CN101862627B - Preparation method of titanium dioxide microcapsule coating noble metal nano particles - Google Patents
Preparation method of titanium dioxide microcapsule coating noble metal nano particles Download PDFInfo
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- CN101862627B CN101862627B CN2010101653384A CN201010165338A CN101862627B CN 101862627 B CN101862627 B CN 101862627B CN 2010101653384 A CN2010101653384 A CN 2010101653384A CN 201010165338 A CN201010165338 A CN 201010165338A CN 101862627 B CN101862627 B CN 101862627B
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Abstract
The invention belongs to the preparation of titanium dioxide microcapsules, in particular to a preparation method of a titanium dioxide microcapsule coating noble metal nano particles. The prior art has the defect that microcapsule preparation process is complicated and can causes the fracture of a coating shell when a template is removed. The preparation method comprises the steps of: preparing a precursor solution at a normal temperature; then transferring the precursor solution to a polytetrafluoroethylene hydrothermal kettle; carrying out secondary hydro-thermal treatment on settlement under certain temperature and time conditions; and finally, cooling to room temperature to obtain the titanium dioxide microcapsule coating noble metal nano particles. The invention has the advantages of simple preparation process and high production efficiency, can be used for preparing the titanium dioxide microcapsule coating different noble metal nano particles according to the requirement; and prepared noble metal microcapsule has high catalysis activity.
Description
Technical field
The present invention is the preparation of titanium dioxide microcapsule, specifically a kind of preparation method of titanium dioxide microcapsule of coating noble metal nano particles.
Technical background
It is found that nanometer size effect the beginning of the eighties in last century, and along with reducing of particle diameter, the specific area of nano material increases significantly, and the ratio that the surface atom number accounts for whole particle also greatly increases.The increase of surface atom sum causes the raising of surface atom coordination unsaturation, thereby has produced a large amount of outstanding key and unsaturated bond, and surface step, fold and defective increase thereupon, nano material is compared with the catalyst of large scale had higher catalytic activity.For example: gold is considered to a kind of SA catalysis material always, but when gold is broken up into nanoscale, can show very high catalytic activity.The precious metal material of nanoscale because of its outstanding catalytic property, electrical property, magnetic property and optical property, has become most important nano material and nanosecond science and technology research field.
Because precious metal surface can be big, reunites easily, generally all loads to carrier during use, the carrying method of prior art is a dipping.This method can only make noble metal be adsorbed on the surface of carrier, and noble metal is run off, and active sites is lost, active decline.Be wrapped in noble metal in the carrier, just can reduce the probability of catalysqt deactivation.Prior art is the method for (layer by layer) of being layering, and outside template, adsorbs noble metal nano particles earlier, and then at area load one deck carrier, the template of removing the inside at last obtains the catalyst of coating noble metal nano particles.The shortcoming of prior art is: the building-up process complicated steps is loaded down with trivial details, and the shell that can cause wrapping up can break when removing template.So inventing the preparation method of titanium dioxide microcapsule of the coating noble metal nano particles that a kind of technology is simple, convenient and swift, production efficiency is high is very important.
Summary of the invention
The preparation method of titanium dioxide microcapsule that the purpose of this invention is to provide the coating noble metal nano particles that a kind of technology is simple, convenient and swift, production efficiency is high.
The objective of the invention is to realize like this:
A kind of preparation method of titanium dioxide microcapsule of coating noble metal nano particles, step is following:
(1) preparation noble metal precursor solution: the noble metal precursor thing is added in the absolute ethyl alcohol, make noble metal precursor solution;
(2) preparation solution A: normal temperature slowly splashes into 5-15mL glycerine in the 20mL noble metal precursor solution, and vigorous stirring 10-30min under the room temperature gets intermediate product solution A;
(3) preparation TiO
2Colloidal sol: the predecessor of getting titanium splashes in the solution A vigorous stirring; Drip off continued and stir 30min, make the TiO of homogeneous transparent
2Colloidal sol;
(4) preparation sol B: the 5ml-15ml ether is added in the colloidal sol that step (3) makes, stirs 10min, sol B;
(5) preparation TiO
2Predecessor: sol B is moved in the 50mL water heating kettle, and temperature 373-433K leaves standstill the 0.5-6h ageing, takes out, naturally cools to room temperature; Taking precipitate is with washing with alcohol 3 times, and it is dry to put into baking oven 373K behind the suction filtration;
(6) titanium dioxide microcapsule of preparation coating noble metal nano particles: the TiO that step (5) is made
2Predecessor moves in the 50mL water heating kettle, adds redistilled water 40ml, keeps temperature 373-433K, leaves standstill the 1-12h ageing; Take out, naturally cool to room temperature; Taking precipitate is put into the 373K oven drying with washing with alcohol 3 times behind the suction filtration; Get the titanium dioxide microcapsule of coating noble metal nano particles.
