CN102491263B - Method for preparing new vanadium pentoxide nanoparticle-loaded one-dimensional nano titanium dioxide tube array material - Google Patents
Method for preparing new vanadium pentoxide nanoparticle-loaded one-dimensional nano titanium dioxide tube array material Download PDFInfo
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- CN102491263B CN102491263B CN201110454796.4A CN201110454796A CN102491263B CN 102491263 B CN102491263 B CN 102491263B CN 201110454796 A CN201110454796 A CN 201110454796A CN 102491263 B CN102491263 B CN 102491263B
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Abstract
The invention provides a method for preparing a new vanadium pentoxide nanoparticle -loaded one-dimensional nano titanium dioxide tube array material. The method comprises the following steps of: a) cleaning a titanium foil; b) preparing a titanium dioxide nanotube array; c) roasting; and d) uniformly loading vanadium pentoxide nanoparticles. By the method, the one-dimensional titanium dioxide nanotube array prepared by an anode oxidation method is loaded with the vanadium pentoxide nanoparticles by a pulse electrodeposition technology for the first time, the functional properties of the titanium dioxide nanotube are improved and the application range of the titanium dioxide nanotube is widened; in the composite material, the vanadium pentoxide nanoparticles are uniformly loaded on the titanium dioxide nanotube array, and have controllable particle size (the diameter is 10-120nm) and high dispersibility, and materials can be saved; and the material can be applied to many high-tech fields such as high performance catalysts, electrode materials, super capacitors, photoelectrocatalysis and the like.
Description
Technical field
The present invention relates to a kind of preparation method of nano-metal-oxide/titanium dioxide nanotube array composite material, an accurate control nano-metal-oxide microscopic appearance particularly, the method for load vanadic anhydride nano particle on titanium dioxide nanotube array.
Background technology
Titanium dioxide, because of its unique physics, chemistry, photoelectric properties, has broad application prospects at aspects such as solar cell, sensor, lithium ion battery, the hydrogen manufacturing of photodestruciton water and photocatalytic degradation atmosphere and water pollutants, is paid close attention to widely.The titania nanotube that particularly anodizing is prepared has the structure of high orientation, large specific area and very strong ion-exchange or nano particle and embeds ability.But as a kind of environmental friendliness shaped material, also there are some defects in titanium dioxide, is mainly manifested in: (1), greater band gap (3.2eV); (2), photo-quantum efficiency is very low; (3), poorly conductive.For overcoming these shortcomings, the group of many scientific research in recent years passes through TiO
2nanotube and heavy metal, noble metal and oxide thereof form composite and improve the functional character of titania nanotube and expand its range of application.
Vanadic anhydride is widely used in a plurality of chemical fields as a kind of industrial conventional catalyst material.That reports at present prepares vanadic anhydride/titania nanotube composite mainly in nano-particle material, deposits vanadic anhydride nano particle and but there is not yet report on the titanium dioxide nanotube array of high-sequential.
Moreover compare traditional DC electrodeposition, size, shape and decentralization that pulse electrodeposition method can more effective regulation and control electro-deposition crystal grain, therefore can obtain densification, and light is coating uniformly, and can save raw material.
This laboratory by lot of experiments first by pulse electrodeposition method for the manufacture of Nano-Zinc/zinc/titanium dioxide nanotube array compound materials, the method not only can realize on titanium dioxide nanotube array zinc supported nano particle equably, the particle diameter of nano particle is controlled, decentralization is high, and there is saving material, the advantages such as highly versatile.This has been applied for to the patent application that the patent No. is 201010221666.1 on July 9th, 2010.But, the structure of matter, crystal formation difference due to metallic zinc and metal oxide vanadic anhydride itself, it is different that metal, metal oxide carry out process and the mechanism of electrochemical reaction separately, causing vanadic anhydride nano particle form, particle diameter, degree of scatter can not adopt the patent No. is that described in 201010221666.1, method is controlled, copy completely or simply with reference to the method, cannot realize at all vanadic anhydride nano particle is loaded on titanium dioxide nanotube array uniformly, more cannot accurately control nano-metal-oxide microscopic appearance.
For above-mentioned deficiency, inventor is by a large amount of contrast tests and summary, dwindling and Optimal Experimental test procedure and test parameters repeatedly, has finally successfully prepared the new material of load vanadic anhydride nano particle on the one-dimensional titanium dioxide nanotube array of preparing in anodizing.
Summary of the invention
In view of this, the object of the invention is to adopt load vanadic anhydride nano particle on the one-dimensional titanium dioxide nanotube array that impulse electrodeposition technology prepares in anodizing, improve the functional character of titania nanotube and expand its range of application.
