CN100500576C - Method for preparing nano tube of zirconium dioxide - Google Patents
Method for preparing nano tube of zirconium dioxide Download PDFInfo
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- CN100500576C CN100500576C CNB2007100574260A CN200710057426A CN100500576C CN 100500576 C CN100500576 C CN 100500576C CN B2007100574260 A CNB2007100574260 A CN B2007100574260A CN 200710057426 A CN200710057426 A CN 200710057426A CN 100500576 C CN100500576 C CN 100500576C
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Abstract
This invention relates to a method for preparing ZrO2 nanotubes by anodic oxidation. The method comprises: mixing formamide and alcohol solvent at a volume ratio of (1-3):1 to obtain a mixed solvent, preparing 0.5-1.5 wt.% fluoride solution, introducing the fluoride solution into a reactor with Zr plate as the anode and Pt plate or graphite plate as the cathode, performing anodic oxidation under 10-90 V DC at room temperature to generate ZrO2 nanotubes on the Zr plate, falling off during the reaction, separating precipitated to the bottom of the reactor, washing with water, and drying at 105 deg.C to obtain ZrO2 nanotubes. The distance between the anode and the cathode is 1.5 cm. The method has such advantages as simple process, low cost, no pollution and uniform wall thickness of ZrO2 nanotubes.
Description
Technical field
Technical scheme of the present invention belongs to the oxide compound of zirconium, specifically, relates to a kind of preparation method of Nano tube of zirconium dioxide.
Background technology
Zirconium white is unique a kind of metal oxide 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.Chemmun. " (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, uses 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 acid treatment 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 rare 48% HF and methanol wash, and drying is at last 700 ℃ of heat treated 48 hours, remove carbon nanotube, obtain the zirconium white nanotube.This method not only needs to prepare carbon nanotube, complex technical process, and the raw materials cost height, and also the even tube wall of gained zirconium white nanotube is relatively poor." Advanced Materia1s " (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 deposits one deck self-assembly OTS-SAM (octadecyl tetrachloro silicane) on template, and internal layer is removed polycarbonate with chloroform at last by ALD method deposition zirconium white component then, obtains the zirconium white nanotube.This method needs expensive atomic layer deposition system, and nanotube thickness of pipe rate of growth is slow, and common every circulation primary thickness of pipe growth only is
, needing 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, the cost height is difficult to realize suitability for industrialized production." modern chemical industry " (2005,25 (5), the P38-39) method of a kind of Hydrothermal Preparation zirconium white nanotube of report, this method is carried out coprecipitation reaction with zirconyl chloride and ammoniacal liquor earlier, obtains white flocks, is precipitated to detection with distilled water wash and does not go out Cl
-, with the presoma of throw out, mixing then with sodium hydroxide solution as hydro-thermal reaction, the hydrothermal reaction kettle of packing into after stirring at 250 ℃ of following hydro-thermal reaction 24-48 hours, obtains the zirconium white nanotube.Made nanotube pattern of this method and uniform diameter are relatively poor, and length-to-diameter ratio is little, also have long reaction time, shortcoming that waste liquid amount is big in addition.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method that a kind of Nano tube of zirconium dioxide is provided, it is an anonizing, with solve existing Nano tube of zirconium dioxide preparation method complex technical process, cost height, to environment pollute, the shortcoming of the even tube wall difference of nanotube.
The present invention solves this technical problem the technical scheme that is adopted: adopt anonizing to prepare Nano tube of zirconium dioxide, concrete steps are, with methane amide and alcoholic solvent 1:1～3:1 mixing by volume, it with this mixed solvent preparation weight percent concentration 0.5～1.5% fluoride aqueous solution, again this fluoride aqueous solution is added in the reaction vessel, the zirconium sheet is made anode, platinized platinum or graphite flake are made negative electrode, anode and cathode spacing are from being 1.5cm, at room temperature adopt 10～90V direct current to carry out anodic oxidation reactions, generate Nano tube of zirconium dioxide, carry out with reaction on zirconium sheet surface, the Nano tube of zirconium dioxide that zirconium sheet surface generates constantly comes off, reaction after finishing is told the Nano tube of zirconium dioxide that is sunken to reaction container bottom, washes with water, in 105 ℃ of oven dry, promptly make the Nano tube of zirconium dioxide product.
Prepared as stated above Nano tube of zirconium dioxide even tube wall, caliber 30～200nm, length 5～150 μ m.
In aforesaid method, described alcoholic solvent is ethanol, ethylene glycol, 1, the mixture of one or more in 2-propylene glycol, the glycerine.
In aforesaid method, described fluorochemical is a kind of, two or three the mixture in Sodium Fluoride, Potassium monofluoride, the Neutral ammonium fluoride.
In aforesaid method, the purity of described zirconium sheet is not less than 99.9%.