In the step (1), the noble metal precursor thing is a gold chloride, chloroplatinic acid, palladium bichloride, a kind of in the silver chlorate.
The predecessor of titanium is a kind of in titanium sulfate, the titanyl sulfate in the step (2), is preferably titanyl sulfate.
Preferred temperature is 382-384K in the step (5); Preferred digestion time is 1h.
Preferred temperature is 382-384K in the step (6), and preferred digestion time is 4h.
Main points of the present invention are:
Combine secondary Hydrothermal Preparation technology through simple solvent thermal, can obtain the titanium dioxide microcapsule of coating noble metal nano particles; Kind through changing noble metal precursor solution can prepare the titanium dioxide microcapsule that wraps up different noble metal nano particles.
Concrete grammar of the present invention is divided into following steps:
At first at normal temperatures, preparation precursor aqueous solution; Then precursor aqueous solution is transferred in the polytetrafluoroethylene (PTFE) water heating kettle, the sediment that obtains carries out the secondary hydrothermal treatment consists under certain temperature and time condition; At last, be cooled to the titanium dioxide microcapsule that room temperature can obtain coating noble metal nano particles.
The noble metal precursor thing can be a gold chloride, chloroplatinic acid, palladium bichloride, a kind of in the silver chlorate; Also can be the predecessor of other various noble metals, how many amounts of noble metal can throwing in according to load capacity.
The predecessor of titanium is a kind of in titanium sulfate, the titanyl sulfate, wherein is best with the titanyl sulfate.
Precursor aqueous solution is the absolute ethyl alcohol that the titanium precursor thing of 0.5-2mL is slowly splashed into 10-30mL, and 5ml-15ml glycerine makes A liquid in the mixture of 5ml-15ml ether and a certain amount of noble metal precursor thing, and A liquid is strong agitation 10-30min at room temperature.
The above-mentioned A liquid that makes is put into the 50ml water heating kettle leave standstill the 0.5-6h ageing at 373-433K and make precursor B, preferred digestion time is 1h; Preferred ageing temperature is 382-384K.
Sediment after the above-mentioned precursor B ageing being transferred in the beaker, added absolute ethanol washing for several times, is colourless up to the ethanol that washs.Last suction filtration, put into the oven dry of 373K vacuum drying oven;
Above-mentioned substance is put into the 50ml water heating kettle again, add the 40ml redistilled water and leave standstill the 1-12h ageing at 373-433K and make titanium dioxide microcapsule, preferred digestion time is: 4h; Preferred ageing temperature is 382-384K.Sediment D after the ageing is transferred in the beaker, added absolute ethanol washing for several times, colourless up to the ethanol of washing.Last suction filtration, put into the titanium dioxide powder that the oven dry of 373K vacuum drying oven obtains, be the titanium dioxide microcapsule end product of coating noble metal nano particles.
Advantage of the present invention is:
1, preparation technology is simple, easy to operate.
2, titanium dioxide microcapsule production efficiency is high.
3, can prepare the titanium dioxide microcapsule that wraps up different noble metal nano particles as required.
4, the coating noble metal nano particles titanium dioxide microcapsule of preparation uses catalytic activity high as catalyst.
Description of drawings
Fig. 1 is Au forerunner's sample (a-b) and process secondary hydro-thermal (c-d) the nucleocapsid structure Au/TiO that does not have the secondary hydro-thermal
2The SEM of microcapsules and TEM figure.
Fig. 2 is Au-TiO
2The high magnification micrographs of microcapsules.
Fig. 3 is Au-TiO
2The Au particle diameter distribution map of microcapsules.
Fig. 4 is the SEM and the TEM figure of the titanium dioxide microcapsule of the different noble metal nano particles of parcel.
