CN102220617A - Preparation method for titanium dioxide nanotube arrays in formamide-containing electrolyte - Google Patents
Preparation method for titanium dioxide nanotube arrays in formamide-containing electrolyte Download PDFInfo
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- CN102220617A CN102220617A CN 201110138431 CN201110138431A CN102220617A CN 102220617 A CN102220617 A CN 102220617A CN 201110138431 CN201110138431 CN 201110138431 CN 201110138431 A CN201110138431 A CN 201110138431A CN 102220617 A CN102220617 A CN 102220617A
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- methane amide
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Abstract
The invention relates to a preparation method for titanium dioxide nanotube arrays in a formamide-containing electrolyte. The method comprises the following steps of: sanding the surface of a titanium sheet with sandpaper, polishing with a chemical polishing liquid and drying; preparing the electrolyte from a fluoride used as the solute, a formamide aqueous solution used as the solvent and an alcohol additive, wherein the content of the fluoride is 0.3-0.8wt% of the electrolyte; and carrying out electrochemical anodic oxidation by using a two-electrode system electrolytic cell, the titanium sheet as the anode and a platinum sheet as the counter electrode to generate a layer of TiO2 nanotube array film on the surface of the titanium sheet. Compared with the electrolyte by using glycerol and water, the electrolyte containing formamide used to replace partial water limits the H<+> concentration in the electrolyte, reduces the ionic conductivity and reduces the chemical dissolution to the sidewalls of the nanotubes, thus acquiring the nanotubes with smaller aperture and thicker sidewalls.
Description
Technical field
The invention belongs to the Nano tube array of titanium dioxide preparing technical field, especially relate to a kind of method that in containing methane amide electrolytic solution, prepares Nano tube array of titanium dioxide.
Background technology
TiO
2Nanotube is compared TiO as a kind of important inorganic functional material
2Nanometer powder has bigger specific surface area and stronger adsorptive power, thereby show higher hydrogen-sensitivity, electricity conversion and photocatalysis performance, make it have immeasurable potential using value at aspects such as air-sensitive sensing material, solar cell, photochemical catalysis, attracted the extensive concern of various countries' researchers, a large amount of bibliographical informations relevant TiO
2The research of nanotube preparation and application facet thereof.
Present TiO
2The preparation method of nanotube comprises photoelectrochemistry etching, sol-gel, hydrothermal method, template and anonizing etc., anonizing in the wherein fluorine-containing electrolytic solution can easy, effectively be controlled the dimensions of nanotube, is present most widely used TiO
2The preparation method of nanotube.At TiO
2In the preparation process of nanotube, bath composition, pH value of solution value, oxidation voltage and oxidization time are to influence the nanotube length principal element.In aqueous electrolyte, dissociating of water is the key factor that initial hole forms in the anode oxidation process.In addition, oxidation voltage also is the important parameter that influences hole size.Though these factors have the obvious control effect to pipe range, caliber, to influence of wall thickness and not obvious.And scientist Paulose Maggie studies show that TiO
2The wall thickness of nanotube has important effect in the quick application facet of its hydrogen, and (Nanotechnology 2006,17,398-402) for Paulose M, et al.Therefore, the Nano tube array of titanium dioxide that how to prepare particular wall thickness is one of urgent problem.
Summary of the invention
Goal of the invention: the TiO that the present invention is directed to existing anonizing preparation
2The shortcoming of nano-tube array provides a kind of method of adding methane amide and then improving the wall thickness problem in electrolytic solution.This method can effectively increase TiO by the component content that changes in the electrolytic solution
2The wall thickness of nanotube.
Technical scheme: prepare the method for Nano tube array of titanium dioxide in containing methane amide electrolytic solution, preparation process is: with the titanium plate surface sand papering, and chemical brightening solution polishing, drying for standby; Preparation electrolytic solution: solute is a fluorochemical, content is the 0.3wt%～0.8wt% of electrolytic solution total mass, solvent is the methane amide aqueous solution, and adding alcohols additive, wherein the alcohols content of additive is 50%～80% of an electrolytic solution cumulative volume, and the content of methane amide is to be no more than 20% of electrolytic solution cumulative volume; Described fluorochemical is a Neutral ammonium fluoride; The alcohols additive is that glycerol is used two electrode system electrolyzers, and as anode, platinized platinum carries out electrochemical anodic oxidation as counter electrode with the titanium sheet, can generate one deck TiO at titanium plate surface
2Film of Nano tube array.
