CN102491263A - 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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- CN102491263A CN102491263A CN2011104547964A CN201110454796A CN102491263A CN 102491263 A CN102491263 A CN 102491263A CN 2011104547964 A CN2011104547964 A CN 2011104547964A CN 201110454796 A CN201110454796 A CN 201110454796A CN 102491263 A CN102491263 A CN 102491263A
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- vanadic anhydride
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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 the preparation method of a kind of nano-metal-oxide/titanium dioxide nanotube array composite material; Particularly a kind of accurate control nano-metal-oxide microscopic appearance, the method for load vanadic anhydride nano particle on titanium dioxide nanotube array.
Background technology
Titanium dioxide has broad application prospects at solar cell, sensor, lithium ion battery, the hydrogen manufacturing of photodestruciton water and aspects such as photocatalytic degradation atmosphere and water pollutant because of its unique physics, chemistry, photoelectric properties, receives widely paying close attention to.Particularly the titania nanotube prepared of anodizing has the structure of high orientation, big specific area and very strong ion-exchange or nano particle and embeds ability.But as a kind of environmental friendliness type material, also there are some defectives in titanium dioxide, mainly shows: (1), greater band gap (3.2eV); (2), photo-quantum efficiency is very low; (3), poorly conductive.For overcoming these shortcomings, many in recent years scientific researches group passes through TiO
2Nanotube and heavy metal, noble metal and oxide thereof form composite and improve the functional character of titania nanotube and enlarge its range of application.
Vanadic anhydride is widely used in a plurality of chemical fields as catalyst material commonly used in a kind of industry.Preparation vanadic anhydride/titania nanotube composite of being reported at present is primarily aimed in nano-particle material, and deposition vanadic anhydride nano particle does not but appear in the newspapers as yet on the titanium dioxide nanotube array of high-sequential.
Moreover compare traditional dc electrodeposition, therefore size, shape and decentralization that the pulse electrodeposition method can more effective regulation and control electro-deposition crystal grain can obtain densification, bright and uniform coating, and can save raw material.
This laboratory is used to make nanometer zinc/zinc/titanium dioxide nanotube array compound materials with the pulse electrodeposition method first through a large amount of tests; This method not only can be implemented on the titanium dioxide nanotube array zinc supported nano particle equably; The particle diameter of nano particle is controlled; Decentralization is high, and has advantages such as economical with materials, highly versatile.This has been applied for that on July 9th, 2010 patent No. is 201010221666.1 patent application.But; Because the structure of matter, the crystal formation difference of metallic zinc and metal oxide vanadic anhydride itself; It is different that metal, metal oxide carry out the 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 201010221666.1 said method controls; Duplicate fully or simply can't realize the vanadic anhydride nano particle is loaded on the titanium dioxide nanotube array uniformly at all, more can't accurately control the nano-metal-oxide microscopic appearance with reference to this method.
To above-mentioned deficiency; The inventor is through a large amount of contrast tests and summary; Dwindling and optimization experiment test procedure and test parameters repeatedly, the new material of having prepared load vanadic anhydride nano particle on the one-dimensional titanium dioxide nanotube array that anodizing is prepared of last success.
Summary of the invention
In view of this, the objective of the invention is to adopt impulse electrodeposition technology load vanadic anhydride nano particle on the one-dimensional titanium dioxide nanotube array that anodizing is prepared, improve the functional character of titania nanotube and enlarge its range of application.
The objective of the invention is to realize through following technical scheme: a kind of preparation method of 1-dimention nano titanium dioxide pipe array load vanadic anhydride nano particle new material may further comprise the steps:
A, be ultrasonic cleaning 5～15min respectively in 15～30% hydrochloric acid, absolute ethyl alcohol, the distilled water in volume fraction successively more than or equal to 99.6% titanium foil sheet, remove its oxide on surface purity;
B, the titanium foil sheet after cleaning dried be as anode, and platinized platinum places the HF solution of 0.05～0.3M, normal-temperature reaction 0.5～5h under the voltage of 5～30V as negative electrode; Form titanium dioxide nanotube array through this step;
C, with 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, consist of the VOSO of 0.1～0.2 mol/L at solute
46H
2In the O aqueous solution, with pH value of solution value use mass fraction earlier 98% H
2SO
4Be adjusted into 1.0～1.5, again with the titanium dioxide nanotube array (TiO behind the c one-step baking
2/ Ti) as working electrode, platinized platinum is as auxiliary electrode, and the Ag/AgCl electrode promptly adopts three-electrode system as reference electrode; Adopt the pulse electrodeposition method that the vanadic anhydride nano particle is carried on and obtain nanometer vanadic anhydride/titania nanotube composite on the titania nanotube; Wherein, the 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, the reaction temperature during d pace pulse electro-deposition is a room temperature, constantly stirs in the course of reaction, and mixing speed is 40～60 commentaries on classics/s;
Further, sintering temperature was 400～450 ℃ during C went on foot.