The specific embodiment
Embodiment 1:
Normal temperature slowly drips 20mL with the glycerine (available from Shanghai chemical reagents corporation of Chinese Medicine group [experiment reagent CR]) of 10mL and contains in a certain amount of gold chloride ethanol solution, and vigorous stirring obtains solution A.Get titanyl sulfate (available from (15%H of Aldrich chemical reagents corporation [experiment reagent CR]
2SO
4Solution)) splash in the A solution and vigorous stirring, wait to drip off continued and stir the TiO that 30min obtains homogeneous transparent
2Colloidal sol.The 10ml ether is joined in the resulting colloidal sol, continue to stir 10min, get sol B.Sol B is transferred in the 50mL water heating kettle, kept temperature 383K, place 1h, take out and naturally cool to room temperature.It is colourless to ethanol with washing with alcohol 3 times to take out sediment, puts into the 373K oven drying behind the suction filtration.With the TiO that obtains
2Predecessor is transferred in the 50mL water heating kettle, adds redistilled water 40ml, keeps temperature 383K, places 4h, takes out and naturally cool to room temperature.It is colourless to ethanol with washing with alcohol 3 times to take out sediment, puts into the 373K oven drying behind the suction filtration.So just obtained the Au-TiO of parcel golden nanometer particle
2Microcapsules.
Embodiment 2:
Normal temperature slowly splashes into 20mL with the glycerine (available from Shanghai chemical reagents corporation of Chinese Medicine group [experiment reagent CR]) of 10mL and contains in a certain amount of chloroplatinic acid ethanol solution, and vigorous stirring obtains solution A.Get titanyl sulfate (available from Aldrich chemical reagents corporation [experiment reagent CR]) and splash in the A solution and vigorous stirring, wait to drip off continued and stir the TiO that 30min obtains homogeneous transparent
2Colloidal sol.The 10ml ether is joined in the resulting colloidal sol, continue to stir 10min, get sol B.Sol B is transferred in the 50mL water heating kettle, kept temperature 383K, place 1h, take out and naturally cool to room temperature.It is colourless to ethanol with washing with alcohol 3 times to take out sediment, puts into the 373K oven drying behind the suction filtration.With the TiO that obtains
2Predecessor is transferred in the 50mL water heating kettle, adds redistilled water 40ml, keeps temperature 383K, places 4h, takes out and naturally cool to room temperature.It is colourless to ethanol with washing with alcohol 3 times to take out sediment, puts into the 373K oven drying behind the suction filtration.So just obtained the Pt-TiO of parcel nano platinum particle
2Microcapsules.
Embodiment 3:
Normal temperature slowly splashes into 20mL with the glycerine (available from Shanghai chemical reagents corporation of Chinese Medicine group [experiment reagent CR]) of 10mL and contains in a certain amount of palladium bichloride ethanol solution, and vigorous stirring obtains solution A.Get titanyl sulfate (available from Aldrich chemical reagents corporation [experiment reagent CR]) and splash in the A solution and vigorous stirring, wait to drip off continued and stir the TiO that 30min obtains homogeneous transparent
2Colloidal sol.The 10ml ether is joined in the resulting colloidal sol, continue to stir 10min, get sol B.Sol B is transferred in the 50mL water heating kettle, kept temperature 383K, place 1h, take out and naturally cool to room temperature.It is colourless to ethanol with washing with alcohol 3 times to take out sediment, puts into the 373K oven drying behind the suction filtration.With the TiO that obtains
2Predecessor is transferred in the 50mL water heating kettle, adds redistilled water 40ml, keeps temperature 383K, places 4h, takes out and naturally cool to room temperature.It is colourless to ethanol with washing with alcohol 3 times to take out sediment, puts into the 373K oven drying behind the suction filtration.So just obtained the Pd-TiO of parcel Pd nano particle
2Microcapsules.
Embodiment 4:
Normal temperature slowly splashes into 20mL with the glycerine (available from Shanghai chemical reagents corporation of Chinese Medicine group [experiment reagent CR]) of 10mL and contains in a certain amount of silver chlorate ethanol solution, and vigorous stirring obtains solution A.Get titanyl sulfate (available from Aldrich chemical reagents corporation [experiment reagent CR]) and splash in the A solution and vigorous stirring, wait to drip off continued and stir the TiO that 30min obtains homogeneous transparent
2Colloidal sol.The 10ml ether is joined in the resulting colloidal sol, continue to stir 10min, get sol B.Sol B is transferred in the 50mL water heating kettle, kept temperature 383K, place 1h, take out and naturally cool to room temperature.It is colourless to ethanol with washing with alcohol 3 times to take out sediment, puts into the 373K oven drying behind the suction filtration.With the TiO that obtains
2Predecessor is transferred in the 50mL water heating kettle, adds redistilled water 40ml, keeps temperature 383K, places 4h, takes out and naturally cool to room temperature.It is colourless to ethanol with washing with alcohol 3 times to take out sediment, puts into the 373K oven drying behind the suction filtration.So just obtained the Ag-TiO of parcel Nano silver grain
2Microcapsules.
