CN101545129B - A process for synthesizing crystalline titanic oxide nano-tubes - Google Patents
A process for synthesizing crystalline titanic oxide nano-tubes Download PDFInfo
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- CN101545129B CN101545129B CN2009101139631A CN200910113963A CN101545129B CN 101545129 B CN101545129 B CN 101545129B CN 2009101139631 A CN2009101139631 A CN 2009101139631A CN 200910113963 A CN200910113963 A CN 200910113963A CN 101545129 B CN101545129 B CN 101545129B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002071 nanotube Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The invention provides a process for synthesizing crystalline titanic oxide nano-tubes, which takes pure titanium foil as base material, makes heat treatment of hydrogen peroxide of 30% for weight percentage at the temperature of 80degrees or ammonium persulfate at the temperature of 130degrees, and then put the heat-treated titanium foil after soaking in the hydrochloride into the electrolyte containing fluorine and takes anodic oxidation treatment for some while at constant pressure, then the titanic oxide nano-tube of high crystallinity is done. The aforesaid process has advantage of easy operation and good result reproducibility.
Description
Technical field
The present invention relates to a kind of method of synthesizing crystalline titanic oxide nano-tubes.
Background technology
Some metal oxide semiconductors are widely used in various fields such as gas sensor, biological medicine transplanting, high-dielectric coefficient pottery, field emission device and photovoltaic cell.Under nanoscale, the structure of the metal oxide of above-mentioned Application Areas controlled the performance that improves them is had tangible effect.
Current, shown the performance that it is superior by anonizing synthetic titania nanotube in fields such as photochemical catalysis, photovoltaic cell and gas sensors.But, above-mentioned Nano tube array of titanium dioxide all is being not less than under 450 ℃ of temperature thermal treatment more than one hour and obtain to unbodied titania nanotube, and the purpose of the unbodied titania nanotube of its high-temperature heat treatment is the high titania nanotube of degree of crystallinity in order to obtain.Anonizing prepared in the technology of crystalline titanic oxide nano-tubes in the past, all was surperficial by anodic oxidation at pure titanium foil, then through high-temperature heat treatment, can obtain the titania nanotube of better crystallinity degree.But in the process that forms crystalline titanic oxide nano-tubes, increased the thickness of Nano tube array of titanium dioxide and titanium substrate barrier layer simultaneously; The barrier layer thickness that increases has prolonged the distance of the electric transmission of Nano tube array of titanium dioxide to titanium metal substrate, and electric transmission is to the also increase greatly of recombination rate of titanium substrate, thereby has reduced the efficient of opto-electronic conversion.In addition, the Nano tube array of titanium dioxide of the better crystallinity degree that high-temperature heat treatment obtains is in some field, and for example the application of polymer catalytic film aspect is subjected to the restriction of temperature.Therefore, the Nano tube array of titanium dioxide that synthesizes crystal form at low temperatures is subjected to obtain to use aspect the bigger field of temperatures involved to have crucial meaning at some.
The technology of the titania nanotube of preparation better crystallinity degree comprises hydrothermal method, sol-gel method and calcination method at present.The Nano tube array of titanium dioxide of Hydrothermal Preparation because the too much absorption of oxide compound and in forming process to the structural damage of oxide compound micron order, cause the Nano tube array of titanium dioxide of advantages of good crystallization to be easy to reduction, destroyed the composition of original titania nanotube; The Nano tube array of titanium dioxide of sol-gel method preparation then is easy in building-up process owing to the high specific surface of nanotube reunite; The nano titanium oxide array of calcination method preparation can not form thin nanotube tube wall because the titania nanotube xln is too big.
Summary of the invention
The object of the present invention is to provide a kind of technology simple, can be the method that synthesizes the high titania nanotube of degree of crystallinity under the 80-130 ℃ of condition in temperature.
The present invention is base material with the pure titanium foil, be 30% hydrogen peroxide with weight percent 80 ℃ down or with ammonium persulphate under 130 ℃ with pure titanium foil thermal treatment, then that thermal treatment is good titanium foil through after the salt acid soak under constant voltage, be put into and carry out the anodic oxidation treatment certain hour in the fluorine-containing electrolytic solution and promptly obtain the high titania nanotube of degree of crystallinity.
Concrete steps are:
(1) pure titanium foil of choosing the 0.1-0.5 mm thick according to application requiring is cut into institute's size that requires and shape, with No. 500 carborundum paper sanding and polishing titanium foils to obtain coarse surface;
(2) step (1) is polished titanium foil was used deionized water ultrasonic 5 minutes then earlier with acetone ultrasonic cleaning 5 minutes;
(3) to be put into weight percent be 30% hydrogen peroxide to the titanium foil after step (2) is cleaned, 5 mmoles/liter sodium sulfate and the phosphoric acid mixed electrolytic solution of 0.5 mol in, 80 ℃ soaked 48-72 hour down or electrolytic solution at the ammonium persulphate of 0.05 mol in, soaked 3-5 hour down at 130 ℃;
(4) will in the hydrochloric acid soln of 1 mol, under room temperature, wash 2 hours anodic oxidation usefulness fully through the titanium foil of step (3) oxide treatment;
(5) titanium foil of step (4) is immersed in the Neutral ammonium fluoride of 0.2-0.4 mol, in the electrolytic solution of the hydrogen peroxide of the phosphoric acid of 0.1 mol and 0.05 mol,, under 30 volts, carried out anodic oxidation 16-20 hour by the constant voltage constant current power device;
(6) will dry up the titania nanotube that promptly obtains titanium foil surface one deck better crystallinity degree with nitrogen through the anodised titanium foil of step (5).
Simple possible of the present invention, reproducibility of results is good.
