CN103120933A - Preparation method of nanometer TiO2/ZrO2 composite material - Google Patents
Preparation method of nanometer TiO2/ZrO2 composite material Download PDFInfo
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- CN103120933A CN103120933A CN2011103697786A CN201110369778A CN103120933A CN 103120933 A CN103120933 A CN 103120933A CN 2011103697786 A CN2011103697786 A CN 2011103697786A CN 201110369778 A CN201110369778 A CN 201110369778A CN 103120933 A CN103120933 A CN 103120933A
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Abstract
The invention relates to a preparation method of a nanometer TiO2/ZrO2 composite material, mainly aiming at solving the problems of an existing synthetic technology that the process is complicated, the Ti-Zr composite degree is low, and the product grain diameter is large. The preparation method provided by the invention adopts the technical scheme that the water vapor is adopted to hydrolyze an organic titanium and zirconium solution, the problems are preferably solved, and the preparation method can be used in industrial production of the nanometer TiO2/ZrO2 composite material with high loading titanium quantity.
Description
Technical field
The present invention relates to a kind of nano-TiO
2/ ZrO
2The composite manufacture method.
Background technology
The metal low-dimensional nano-oxide TiO of tetravalence
2, ZrO
2, application is extremely widely arranged.Titanium dioxide (TiO
2) be the Chinese white of most important performance the best in the world.Be widely used in coating, papermaking, chemical fibre plastics, rubber medicine, cosmetics, more than 20 industry such as electronic component, metallurgical photochemical catalyst etc.Nano titanium oxide is as a kind of novel photocatalyst, UV resistant agent, and photoelectric effect agent etc. will be with its magical function at environment, and information material plays immeasurable effect in the technological revolution in the fields such as energy medical treatment and health.Nano titanium oxide has the ultraviolet function of absorption, and it all has effective ultraviolet filtering ability in whole ultraviolet districts (UVC+UVB+UVA).Current, nano-TiO
2Photocatalysis research can be used for that the organic matter noble metal reclaims and to organic pollution, nano-TiO in addition in waste water and air
2Can also make microbial bacterial etc. resolve into CO
2And H
2O plays the effect of sterilization and deodorization anti-fouling and self-cleaning.Zirconium and titanium are same major element, and zirconium has been Duoed one-period than titanium, more shows its metallic character, is widely used in ceramic technology; Xenogenesis catalysis; Contain ZrO
2Special ceramic material be the basic material of electronics, space flight, aviation and nuclear industry, its unique ph stability makes it extremely valuable in paraffin industry (isomerization, dehydrogenation etc.).Nano level ZrO
2More be widely used in special cermacis; Ceramic membrane; The aspects such as compound heterogeneous catalyst.In recent years, to TiO
2/ ZrO
2Bielement nano composite research increasingly heat up, this binary material has shown than pure TiO
2Higher photocatalysis property [X.Fu, L.A.Clark, Q.Yang, MA.Anderson, Environ.Sci.Technol.1996,30,647.], and TiO
2/ ZrO
2Composite larger surface area and stronger soda acid character [J.Miciukiewicz, T.Mang, Appl.Catal.A:Gen.1995,122,151.] are also arranged.It has been widely used in NO in vehicle exhaust
XRemove [fourth radiance, Jiang Xiaoyuan, Lin Nianda, chemistry circular 2003,66 (10): 673.], hydrodesulfurization [Daly F.P., Ando H., the Schmitt J.L. of fuel, J.Catal.1987,108 (2): 401.], fluorochlorohydrocarbon removes [Tajima M., Niwa M., Fujii Y., Appl.Catal.B 1997,14 (1-2): 97.] etc. the important catalytic reactions such as vapor phase Beckmann rearrangement, hydrogenation and hydrogen processing of field of Environment Protection and cyclohexanone oxime.
Prepare this bielement nano TiO
2/ ZrO
2The method of composite is a lot, and be summed up substantially to comprise two kinds vapor phase method and liquid phase method: gas-phase chemical reaction can be divided three classes: TiCl
4, ZrOCl
2With O
2Oxidation; The alcohol titanium, the cracking of pure zirconates direct heat; Alcohol titanium, pure zirconates aerosol gas-phase decomposition.Pure titanium salt sol-gel method and TiCl in liquid phase reactor
4, ZrOCl
2Noble gas protection method for hydrolysis.In sum, existing for the preparation of TiO
2/ ZrO
2In the technology of composite or outmoded, otherwise complicated.These factors have limited TiO widely
2/ ZrO
2The development of composite and commercial Application.