The titanium sheet simultaneously contacts electrolytic solution and contact area is a fixed, and two distance between electrodes are 4cm.
Chemical brightening solution is that volume ratio is HF: HNO
3: H
2O=1: 3: 5 solution.
Ultrasonic time is 30min～1.5h.
Anodised control voltage is 5～30V.
The anodised time is 30min～24h.
Beneficial effect: compared with prior art, the present invention has following characteristics:
Compare with the simple use glycerol and the electrolytic solution of water, add methane amide instead of part water after, limited H in the electrolytic solution
+Concentration, reduced ionic conductivity, weakened chemical dissolution, thereby can obtain smaller aperture due and thicker sidewall nanotube sidewall.
Description of drawings
Fig. 1 is the TiO of 1 preparation of embodiment among the present invention
2The stereoscan photograph of nano-tube array (a) is front elevation;
Fig. 2 is the TiO of 1 preparation of embodiment among the present invention
2The stereoscan photograph of nano-tube array (b) is side elevational view;
Fig. 3 is the TiO of 2 preparations of embodiment among the present invention
2The stereoscan photograph of nano-tube array (a) is front elevation;
Fig. 4 is the TiO of 2 preparations of embodiment among the present invention
2The stereoscan photograph of nano-tube array (b) is side elevational view;
Fig. 5 prepares TiO for used among the present invention at titanium sheet single face
2The electrolyzer synoptic diagram of nano-tube array.
Wherein 1 is electrolyzer, the 2nd, and screw knob, the 3rd, lead, lead are located in the screw knob, and screw knob is symmetrically set on the electrolyzer as electrode holder.
Embodiment
Following examples will the invention will be further described in conjunction with the accompanying drawings.
Titanium sheet (diameter is 17mm, thickness 0.5mm) arrives surperficial no marking with sand papering earlier before anodic oxidation, at nitration mixture HF: HNO
3: H
2O=1: soaked 5 minutes in 3: 5 (volume ratio), use the deionized water ultrasonic cleaning, nitrogen drying is stand-by.At room temperature, as counter electrode, get 50mL and contain electrolytic solution, apply the 20V anode voltage, in electrolyzer, carry out electrochemical anodic oxidation 3h with platinized platinum (purity 99.95%).Take out the sample deionized water rinsing, ultrasonic cleaning, drying.Electrolytic solution is formed and experiment condition sees table 1 for details.Fig. 1～2 are the TiO according to the condition preparation of table 1 embodiment 1
2Nano-tube array.
Table 1
Similar to Example 1, its difference is as having added formamide solvent in the electrolytic solution.At room temperature, as counter electrode, get 50mL and contain electrolytic solution, apply the 20V anode voltage, in electrolyzer, carry out electrochemical anodic oxidation 3h with platinized platinum (purity 99.95%).Take out sample deionized water ultrasonic cleaning, drying.The composition and the experiment condition of electrolytic solution see table 1 for details.Fig. 3～4 are the TiO according to the condition preparation of table 2 embodiment 2
2Nano-tube array.Find out obviously that from the data of Fig. 3～4 and table 1 length that adds the nano-tube array for preparing behind the methane amide in electrolytic solution increases to 2 μ m by 1.2 μ m, caliber is reduced to 60nm by 80nm, and wall thickness is increased to 14～15nm from 8～9nm, and wall thickness obtains significantly to increase.
From the contrast of the nano tube structure parameter of table 1 and Fig. 1～2, Fig. 3～4, can obviously draw methane amide to TiO
2The pipe range of nanotube, caliber, especially influence of wall thickness, under oxidation voltage and the identical situation of electrolysis time, adding the nanotube length for preparing behind the methane amide in electrolytic solution increases, and caliber reduces, and wall thickness increases.Because the methane amide bigger polar solvent that is specific inductivity after high polar methane amide instead of part water joins in the glycerol electrolytic solution, has been accelerated TiO
2The speed of growth of nanotube has also increased TiO
2The length of nanotube.Behind the methane amide instead of part water, limited the concentration of H+ in the electrolytic solution, reduced ionic conductivity, weakened chemical dissolution, thereby obtained smaller aperture due and thicker sidewall nanotube sidewall.Wall thickness is to TiO
2The quick effect of the hydrogen of nano-tube array has remarkably influenced.
