CN101955224B - Preparation method of zirconium oxide nanotube - Google Patents
Preparation method of zirconium oxide nanotube Download PDFInfo
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- CN101955224B CN101955224B CN200910065470A CN200910065470A CN101955224B CN 101955224 B CN101955224 B CN 101955224B CN 200910065470 A CN200910065470 A CN 200910065470A CN 200910065470 A CN200910065470 A CN 200910065470A CN 101955224 B CN101955224 B CN 101955224B
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Abstract
The invention provides a preparation method of a zirconium oxide nanotube, comprising the following steps: taking n-zirconic acid prepared from zirconium tetrachloride and sodium hydroxide as a raw material, washing the raw material with deionized water, dissolving with nitric acid, hydrolyzing to generate suspension, filtering, washing the obtained filter cake with deionized water, and finally drying to obtain the zirconium oxide nanotube. The preparation method of the zirconium oxide nanotube has less steps and no severe conditions and is simple and feasible; temperature in technological parameters is within a normal and easily accessible range, thus achieving simple control; the adopted equipment is simple and has strong generality; and the obtained zirconium oxide nanotube has high rate of finished products and good quality, wherein, the diameter of the zirconium oxide nanotube is 30-60nm and the length is 500nm-20mu m.
Description
Technical field
The invention belongs to the making method of nanotube, relate in particular to a kind of preparation method of zirconium white nanotube.
Background technology
Zirconium white is unique a kind of MOX that has acidity, alkalescence, oxidisability and reductibility simultaneously.It is a P-type semiconductor, is easy to produce oxygen vacancies, has crucial scientific research value and application prospect in catalyzer, support of the catalyst, sensitive material field.
Zirconic performance is inseparable with its specific surface area and state of aggregation.Because the zirconium white nanotube has very big specific surface area and specific structure, it is all having very big application prospect aspect heterogeneous catalysis, absorption, separation, the chemical sensor.The zirconium white nanotube can be used as nano-reactor in addition, synthetic nano composite structure material with excellent light, electricity, magnetic and catalytic performance.
At present, the preparation method of zirconium white nanotube mainly contains template, atomic layer deposition method and hydrothermal method." Chem.ChemmtJn. " (1997, P1581-1582) a kind of template of report prepares the method for zirconium white nanotube.This method at first prepares multi-walled carbon nano-tubes, with concentrated nitric acid reflow treatment 12 hours, makes carbon nano tube surface produce the acid activity base; Be template with the carbon nanotube after the s.t. then, react under the argon gas atmosphere condition with the propyl alcohol zirconium, after supersound process; Place moisture eliminator to preserve 48 hours; Products therefrom is removed excessive alkoxy compound with 48% HF and methanol wash, ' 700 ℃ heat treated that drying exists at last 48 hours; Remove carbon nanotube, obtain the zirconium white nanotube.This method not only need prepare carbon nanotube, complex technical process, and raw materials cost is high, and the even tube wall property of gained zirconium white nanotube is relatively poor." AdvancedMaterials " (2004,16, P1197-1200) report the method that a kind of atomic layer deposition method (ALD) prepares the zirconium white nanotube.It is template that this method adopts polycarbonate, at first on template, deposits one deck self-assembly OTS-SAM (octadecyl tetrachloro silicane), and internal layer is removed polycarbonate with chloroform at last through ALD method deposition zirconium white component then, obtains the zirconium white nanotube.This method needs expensive atomic layer deposition system; Nanotube thickness of pipe rate of growth is slow; Common every circulation primary thickness of pipe growth is merely 0.6A; Need hundreds of times of circulation even just can obtain the zirconium white nanotube that thickness of pipe is tens of dusts thousands of times, template is removed the organic solvents such as chloroform that adopt in the step simultaneously all has very big harm to operator and environment.This method complex technical process, cost is high, is difficult to realize suitability for industrialized production.
Summary of the invention
It is simple to the purpose of this invention is to provide a kind of preparation technology, the preparation method of the zirconium white nanotube that equipment interoperability is strong.
Adopt following scheme in order to achieve the above object: a kind of preparation method of zirconium white nanotube, the positive zirconic acid that uses zirconium tetrachloride hydro-oxidation sodium to make is raw material, behind deionized water wash; Add nitric acid dissolve; Through hydrolysis, generate muddy liquid, filter then; And with deionized water with filter cake washing after, drying just makes the zirconium white nanotube again.
When preparing positive zirconic acid, temperature is 15～40 ℃, and pH is 4～9, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; The concentration of used nitric acid is 15～20 mol; Elder generation's controlled temperature is at 55-65 ℃ during with positive zirconic acid mixed dissolution with nitric acid, and insulation 50-100 minute reduces the temperature to 32-50 ℃ subsequently, is incubated 5-8 hour, and the muddy liquid that will generate at last cools to 20-30 ℃; Temperature is 500 ℃ during dry cake, 22～26 hours time of drying.
When preparing positive zirconic acid, record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is at 10-25%.
Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at the 2.0-4.0 mol.
