CN1995494A - Anode oxidation method for preparing one-dimensional titanium dioxide array film - Google Patents

Abstract

The invention discloses a making method one-dimensional titanium oxide array film through anode oxidizing method, which comprises the following steps: (1) dissolving 0.5wt%NH4F in the 44ml water; stirring evenly; adding 176ml glycerol; adjusting pH value to 4. 5-5. 0 through H2SO4; stirring 1h; obtaining stable transparent solution; (2) making cleaned Ti piece as anode and Pt piece as cathode; adding DC under indoor temperature to oxidize under 20V for 8h; fetching Ti piece; cleaning through deionized water; obtaining film material.

Description

Anonizing prepares the method for one-dimensional titanium dioxide array film

Technical field

The invention relates to the method for preparing titanium dioxide array film, relate in particular to the method that anonizing prepares one-dimensional titanium dioxide array film.

Background technology

Titanium dioxide (TiO ₂) be a kind of important wide bandgap semiconductor functional materials, band gap width is 3.0eV (rutile) and 3.2eV (anatase octahedrite) under the room temperature, has wide practical use at photoelectric field, adds that raw material resources is abundant, low price, toxicological harmless is to study focus in recent years in the world.Because one dimension TiO ₂The array nano material has unique photoelectric property and it is with a wide range of applications at aspects such as photochemical catalysis, gas sensor, solar cells.

Prepare high quality TiO at present ₂The method that nano-array adopted mainly contains hydrothermal method, template, solvent-thermal method, anonizing etc.In these methods, hydrothermal method need be than complex apparatus, higher temperature, higher pressure, be not suitable for the large-area preparation film, template causes the destruction of subsiding of film and rod easily in the process of removing template, the film of large-area preparation homogeneous also has difficulties, and solvent-thermal method prepares TiO ₂Film efficient is low, and film is fine and close, and specific surface is less.Anonizing is compared with other method, and equipment is simple, and the reaction conditions gentleness need not catalyzer, and environmental friendliness is large-area preparation one dimension TiO ₂The Perfected process of ordered structure.The originator V.Zwi11ing of this method has early reported to be entitled as in Britain's periodical " Surf.Interface Anal " (surface and interface analysis) 27 phases in 1999 and has used this method " Structure and Physicochemistry of AnodicOxide Films on Titanium and TA6V Alloy " (structure and the physical chemistry of titanium and TA6V alloy anode sull) in and prepare nano-tube array, the CrO of employing 0.5mol/l ₃Or the CrO of 0.5mol/l ₃With the HF mixing solutions of 0.095mol/l be ionogen, adjust pH to 2, adopt two electrode system oxidations, can on the Ti sheet, prepare nanoporous.

The subject matter that anonizing exists at present is: be ionogen with the glyceryl, can significantly increase anodic oxidation TiO ₂The length of nanotube, but along with the increase of oxidization time, when nanotube length increased, the roughness at nano-tube array top increased, and this is quite disadvantageous nano-tube array being applied to little assembling.Therefore, the TiO for preparing nanometer grade diameter with high growth velocity ₂The planeness of improving the nano-tube array top in the time of array is very significant.

Summary of the invention

For overcoming the shortcoming for preparing the roughness increase at nano-tube array top with the glyceryl for the ionogen anodic oxidation, the present invention adopts H first ₂SO ₄Adjust electrolytical pH value, change the corrosion dissolution character of electrolytic solution, provide a kind of and can control the roughness at nano-tube array top, anodic oxidation Ti sheet, preparation at room temperature has the TiO of smooth top ₂But nano-tube array, while are also improved method its speed of growth, the simple scale production of technology.

The present invention is achieved by the following technical programs.

(1) under agitation condition, with 0.5wt%NH ₄F is dissolved in the 44ml water, after stirring, adds glycerol 176ml, uses H ₂SO ₄Adjusting the pH value is 4.5～5.0, then mixing solutions is stirred 1h.Obtain stable clear solution.

(2) will do anode through the Ti sheet that cleans, the Pt sheet is done negative electrode, adds direct current 20V oxidation under the room temperature after 8 hours, and the Ti sheet is taken out, and after washed with de-ionized water, can obtain 1-dimention nano TiO ₂The thin-film material of array.

