CN113699535A - Preparation method of spongy titanium dioxide porous layer - Google Patents
Preparation method of spongy titanium dioxide porous layer Download PDFInfo
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- CN113699535A CN113699535A CN202110984147.9A CN202110984147A CN113699535A CN 113699535 A CN113699535 A CN 113699535A CN 202110984147 A CN202110984147 A CN 202110984147A CN 113699535 A CN113699535 A CN 113699535A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 10
- 239000010439 graphite Substances 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 9
- 238000005498 polishing Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 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 5
- 238000000034 method Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- -1 fluorine ions Chemical class 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000635 electron micrograph Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002071 nanotube Substances 0.000 description 4
- 238000007605 air drying Methods 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The application discloses a preparation method of a spongy titanium dioxide porous layer, which 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 fluosilicic 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; a porous layer preparation step: and placing the polished titanium foil in electrolyte to serve 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 invention has the following beneficial effects: by adopting the electrolyte containing fluosilicic acid, the concentration of fluorine ions in the electrolyte is stably maintained at a lower level, the amount of ionic current is controlled, the amount of electronic current is increased, and oxygen bubbles are randomly generated at multiple positions, so that the spongy morphology with small pore diameter is prepared.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a preparation method of a spongy titanium dioxide porous layer.
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 most applied titanium dioxide materials are mainly nanotubes, nanowires and the like, but the specific surface area of the nanotube or nanowire-shaped titanium dioxide material is small, and the loading capacity is small when the nanotube or nanowire-shaped titanium dioxide material is used as a carrier.
Patent CN107552079B provides a method for preparing titanium dioxide photocatalyst with sponge-like porous structure, the titanium dioxide of this structure has relatively high specific surface area, but this preparation method needs calcination, so it not only has good preparation but also has great safety hazard.
Disclosure of Invention
The invention provides a preparation method of a spongy titanium dioxide porous layer aiming at the problems.
The technical scheme adopted by the invention is as follows:
a preparation method of a spongy titanium dioxide porous layer 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 fluosilicic 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;
a porous layer preparation step: and placing the polished titanium foil in electrolyte to serve as a positive electrode, a graphite electrode as a negative electrode, applying constant current between the positive electrode and the negative electrode, reacting for a period of time, taking out, washing with deionized water, and airing.
In the preparation method, the electrolyte containing fluosilicic acid is adopted, so that the concentration of fluorine ions in the electrolyte is stably maintained at a lower level, the amount of ionic current is controlled, the amount of electronic current is increased, and oxygen bubbles are generated randomly at multiple positions and can escape in a smaller volume, thereby preparing the spongy morphology with smaller pore diameter.
Optionally, in the electrode preparation step, a mixed solution of hydrofluoric acid and nitric acid is used for polishing.
Optionally, the volume ratio of the hydrofluoric acid to the nitric acid is 1: 3.
optionally, the electrolyte includes ethylene glycol, ammonium fluoride, deionized water, and fluorosilicic acid.
Optionally, a constant current of 3mA/cm2 is applied between the anode and the cathode in the electrolyte aging step.
Optionally, the electrifying reaction time in the electrolyte aging step is 20 min.
Optionally, a constant current of 2mA/cm2 is added between the positive electrode and the negative electrode in the porous layer preparation step.
Optionally, the current flowing time in the porous layer preparation step is 30 min.
The invention has the beneficial effects that: by adopting the electrolyte containing fluosilicic acid, the concentration of fluorine ions in the electrolyte is stably maintained at a lower level, the amount of ionic current is controlled, the amount of electronic current is increased, and oxygen bubbles are randomly generated at multiple positions and can escape in a smaller volume, so that the spongy morphology with smaller pore diameter is prepared.
Description of the drawings:
FIG. 1 is an electron micrograph of a porous layer of spongy titanium dioxide,
FIG. 2 is an electron micrograph of a porous layer of titania prepared by conventional anodization.
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 1: 0.1mol/L of ammonium fluoride and deionized water with the mass ratio of 2% are added into ethylene glycol. Preparation of electrolyte 2: deionized water and 0.03mol/L fluosilicic acid are added into the ethylene glycol according to the mass ratio of 2 percent.
And 3, aging of the electrolyte: placing the polished titanium foil in the electrolyte 1 as a positive electrode, a graphite electrode as a negative electrode, and adding 3mA/cm between the positive electrode and the negative electrode2Reacting for 20min, and taking out.
Step 4, preparing a spongy anode titanium dioxide porous layer: the step is similar to the step 3, the polished titanium foil is placed in the electrolyte 2 to be used as a positive electrode, the graphite electrode is used as a negative electrode, and 2mA/cm is added between the positive electrode and the negative electrode2Reacting for 30min, taking out, washing with deionized water, and air drying to obtain the porous titanium dioxide layer.