The object of the invention is to be achieved through the following technical solutions: a kind of preparation method of 1-dimention nano titanium dioxide tube array load vanadic anhydride nano particle new material, comprises the following steps:
A, purity is more than or equal in hydrochloric acid that 99.6% titanium foil sheet is 15～30% in volume fraction successively, absolute ethyl alcohol, distilled water to ultrasonic cleaning 5～15min respectively, removes its oxide on surface;
B, the titanium foil sheet after cleaning is dried are as anode, and platinized platinum is placed in the HF solution of 0.05～0.3M, normal-temperature reaction 0.5～5h under the voltage of 5～30V as negative electrode; By this step, form titanium dioxide nanotube array;
C, by the titanium dioxide nanotube array (TiO of b step reaction gained
2/ Ti) roasting 1～5h in nitrogen atmosphere, sintering temperature is 300～600 ℃;
D, at solute, consist of the VOSO of 0.1～0.2 mol/L
46H
2in the O aqueous solution, the H that is first 98% by pH with mass fraction
2sO
4be adjusted into 1.0～1.5, then by the titanium dioxide nanotube array (TiO after c one-step baking
2/ Ti) as working electrode, platinized platinum is as auxiliary electrode, and Ag/AgCl electrode, as reference electrode, adopts three-electrode system; Adopt pulse electrodeposition method that vanadic anhydride nano particle is carried on and on titania nanotube, obtains nanometer vanadic anhydride/titania nanotube composite; Wherein, pulse electrodeposition method adopts current control mode, and pulse anode current density is 35～140mA/cm
2, pulse cathode current density is 35～140mA/cm
2, negative electrode and anodic current density equate, anodic pulse ON time 8～14ms, cathode pulse ON time 1～4ms, turn-off time 0.1～1s, electrodeposition time 20～60min.
Further, reaction temperature during d pace pulse electro-deposition is room temperature, in course of reaction, constantly stirs, and mixing speed is 40～60 turn/s;
Further, in C step, sintering temperature is 400～450 ℃.
In addition, in the method, during d pace pulse electro-deposition, also can adopt two electrode systems, with the titanium dioxide nanotube array (TiO after c one-step baking
2/ Ti), as working electrode, platinized platinum is as auxiliary electrode.
The invention has the beneficial effects as follows: the present invention adopts load vanadic anhydride nano particle on the one-dimensional titanium dioxide nanotube array that impulse electrodeposition technology prepares in anodizing first, improve the functional character of titania nanotube and expand its range of application; In this composite, vanadic anhydride nano particle is carried on titanium dioxide nanotube array equably, the particle diameter of nano particle controlled (diameter 10～120nm), and decentralization is high, and can save material; This material can be applicable to many high-tech areas such as high performance catalyst, electrode material, ultracapacitor, photoelectrocatalysis.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described;
Fig. 1 is the field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials of obtaining of embodiment 1;
Fig. 2 is the field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials of obtaining of embodiment 2;
Fig. 3 is the field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials of obtaining of embodiment 3;
Fig. 4 is the field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials of obtaining of embodiment 4;
Fig. 5 is the field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials of obtaining of embodiment 5;
Fig. 6 is the field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials of obtaining of embodiment 6;
Fig. 7 is the field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials of obtaining of embodiment 7;
Fig. 8 is the field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials of obtaining of embodiment 8;
Fig. 9 is the field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials of obtaining of embodiment 9;
Figure 10 is the field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials of obtaining of embodiment 10;
Figure 11 is not for implementing the 4th) the field emission microscope photo of the titanium dioxide nanotube array material that obtains of step;
Figure 12 is the X-ray diffractogram of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials of preparing of the present invention.
The specific embodiment
Embodiment 1
By titanium foil sheet (purity 99.6%), after surperficial oxide is removed in abrasive paper for metallograph polishing, ultrasonic 10min respectively in 18% hydrochloric acid, absolute ethyl alcohol, the second distillation aqueous solution respectively, further to remove oxide on surface.Titanium foil sheet after cleaning is dried is as anode, and platinized platinum is the HF solution that negative electrode is placed in 0.15M, and under the voltage of 20V, normal-temperature reaction 1.75h, forms titanium dioxide nanotube array.Follow 450 ℃ of roasting 3h in nitrogen.At solute, consist of the VOSO of 0.1mol/L
46H
2in the O aqueous solution, first by pH H
2sO
4(mass fraction 98%) is adjusted into 1.5.The titanium dioxide nanotube array of usining after roasting is as working electrode, platinized platinum as auxiliary electrode, and Ag/AgCl, as reference electrode, under current control mode, adopts following pulse electrodeposition parameter: pulse anode current density 140mA/cm
2, pulse cathode current density-140 mA/cm
2, anodic pulse ON time 8ms, cathode pulse ON time 2ms, turn-off time 0.1s, electrodeposition time is 40min.Reaction temperature is controlled at room temperature, and mixing speed is 40 turn/s, obtains vanadic anhydride/zinc/titanium dioxide nanotube array compound materials.
