CN113699575A - Preparation method of titanium dioxide nanotube - Google Patents
Preparation method of titanium dioxide nanotube Download PDFInfo
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- CN113699575A CN113699575A CN202110984156.8A CN202110984156A CN113699575A CN 113699575 A CN113699575 A CN 113699575A CN 202110984156 A CN202110984156 A CN 202110984156A CN 113699575 A CN113699575 A CN 113699575A
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- electrolyte
- titanium dioxide
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- electrode
- titanium
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002071 nanotube Substances 0.000 title claims abstract description 51
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 6
- 238000005498 polishing Methods 0.000 claims abstract description 5
- 229910003638 H2SiF6 Inorganic materials 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910004074 SiF6 Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
Abstract
The application discloses a preparation method of a titanium dioxide nanotube, which comprises the following steps of: polishing the titanium foil, and then washing the titanium foil clean by deionized water; preparing an electrolyte: preparing an electrolyte, wherein the electrolyte contains 0.05mol/L of H2SiF6And 5% by mass of phosphoric acid; and (3) electrolyte aging: placing the polished titanium foil in electrolyte as a positive electrode, taking a graphite electrode as a negative electrode, applying constant current between the positive electrode and the negative electrode, reacting for a period of time, and taking out; the preparation steps of the nanotube are as follows: placing the polished titanium foil in electrolyte as a positive electrode, a graphite electrode as a negative electrode, applying constant voltage current between the positive electrode and the negative electrode, reacting for a period of time, and taking out; post-treatment: the titanium foil containing the anodic titanium dioxide nanotubes was cleaned and then placed in a sodium hydroxide solution for a period of time. The invention has the following beneficial effects: eliminating the gap between the anode titanium dioxide nano-tubes and enhancing the binding force between the tubes.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a preparation method of a titanium dioxide nanotube.
Background
Titanium dioxide is a semiconductor material with a great number of applications, and porous titanium dioxide has wide application in the fields of heterogeneous catalysis, gas sensitivity and the like. At present, the preparation of porous titanium dioxide is usually prepared by an anodic oxidation method, but the titanium dioxide nanotube prepared by the anodic oxidation method has low binding force with a titanium substrate, and the surface of the titanium dioxide nanotube is easy to generate cracks and is easy to be peeled from the titanium substrate; and obvious gaps exist among the nanotubes, and the bonding force is weak.
Disclosure of Invention
The invention provides a preparation method of a titanium dioxide nanotube aiming at the problems.
The technical scheme adopted by the invention is as follows:
a preparation method of a titanium dioxide nanotube comprises the following steps,
the preparation method of the electrode comprises the following steps: polishing the titanium foil, and then washing the titanium foil clean by deionized water;
preparing an electrolyte: preparing an electrolyte, wherein the electrolyte contains 0.05mol/L of H2SiF6And 5% by mass of phosphoric acid;
and (3) electrolyte aging: placing the polished titanium foil in electrolyte as a positive electrode, taking a graphite electrode as a negative electrode, applying constant current between the positive electrode and the negative electrode, reacting for a period of time, and taking out;
the preparation steps of the nanotube are as follows: placing the polished titanium foil in electrolyte as a positive electrode, a graphite electrode as a negative electrode, applying constant voltage current between the positive electrode and the negative electrode, reacting for a period of time, and taking out;
post-treatment: the titanium foil containing the anodic titanium dioxide nanotubes was cleaned and then placed in a sodium hydroxide solution for a period of time.
The principle of the treatment process is as follows, the electrolyte containing phosphate radical is usually used for preparing the compact anodic titanium dioxide layer, the electrolyte containing fluorine is usually used for preparing the anodic titanium dioxide nanotube, but the anodic titanium dioxide nanotube has obvious gaps between the tubes, the bonding force between the nanotube and the titanium substrate is weak, the surface is easy to generate cracks, and the nanotube is also easy to be peeled off from the titanium substrate, thereby greatly influencing the application performance of the anodic titanium dioxide nanotube. For example, when the anodic titanium dioxide nanotube is applied to a dye-sensitized solar cell, the anodic titanium dioxide nanotube layer needs not to have cracks, and has good bonding force with a substrate (titanium foil). The invention combines the preparation methods of the compact oxide film and the anode titanium dioxide nanotube, reduces the gap between the nanotubes, and fills the gap between the nanotubes with titanium dioxide by utilizing the crystal form change of amorphous titanium dioxide in alkali liquor so as to enhance the binding force between the titanium dioxide nanotubes.