The invention has the beneficial effects as follows:
(1) substantive distinguishing features of the inventive method is, with methane amide and alcoholic solvent 1:1～3:1 mixing by volume, with mixed solvent preparation 0.5～1.5% fluoride aqueous solution, is reaction medium with this solution, adopts anonizing to prepare Nano tube of zirconium dioxide.Its successful key is: because different solvents has dissimilar polarity and ion(ic)activity, it is the methane amide of 1:1～3:1 and the mixed solvent of alcohols that the present invention adopts volume ratio, has obtained suitable polarity and ion(ic)activity.The inventive method is that than the marked improvement of prior art technology is simple, and is easy to operate, and cost is low, and caliber and pipe range homogeneous and controllable are easy to suitability for industrialized production, and used mixed solvent is nontoxic substantially, recyclable, recycle.
(2) another innovative point of the inventive method is, is raw material with the metal zirconium.Zirconium sheet surface forms Nano tube of zirconium dioxide under electric field action, and growth gradually; Come off when the Nano tube of zirconium dioxide length on zirconium sheet surface reaches certain value, and have new Nano tube of zirconium dioxide to form, grow, this process moves in circles, until zirconium sheet complete reaction.
(3) to select suitable anodic oxidation voltage for use be 10～90V in the present invention, and voltage raises, and speed of response is accelerated, and caliber increases; Loss of voltage, speed of response slows down, and caliber dwindles.
In a word, the inventive method just can be prepared the Nano tube of zirconium dioxide of caliber 30～200nm, length 5～150 μ m, even tube wall by adjusting reaction medium composition, concentration and anodic oxidation voltage.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is the photo in kind of the prepared Nano tube of zirconium dioxide of the inventive method.
Embodiment
Fig. 1 shows Nano tube of zirconium dioxide caliber, the even tube wall that is made by the following example of the present invention, and length-to-diameter ratio is big.Embodiment 1
With methane amide and glycerine 1:1 mixing by volume, it with this mixed solvent preparation weight percent concentration 0.5% Fluorinse, this Fluorinse is added in the reaction vessel, the zirconium sheet is made anode, and platinized platinum is made negative electrode, and anode and cathode spacing are from being 1.5cm, adopt 90V direct current room temperature to carry out anodic oxidation reactions, generate Nano tube of zirconium dioxide on zirconium sheet surface, carry out with reaction, the Nano tube of zirconium dioxide that zirconium sheet surface generates constantly comes off.Reaction after finishing is told the Nano tube of zirconium dioxide that is sunken to reaction container bottom, washes with water, in 105 ℃ of oven dry, promptly makes the Nano tube of zirconium dioxide product.
Embodiment 2
With methane amide and ethylene glycol 2:1 mixing by volume, with this mixed solvent preparation weight percent concentration is 0.5% Potassium monofluoride and 0.5% ammonium fluoride solution, this fluoride aqueous solution is added in the reaction vessel, the zirconium sheet is made anode, platinized platinum is made negative electrode, anode and cathode spacing adopt 30V direct current room temperature to carry out anodic oxidation reactions from being 1.5cm.Reaction after finishing is told the Nano tube of zirconium dioxide that is sunken to reaction container bottom, washes with water, in 105 ℃ of oven dry, promptly makes the Nano tube of zirconium dioxide product.
Embodiment 3
With methane amide and ethanol 3:1 mixing by volume, it with this mixed solvent preparation weight percent concentration 1.5% ammonium fluoride solution, this ammonium fluoride solution is added in the reaction vessel, the zirconium sheet is made anode, graphite flake is made negative electrode, anode and cathode spacing adopt 10V direct current room temperature to carry out anodic oxidation reactions from being 1.5cm.Reaction after finishing is told the Nano tube of zirconium dioxide that is sunken to reaction container bottom, washes with water, in 105 ℃ of oven dry, promptly makes the Nano tube of zirconium dioxide product.
Embodiment 4
With methane amide and 1,2-propylene glycol 1.5:1 by volume mixes, with this mixed solvent preparation weight percent concentration is 0.4% Potassium monofluoride and 0.4% Fluorinse, this fluoride aqueous solution is added in the reaction vessel, the zirconium sheet is made anode, graphite flake is made negative electrode, and anode and cathode spacing adopt 70V direct current room temperature to carry out anodic oxidation reactions from being 1.5cm.Reaction after finishing is told the Nano tube of zirconium dioxide that is sunken to reaction container bottom, washes with water, in 105 ℃ of oven dry, promptly makes the Nano tube of zirconium dioxide product.
Embodiment 5
With the 3:1:1 mixing by volume of methane amide, glycerine, ethanol, it with this mixed solvent preparation weight percent concentration 1.0% Fluorinse, this Fluorinse is added in the reaction vessel, the zirconium sheet is made anode, platinized platinum is made negative electrode, anode and cathode spacing adopt 50V direct current room temperature to carry out anodic oxidation reactions from being 1.5cm.Reaction after finishing is told the Nano tube of zirconium dioxide that is sunken to reaction container bottom, washes with water, in 105 ℃ of oven dry, promptly makes the Nano tube of zirconium dioxide product.
Embodiment 6
Remove with 1, the 2-propylene glycol is replaced ethanol, ethylene glycol is replaced outside the glycerine, and other make the Nano tube of zirconium dioxide product thus all with embodiment 5.
Embodiment 7
Replacing weight percent concentration except that the Fluorinse that with weight percent concentration is 0.5% Neutral ammonium fluoride and 0.5% is that other make the Nano tube of zirconium dioxide product thus all with embodiment 5 1.0% the Fluorinse.
