CN1358670A - Method for synthesizing zirconium oxide nano wire - Google Patents

Method for synthesizing zirconium oxide nano wire Download PDF

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Publication number
CN1358670A
CN1358670A CN 02100261 CN02100261A CN1358670A CN 1358670 A CN1358670 A CN 1358670A CN 02100261 CN02100261 CN 02100261 CN 02100261 A CN02100261 A CN 02100261A CN 1358670 A CN1358670 A CN 1358670A
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zirconium
zrocl
nano wire
oxalic acid
solution
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CN1171798C (en
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邱显清
曹化强
罗滨
梁瑜
左卫雄
朱起明
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Tsinghua University
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Tsinghua University
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Abstract

In method for synthesizing zirconia nano wire, ZrOCl2.8H2O and H2C2O4.2H2O are used as raw material, the process includes the following steps: respectively preparing zirconium oxychloride (ZrOCl2) and oxalic acid (H2C2O4) aqueous solutions, under the condition of continuously stirring ZrOCl2 solution slowly adding H2C2O4 solution into the ZrOCl2 solution, then continuously stirring to obtain zirconium sol; then impregnating porous alumina membrane with zirconium sol for 10 min., pressing for 5 hr. at 1.3 MPa, taking out said membrane from sol, drying under the infrared lamp., and roasting for 5 hr, at 500 deg.C and normal pressure under the condition of argon atmosphere so as to obtain the zirconia nano wire array. Said method can synthesize zirconia nano wire whose diameter is 50-300 nano and length is 10 micrometers, and said product can possess extensive application range.