Embodiment 2
By titanium foil sheet (purity 99.6%), after surperficial oxide is removed in abrasive paper for metallograph polishing, ultrasonic 10min respectively in 18% hydrochloric acid, absolute ethyl alcohol, the second distillation aqueous solution respectively, further to remove oxide on surface.Titanium foil sheet after cleaning is dried is as anode, and platinized platinum is the HF solution that negative electrode is placed in 0.15M, and under the voltage of 20V, normal-temperature reaction 1.75h, forms titanium dioxide nanotube array.Follow 450 ℃ of roasting 3h in nitrogen.At solute, consist of the VOSO of 0.1mol/L
46H
2in the O aqueous solution, first by pH H
2sO
4(mass fraction 98%) is adjusted into 1.5.The titanium dioxide nanotube array of usining after roasting is as working electrode, platinized platinum as auxiliary electrode, and Ag/AgCl is as reference electrode.Under current control mode, adopt following pulse electrodeposition parameter: pulse anode current density 35mA/cm
2, pulse cathode current density-35 mA/cm
2, anodic pulse ON time 8ms, cathode pulse ON time 2ms, turn-off time 0.5s, electrodeposition time is 60min.Reaction temperature is controlled at room temperature, and mixing speed is 40 turn/s, obtains vanadic anhydride/zinc/titanium dioxide nanotube array compound materials.
With reference to embodiment 2, electrolyte solution compositions is wherein 0.2mol/L, pulse anode current density 140mA/cm
2, pulse cathode current density-140 mA/cm
2, turn-off time 0.5s, electrodeposition time is 20min, other conditions are constant.
With reference to embodiment 2, electrolyte solution compositions is wherein 0.1mol/L, pulse anode current density 70mA/cm
2, pulse cathode current density-70 mA/cm
2, turn-off time 0.1s, electrodeposition time is 40min, other conditions are constant.
Embodiment 5
With reference to embodiment 2, electrolyte solution compositions is wherein 0.1mol/L, pulse anode current density 140mA/cm
2, pulse cathode current density-140 mA/cm
2, turn-off time 0.1s, electrodeposition time is 60min, other conditions are constant.
Embodiment 6
With reference to embodiment 2, electrolyte solution compositions is wherein 0.2mol/L, pulse anode current density 70mA/cm
2, pulse cathode current density-70 mA/cm
2, turn-off time 0.1s, electrodeposition time is 40min, other conditions are constant.
Embodiment 7
With reference to embodiment 2, electrolyte solution compositions is wherein 0.1mol/L, pulse anode current density 70mA/cm
2, pulse cathode current density-70 mA/cm
2, turn-off time 1s, electrodeposition time is 60min, other conditions are constant.
With reference to embodiment 2, electrolyte solution compositions is wherein 0.1mol/L, pulse anode current density 70mA/cm
2, pulse cathode current density-70 mA/cm
2, turn-off time 1s, electrodeposition time is 40min, other conditions are constant.
Embodiment 9
With reference to embodiment 2, electrolyte solution compositions is wherein 0.2mol/L, pulse anode current density 35mA/cm
2, pulse cathode current density-35 mA/cm
2, turn-off time 0.1s, electrodeposition time is 60min, other conditions are constant.
Embodiment 10
With reference to embodiment 2, electrolyte solution compositions is wherein 0.1mol/L, pulse anode current density 70mA/cm
2, pulse cathode current density-70 mA/cm
2, turn-off time 0.5s, electrodeposition time is 20min, other conditions are constant.
Accompanying drawing 12 is the X-ray diffractogram of the nanometer vanadic anhydride/zinc/titanium dioxide nanotube array compound materials of embodiment 5 preparations.As shown in the figure, in figure, 2 θ equal 20.26 °, and 26.12 ° and 31.00 ° is nanometer vanadic anhydride characteristic diffraction peak, and what load was described is vanadic anhydride nano particle.
Following table is the vanadic anhydride nano particle load TiO that different preparation parameters (embodiment 1-10) obtain different size
2nanotube array:
As can be seen from the table, in the situation that other Parameter Conditions are identical, by changing turn-off time and sedimentation time, can change the size of the vanadic anhydride nano particle of gained nanometer vanadic anhydride/zinc/titanium dioxide nanotube array compound materials surface institute load, when therefore explanation adopts this method to prepare nanometer vanadic anhydride/zinc/titanium dioxide nanotube array compound materials, surperficial vanadic anhydride nanoparticle size is controlled.