In conclusion, the invention adopts the electrolyte with the added phosphate ions to reduce the gaps among the nano-tubes, and finishes the preparation of soaking the titanium foil containing the nano-tubes in the alkali liquor to ensure that the amorphous titanium dioxide continuously grows and finally fills the gaps among the nano-tubes, thereby eliminating the gaps among the anode titanium dioxide nano-tubes and enhancing the bonding force among the nano-tubes.
Optionally, in the step of preparing the electrode, the electrode is firstly placed in a mixed solution of hydrofluoric acid and nitric acid, and then is cleaned by deionized water.
Optionally, the volume ratio of the hydrofluoric acid to the nitric acid is 1: 3.
optionally, in the electrolyte aging step, a constant current of 4mA/cm2 is applied between the anode and the cathode, and the electrolyte is taken out after reacting for half an hour.
Optionally, in the step of preparing the nanotube, a constant voltage current of 30V is applied between the anode and the cathode, and the reaction time is 10 min.
Optionally, the concentration of the sodium hydroxide solution in the post-treatment step is 1 mol/L.
Optionally, the temperature of the sodium hydroxide solution in the post-treatment step is 50 ℃, and the standing time is 24 hours.
Optionally, in the electrolyte preparation step, 0.1mol/L of ammonium fluoride, 2% by mass of deionized water and 0.05mol/L of H are added into ethylene glycol2SiF6And 5% by mass of phosphoric acid.
The invention has the beneficial effects that: phosphate ions are added into the electrolyte, so that gaps among the nano-tubes are reduced, the preparation is completed, the titanium foil containing the nano-tubes is soaked in the alkali liquor, amorphous titanium dioxide continuously grows, the gaps among the nano-tubes are filled finally, the gaps among the anode titanium dioxide nano-tubes are eliminated, and the binding force among the nano-tubes is enhanced.
Description of the drawings:
FIG. 1 is an electron micrograph of the titanium dioxide nanotubes prepared according to the present invention.
The specific implementation mode is as follows:
the present invention will be described in detail below with reference to examples and electron micrographs.
Example 1
Step 1, preparing an electrode: polishing the titanium foil in hydrofluoric acid and nitric acid polishing solution with the volume ratio of 1:3 for 10s, taking out and cleaning with deionized water.
Step 2, preparing electrolyte: 0.1mol/L of ammonium fluoride, deionized water with the mass ratio of 2%, 0.05mol/L of H2SiF6 and phosphoric acid with the mass ratio of 5% are added into ethylene glycol.
And 3, aging of the electrolyte: and placing the polished titanium foil in electrolyte to serve as a positive electrode, taking a graphite electrode as a negative electrode, adding a constant current of 4mA/cm2 between the positive electrode and the negative electrode, reacting for half an hour, and taking out.
Step 4, preparing the anode titanium dioxide nanotube: and (3) placing the polished titanium foil in an electrolyte as a positive electrode, taking a graphite electrode as a negative electrode, applying a constant voltage current of 30V between the positive electrode and the negative electrode, reacting for 10min, and taking out the titanium foil after the anodic oxidation area is 1cm multiplied by 3cm (namely 3 square centimeters).
And 5, post-treatment of the anode titanium dioxide nanotube: washing the titanium foil with the anode titanium dioxide nanotube in deionized water, then placing the titanium foil in 1mol/L sodium hydroxide solution, and placing the titanium foil for 1d at a constant temperature of 50 ℃.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, which is defined by the claims and their equivalents, and can be directly or indirectly applied to other related fields of technology.
Claims (8)
1. A preparation method of a titanium dioxide nanotube is characterized by comprising the following steps,
the preparation method of the electrode comprises the following steps: polishing the titanium foil, and then washing the titanium foil clean by deionized water;
preparing an electrolyte: preparing an electrolyte, wherein the electrolyte contains 0.05mol/L of H2SiF6And 5% by mass of phosphoric acid;
and (3) electrolyte aging: placing the polished titanium foil in electrolyte as a positive electrode, taking a graphite electrode as a negative electrode, applying constant current between the positive electrode and the negative electrode, reacting for a period of time, and taking out;
the preparation steps of the nanotube are as follows: placing the polished titanium foil in electrolyte as a positive electrode, a graphite electrode as a negative electrode, applying constant voltage current between the positive electrode and the negative electrode, reacting for a period of time, and taking out;
post-treatment: the titanium foil containing the anodic titanium dioxide nanotubes was cleaned and then placed in a sodium hydroxide solution for a period of time.