Description

A kind of synthetic method of zirconium oxide nano wire
Technical field
The present invention relates to a kind of preparation of nano ceramic material, particularly a kind of synthesis technique of zirconium oxide nano wire and method.
Background technology
Zirconium white is considered to a kind of very important new ceramic material now.Comprise catalysis, film, be widely used in the numerous areas such as coating, oxygen sensor, ceramic toughening, Solid Oxide Fuel Cell relating to.Zirconium white can be in hydrogenation/dehydrogenation, adds in water/reactions such as dehydration to demonstrate good catalytic activity.
Chinese invention patent " preparation method of the weakly agglomerated nano zirconium oxide powder of surface doping " (publication number: 1259488) and " loaded nano oxidation Zirconium complex carrier and preparation method thereof " (publication number: 1307933) relate to the synthetic method of nano oxidized Zirconium, described method all is synthetic nm-class powder of zirconium oxide material.Zirconium oxide nano wire then belongs to a kind of nano structural material, and nanostructure is the important foundation of nanosecond science and technology, no matter in academic research or in application facet, all has very important meaning.Because the nano wire specific surface area is big, zirconium oxide nano wire is at the novel material that all has fine performance aspect catalysis, the ceramic toughening.The synthetic patent report that zirconium oxide nano wire is not arranged at present as yet.
Summary of the invention
The object of the present invention is to provide the method for the synthetic zirconium oxide nano wire of a kind of easy preparation.
The present invention is achieved through the following technical solutions: a kind of synthetic method of zirconium oxide nano wire is characterized in that this method carries out as follows:
A kind of synthetic method of zirconium oxide nano wire, this method is carried out as follows:
A. at room temperature, with zirconium oxychloride (ZrOCl 28H 2O), oxalic acid (H 2C 2O 42H 2O) be raw material, prepare respectively zirconium oxychloride (ZrOCl 2) and oxalic acid (H 2C 2O 4) aqueous solution, constantly stirring zirconium oxychloride (ZrOCl 2) in the situation of solution, with oxalic acid (H 2C 2O 4) aqueous solution slowly joins zirconium oxychloride (ZrOCl 2) in the solution, and stir, obtain zirconium colloidal sol; with keeping Zirconium oxychloride (ZrOCl 2) concentration range can be between 0.1～0.5M, corresponding oxalic acid (H 2C 2O 4) concentration range can be between 0.05～0.25M; Zirconium oxychloride (ZrOCl 2) aqueous solution and oxalic acid (H 2C 2O 4) aqueous solution is 2: 1 by the mole concentration ratio, volume ratio is that 1: 1～1: 1.5 scope is mixed;
B. multiaperture pellumina being immersed in the zirconium colloidal sol of step a gained after 10 minutes, is pressurization 5 hours under the 1.3Mpa situation at pressure;
C. will take out from colloidal sol through the film that step b processed, dry under infrared lamp, again normal pressure roasting 5 hours under 500 ℃, argon atmospher namely obtains the zirconium oxide nano wire array.
Material therefor is easy to get in the synthetic method of the present invention, and its technological process is easy, and can synthesize diameter is 50～300 nanometers, and length is greater than 10 microns zirconium oxide nano wire.
Description of drawings
Fig. 1: be the zirconium oxide nano wire of embodiment 1 electron scanning micrograph after with the molten aluminum oxide that removes partial oxidation aluminum alloy pattern plate upper surface of sodium hydroxide solution.
Fig. 2: be the zirconium oxide nano wire of embodiment 1 transmission electron microscope photo and the electron diffraction after with the aluminum oxide of the molten deoxidation aluminum alloy pattern plate of sodium hydroxide solution upper surface.
Fig. 3: be the zirconium oxide nano wire of embodiment 2 electron scanning micrograph after with the molten aluminum oxide that removes partial oxidation aluminum alloy pattern plate upper surface of sodium hydroxide solution.
Fig. 4: be the zirconium oxide nano wire of embodiment 3 electron scanning micrograph after with the molten aluminum oxide that removes partial oxidation aluminum alloy pattern plate upper surface of sodium hydroxide solution.
Fig. 5: be the zirconium oxide nano wire of embodiment 4 electron scanning micrograph after with the molten aluminum oxide that removes partial oxidation aluminum alloy pattern plate upper surface of sodium hydroxide solution.
Embodiment
Below by specific embodiment the present invention further is illustrated.
Embodiment 1:
---at room temperature, with zirconium oxychloride (ZrOCl 28H 2O), oxalic acid (H 2C 2O 42H 2O) be raw material, the ZrOCl of preparation 0.1M 2And 0.05MH 2C 2O 4The aqueous solution at room temperature, is constantly stirring ZrOCl 2In the situation of solution, with isopyknic H 2C 2O 4Solution slowly adds, and stirs with keeping, obtains zirconium colloidal sol.
---with the aperture of commercialization is that 20 nano-porous alumina films immerse in the above-mentioned zirconium colloidal sol, and after 10 minutes, pressurization (1.3MPa) is 5 hours in reaction vessel.
---will take out from colloidal sol through the film that said method was processed, dry under infrared lamp, again normal pressure roasting 5 hours in 500 ℃, argon atmospher namely obtains the zirconium oxide nano wire array.
This nanowire length can be determined this nanowire diameter greater than 10 microns between the 50-300 nanometer by Fig. 2 a as seen from Figure 1, and can be defined as cubic oxidation Zirconium monocrystalline by Fig. 2 b.
Embodiment 2:
---at room temperature, with zirconium oxychloride (ZrOCl 28H 2O), oxalic acid (H 2C 2O 42H 2O) be raw material, the ZrOCl of preparation 0.37M 2And 0.21MH 2C 2O 4The aqueous solution at room temperature, is constantly stirring ZrOCl 2In the situation of solution, with isopyknic H 2C 2O 4Solution slowly adds, and stirs with keeping, obtains zirconium colloidal sol.
---with the aperture of commercialization is that 20 nano-porous alumina films immersed in the above-mentioned zirconium colloidal sol after 10 minutes, and pressurization (1.3MPa) is 5 hours in reaction vessel.
---will take out from colloidal sol through the film that said method was processed, dry under infrared lamp, again normal pressure roasting 5 hours in 500 ℃, argon atmospher namely obtains the zirconium oxide nano wire array.
This nanowire length is greater than 10 microns as seen from Figure 3.
Embodiment 3:
---at room temperature, with zirconium oxychloride (ZrOCl 28H 2O), oxalic acid (H 2C 2O 42H 2O) be raw material, the ZrOCl of preparation 0.25 2And 0.12MH 2C 2O 4The aqueous solution at room temperature, is constantly stirring ZrOCl 2In the situation of solution, with isopyknic H 2C 2O 4Solution slowly adds, and stirs with keeping, obtains zirconium colloidal sol.
---with the aperture of commercialization is that 20 nano-porous alumina films immersed in the above-mentioned zirconium colloidal sol after 10 minutes, and pressurization (1.3MPa) is 5 hours in reaction vessel.
---will take out from colloidal sol through the film that said method was processed, dry under infrared lamp, again normal pressure roasting 5 hours in 500 ℃, argon atmospher namely obtains the zirconium oxide nano wire array.
This nanowire length is greater than 10 microns as seen from Figure 4.
Embodiment 4:
---at room temperature, with zirconium oxychloride (ZrOCl 28H 2O), oxalic acid (H 2C 2O 42H 2O) be raw material, the ZrOCl of preparation 20ml, 0.1M 2H with 30ml, 0.05M 2C 2O 4The aqueous solution at room temperature, is constantly stirring ZrOCl 2In the situation of solution, with 30mlH 2C 2O 4Solution slowly adds, and stirs with keeping, obtains zirconium colloidal sol.
---with the aperture of commercialization is that 20 nano-porous alumina films immersed in the above-mentioned zirconium colloidal sol after 10 minutes, and pressurization (1.3MPa) is 5 hours in reaction vessel.
---will take out from colloidal sol through the film that said method was processed, dry under infrared lamp, again normal pressure roasting 5 hours in 500 ℃, argon atmospher namely obtains the zirconium oxide nano wire array.
This nanowire length is greater than 10 microns as seen from Figure 5.