Described step (1) use H ₂SO ₄Adjusting the pH value is 5.0.

The invention has the beneficial effects as follows, in full-bodied glycerol (glycerine) base electrolyte solution, add H ₂SO ₄Adjust the pH value, effectively suppressed local H ⁺The phenomenon that density unevenness is even, and improved electrolytical ionic conductance, compare with the ionogen of not adjusting the pH value, the planeness at nanotube top improves greatly, also improved simultaneously the speed of growth of nanotube, this method preparation technology is easy to control, can realize cheap scale operation.

Description of drawings

Fig. 1: the TiO that is prior art ₂The electron scanning micrograph figure on nano-tube array surface;

Fig. 2: be that the pH value is 5.0 o'clock TiO ₂The electron scanning micrograph figure on nano-tube array surface;

Fig. 3: be that the pH value is 4.5 o'clock TiO ₂The electron scanning micrograph figure on nano-tube array surface.

Embodiment

Under agitation condition, with chemical pure NH ₄F is dissolved in the water, and after stirring, adds chemical pure glycerol (glycerine), uses H ₂SO ₄Adjust the pH value, then mixing solutions is stirred 1h.Obtain stable clear solution.

To do anode through the Ti sheet that cleans, the Pt sheet is done negative electrode, add direct current 20V oxidation 8h under the room temperature after, the Ti sheet is taken out, after washed with de-ionized water, can obtain 1-dimention nano TiO ₂The thin-film material of array.

The preparing craft of specific embodiment sees table 1 for details.

Table 1

NQ	NH 4F	H 2O(ml)	Glycerol (ml)	pH(H 2SO 4)	The mixing solutions churning time	Oxidation voltage (V)	Reaction times
								1#	0.5wt％	44	176	-	1h	20	8h
2#	0.5wt％	44	176	5.0	1h	20	8h
								3#	0.5wt％	44	176	4.5	1h	20	8h

Gained 1-dimention nano TiO ₂The relevant numerical value of array film sees Table 2.

Table 2

	The average tube internal diameter	The average tube wall thickness	Average tube length
				1#	80nm	20nm	950nm
2#	80nm	20nm	1000nm
				3#	80nm	20nm	930nm

By accompanying drawing and table two as can be seen, the TiO of prior art ₂The top of nanotube is uneven, as shown in Figure 1.Add H ₂SO ₄Adjust the pH value, the TiO that obtains ₂The electron scanning micrograph on nano-tube array surface, as shown in Figure 2, when the pH value of solution value was 5.0, the planeness at nanotube top improved greatly, and nanotube length also increases to 1000nm by 950nm.When using H ₂SO ₄Adjusting the pH value of solution value is 4.5 o'clock, and as shown in Figure 3, the planeness at nanotube top is improved equally, but nanotube length increase not significantly (950nm is to 930nm).

Add H ₂SO ₄After, film is by the TiO perpendicular to substrate surface ₂Pipe constitutes, and excellent size is regular, and the planeness at nanotube top increases, and the speed of growth is not adjusted speed under the pH value condition relatively and increased (by the contrast of the average tube length of embodiment in the table 21 and 2 as can be seen).

Claims (2)

1. an anonizing prepares the method for one-dimensional titanium dioxide array film, it is characterized in that, comprises the steps:

(1) under agitation condition, 0.5wt%NH4F is dissolved in the 44ml water, after stirring, add glycerol 176ml, use H ₂SO ₄Adjusting the pH value is 4.5～5.0, then mixing solutions is stirred 1h, obtains stable clear solution;

(2) will do anode through the Ti sheet that cleans, the Pt sheet is done negative electrode, adds direct current 20V oxidation under the room temperature after 8 hours, and the Ti sheet is taken out, and after washed with de-ionized water, can obtain 1-dimention nano TiO ₂The thin-film material of array.

2. prepare the method for one-dimensional titanium dioxide array film according to the anonizing of claim 1, it is characterized in that, described step (1) use H ₂SO ₄Adjusting the pH value is 5.0.