Summary of the invention
Technical problem to be solved by this invention is that the process that exists in existing synthetic technology is complicated, titanium zirconium Compound Degree is low, and the problem that product cut size is large provides a kind of new nanoscale TiO
2/ ZrO
2The composite manufacture method.The method has succinctly, efficient, the nanometer agglomeration problems that can avoid the capillary condensation effect to cause, and gained TiO
2/ ZrO
2Composite has compound good, and particle diameter is less than the advantage of 10 nanometers.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of nano-TiO
2/ ZrO
2The composite manufacture method comprises the following steps: a) organic titanium and organic zirconium are scattered in the organic solvent higher than water boiling point and obtain mixed liquor I, the mol ratio of Ti in mixed liquor I: Zr is 0.01～100: 1; The total mole number of titanium and zirconium and the mole ratio of organic solvent are 0.01～100: 1; B) under 100～240 ℃ of conditions, steam is contacted with mixed liquor I, make organic titanium and organic zirconium in mixed liquor I that hydrolysis occur simultaneously, obtain nano-TiO
2/ ZrO
2The precursor II of composite; C) under 300～1000 ℃ of conditions, the precursor II roasting was got TiO in 4～72 hours
2/ ZrO
2Composite.
In technique scheme, at least a in the organic titanium of pure titanium or titanium ester of titanium source preferred version; Zirconium source preferred version is selected from least a in the organic zirconium of pure zirconium or zirconium ester.The organic solvent preferred version is the weak polar solvent of indissoluble water, and the reaction temperature preferable range is 100～240 ℃.
By technique scheme, the nanometer agglomeration problems of effectively having avoided the capillary condensation effect to cause, and do not need to add any template, polymerization inhibitor greatly reduces complexity and the cost of reaction.Method due to use steam hydrolysis organic solution in the present invention prepares nano-TiO in reactor
2/ ZrO
2Composite, before hydrolysis, titanium zirconium organic source atom level fully contacts, and after crystallization, the product cut size that obtains only has several nanometers.Because product cut size only has several nanometers, greatly increased TiO
2With ZrO
2Between interaction, Compound Degree is high.In addition, owing to not containing any template, greatly reduce cost in the inventive method, obtained technique effect preferably.
Description of drawings
Fig. 1 is prepared nano-TiO
2/ ZrO
2Composite (Ti: Zr=1: 15～15: 1) the X-ray diffraction spectrogram after 600 ℃ of roastings.
Fig. 2 is prepared nano-TiO
2/ ZrO
2Composite (Ti: Zr=1: 15～15: the 1) figure of the ultraviolet absorption spectrum (UV) after 600 ℃ of roastings.
Fig. 3 is prepared nano-TiO
2/ ZrO
2Composite (Ti: Zr=1: 1) the projection Electronic Speculum of the purple after 600 ℃ of roastings (TEM) figure.
In Fig. 1, XRD composes the obvious broadening in peak, shows the TiO of preparation
2/ ZrO
2Composite is nanocrystalline.Spectral line c wherein, (at Ti: Zr=1: in 1 situation) shows both perfect compound.It is the characteristic spectral line that XRD does not show any independent a kind of oxide.
In Fig. 2, surperficial this nano material of UV absorption result has fabulous light absorptive.
In Fig. 3, the prepared composite of transmission electron microscope explanation is thrown away the size with homogeneous after high-temperature roasting, and its granularity is at 20nm.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
The high nano-TiO that carries the titanium amount
2/ ZrO
2The composite manufacture method.At first isopropyl titanate and zirconium iso-propoxide are scattered in and obtain mixed liquor I in toluene, (the toluene boiling point helps water preferentially to be diffused into the organic solution surface with vapor form higher than water, nanocrystal after hydrolysis is collected in organic solvent, the nanometer caking of effectively having avoided the capillary condensation effect to cause).The mol ratio of the Ti of mixed liquor I: Zr is 1: 1; Wherein the total mole number of titanium and zirconium is 0.1: 1 with the ratio of organic solvent.Under 150 ℃ of conditions, steam is contacted with mixed liquor I, make isopropyl titanate and zirconium iso-propoxide in mixed liquor I that hydrolysis occur simultaneously, obtain nano-TiO
2/ ZrO
2The precursor II of composite.After air drying, the precursor II roasting was got the TiO about granularity 20 nanometers under 600 ℃ of conditions in 12 hours
2/ ZrO
2Composite.XRD powder diffraction spectrum before and after the product roasting is as shown in Fig. 1 c: X-ray spectrum discloses TiO
2/ ZrO
2Composite perfect compound.It is the characteristic spectral line that XRD does not show any independent a kind of oxide.Fig. 2 is the ultraviolet absorption spectrum transmission electron microscope picture, and the nanocrystalline good light absorptive of preparation is described.
[embodiment 2～8]
According to the method for embodiment 1, just change reaction temperature, organic titanium, the kind of zirconium and different titanium zirconium molar ratio can be to nano-TiOs
2/ ZrO
2Composite carries out granularity, Ti: Zr obtains different size than further regulating, the different nano-TiOs that carry the titanium amount
2/ ZrO
2Composite.
