon nanotube self that it is improved the mechanical property (Ann.Rev.Mater.Res.2003,33,419) of matrix (metal, pottery, high polymers) material as enhancing.
Be that the method that matrix prepares matrix material mainly contains three types with the carbon nanotube, the first directly and other materials mix the matrix material that obtains doped carbon nanometer pipe; It two is matrix materials through the functionalized acquisition chemically bonded of carbon nano tube surface; It three is to apply or long in other substrates and the matrix material of acquisitions needs at the carbon nano tube surface plated film with carbon nanotube.First kind method is simple, and is convenient, but efficient is very low.Though second type and the 3rd type can obtain matrix material preferably, step is comparatively loaded down with trivial details, also will use the heat method to obtain matrix material.In addition, second class methods need be carried out the oxygenant pre-treatment to carbon nanotube, introduce reactive group in carbon nano tube surface, but the electronic structure of carbon nanotube itself has been caused destruction.Therefore, need to explore more how suitable compound method, under the prerequisite of the electronic structure of destroying carbon nanometer tube not own, the scattering problem of carbon nanotube and other materials in the solution matrix material, and carbon nanotube is as the combine problem of wild phase with substrate.
There are some researches show; Carbon nanotube is carried out hydrogen plasma to be handled; Can improve the field emission performance of carbon nanotube; And the present invention proposes with hydrogen plasma carbon nanotube to be carried out pre-treatment, under the prerequisite of the electronic structure of destroying carbon nanometer tube not itself, increases its surfactivity, thereby improves nucleation site density and intensity that carbon nano tube surface is adsorbed metal or metal oxide materials.
Summary of the invention
The simple and practical preparation method who the purpose of this invention is to provide a kind of metal or metal oxide/carbon nano-tube nano composite material.
The objective of the invention is to realize like this: the present invention provides the preparation method of the nano composite material of a kind of metal or metal oxide/carbon nano-tube; This method is divided into the pre-treatment of carbon nanotube, the preparation and three steps of subsequent disposal of matrix material, but final step not necessarily.
(1) pre-treatment of carbon nanotube
At first, carbon nanotube (CNT) is carried out the hydrogen plasma pre-treatment.Its equipment is as shown in Figure 1.Sample table not only can be gone up and down, rotated, and can also heat.The distance of sample and plasma body can be controlled through lifting table, and the distance of sample table and top electrode is 10cm-50cm in the experiment, and temperature is a room temperature-1000 ℃.Can be to feed the pure hydrogen or the mixed gas of hydrogen and argon gas in the time of pre-treatment.To the hydrogen plasma soak time is 30min-3h.The used carbon nanotube of the present invention can or be bought and conveniently obtains through preparation.The volume percent of argon gas is 5%～30% in the mixed gas.
(2) preparation of matrix material
Carbon nanotube with after the aforesaid method processing is a matrix, adopts methods such as radio-frequency sputtering sedimentation, pulsed laser deposition, spraying cracking process, thermal evaporation, hydrothermal method to prepare Fe, Co, Ni, Cu, Si, Ag, Au, Ti, Zn, Al, Mg, Ta, Pd, Mo, Sn, Pt and oxide-based nanomaterial thereof.According to the control of experiment condition, can form metal or metal oxide nanoparticles and nano thin-film in carbon nano tube surface.
One of method is, adopts pulsed laser deposition, and target is selected high pure metal target or MOX target for use.Target is 40-50mm to substrate distance, and underlayer temperature is a room temperature-700 ℃, is evacuated to vacuum tightness>=10
-3More than the Pa, oxygen partial pressure is 10
-3-20Pa (metal oxide film).
Two of method is, adopts thermal evaporation, and being evacuated to vacuum tightness is 5 * 10
-3Pa or higher, 970 ℃ of tungsten filament temperature, carbon nanotube substrate does not heat.
Three of method is to adopt RF sputtering method to obtain above-mentioned film.Source metal adopts the disc of associated metal, is evacuated to 5 * 10
-3Pa or higher feeds rare gas element such as argon gas (metallic membrane), argon gas oxygen (metal oxide film); Flow is 10-100sccm; The question response room pressure is stabilized in to be opened radio-frequency power supply behind the 2-10Pa power is transferred to 100-400W, produces plasma body, and the plated film time is confirmed according to required film thickness.
Four of method is; Adopt the spraying cracking process; With 402 type ultrasonic atomizers will be by a certain percentage the atomizing of blended precursor solution, be that 99.99% nitrogen is done carrier gas the atomizing vapour of precursor is delivered to the needed sull of deposition on the substrate in the filming chamber by purity then.Through regulating flow rate of carrier gas and spraying gun power control film deposition rate,, at last sedimentary film sample is naturally cooled to room temperature through depositing time control film thickness.Underlayer temperature is a room temperature-400 ℃.