In addition, in this method, also can adopt two electrode systems during d pace pulse electro-deposition, with the titanium dioxide nanotube array (TiO behind the 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 impulse electrodeposition technology load vanadic anhydride nano particle on the one-dimensional titanium dioxide nanotube array that anodizing is prepared first, improves the functional character of titania nanotube and enlarges its range of application; In this composite, the vanadic anhydride nano particle is carried on the titanium dioxide nanotube array equably, the particle diameter of nano particle controlled (diameter 10～120nm), decentralization is high, and can economical with materials; This material can be applicable to many high-tech areas such as high performance catalyst, electrode material, ultracapacitor, photoelectrocatalysis.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further described;
The field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials that Fig. 1 obtains for embodiment 1;
The field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials that Fig. 2 obtains for embodiment 2;
The field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials that Fig. 3 obtains for embodiment 3;
The field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials that Fig. 4 obtains for embodiment 4;
The field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials that Fig. 5 obtains for embodiment 5;
The field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials that Fig. 6 obtains for embodiment 6;
The field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials that Fig. 7 obtains for embodiment 7;
The field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials that Fig. 8 obtains for embodiment 8;
The field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials that Fig. 9 obtains for embodiment 9;
The field emission microscope photo of vanadic anhydride/zinc/titanium dioxide nanotube array compound materials that Figure 10 obtains for 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 the vanadic anhydride/zinc/titanium dioxide nanotube array compound materials of the present invention's preparation.
The specific embodiment
Embodiment 1
After titanium foil sheet (purity 99.6%) removed the oxide on surface through abrasive paper for metallograph polishing, ultrasonic 10min respectively in 18% hydrochloric acid, absolute ethyl alcohol, the second distillation aqueous solution respectively was with further removal oxide on surface.Titanium foil sheet after cleaning dried is as anode, and platinized platinum is the HF solution that negative electrode places 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.Consist of the VOSO of 0.1mol/L at solute
46H
2In the O aqueous solution, earlier the pH value of solution value is used H
2SO
4(mass fraction 98%) is adjusted into 1.5.With the titanium dioxide nanotube array after the roasting as working electrode, platinized platinum as auxiliary electrode, Ag/AgCl under current control mode, adopts following pulse electrodeposition parameter: pulse anode current density 140mA/cm as reference electrode
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 are 40min.Reaction temperature is controlled at room temperature, and mixing speed is 40 commentaries on classics/s, promptly gets vanadic anhydride/zinc/titanium dioxide nanotube array compound materials.
Embodiment 2
After titanium foil sheet (purity 99.6%) removed the oxide on surface through abrasive paper for metallograph polishing, ultrasonic 10min respectively in 18% hydrochloric acid, absolute ethyl alcohol, the second distillation aqueous solution respectively was with further removal oxide on surface.Titanium foil sheet after cleaning dried is as anode, and platinized platinum is the HF solution that negative electrode places 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.Consist of the VOSO of 0.1mol/L at solute
46H
2In the O aqueous solution, earlier the pH value of solution value is used H
2SO
4(mass fraction 98%) is adjusted into 1.5.With the titanium dioxide nanotube array after the roasting as working electrode, platinized platinum as auxiliary electrode, 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 are 60min.Reaction temperature is controlled at room temperature, and mixing speed is 40 commentaries on classics/s, promptly gets vanadic anhydride/zinc/titanium dioxide nanotube array compound materials.
With reference to embodiment 2, electrolyte solution wherein consists of 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 are 20min, other conditions are constant.
With reference to embodiment 2, electrolyte solution wherein consists of 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 are 40min, other conditions are constant.
Embodiment 5
With reference to embodiment 2, electrolyte solution wherein consists of 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 are 60min, other conditions are constant.
Embodiment 6
With reference to embodiment 2, electrolyte solution wherein consists of 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 are 40min, other conditions are constant.
Embodiment 7
With reference to embodiment 2, electrolyte solution wherein consists of 0.1mol/L, pulse anode current density 70mA/cm
2, pulse cathode current density-70 mA/cm
2, turn-off time 1s, electrodeposition time are 60min, other conditions are constant.
Embodiment 8
With reference to embodiment 2, electrolyte solution wherein consists of 0.1mol/L, pulse anode current density 70mA/cm
2, pulse cathode current density-70 mA/cm
2, turn-off time 1s, electrodeposition time are 40min, other conditions are constant.
Embodiment 9
With reference to embodiment 2, electrolyte solution wherein consists of 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 are 60min, other conditions are constant.