The method that in containing methane amide electrolytic solution, prepares Nano tube array of titanium dioxide, preparation process is: with the titanium plate surface sand papering, chemical brightening solution polishing, drying for standby; Preparation electrolytic solution: solute is a fluorochemical, content is the 0.3wt%～0.8wt% of electrolytic solution total mass, solvent is the methane amide aqueous solution, and adding alcohols additive, wherein the alcohols content of additive is 50%～80% of an electrolytic solution cumulative volume, and the content of methane amide is to be no more than 20% of electrolytic solution cumulative volume; Described fluorochemical is a Neutral ammonium fluoride; The alcohols additive is that glycerol is used two electrode system electrolyzers, and as anode, platinized platinum carries out electrochemical anodic oxidation as counter electrode with the titanium sheet, can generate one deck TiO at titanium plate surface
2Film of Nano tube array.The titanium sheet simultaneously contacts electrolytic solution and contact area is a fixed, and two distance between electrodes are 4cm.Chemical brightening solution is that volume ratio is HF: HNO
3: H
2O=1: 3: 5 solution.Ultrasonic time is 30min～1.5h.Anodised control voltage is 5～30V.The anodised time is 30min～24h.
Claims (6)
1. the method for preparing Nano tube array of titanium dioxide in containing methane amide electrolytic solution is characterized in that preparation process is:
A. with the titanium plate surface sand papering, chemical brightening solution polishes, drying for standby;
B. prepare electrolytic solution: solute is a fluorochemical, content is the 0.3wt% ~ 0.8wt% of electrolytic solution total mass, solvent is the methane amide aqueous solution, and adding alcohols additive, wherein the alcohols content of additive is 50% ~ 80% of an electrolytic solution cumulative volume, and the content of methane amide is to be no more than 20% of electrolytic solution cumulative volume; Described fluorochemical is a Neutral ammonium fluoride; The alcohols additive is a glycerol;
C. use two electrode system electrolyzers, as anode, platinized platinum carries out electrochemical anodic oxidation as counter electrode with the titanium sheet, can generate one deck TiO at titanium plate surface
2Film of Nano tube array.
2. the described method for preparing Nano tube array of titanium dioxide in containing methane amide electrolytic solution according to claim 1 is characterized in that the titanium sheet simultaneously contacts electrolytic solution and contact area is a fixed, and two distance between electrodes are 4cm.
3. the described method for preparing Nano tube array of titanium dioxide in containing methane amide electrolytic solution according to claim 1 is characterized in that chemical brightening solution is that volume ratio is HF:HNO
3: H
2The solution of O=1:3:5.
4. the described method for preparing Nano tube array of titanium dioxide in containing methane amide electrolytic solution according to claim 1 is characterized in that ultrasonic time is 30min ~ 1.5h.
5. the described method for preparing Nano tube array of titanium dioxide in containing methane amide electrolytic solution according to claim 1 is characterized in that anodised control voltage is 5 ~ 30V.
6. the described method for preparing Nano tube array of titanium dioxide in containing methane amide electrolytic solution according to claim 1 is characterized in that the anodised time is 30min ~ 24h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106367794A (en) * | 2016-09-05 | 2017-02-01 | 南京理工大学 | Method for rapidly preparing ordered anodic titanium oxide nanotube array film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598075A (en) * | 2004-07-29 | 2005-03-23 | 大连理工大学 | Titanium dioxide nano tube electrode and its preparation process and application |
| CN101187043A (en) * | 2007-09-17 | 2008-05-28 | 西北有色金属研究院 | Preparation method for super long titanium dioxide nanotube array with photocatalytic performance |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598075A (en) * | 2004-07-29 | 2005-03-23 | 大连理工大学 | Titanium dioxide nano tube electrode and its preparation process and application |
| CN101187043A (en) * | 2007-09-17 | 2008-05-28 | 西北有色金属研究院 | Preparation method for super long titanium dioxide nanotube array with photocatalytic performance |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106367794A (en) * | 2016-09-05 | 2017-02-01 | 南京理工大学 | Method for rapidly preparing ordered anodic titanium oxide nanotube array film |
| CN106367794B (en) * | 2016-09-05 | 2018-07-31 | 南京理工大学 | A kind of quick method for preparing orderly anodic titanium dioxide nanotube array film |
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