Embodiment 8
With the 6:1:1:1 mixing by volume of methane amide, ethylene glycol, glycerine, ethanol, with this mixed solvent preparation weight percent concentration is 0.6% Potassium monofluoride and 0.6% ammonium fluoride solution, this fluoride aqueous solution is added in the reaction vessel, the zirconium sheet is made anode, graphite flake is made negative electrode, anode and cathode spacing adopt 20V direct current room temperature to carry out anodic oxidation reactions from being 1.5cm.Reaction after finishing is told the Nano tube of zirconium dioxide that is sunken to reaction container bottom, washes with water, in 105 ℃ of oven dry, promptly makes the Nano tube of zirconium dioxide product.
Embodiment 9
With methane amide, ethylene glycol, glycerine, ethanol, 1,2-propylene glycol 6:1:1:1:1 by volume mixes, with this mixed solvent preparation weight percent concentration is 0.3% Neutral ammonium fluoride, 0.3% Sodium Fluoride and 0.3% potassium fluoride solution, this fluoride aqueous solution is added in the reaction vessel, the zirconium sheet is made anode, platinized platinum is made negative electrode, and anode and cathode spacing adopt 60V direct current room temperature to carry out anodic oxidation reactions from being 1.5cm.Reaction after finishing is told the Nano tube of zirconium dioxide that is sunken to reaction container bottom, washes with water, in 105 ℃ of oven dry, promptly makes the Nano tube of zirconium dioxide product.
Claims (3)
1. the preparation method of Nano tube of zirconium dioxide, it is characterized in that: adopt anonizing to prepare Nano tube of zirconium dioxide, concrete steps are, with methane amide and alcoholic solvent 1:1～3:1 mixing by volume, it with this mixed solvent preparation weight percent concentration 0.5～1.5% fluoride aqueous solution, again this fluoride aqueous solution is added in the reaction vessel, the zirconium sheet is made anode, platinized platinum or graphite flake are made negative electrode, anode and cathode spacing are from being 1.5cm, at room temperature adopt 10～90V direct current to carry out anodic oxidation reactions, generate Nano tube of zirconium dioxide, carry out with reaction on zirconium sheet surface, the Nano tube of zirconium dioxide that zirconium sheet surface generates constantly comes off, reaction after finishing is told the Nano tube of zirconium dioxide that is sunken to reaction container bottom, washes with water, in 105 ℃ of oven dry, promptly make the Nano tube of zirconium dioxide product, above-mentioned alcoholic solvent is an ethanol, ethylene glycol, 1, the 2-propylene glycol, the mixture of one or more in the glycerine.
2. according to the preparation method of the described Nano tube of zirconium dioxide of claim 1, it is characterized in that: described fluorochemical is the mixture of two or three in a kind of or Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride in Sodium Fluoride or the Potassium monofluoride.
3. according to the preparation method of the described Nano tube of zirconium dioxide of claim 1, it is characterized in that: the purity of described zirconium sheet is not less than 99.9%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101569595B (en) * | 2009-06-16 | 2010-12-08 | 李榕卿 | Preparation technology of dental material for cavity restoration |
| CN101955224B (en) * | 2009-07-20 | 2012-09-26 | 焦作市维纳精细陶瓷有限公司 | Preparation method of zirconium oxide nanotube |
| CN102068989B (en) * | 2010-12-02 | 2012-10-03 | 河北工业大学 | Method for preparing ZrO2 nanotube supported copper catalyst |
| CN102125825B (en) * | 2010-12-02 | 2012-05-23 | 河北工业大学 | Preparation method of ZrO2 nanotube supported B2O3 catalyst |
| CN102690202B (en) * | 2012-06-07 | 2014-03-05 | 河北工业大学 | Preparation method of dodecanol benzoate |
| CN103340754B (en) * | 2013-06-05 | 2014-12-10 | 河北工业大学 | Preparation method of zirconia nanotube reinforced denture powder |
| CN109183124B (en) * | 2018-10-30 | 2020-05-01 | 湖南大学 | Narrow-forbidden-band black zirconia nanotube film and preparation method thereof |
| CN113877574B (en) * | 2021-11-11 | 2024-02-02 | 河北工业大学 | Preparation method and application of zirconium dioxide nanotube array immobilized monoatomic catalyst |
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Non-Patent Citations (6)
| Title |
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| Fabrication and characterization of smooth high aspect ratio zirconia nanotubes. Hiroaki Tsuchiya，et.al.Chemical Physics Letters,No.410. 2005 |
| Fabrication and characterization of smooth high aspect ratio zirconia nanotubes. Hiroaki Tsuchiya，et.al.Chemical Physics Letters,No.410. 2005 * |
| 二氧化锆纳米管的制备与结构性质研究. 徐惠，杨志，翟钧等.兰州大学学报( 自然科学版)，第39卷第5期. 2003 |
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| 水热法制备氧化锆纳米管的影响因素及形成机理. 尹衍升，卢瑶，陈守刚.现代化工，第25卷第5期. 2005 |
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