CN104032292B - A kind of method preparing anatase titania nano-band array film - Google Patents
A kind of method preparing anatase titania nano-band array film Download PDFInfo
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- CN104032292B CN104032292B CN201410256351.9A CN201410256351A CN104032292B CN 104032292 B CN104032292 B CN 104032292B CN 201410256351 A CN201410256351 A CN 201410256351A CN 104032292 B CN104032292 B CN 104032292B
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Abstract
The method preparing anatase titania nano-band array film disclosed by the invention, employing be non-hydrothermal deposition method, the steps include: metallic titanium plate after pickling to be immersed in be added with in the hydrogen peroxide reaction solution of trimeric cyanamide and wolframic acid, 60 ~ 90
oreact 6 ~ 60 hours under C, reacted titanium plate deionized water rinsing, dry, 450
oc is incubated 1 hour.The present invention is without the need to the thermal and hydric environment of High Temperature High Pressure, syntheti c route is simple and easy to do, cost is low, the anatase titania nano-band array film of preparation evenly, well-crystallized, be combined firmly with matrix, be applicable to large-scale industrial production, be expected to obtain practical application in fields such as photochemical catalysis, photoelectrocatalysis and thin-film solar cell photoelectric poles.
Description
Technical field
The present invention relates to a kind of preparation method of titanium dioxide nano-belts array film, be specifically related to a kind of non-hydrothermal deposition method of anatase titania nano-band array film.
Background technology
Titanium deoxid film has a wide range of applications in fields such as photochemical catalysis, photoelectrocatalysis, solar cell, electrochromism, gas sensors.Research shows, the pattern of titanium dioxide is for its performance important, and therefore, the research preparing the titanium dioxide nano material of special appearance is in widespread attention.So far, the pattern prepared has nanotube, nano wire, nanometer rod, nanometer sheet, nano flower, tiny balloon etc., and relatively less to the research of nano belt.Nano belt has the sheet structure compared with aspect ratio, and its size characteristic, between one-dimensional nano line and two-dimensional nano sheet, has been taken into account the advantage of electronics fast transport characteristic that 1-dimention nano line structure has and two-dimensional nano sheet bigger serface, had application prospect.
The main alkali thermal technology that adopts prepares nano belt structure titanium dioxide, at high temperature (150 ~ 250 at present
oin the hydrothermal reaction kettle of C) high pressure, titanium metal or titania nanoparticles and high density (5 ~ 10 mol/L) sodium hydroxide solution are reacted and obtains sodium titanate nano belt, then carry out repeatedly pickling (proton exchange) and obtain hydrogen metatitanic acid, last thermal treatment converts titanium dioxide nano-belts to.The method needs high temperature and high pressure environment, and energy consumption is large, and environment friendly is poor, and there is larger potential safety hazard, industrialization cost is higher.Patent of invention CN101306839A discloses a kind of method utilizing method of electrostatic spinning to prepare titanium dioxide nano-belts, but the titanium source that the method uses is Titanium alkoxides, facile hydrolysis; Need the mixture introducing polymethylmethacrylate (PMMA) and polyvinylpyrrolidone (PVP) as chelating polymer template; Simultaneously higher to equipment requirements.So far, also do not have a kind of simple, without the need to the method preparing titanium dioxide nano-belts array film of template.
Summary of the invention
The object of this invention is to provide a kind of process simple, without the method preparing anatase titania nano-band array film of template, low cost.
The method preparing anatase titania nano-band array film of the present invention, employing be non-hydrothermal deposition method, its concrete steps are as follows:
1) by mass percent concentration be 50 ~ 55% hydrofluoric acid, mass percent concentration be 65 ~ 68% nitric acid and deionized water by volume 1:3:6 mix, obtain pickle solution;
2) at mass percent concentration be 30% hydrogen peroxide solution in add the trimeric cyanamide of 0.0024 mol/L and the wolframic acid of 0.004 ~ 0.04 mol/L, obtain reaction solution.
3) metallic titanium plate after surface acid-washing is immersed in step 2) reaction solution in, 60 ~ 90 times reaction 6 ~ 60 hours;
4) reacted titanium plate washed with de-ionized water, after drying, 450
oc thermal treatment 1 hour.
The present invention, can the pH value of synchronization modulation reaction system and the growth dimension of crystal by changing the addition of wolframic acid, realizes the deposition of titanium dioxide nano-belts array film under non-thermal and hydric environment.
In preparation process, the nano-band array film before thermal treatment is hydrogen metatitanic acid, obtains through Overheating Treatment the titanium dioxide nano-belts structure that crystalline structure is anatase octahedrite.Anatase titania nano-band array mean length is 200 ~ 380 nanometers, and width average is 35 ~ 60 nanometers, and long-width ratio is approximately 5 ~ 7, and thickness is about 10 nanometers.