Five of method is that the employing hydrothermal method both was sealed in required reactant in the stainless steel cauldron of inner liner polytetrafluoroethylene, was placed in the constant temperature oven then.Temperature is indoor-120 ℃, and be 6h-240h storage period, volumetric ratio≤75% that reactant is shared.
(3) subsequent disposal
On above-mentioned two step bases, can the metal or the metal oxide/carbon nano-tube nano composite material of preparation be heat-treated in air or oxygen.Thermal treatment temp is 300-500 ℃, and pressure is 0.1-1Mpa, and the treatment time is 1-3 hour.
The inventive method major advantage is and can controls scantling, shape and the uniform distribution property that is precipitated out through simple control experiment condition, has technical process weak point, stable processing technique, characteristics that cost is low.Metal or metal oxide/carbon nano-tube nano composite material have the huge applications prospect in fields such as transmitter, nano electron device, superelevation magnetic storage, photochemical catalysis and energy storages.
Description of drawings
Fig. 1 is the pretreated setting drawing of carbon nanotube hydrogen plasma
Fig. 2 is the SEM figure of Ag/CNT
Fig. 3 shows the XRD figure of Ag/CNT matrix material.
Fig. 4 is the TEM figure of Ag/CNT
Fig. 5 is the SEM photo of the matrix material of vapor deposition Cu7min acquisition
Fig. 6 is the TEM photo of the matrix material of vapor deposition Cu7min acquisition
Fig. 7 is matrix material SEM photo behind the thermal treatment 2h in air that vapor deposition Cu7min forms
Fig. 8 is that matrix material low power behind the thermal treatment 2h in air that vapor deposition Cu7min forms is amplified the TEM photo.
Fig. 9 is a ZnO/CNT matrix material TEM photo
Figure 10 is ZnO and matrix material reflex blue photocatalytic degradation correlation curve thereof
Embodiment
Below through embodiment further illustrating substantive distinguishing features of the present invention and obvious improvement, but the present invention only is confined to embodiment by no means.
Embodiment 1:
Prepare carbon nanotube with chemical gas-phase method.With purified carbon nanotube in the radio-frequency sputtering cvd furnace with hydrogen plasma activation 1h.Then the carbon nanotube of dispersed deposition on Cu net grid is put in the thermal evaporation stove, adopts thermal evaporation, be evacuated to 5 * 10
-3Pa, the vapor deposition time is 2min.The Ag/CNT nano composite material of Ag nano particle that obtained surface deposition.Fig. 2, Fig. 3, Fig. 4 are respectively SEM photo, XRD figure and the TEM photos of Ag/CNT nano composite material.Experiment shows, has deposited the firm Ag nano particle of a large amount of combinations in carbon nano tube surface.
Embodiment 2:
The preparation of carbon nanotube and processing are with embodiment 1, with radio-frequency sputtering sedimentation depositing nano Cu on carbon nanotube.Target is selected high-purity Cu disc for use, is evacuated to 5 * 10
-3Pa feeds argon gas, and flow is 20sccm, and the question response room pressure is stabilized in to be opened radio-frequency power supply behind the 2Pa power is transferred to 200W, produces plasma body, and the plated film time is 7min.Take out sample after being cooled to room temperature, be placed on sample segment in the air and heat-treat, time 2h, thermal treatment temp is 400 ℃, condition is an air.
The Cu that Fig. 5, Fig. 6 obtain for vapor deposition 7min and the SEM photo and the TEM photo of carbon nano tube compound material.The result shows that the film wrapped of a large amount of Cu granulometric composition forms a kind of composite structure of cable type on the surface of carbon nanotube.When in air, behind the thermal treatment 2h, finding this material, formed CuO nanometer whiskers at the Cu of carbon nano tube surface particulate oxidation, thereby obtained special construction material as shown in Figure 8.
Embodiment 3:
With the carbon nanotube ultra-sonic dispersion after 15mg such as the embodiment 1 said hydrogen plasma activation in the absolute ethyl alcohol aqueous solution (volume ratio 1: 1) of 80ml; The acetic acid zinc solution (0.02mol/l) that adds 20ml; After magnetic stirred, the pH value that adds 50% ammoniacal liquor to solution was 8-11, fully stirs after-filtration; Solid phase is scattered in the 100ml water, with the pH value of ammoniacal liquor regulator solution.Above reactant is sealed in the reaction kettle of inner liner polytetrafluoroethylene, leaves standstill 10h at 200 ℃, be quickly cooled to room temperature then, product filters with deionized water wash, and is dry down in 80 ℃.Do not adding under the situation of carbon nanotube, preparing nano granular of zinc oxide with the above-mentioned acetic acid zinc solution of 10ml with identical process, like Fig. 9.Then the sample that makes has been carried out the experiment of reflex blue photocatalytic degradation, like Figure 10.The result shows; White light has certain Degradation to reflex blue, but efficient is very low, and the Zinc oxide particles degradation efficiency is higher; But As time goes on; Degradation process under Zinc oxide particles catalysis stops gradually, and Zinc oxide particles by contrast and carbon nano tube compound material but can still keep good catalytic activity in for a long time.