An electron micrograph of the titania porous layer prepared in this example is shown in FIG. 1.
Comparative example
The traditional anodic oxidation process:
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 and deionized water with the mass ratio of 2% are added into ethylene glycol.
And 3, aging of the electrolyte: placing the polished titanium foil in electrolyte as a positive electrode, a graphite electrode as a negative electrode, and adding 10mA/cm between the positive electrode and the negative electrode2Reacting for 20min, and taking out.
Step 4, preparing the anode titanium dioxide nanotube: the step is similar to the step 3, the polished titanium foil is placed in electrolyte to be used as a positive electrode, a graphite electrode is used as a negative electrode, and 10mA/cm is added between the positive electrode and the negative electrode2Reacting for 30min, taking out, washing with deionized water, and air drying to obtain the final product.
An electron micrograph of the titania porous layer prepared in this comparative example is shown in FIG. 2.
By comparing the embodiment 1 with the comparison example and comparing the attached drawings 1 and 2, the technical scheme of the invention has the following advantages: 1. ammonium fluoride is changed into fluosilicic acid, so that the concentration of fluorine ions in the electrolyte is stably maintained at a lower level; 2. a smaller anodization current is used to avoid breakdown or formation of large bubbles.
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 method for preparing a spongy titanium dioxide porous layer 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 fluosilicic 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;
a porous layer preparation step: and placing the polished titanium foil in electrolyte to serve as a positive electrode, a graphite electrode as a negative electrode, applying constant current between the positive electrode and the negative electrode, reacting for a period of time, taking out, washing with deionized water, and airing.
2. The method for producing a porous sponge-like titanium dioxide layer according to claim 1, wherein in the electrode production step, polishing is performed with a mixed solution of hydrofluoric acid and nitric acid.
3. The method for producing a porous sponge-like titanium dioxide layer according to claim 1, wherein the volume ratio of hydrofluoric acid to nitric acid is 1: 3.
4. the method for producing a porous sponge-like titanium dioxide layer according to claim 1, wherein said electrolyte comprises ethylene glycol, ammonium fluoride, deionized water and fluorosilicic acid.
5. The method for producing a porous sponge-like titanium dioxide layer according to claim 1, wherein a constant current of 3mA/cm2 is applied between the positive and negative electrodes in the electrolyte aging step.
6. The method for producing a porous sponge-like titanium dioxide layer according to claim 5, wherein the energization reaction time in the electrolyte aging step is 20 min.
7. The method for producing a porous titania layer in a sponge form as claimed in claim 1, wherein 2mA/cm is added between the positive and negative electrodes in the porous layer producing step2The constant current of (1).
8. The method for producing a porous titania layer in a sponge form according to claim 7, wherein the energization time in the porous layer producing step is 30 min.
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| CN202110984147.9A CN113699535A (en) | 2021-08-25 | 2021-08-25 | Preparation method of spongy titanium dioxide porous layer |
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| CN202110984147.9A CN113699535A (en) | 2021-08-25 | 2021-08-25 | Preparation method of spongy titanium dioxide porous layer |
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Citations (4)
| 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 |
| CN102864481A (en) * | 2012-09-18 | 2013-01-09 | 中国科学院宁波材料技术与工程研究所 | Titanium dioxide photo-catalyzed film and preparation method thereof |
| JP2015190039A (en) * | 2014-03-28 | 2015-11-02 | 国立大学法人岩手大学 | Method for producing porous anodic oxidation film and the porous anodic oxidation film |
| CN112170847A (en) * | 2020-09-09 | 2021-01-05 | 江苏海洋大学 | Three-dimensional two-stage porous spongy titanium dioxide thin plate and preparation method thereof |
-
2021
- 2021-08-25 CN CN202110984147.9A patent/CN113699535A/en active Pending
Patent Citations (4)
| 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 |
| CN102864481A (en) * | 2012-09-18 | 2013-01-09 | 中国科学院宁波材料技术与工程研究所 | Titanium dioxide photo-catalyzed film and preparation method thereof |
| JP2015190039A (en) * | 2014-03-28 | 2015-11-02 | 国立大学法人岩手大学 | Method for producing porous anodic oxidation film and the porous anodic oxidation film |
| CN112170847A (en) * | 2020-09-09 | 2021-01-05 | 江苏海洋大学 | Three-dimensional two-stage porous spongy titanium dioxide thin plate and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| HANNA SOPHA等: ""Effect of electrolyte age and potential changes on the morphology of TiO2 nanotubes"", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
| K.S.RAJA等: ""Effect of water content of ethylene glycol as electrolyte for synthesis of ordered titania nanotubes"", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
| 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"", 《中国博士学位论文全文数据库工程科技I辑》 * |
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