2. The method of preparing titanium dioxide nanotubes of claim 1, wherein in the step of preparing the electrode, the electrode is first placed in a mixture of hydrofluoric acid and nitric acid, and then washed with deionized water.
3. The method for preparing titanium dioxide nanotubes according to claim 2, wherein the volume ratio of hydrofluoric acid to nitric acid is 1: 3.
4. the method for preparing titanium dioxide nanotubes as claimed in claim 1, wherein a constant current of 4mA/cm2 is applied between the positive and negative electrodes in the step of aging the electrolyte, and the reaction is carried out for half an hour before taking out.
5. The method of preparing titanium dioxide nanotubes according to claim 1, wherein a constant voltage current of 30V is applied between the positive and negative electrodes in the step of preparing the nanotubes, and the reaction time is 10 min.
6. The method for preparing titanium dioxide nanotubes according to claim 1, wherein the concentration of the sodium hydroxide solution in the post-treatment step is 1 mol/L.
7. The method for preparing titanium dioxide nanotubes according to claim 6, wherein the temperature of the solution of sodium hydroxide in the post-treatment step is 50 ℃ and the standing time is 24 hours.
8. The method for preparing the titanium dioxide nanotube as claimed in claim 1, wherein in the step of preparing the electrolyte, 0.1mol/L ammonium fluoride, 2% deionized water by mass and 0.05mol/L H are added into ethylene glycol2SiF6And 5% by mass of phosphoric acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110984156.8A CN113699575A (en) | 2021-08-25 | 2021-08-25 | Preparation method of titanium dioxide nanotube |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110984156.8A CN113699575A (en) | 2021-08-25 | 2021-08-25 | Preparation method of titanium dioxide nanotube |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090183994A1 (en) * | 2005-09-09 | 2009-07-23 | University Of Nevada, Reno | Preparation of nano-tubular titania substrate with oxygen vacancies and their use in photo-electrolysis of water |
| CN102383164A (en) * | 2011-11-08 | 2012-03-21 | 天津大学 | Titanium dioxide nano-honeycomb nested nanowire array film and preparation method thereof |
| CN102418133A (en) * | 2011-12-12 | 2012-04-18 | 天津大学 | Nano honeycomb titanium dioxide structure thin film with rough surface and preparation method of nanohoneycomb titanium dioxide structure thin film |
| CN104694991A (en) * | 2014-12-30 | 2015-06-10 | 云南大学 | Method for preparing platinum-gold double metal doped TiO2 nanotube electrode |
| CN106086991A (en) * | 2016-08-19 | 2016-11-09 | 长江水利委员会长江科学院 | A kind of controlling type metal ion doping TiO in situ2the preparation method of nano-tube array |
-
2021
- 2021-08-25 CN CN202110984156.8A patent/CN113699575A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090183994A1 (en) * | 2005-09-09 | 2009-07-23 | University Of Nevada, Reno | Preparation of nano-tubular titania substrate with oxygen vacancies and their use in photo-electrolysis of water |
| CN102383164A (en) * | 2011-11-08 | 2012-03-21 | 天津大学 | Titanium dioxide nano-honeycomb nested nanowire array film and preparation method thereof |
| CN102418133A (en) * | 2011-12-12 | 2012-04-18 | 天津大学 | Nano honeycomb titanium dioxide structure thin film with rough surface and preparation method of nanohoneycomb titanium dioxide structure thin film |
| CN104694991A (en) * | 2014-12-30 | 2015-06-10 | 云南大学 | Method for preparing platinum-gold double metal doped TiO2 nanotube electrode |
| CN106086991A (en) * | 2016-08-19 | 2016-11-09 | 长江水利委员会长江科学院 | A kind of controlling type metal ion doping TiO in situ2the preparation method of nano-tube array |
Non-Patent Citations (2)
| Title |
|---|
| HANNA SOPHA等: ""Effect of electrolyte age and potential changes on the morphology of TiO2 nanotubes"", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
| 张少瑜: ""钛的阳极氧化过程及阳极氧化钛纳米结构的形成机理研究"", 《中国博硕士学位论文全文数据库（博士）工程科技I辑》 * |
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Application publication date: 20211126 |