Adopt the preparation method of zirconium white nanotube of the present invention, step is few, and condition is not harsh, simple possible; Temperature all is being easier within the scope that reaches normally in the processing parameter, controls simpler; The equipment that uses is simple, and equipment interoperability is strong, and the zirconium white nanotube yield rate of manufacturing is high, and quality is good, and the zirconium white nanotube caliber that obtains is that 30-60nm, length are 500nm-20 μ m.
Embodiment
The several embodiment of various details, but content of the present invention is not limited to therewith fully.
Embodiment 1
Under 15～40 ℃ of temperature, transferring pH is 4～9, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is at 10-25%.Behind deionized water wash, adding concentration is the nitric acid dissolve of 15～20 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at the 2.0-4.0 mol.Elder generation's controlled temperature is at 55-65 ℃ during dissolving, and insulation 50-100 minute, to promote dissolving, produces nucleus subsequently; Reduce the temperature to 32-50 ℃ subsequently, be incubated 5-8 hour, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 20-30 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, under 500 ℃ temperature, dry 22～26 hours, can make caliber was that 30-60nm, length are the zirconium white nanotube of 500nm-20 μ m with filter cake.
Embodiment 2
Under 15 ℃ of temperature, transferring pH is 9, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is 25%.Behind deionized water wash, adding concentration is the nitric acid dissolve of 20 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at 4.0 mol.Elder generation's controlled temperature and is incubated 50 minutes at 65 ℃ during dissolving, to promote dissolving, produces nucleus subsequently; Reduce the temperature to 50 ℃ subsequently, be incubated 5 hours, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 30 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, filter cake under 500 ℃ temperature, dry 22 hours, can be made the zirconium white nanotube.
Embodiment 3
Under 40 ℃ of temperature, transferring pH is 9, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is 10%.Behind deionized water wash, adding concentration is the nitric acid dissolve of 15 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at 2.0 mol.Elder generation's controlled temperature and is incubated 100 minutes at 55 ℃ during dissolving, to promote dissolving, produces nucleus subsequently; Reduce the temperature to 32 ℃ subsequently, be incubated 8 hours, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 20 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, filter cake under 500 ℃ temperature, dry 26 hours, can be made the zirconium white nanotube.
Embodiment 4
Under 25 ℃ of temperature, transferring pH is 7, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is 15%.Behind deionized water wash, adding concentration is the nitric acid dissolve of 17 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at 3.0 mol.Elder generation's controlled temperature and is incubated 80 minutes at 60 ℃ during dissolving, to promote dissolving, produces nucleus subsequently; Reduce the temperature to 40 ℃ subsequently, be incubated 7 hours, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 25 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, filter cake under 500 ℃ temperature, dry 24 hours, can be made the zirconium white nanotube.
Embodiment 5
Under 30 ℃ of temperature, transferring pH is 6～8, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is at 25-20%.Behind deionized water wash, adding concentration is the nitric acid dissolve of 20 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at the 2.5-3.5 mol.Elder generation's controlled temperature and is incubated 90 minutes at 58-62 ℃ during dissolving, to promote dissolving, produces nucleus subsequently; Reduce the temperature to 35 ℃ subsequently, be incubated 6 hours, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 28 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, filter cake under 500 ℃ temperature, dry 25 hours, can be made the zirconium white nanotube.
Embodiment 6
Under 25～30 ℃ of temperature, transferring pH is 7, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is at 22-24%.Behind deionized water wash, adding concentration is the nitric acid dissolve of 17 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at 2.8 mol.Elder generation's controlled temperature is at 55 ℃ during dissolving, and insulation 70-80 minute, to promote dissolving, produces nucleus subsequently; Reduce the temperature to 35 ℃ subsequently, be incubated 6 hours, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 24 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, filter cake under 500 ℃ temperature, dry 24 hours, can be made the zirconium white nanotube.
Embodiment 7
Under 15～20 ℃ of temperature, transferring pH is 4～6, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is at 10-15%.Behind deionized water wash, adding concentration is the nitric acid dissolve of 20 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at the 2.0-4.0 mol.Elder generation's controlled temperature and is incubated 60 minutes at 60 ℃ during dissolving, to promote dissolving, produces nucleus subsequently; Reduce the temperature to 40 ℃ subsequently, be incubated 6 hours, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 25 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, under 500 ℃ temperature, dry 22 hours, can make caliber was that 30-60nm, length are the zirconium white nanotube of 500nm-20 μ m with filter cake.
Embodiment 8
Under 35 ℃ of temperature, transferring pH is 8～9, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is at 22-25%.Behind deionized water wash, adding concentration is the nitric acid dissolve of 15 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at the 2.0-4.0 mol.Elder generation's controlled temperature and is incubated 90 minutes at 58 ℃ during dissolving, to promote dissolving, produces nucleus subsequently; Reduce the temperature to 45 ℃ subsequently, be incubated 8 hours, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 30 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, filter cake under 500 ℃ temperature, dry 26 hours, can be made the zirconium white nanotube.