Following table is the structural parameters of the titanium dioxide microcapsule of the different noble metal nano particles of parcel among the embodiment 1,2,3,4.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. the preparation method of titanium dioxide microcapsule of a coating noble metal nano particles, step is following:
(1) preparation noble metal precursor solution: the noble metal precursor thing is added in the absolute ethyl alcohol, make noble metal precursor solution;
(2) preparation solution A: normal temperature slowly drips 5-15mL glycerine in the 20mL noble metal precursor solution, and vigorous stirring 10-30min under the room temperature gets intermediate product solution A;
(3) preparation TiO
2Colloidal sol: the predecessor of getting titanium splashes in the solution A vigorous stirring; Drip off continued and stir 30min, make the TiO of homogeneous transparent
2Colloidal sol;
(4) preparation sol B: the 5ml-15ml ether is added in the colloidal sol that step (3) makes, stirs 10min, sol B;
(5) preparation TiO
2Predecessor: sol B is moved in the 50mL water heating kettle, and temperature 373-433K leaves standstill the 0.5-6h ageing, takes out, naturally cools to room temperature; Taking precipitate is with washing with alcohol 3 times, and it is dry to put into baking oven 373K behind the suction filtration;
(6) titanium dioxide microcapsule of preparation coating noble metal nano particles: the TiO that step (5) is made
2Predecessor moves in the 50mL water heating kettle, adds redistilled water 40ml, keeps temperature 373-433K, leaves standstill the 1-12h ageing; Take out, naturally cool to room temperature; Taking precipitate is put into the 373K oven drying with washing with alcohol 3 times behind the suction filtration; Get the titanium dioxide microcapsule of coating noble metal nano particles.
2. the preparation method of titanium dioxide microcapsule of coating noble metal nano particles according to claim 1, it is characterized in that: in the step (1), the noble metal precursor thing is a gold chloride, chloroplatinic acid, palladium bichloride, a kind of in the silver chlorate.
3. the preparation method of titanium dioxide microcapsule of coating noble metal nano particles according to claim 1 is characterized in that: the predecessor of titanium is a kind of in titanium sulfate, the titanyl sulfate in the step (3).
4. the preparation method of titanium dioxide microcapsule of coating noble metal nano particles according to claim 1 is characterized in that: preferred temperature is 382-384K in the step (5); Preferred digestion time is 1h.
5. the preparation method of titanium dioxide microcapsule of coating noble metal nano particles according to claim 1 is characterized in that: preferred temperature is 382-384K in the step (6), and preferred digestion time is 4h.
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| CN103192075B (en) * | 2013-04-16 | 2015-04-22 | 杨晓红 | Preparation method of core-shell composite material wrapped in titanium dioxide nanoparticle coating |
| CN109331813A (en) * | 2018-11-02 | 2019-02-15 | 中国科学院重庆绿色智能技术研究院 | Catalyst, preparation method, catalysis Enhancement Method, purification device |
| CN110240891B (en) * | 2019-07-09 | 2021-04-27 | 武汉中科先进技术研究院有限公司 | Preparation method and application of precious metal particle/silicon dioxide wall material phase change microcapsule composite material |
| CN112007593A (en) * | 2020-09-04 | 2020-12-01 | 天津城建大学 | Titanium dioxide phase change microcapsule material taking titanyl sulfate as titanium source and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4460563A (en) * | 1980-04-09 | 1984-07-17 | Eurand S.P.A. | Process for preparing microcapsules in a liquid vehicle |
| CN1492275A (en) * | 2002-10-21 | 2004-04-28 | 西北工业大学 | White electronic ink micro capsule |
| CN1622853A (en) * | 2001-12-27 | 2005-06-01 | 宝力科莱株式会社 | Method of preparing functional microcapsule incorporating silver nanoparticles |
| CN101259399A (en) * | 2007-12-18 | 2008-09-10 | 浙江大学 | Method for preparing inorganic nano microcapsule by one-step method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60198558A (en) * | 1984-03-21 | 1985-10-08 | Fuji Photo Film Co Ltd | Production of capsule toner |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4460563A (en) * | 1980-04-09 | 1984-07-17 | Eurand S.P.A. | Process for preparing microcapsules in a liquid vehicle |
| CN1622853A (en) * | 2001-12-27 | 2005-06-01 | 宝力科莱株式会社 | Method of preparing functional microcapsule incorporating silver nanoparticles |
| CN1492275A (en) * | 2002-10-21 | 2004-04-28 | 西北工业大学 | White electronic ink micro capsule |
| CN101259399A (en) * | 2007-12-18 | 2008-09-10 | 浙江大学 | Method for preparing inorganic nano microcapsule by one-step method |
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