The inventive method big area can prepare anatase titania nano-band array film, and without the need to template, process is simple, and reproducible, cost is low, low for equipment requirements, gained film evenly, well-crystallized, to be combined firmly with substrate.Have a wide range of applications in various fields such as photochemical catalysis, photoelectrocatalysis, thin-film solar cells, gas sensor, biomaterials.
Accompanying drawing explanation
Fig. 1 is the high power field emission scanning electron microscope picture covering the titanium dioxide nano-belts film of titanium plate surface prepared by embodiment 1;
Fig. 2 is the X-ray diffractogram of the titanium sheet of surface coverage titanium dioxide nano-belts array film prepared by embodiment 1, in X-ray diffractogram, and A: anatase octahedrite, R: rutile, Ti: titanium;
Fig. 3 is the high power field emission scanning electron microscope picture covering the titanium dioxide nano-belts film of titanium plate surface prepared by embodiment 2;
Fig. 4 is the high power field emission scanning electron microscope picture covering the titanium dioxide nano-belts film of titanium plate surface prepared by embodiment 3;
Fig. 5 is the high power field emission scanning electron microscope picture covering the titanium dioxide nano-belts film of titanium plate surface prepared by embodiment 4;
Fig. 6 is the high power field emission scanning electron microscope picture covering the titanium dioxide nano-belts film of titanium plate surface prepared by embodiment 5.
Embodiment
Set forth the present invention further below in conjunction with embodiment, but the present invention is not only confined to following embodiment.
Embodiment 1
1) by mass percent concentration be 55% hydrofluoric acid, mass percent concentration be that the ratio of nitric acid and the deionized water 1:3:6 by volume of 65% mixes, obtain pickle solution;
2) be in the hydrogen peroxide solution of 30%, add the trimeric cyanamide of 0.0024 mol/L and the wolframic acid of 0.04 mol/L at 50 milliliters of mass percent concentrations, obtain reaction solution;
3) 5 × 5 × 0.01(cm will be of a size of
3) pickling metal titanium plate with after pickle solution pickling, then cleans up in ultrasonic wave with deionized water.The metallic titanium plate cleaned up is immersed in the reaction solution of 50 milliliters, 90
oreact 60 hours under C;
4) reacted titanium plate washed with de-ionized water, after drying, 450
oc thermal treatment 1 hour.
Reaction result
Titanium plate surface uniform generates titanium dioxide nano-belts film as shown in Figure 1, and the width average of nano belt is about 55 nanometers, and mean length is about 380 nanometers, and long-width ratio is about 6, and mean thickness is about 15 nanometers.The crystalline structure that Fig. 2 shows nano-band array is mainly Anatase, containing a small amount of Rutile Type, and well-crystallized.
Embodiment 2
1) by mass percent concentration be 55% hydrofluoric acid, mass percent concentration be that the ratio of nitric acid and the deionized water 1:3:6 by volume of 65% mixes, obtain pickle solution;
2) be in the hydrogen peroxide solution of 30%, add the trimeric cyanamide of 0.0024 mol/L and the wolframic acid of 0.004 mol/L at 50 milliliters of mass percent concentrations, obtain reaction solution;
3) 5 × 5 × 0.01(cm will be of a size of
3) pickling metal titanium plate with after pickle solution pickling, then cleans up in ultrasonic wave with deionized water.The metallic titanium plate cleaned up is immersed in the reaction solution of 50 milliliters, 60
oreact 12 hours under C;
4) reacted titanium plate washed with de-ionized water, after drying, 450
oc thermal treatment 1 hour.
Reaction result
Titanium plate surface uniform generates titanium dioxide nano-belts film as shown in Figure 3, and the width average of nano belt is about 35 nanometers, and mean length is about 200 nanometers, and long-width ratio is about 6.
Embodiment 3
1) by mass percent concentration be 55% hydrofluoric acid, mass percent concentration be that the ratio of nitric acid and the deionized water 1:3:6 by volume of 65% mixes, obtain pickle solution;
2) be in the hydrogen peroxide solution of 30%, add the trimeric cyanamide of 0.0024 mol/L and the wolframic acid of 0.008 mol/L at 50 milliliters of mass percent concentrations, obtain reaction solution;
3) 5 × 5 × 0.01(cm will be of a size of
3) pickling metal titanium plate with after pickle solution pickling, then cleans up in ultrasonic wave with deionized water.The metallic titanium plate cleaned up is immersed in the reaction solution of 50 milliliters, 85
oreact 48 hours under C;
4) reacted titanium plate washed with de-ionized water, after drying, 450
oc thermal treatment 1 hour.