Claims (1)

1, a kind of synthetic method of zirconium oxide nano wire, this method is carried out as follows:
A. at room temperature, with zirconium oxychloride (ZrOCl 28H 2O), oxalic acid (H 2C 2O 42H 2O) be raw material, prepare respectively zirconium oxychloride (ZrOCl 2) and oxalic acid (H 2C 2O 4) aqueous solution, constantly stirring zirconium oxychloride (ZrOCl 2) in the situation of solution, with oxalic acid (H 2C 2O 4) aqueous solution slowly joins zirconium oxychloride (ZrOCl 2) in the solution, and stir, obtain zirconium colloidal sol; with keeping Zirconium oxychloride (ZrOCl 2) concentration range can be between 0.1～0.5M, corresponding oxalic acid (H 2C 2O 4) concentration range can be between 0.05～0.25M; Zirconium oxychloride (ZrOCl 2) aqueous solution and oxalic acid (H 2C 2O 4) aqueous solution is 2: 1 by the mole concentration ratio, volume ratio is that 1: 1～1: 1.5 scope is mixed;
B. multiaperture pellumina being immersed in the zirconium colloidal sol of step a gained after 10 minutes, is pressurization 5 hours under the 1.3Mpa situation at pressure;
C. will take out from colloidal sol through the film that step b processed, dry under infrared lamp, again normal pressure roasting 5 hours under 500 ℃, argon atmospher namely obtains the zirconium oxide nano wire array.
CNB021002614A 2002-01-11 2002-01-11 Method for synthesizing zirconium oxide nano wire Expired - Fee Related CN1171798C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7303723B2 (en) 2002-10-04 2007-12-04 The Ohio State University Research Foundation Method of forming nanostructures on ceramics
CN100423346C (en) * 2004-06-18 2008-10-01 中国科学院过程工程研究所 Method for low-temp. preparing nano-crystal zirconium-oxide base solid electrolyte
CN101311381A (en) * 2008-03-14 2008-11-26 南京大学 ZrS3 and ZrS2 nano-belts and method for making same
CN101823765A (en) * 2010-05-17 2010-09-08 山东理工大学 Preparation method of high dispersion rod type nanometer zirconium oxide
CN103045247A (en) * 2012-12-26 2013-04-17 青岛盛嘉信息科技有限公司 Oxide nanowire and preparation method thereof
CN112960991A (en) * 2021-02-26 2021-06-15 深圳陶陶科技有限公司 Ceramic polymer composite material and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7303723B2 (en) 2002-10-04 2007-12-04 The Ohio State University Research Foundation Method of forming nanostructures on ceramics
CN100423346C (en) * 2004-06-18 2008-10-01 中国科学院过程工程研究所 Method for low-temp. preparing nano-crystal zirconium-oxide base solid electrolyte
CN101311381A (en) * 2008-03-14 2008-11-26 南京大学 ZrS3 and ZrS2 nano-belts and method for making same
CN101311381B (en) * 2008-03-14 2010-08-18 南京大学 ZrS3 and ZrS2 nano-belts and method for making same
CN101823765A (en) * 2010-05-17 2010-09-08 山东理工大学 Preparation method of high dispersion rod type nanometer zirconium oxide
CN101823765B (en) * 2010-05-17 2011-08-31 山东理工大学 Preparation method of high dispersion rod type nanometer zirconium oxide
CN103045247A (en) * 2012-12-26 2013-04-17 青岛盛嘉信息科技有限公司 Oxide nanowire and preparation method thereof
CN112960991A (en) * 2021-02-26 2021-06-15 深圳陶陶科技有限公司 Ceramic polymer composite material and preparation method thereof

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