Embodiment 9
Under 20～25 ℃ of temperature, transferring pH is 7, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is 16～18%.Behind deionized water wash, adding concentration is the nitric acid dissolve of 18 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at 2.8～3.2 mol.Elder generation's controlled temperature and is incubated 60 minutes at 63 ℃ during dissolving, to promote dissolving, produces nucleus subsequently; Reduce the temperature to 40 ℃ subsequently, be incubated 6 hours, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 22 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, filter cake under 500 ℃ temperature, dry 24～26 hours, can be made the zirconium white nanotube.
Embodiment 10
Under 37 ℃ of temperature, transferring pH is 5, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is at 13-17%.Behind deionized water wash, adding concentration is the nitric acid dissolve of 17 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at 2.2～2.5 mol.Elder generation's controlled temperature and is incubated 75 minutes at 65 ℃ during dissolving, to promote dissolving, produces nucleus subsequently; Reduce the temperature to 33 ℃ subsequently, be incubated 5.5 hours, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 26 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, filter cake under 500 ℃ temperature, dry 22～24 hours, can be made the zirconium white nanotube.
Embodiment 11
Under 18 ℃ of temperature, transferring pH is 8, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is at 22-24%.Behind deionized water wash, adding concentration is the nitric acid dissolve of 16 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at the 3.3-3.6 mol.Elder generation's controlled temperature and is incubated 85 minutes at 57 ℃ during dissolving, to promote dissolving, produces nucleus subsequently; Reduce the temperature to 48 ℃ subsequently, be incubated 6.5 hours, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 23 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, filter cake under 500 ℃ temperature, dry 22～26 hours, can be made the zirconium white nanotube.
Embodiment 12
Under 15～40 ℃ of temperature, transferring pH is 4～9, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is at 10-25%.Behind deionized water wash, adding concentration is the nitric acid dissolve of 17 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at 3.0 mol.Elder generation's controlled temperature and is incubated 60 minutes at 60 ℃ during dissolving, to promote dissolving, produces nucleus subsequently; Reduce the temperature to 44 ℃ subsequently, be incubated 7 hours, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 24～26 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, filter cake under 500 ℃ temperature, dry 24 hours, can be made the zirconium white nanotube.
Embodiment 13
Under 25～30 ℃ of temperature, transferring pH is 5～8, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is 20～25%.Behind deionized water wash, adding concentration is the nitric acid dissolve of 20 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at the 2.0-4.0 mol.Elder generation's controlled temperature is at 60-65 ℃ during dissolving, and insulation 80-100 minute, to promote dissolving, produces nucleus subsequently; Reduce the temperature to 35-40 ℃ subsequently, be incubated 6-8 hour, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 25-30 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, filter cake under 500 ℃ temperature, dry 26 hours, can be made the zirconium white nanotube.
Claims (2)
1. the preparation method of a zirconium white nanotube is characterized in that: under 15～40 ℃ of temperature, transferring pH is 4～9, prepares positive zirconic acid with zirconium tetrachloride hydro-oxidation sodium, and the mass ratio of zirconium tetrachloride and sodium hydroxide is 1: 0.75; Behind deionized water wash, adding concentration is the nitric acid dissolve of 15～20 mol, and the Zircosol ZN concentration after nitric acid dissolves with positive zirconic acid is controlled at the 2.0-4.0 mol; Elder generation's controlled temperature is at 55-65 ℃ during dissolving; And be incubated 50-100 minute, to promote dissolving, produce nucleus subsequently; Reduce the temperature to 32-50 ℃ subsequently, be incubated 5-8 hour, promote the growth of nanostructure; The muddy liquid that will generate at last cools to 20-30 ℃; Filter then, and with deionized water wash to PH=7, obtain filter cake, filter cake under 500 ℃ temperature, dry 22～26 hours, is made the zirconium white nanotube.
2. the preparation method of zirconium white nanotube according to claim 1 is characterized in that: when preparing positive zirconic acid, record wherein zirconic quality with weighting method, the quality percentage composition of controlled oxidation zirconium is at 10-25%.
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| CN112811903B (en) * | 2021-01-12 | 2022-11-15 | 浙江金琨锆业有限公司 | Remove Cl in zirconia powder - Method (2) |
| CN116199259A (en) * | 2023-03-20 | 2023-06-02 | 洛阳理工学院 | Preparation method of tetragonal zirconia nano tubular crystal |
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| CN1482065A (en) * | 2003-04-15 | 2004-03-17 | 清华大学 | Process for preparing nanometer zirconium dioxide powder by hydrolyzing zirconium oxynitrate |
| CN101049964A (en) * | 2007-05-23 | 2007-10-10 | 河北工业大学 | Method for preparing Nano tube of zirconium dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1482065A (en) * | 2003-04-15 | 2004-03-17 | 清华大学 | Process for preparing nanometer zirconium dioxide powder by hydrolyzing zirconium oxynitrate |
| CN101049964A (en) * | 2007-05-23 | 2007-10-10 | 河北工业大学 | Method for preparing Nano tube of zirconium dioxide |
Non-Patent Citations (1)
| Title |
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| 尹衍升等.水热法制备氧化锆纳米管的影响因素及形成机理.《现代化工》.2005,第25卷(第5期), * |
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