Embodiment 10
With reference to embodiment 2, electrolyte solution wherein consists of 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 are 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, 2 θ equal 20.26 ° among the figure, and 26.12 ° and 31.00 ° is nanometer vanadic anhydride characteristic diffraction peak, and what load was described is the 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:
From table, can find out; Under the identical situation of other parameter conditions; Through 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 adopted this method to prepare nanometer vanadic anhydride/zinc/titanium dioxide nanotube array compound materials, surperficial vanadic anhydride nanoparticle size was 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 simultaneously and measure; Accompanying drawing 1 is in accompanying drawing 10; White or grizzled particle and floccule are the nanometer vanadic anhydride of load; Through comparing 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, the surface is uniformly distributed with nanometer vanadic anhydride particle or floccule, and decentralization is higher.
Explanation is at last; Above embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although with reference to preferred embodiment the present invention is specified, those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement technical scheme of the present invention; And not breaking away from the aim and the scope of technical scheme of the present invention, it all should be encompassed in the middle of the power claimed range of the present invention.
Claims (4)
1. the preparation method of a 1-dimention nano titanium dioxide pipe array load vanadic anhydride nano particle new material is characterized in that, may further comprise the steps:
A, be ultrasonic cleaning 5～15min respectively in 15～30% hydrochloric acid, absolute ethyl alcohol, the distilled water in volume fraction successively more than or equal to 99.6% titanium foil sheet, remove its oxide on surface purity;
B, the titanium foil sheet after cleaning dried be as anode, and platinized platinum places the HF solution of 0.05～0.3M, normal-temperature reaction 0.5～5h under the voltage of 5～30V as negative electrode; Form titanium dioxide nanotube array through this step;
C, with 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, consist of the VOSO of 0.1～0.2 mol/L at solute
46H
2In the O aqueous solution, with pH value of solution value use mass fraction earlier 98% H
2SO
4Be adjusted into 1.0～1.5, again with the titanium dioxide nanotube array (TiO behind the c one-step baking
2/ Ti) as working electrode, platinized platinum is as auxiliary electrode, and the Ag/AgCl electrode promptly adopts three-electrode system as reference electrode; Adopt the pulse electrodeposition method that the vanadic anhydride nano particle is carried on and obtain nanometer vanadic anhydride/titania nanotube composite on the titania nanotube; Wherein, the 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 pipe array load vanadic anhydride nano particle new material according to claim 1; It is characterized in that: the reaction temperature during d pace pulse electro-deposition is a room temperature; Constantly stir in the course of reaction, mixing speed is 40～60 commentaries on classics/s.
3. the preparation method of 1-dimention nano titanium dioxide pipe array load vanadic anhydride nano particle new material according to claim 2 is characterized in that: sintering temperature was 400～450 ℃ during C went on foot.
4. according to the preparation method of the arbitrary described 1-dimention nano titanium dioxide pipe array load vanadic anhydride nano particle new material of claim 1 to 3; It is characterized in that: also can adopt two electrode systems during d pace pulse electro-deposition, with the titanium dioxide nanotube array (TiO behind the c one-step baking
2/ Ti) as working electrode, platinized platinum is as auxiliary electrode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104807952A (en) * | 2015-05-11 | 2015-07-29 | 梧州市产品质量检验所 | Titanium dioxide purity detecting method |
| WO2020259423A1 (en) * | 2019-06-24 | 2020-12-30 | 上海海事大学 | Preparation method for doped vanadium dioxide microtube array, vanadium dioxide microtube array, and vanadium dioxide microtube |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101322943A (en) * | 2007-06-15 | 2008-12-17 | 南京大学 | Ti2O nano tube supported V2O5 composite catalyst |
| CN101613080A (en) * | 2009-07-23 | 2009-12-30 | 重庆大学 | A kind of method for preparing composite material for nanometer nickel/titanium dioxide nanotube array |
| CN101905863A (en) * | 2010-07-09 | 2010-12-08 | 重庆大学 | Method for preparing nanometer zinc/titanium dioxide nanotube array compound materials |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101322943A (en) * | 2007-06-15 | 2008-12-17 | 南京大学 | Ti2O nano tube supported V2O5 composite catalyst |
| CN101613080A (en) * | 2009-07-23 | 2009-12-30 | 重庆大学 | A kind of method for preparing composite material for nanometer nickel/titanium dioxide nanotube array |
| CN101905863A (en) * | 2010-07-09 | 2010-12-08 | 重庆大学 | Method for preparing nanometer zinc/titanium dioxide nanotube array compound materials |
Non-Patent Citations (2)
| Title |
|---|
| 《Electrochemistry Communications》 20110612 Yang Yang et al. Electrochromic properties of anodically grown mixed V2O5-TiO2 nanotubes 第1021-1025页 第13卷, * |
| YANG YANG ET AL.: "Electrochromic properties of anodically grown mixed V2O5–TiO2 nanotubes", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104807952A (en) * | 2015-05-11 | 2015-07-29 | 梧州市产品质量检验所 | Titanium dioxide purity detecting method |
| WO2020259423A1 (en) * | 2019-06-24 | 2020-12-30 | 上海海事大学 | Preparation method for doped vanadium dioxide microtube array, vanadium dioxide microtube array, and vanadium dioxide microtube |
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