Reaction result
Titanium plate surface uniform generates titanium dioxide nano-belts film as shown in Figure 4, and the mean diameter of nano belt is about 58 nanometers, and mean length is about 300 nanometers, and long-width ratio is about 5.
Embodiment 4
1) by mass percent concentration be 55% hydrofluoric acid, mass percent concentration be that the ratio of nitric acid and the deionized water 1:3:6 by volume of 65% mixes, obtain pickle solution;
2) be in the hydrogen peroxide solution of 30%, add the trimeric cyanamide of 0.0024 mol/L and the wolframic acid of 0.008 mol/L at 50 milliliters of mass percent concentrations, obtain reaction solution;
3) 5 × 5 × 0.01(cm will be of a size of
3) pickling metal titanium plate with after pickle solution pickling, then cleans up in ultrasonic wave with deionized water.The metallic titanium plate cleaned up is immersed in the reaction solution of 50 milliliters, 85
oreact 60 hours under C;
4) reacted titanium plate washed with de-ionized water, after drying, 450
oc thermal treatment 1 hour.
Reaction result
Titanium plate surface uniform generates titanium dioxide nano-belts film as shown in Figure 5, and the width average of nano belt is about 55 nanometers, and mean length is about 300 nanometers, and long-width ratio is about 6, and mean thickness is about 10 nanometers.
Embodiment 5
1) by mass percent concentration be 55% hydrofluoric acid, mass percent concentration be that the ratio of nitric acid and the deionized water 1:3:6 by volume of 65% mixes, obtain pickle solution;
2) be in the hydrogen peroxide solution of 30%, add the trimeric cyanamide of 0.0024 mol/L and the wolframic acid of 0.04 mol/L at 50 milliliters of mass percent concentrations, obtain reaction solution;
3) 5 × 5 × 0.01(cm will be of a size of
3) pickling metal titanium plate with after pickle solution pickling, then cleans up in ultrasonic wave with deionized water.The metallic titanium plate cleaned up is immersed in the reaction solution of 50 milliliters, 85
oreact 6 hours under C;
4) reacted titanium plate washed with de-ionized water, after drying, 450
oc thermal treatment 1 hour.
Reaction result
Titanium plate surface uniform generates titanium dioxide nano-belts film as shown in Figure 6, and the width average of nano belt is about 35 nanometers, and mean length is about 330 nanometers, and long-width ratio is about 10.
Claims (1)
1. prepare a method for anatase titania nano-band array film, what it is characterized in that employing is non-hydrothermal deposition method, and its concrete steps are as follows:
1) by mass percent concentration be 50 ~ 55% hydrofluoric acid, mass percent concentration be 65 ~ 68% nitric acid and deionized water by volume 1:3:6 mix, obtain pickle solution;
2) at mass percent concentration be 30% hydrogen peroxide solution in add the trimeric cyanamide of 0.0024 mol/L and the wolframic acid of 0.004 ~ 0.04 mol/L, obtain reaction solution;
3) metallic titanium plate after surface acid-washing is immersed in step 2) reaction solution in, 60 ~ 90
oreact 6 ~ 60 hours under C;
4) reacted titanium plate washed with de-ionized water, after drying, 450
oc thermal treatment 1 hour.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279250A (en) * | 2008-02-01 | 2008-10-08 | 浙江大学 | Load type nitrogen intermingle with one-dimensional structure TiO2 and preparation method thereof |
| CN101508463A (en) * | 2009-03-19 | 2009-08-19 | 浙江大学 | Method for producing nano-wire array film of titanium dioxide |
| CN102275986A (en) * | 2011-05-27 | 2011-12-14 | 吉林大学 | Controllable hydro-thermal preparation method for titanium dioxide nanobelts of different crystal forms |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279250A (en) * | 2008-02-01 | 2008-10-08 | 浙江大学 | Load type nitrogen intermingle with one-dimensional structure TiO2 and preparation method thereof |
| CN101508463A (en) * | 2009-03-19 | 2009-08-19 | 浙江大学 | Method for producing nano-wire array film of titanium dioxide |
| CN102275986A (en) * | 2011-05-27 | 2011-12-14 | 吉林大学 | Controllable hydro-thermal preparation method for titanium dioxide nanobelts of different crystal forms |
Non-Patent Citations (1)
| Title |
|---|
| 溶胶凝胶法合成莫来石纳米带;孔德强 等;《无机化学学报》;20060228;第22卷(第2期);第362页左栏第1－4段 * |
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