Embodiment
Embodiment 1:
(1) to be cut into the length of side with scissors be 20 millimeters shape to the pure titanium foil of choosing 0.25 mm thick, with No. 500 carborundum paper sanding and polishing titanium foils to obtain coarse surface;
(2) step (1) is polished titanium foil was used deionized water ultrasonic 5 minutes then earlier with acetone ultrasonic cleaning 5 minutes;
(3) to be put into weight percent be 30% hydrogen peroxide to the titanium foil after step (2) is cleaned, 5 mmoles/liter sodium sulfate and the phosphoric acid mixed electrolytic solution of 0.5 mol in, soaked 48 hours down at 80 ℃;
(4) will in the hydrochloric acid soln of 1 mol, under room temperature, wash 2 hours anodic oxidation usefulness fully through the titanium foil of step (3) oxide treatment;
(5) titanium foil of step (4) is immersed in the Neutral ammonium fluoride of 0.2 mol, in the electrolytic solution of the hydrogen peroxide of the phosphoric acid of 0.1 mol and 0.05 mol,, under 30 volts, carries out anodic oxidation 16 hours by the constant voltage constant current power device;
(6) will dry up the titania nanotube that promptly obtains titanium foil surface one deck better crystallinity degree with nitrogen through the anodised titanium foil of step (5).
Embodiment 2:
(1) pure titanium foil of choosing 0.1 mm thick is cut into the rectangle that is of a size of 20 millimeters of wide 10 millimeters long with scissors, with No. 500 carborundum paper sanding and polishing titanium foils to obtain coarse surface;
(2) step (1) is polished titanium foil was used deionized water ultrasonic 5 minutes then earlier with acetone ultrasonic cleaning 5 minutes;
(3) titanium foil after step (2) is cleaned is placed in the electrolytic solution of ammonium persulphate of 0.05 mol, soaks 5 hours down at 130 ℃;
(4) product with step (3) washes 2 hours anodic oxidation usefulness fully under room temperature in the hydrochloric acid soln of 1 mol.
(4) will be immersed in the Neutral ammonium fluoride of 0.4 mol through the titanium foil of step (3) oxide treatment, in the electrolytic solution of the hydrogen peroxide of the phosphoric acid of 0.1 mol and 0.05 mol,, under 30 volts, carry out anodic oxidation 20 hours by the constant voltage constant current power device.
(6) will dry up the titania nanotube that promptly obtains titanium foil surface one deck better crystallinity degree with nitrogen through the anodised titanium foil of step (5).
Claims (1)
1. the method for a synthesizing crystalline titanic oxide nano-tubes, it is characterized in that: concrete steps are:
(1) pure titanium foil of choosing the 0.1-0.5 mm thick according to application requiring is cut into institute's size that requires and shape, with No. 500 carborundum paper sanding and polishing titanium foils to obtain coarse surface;
(2) step (1) is polished titanium foil was used deionized water ultrasonic 5 minutes then earlier with acetone ultrasonic cleaning 5 minutes;
(3) to be put into weight percent be 30% hydrogen peroxide to the titanium foil after step (2) is cleaned, 5 mmoles/liter sodium sulfate and the phosphoric acid mixed electrolytic solution of 0.5 mol in, 80 ℃ soaked 48-72 hour down or electrolytic solution at the ammonium persulphate of 0.05 mol in, soaked 3-5 hour down at 130 ℃;
(4) will in the hydrochloric acid soln of 1 mol, under room temperature, wash 2 hours anodic oxidation usefulness fully through the titanium foil of step (3) oxide treatment;
(5) titanium foil of step (4) is immersed in the Neutral ammonium fluoride of 0.2-0.4 mol, in the electrolytic solution of the hydrogen peroxide of the phosphoric acid of 0.1 mol and 0.05 mol,, under 30 volts, carried out anodic oxidation 16-20 hour by the constant voltage constant current power device;
(6) will dry up the titania nanotube that promptly obtains titanium foil surface one deck better crystallinity degree with nitrogen through the anodised titanium foil of step (5).
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009101139631A CN101545129B (en) | 2009-04-02 | 2009-04-02 | A process for synthesizing crystalline titanic oxide nano-tubes |
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| CN2009101139631A CN101545129B (en) | 2009-04-02 | 2009-04-02 | A process for synthesizing crystalline titanic oxide nano-tubes |
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| CN101545129B true CN101545129B (en) | 2010-08-11 |
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| CN101899701B (en) * | 2010-07-19 | 2012-07-11 | 西南交通大学 | Method for preparing composite material of copper sulfide and titanium dioxide nano-tube |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191248A (en) * | 2006-12-01 | 2008-06-04 | 西南交通大学 | Method for preparing titanium dioxide nano tube array on titanium-substrate material surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101191248A (en) * | 2006-12-01 | 2008-06-04 | 西南交通大学 | Method for preparing titanium dioxide nano tube array on titanium-substrate material surface |
Non-Patent Citations (6)
| Title |
|---|
| Mor, GK |
| Sharma, S,etal..Synthesis of ordered arrays of discrete, partially crystalline titania nanotubes by Ti anodization using diethylene glycol electrolytes.JOURNAL OF MATERIALS CHEMISTRY.2008,18(28),3332-3336. |
| Yoriya, S |
| Yoriya, S;Mor, GK;Sharma, S,etal..Synthesis of ordered arrays of discrete, partially crystalline titania nanotubes by Ti anodization using diethylene glycol electrolytes.JOURNAL OF MATERIALS CHEMISTRY.2008,18(28),3332-3336. * |
| 孙岚等.钛基TiO2纳米管阵列电极的光电催化性能.无机化学学报.2009,25(2),334-338. |
| 钛基TiO2纳米管阵列电极的光电催化性能;孙岚等;无机化学学报;20090228;25(2);334-338 * |
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