Claims (9)
1. the preparation method of metal or metal oxide/carbon nano-tube composite material is characterized in that adopting in following two kinds of methods any:
Method one:
(a) pre-treatment of carbon nanotube
At first, carbon nanotube being carried out radio frequency discharge hydrogen plasma etching processing, feed the pure hydrogen or the mixed gas of hydrogen and argon gas during pre-treatment, is 30min-3h to the hydrogen plasma soak time;
(b) preparation of matrix material
With the pretreated carbon nanotube of step a is matrix, adopts radio-frequency sputtering sedimentation, pulse to swash
Any method in light deposition method, spraying cracking process, thermal evaporation or the hydrothermal method prepares any simple substance and oxide-based nanomaterial thereof among Fe, Co, Ni, Cu, Si, Ag, Au, Ti, Zn, Al, Mg, Ta, Pd, Mo, Sn and the Pt, and forms simple substance or simple substance oxide nano particles or nano thin-film in carbon nano tube surface;
Method two:
(a) pre-treatment of carbon nanotube
At first, carbon nanotube being carried out radio frequency discharge hydrogen plasma etching processing, feed the pure hydrogen or the mixed gas of hydrogen and argon gas during pre-treatment, is 30min-3h to the hydrogen plasma soak time;
(b) preparation of matrix material
With the pretreated carbon nanotube of step a is matrix, adopts radio-frequency sputtering sedimentation, pulse to swash
Any method in light deposition method, spraying cracking process, thermal evaporation or the hydrothermal method prepares any simple substance and oxide-based nanomaterial thereof among Fe, Co, Ni, Cu, Si, Ag, Au, Ti, Zn, Al, Mg, Ta, Pd, Mo, Sn and the Pt, and forms simple substance or simple substance oxide nano particles or nano thin-film in carbon nano tube surface;
(c) subsequent disposal
To the metal or the metal oxide/carbon nano-tube nano composite material of step b preparation, in air or oxygen, to heat-treat, thermal treatment temp is 300-500 ℃, pressure is 0.1-1Mpa.
Source metal in the described radio-frequency sputtering deposition method adopts the corresponding metal disc, and being evacuated to vacuum tightness is 5 * 10
-3Pa or higher feeds rare gas element, opens radio-frequency power supply after the question response room pressure is stable, and power is transferred to 100-400W, produces plasma body, and the plated film time is confirmed according to required film thickness.
2. by the preparation method of described metal of claim 1 or metal oxide/carbon nano-tube composite material, the flow that it is characterized in that rare gas element is the 10-100 standard liter/min, and metallic membrane is used argon gas, and metal oxide film is used the argon gas oxygen.
3. by the preparation method of described metal of claim 1 or metal oxide/carbon nano-tube composite material, it is characterized in that reaction chamber internal gas pressure steady pressure is 2-10Pa.
4. press the preparation method of described metal of claim 1 or metal oxide/carbon nano-tube composite material; The target that it is characterized in that described pulsed laser deposition is corresponding high pure metal target or MOX target; Target is 40-50mm to substrate distance; Underlayer temperature is room temperature～700 ℃, and being evacuated to vacuum tightness is 5 * 10
-3Pa or higher.
5. by the preparation method of described metal of claim 1 or metal oxide/carbon nano-tube composite material, it is characterized in that suction is>=5 * 10 in the said thermal evaporation
-3Pa, the tungsten filament temperature is 970 ℃, carbon nanotube does not heat.
6. press the preparation method of described metal of claim 1 or metal oxide/carbon nano-tube composite material; It is characterized in that adopting the spraying cracking process; With ultrasonic atomizer blended precursor solution atomizing by a certain percentage; Be that 99.99% nitrogen is done carrier gas the atomizing vapour of precursor is delivered to the needed sull of deposition on the substrate in the filming chamber by purity then,, control film thickness through depositing time through regulating flow rate of carrier gas and spraying gun power control film deposition rate; At last sedimentary film sample is naturally cooled to room temperature, underlayer temperature is a room temperature to 400 ℃.
7. press the preparation method of described metal of claim 1 or metal oxide/carbon nano-tube composite material; It is characterized in that adopting hydrothermal method is that required reactant is sealed in the stainless steel cauldron that liner is a tetrafluoroethylene; Temperature of reaction is room temperature～120 ℃, and the time is 6h-24h.
8. by the preparation method of the described metal of claim 1 or metal oxide/carbon nano-tube composite material, it is characterized in that the percent by volume of hydrogen in the mixed gas of the described hydrogen of step a and argon gas in method one and the method two is 5%～30%.
9. by the preparation method of described metal of claim 1 or metal oxide/carbon nano-tube composite material, it is characterized in that the step c subsequent disposal time is 1～3 hour in the method two.
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