In addition, accompanying drawing 11 is the field emission microscope photo of the titanium dioxide nanotube array material of not loaded with nano vanadic anhydride particle.Utilize field emission scanning electron microscope to observe with the zinc/titanium dioxide nanotube array compound materials that adopts method of the present invention to carry out nanometer vanadic anhydride particulate load the titanium dioxide nanotube array material that does not adopt method of the present invention to carry out nanometer vanadic anhydride particulate load, and carry out microscopic dimensions measurement simultaneously, accompanying drawing 1 is in accompanying drawing 10, white or grizzled particle and floccule are the nanometer vanadic anhydride of load, by contrasting with accompanying drawing 11, obviously can find out the nanometer vanadic anhydride/zinc/titanium dioxide nanotube array compound materials that adopts method system of the present invention, surface uniform be distributed with nanometer vanadic anhydride particle or floccule, and decentralization is higher.
Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of power claimed range of the present invention.
Claims (4)
1. a preparation method for 1-dimention nano titanium dioxide tube array load vanadic anhydride nano particle new material, is characterized in that, comprises the following steps:
A, purity is more than or equal in hydrochloric acid that 99.6% titanium foil sheet is 15～30% in volume fraction successively, absolute ethyl alcohol, distilled water to ultrasonic cleaning 5～15min respectively, removes its oxide on surface;
B, the titanium foil sheet after cleaning is dried are as anode, and platinized platinum is placed in the HF solution of 0.05～0.3M, normal-temperature reaction 0.5～5h under the voltage of 5～30V as negative electrode; By this step, form titanium dioxide nanotube array;
C, by the titanium dioxide nanotube array (TiO of b step reaction gained
2/ Ti) roasting 1～5h in nitrogen atmosphere, sintering temperature is 300～600 ℃;
D, at solute, consist of the VOSO of 0.1～0.2 mol/L
46H
2in the O aqueous solution, the H that is first 98% by pH with mass fraction
2sO
4be adjusted into 1.0～1.5, then by the titanium dioxide nanotube array (TiO after c one-step baking
2/ Ti) as working electrode, platinized platinum is as auxiliary electrode, and Ag/AgCl electrode, as reference electrode, adopts three-electrode system; Adopt pulse electrodeposition method that vanadic anhydride nano particle is carried on and on titania nanotube, obtains nanometer vanadic anhydride/titania nanotube composite; Wherein, pulse electrodeposition method adopts current control mode, and pulse anode current density is 35～140mA/cm
2, pulse cathode current density is 35～140mA/cm
2, negative electrode and anodic current density equate, anodic pulse ON time 8～14ms, cathode pulse ON time 1～4ms, turn-off time 0.1～1s, electrodeposition time 20～60min.
2. the preparation method of 1-dimention nano titanium dioxide tube array load vanadic anhydride nano particle new material according to claim 1, it is characterized in that: reaction temperature during d pace pulse electro-deposition is room temperature, in course of reaction, constantly stir, mixing speed is 40～60 turn/s.
3. the preparation method of 1-dimention nano titanium dioxide tube array load vanadic anhydride nano particle new material according to claim 2, is characterized in that: in C step, sintering temperature is 400～450 ℃.
4. a preparation method for 1-dimention nano titanium dioxide tube array load vanadic anhydride nano particle new material, is characterized in that, comprises the following steps:
A, purity is more than or equal in hydrochloric acid that 99.6% titanium foil sheet is 15～30% in volume fraction successively, absolute ethyl alcohol, distilled water to ultrasonic cleaning 5～15min respectively, removes its oxide on surface;
B, the titanium foil sheet after cleaning is dried are as anode, and platinized platinum is placed in the HF solution of 0.05～0.3M, normal-temperature reaction 0.5～5h under the voltage of 5～30V as negative electrode; By this step, form titanium dioxide nanotube array;
C, by the titanium dioxide nanotube array (TiO of b step reaction gained
2/ Ti) roasting 1～5h in nitrogen atmosphere, sintering temperature is 300～600 ℃;
D, at solute, consist of the VOSO of 0.1～0.2 mol/L
46H
2in the O aqueous solution, the H that is first 98% by pH with mass fraction
2sO
4be adjusted into 1.0～1.5, then by the titanium dioxide nanotube array (TiO after c one-step baking
2/ Ti), as working electrode, platinized platinum, as auxiliary electrode, adopts two electrode systems; Adopt pulse electrodeposition method that vanadic anhydride nano particle is carried on and on titania nanotube, obtains nanometer vanadic anhydride/titania nanotube composite; Wherein, pulse electrodeposition method adopts current control mode, and pulse anode current density is 35～140mA/cm
2, pulse cathode current density is 35～140mA/cm
2, negative electrode and anodic current density equate, anodic pulse ON time 8～14ms, cathode pulse ON time 1～4ms, turn-off time 0.1～1s, electrodeposition time 20～60min.
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| CN201110454796.4A CN102491263B (en) | 2011-12-30 | 2011-12-30 | Method for preparing new vanadium pentoxide nanoparticle-loaded one-dimensional nano titanium dioxide tube array material |
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