Specific embodiment result and comparative example the results are shown in following table.
| Embodiment | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Synthesis temperature (℃) | 110 | 130 | 150 | 170 | 190 | 210 | 240 |
| Reaction time (h) | 8 | 12 | 12 | 16 | 18 | 10 | 20 |
| Sintering temperature (℃) | 500 | 600 | 700 | 800 | 500 | 700 | 800 |
| The organic titanium source | Isopropyl titanate | With 2 | With 2 | With 2 | With 2 | Butyl titanate | With 7 |
| The organic zirconium source | Zirconium iso-propoxide | With 2 | With 2 | With 2 | With 2 | With 2 | With 2 |
| |
1∶15 | 1∶5 | 1∶1 | 5∶1 | 15∶1 | 1∶5 | 5∶1 |
| Particle diameter (d/nm) | 6.1 | 13.3 | 19.5 | 24.7 | 29.9 | 18.5 | 21.0 |
| The zirconium crystalline phase | Four directions+monocline | With 2 | Nothing | The four directions | The four directions | With 2 | The four directions |
| The titanium crystalline phase | Anatase | With 2 | With 2 | With 2 | With 2 | With 2 | With 2 |
Claims (5)
1. nano-TiO
2/ ZrO
2The composite manufacture method comprises the following steps: a) organic titanium and organic zirconium are scattered in the organic solvent higher than water boiling point and obtain mixed liquor I, the mol ratio of Ti in mixed liquor I: Zr is 0.01～100: 1; The total mole number of titanium and zirconium and the mole ratio of organic solvent are 0.01～100: 1; B) under 100～240 ℃ of conditions, steam is contacted with mixed liquor I, make organic titanium and organic zirconium in mixed liquor I that hydrolysis occur simultaneously, obtain nano-TiO
2/ ZrO
2The precursor II of composite; C) under 300～1000 ℃ of conditions, the precursor II roasting was got nano-TiO in 4～72 hours
2/ ZrO
2Composite.
2. nano-TiO according to claim 1
2/ ZrO
2The composite manufacture method is characterized in that the titanium source is selected from least a in the organic titanium of pure titanium or titanate esters.
3. nano-TiO according to claim 1
2/ ZrO
2The composite manufacture method is characterized in that the zirconium source is selected from least a in the organic zirconiums such as pure zirconium or zirconate.
4. nano-TiO according to claim 1
2/ ZrO
2The composite manufacture method is characterized in that the weak polar solvent of the difficult dissolved water of organic solvent.
5. nano-TiO according to claim 1
2/ ZrO
2The composite manufacture method is characterized in that reaction temperature is 80～260 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106118525A (en) * | 2016-06-24 | 2016-11-16 | 合肥得润电子器件有限公司 | A kind of nano-oxide doped and compounded microporous membrane insulating bag band |
| CN106698509A (en) * | 2015-11-17 | 2017-05-24 | 林莉 | Composite nano zirconium oxide with uniform particle size distribution, and continuous preparation method and equipment thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4687643A (en) * | 1983-02-25 | 1987-08-18 | Montedison S.P.A. | Apparatus for preparing monodispersed, spherical, non-agglomerated metal oxide particles having a size below one micron |
| CN1259488A (en) * | 1999-01-04 | 2000-07-12 | 北京大学 | Prepn. method of surface doped and weakly agglomerated nanometer zirconium oxide powder |
| CN1800132A (en) * | 2005-01-05 | 2006-07-12 | 湖南大学 | Arene olefin catalytic oxidation for preparing aromatic aldehyde |
| CN101073769A (en) * | 2007-06-25 | 2007-11-21 | 沈阳化工学院 | Method for producing nano-titanic oxide light catalyst by steam hydrolysis |
-
2011
- 2011-11-18 CN CN2011103697786A patent/CN103120933A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4687643A (en) * | 1983-02-25 | 1987-08-18 | Montedison S.P.A. | Apparatus for preparing monodispersed, spherical, non-agglomerated metal oxide particles having a size below one micron |
| CN1259488A (en) * | 1999-01-04 | 2000-07-12 | 北京大学 | Prepn. method of surface doped and weakly agglomerated nanometer zirconium oxide powder |
| CN1800132A (en) * | 2005-01-05 | 2006-07-12 | 湖南大学 | Arene olefin catalytic oxidation for preparing aromatic aldehyde |
| CN101073769A (en) * | 2007-06-25 | 2007-11-21 | 沈阳化工学院 | Method for producing nano-titanic oxide light catalyst by steam hydrolysis |
Non-Patent Citations (1)
| Title |
|---|
| KOICHI KUBO等: "Synthesis of ZrO2–TiO2 solid solutions by various synthetic methods in the region of high zirconium contents", 《J MATER SCI》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698509A (en) * | 2015-11-17 | 2017-05-24 | 林莉 | Composite nano zirconium oxide with uniform particle size distribution, and continuous preparation method and equipment thereof |
| CN106698509B (en) * | 2015-11-17 | 2019-06-11 | 林莉 | Composite Nano zirconium oxide, continuous preparation method and its equipment of even particle size distribution |
| CN106118525A (en) * | 2016-06-24 | 2016-11-16 | 合肥得润电子器件有限公司 | A kind of nano-oxide doped and compounded microporous membrane insulating bag band |
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Application publication date: 20130529 |