CN1683068A - Method for preparing metal oxide hollow microcapsule - Google Patents
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- CN1683068A CN1683068A CN 200510023935 CN200510023935A CN1683068A CN 1683068 A CN1683068 A CN 1683068A CN 200510023935 CN200510023935 CN 200510023935 CN 200510023935 A CN200510023935 A CN 200510023935A CN 1683068 A CN1683068 A CN 1683068A
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Abstract
The present invention relates to the preparation process of a kind of hollow metal oxide microcapsule. After mesoporous silica microball as template is alkyl group modified, nano metal oxide is filled into the microball hole canal and one layer of polyelectrolyte is adsorbed to the surface, and silica is finally leached out through treatment in alkali solution condition to prepare the hollow metal oxide microcapsule. Said process is simple, has adjustable shell material component and is suitable for the preparation of functional microcapsule. The microcapsule product has fine appearance and excellent performance, and may find its wide application in different fields, such as medicine preparation, catalyzing, electrochemistry, etc.
Description
Technical field
The present invention be a kind of be the method for template for preparing metal oxide hollow microcapsule with the mesopore silicon oxide microballoon.
Background technology
Have different shell components such as metal oxide, the hollow micro capsule of sulfide and precious metal since the characteristics such as big cavity volume, functional shell component and high-specific surface area of its uniqueness at catalysis, optics, have wide practical use in electrochemistry and other field of functional materials, become one of main research focus in recent years.
At present, synthetic spraying drying (P.J.Bminsma, the A.Y.Kim of mainly depending on of hollow micro capsule, J.Liu, S.Baskaran, Chem.Mater., 1997,9,2507), emulsion/be separated (H.Lin, Y.Cheng, C.Mou, Chem.Mater., 1998,10,3772) and the sacrificial core technology (L.D lhne, S.Leporatti; E.Donath, H.M hwald, J.Am.Chem.Soc., 2001,123,5431; S.M.Marinakos, J.P.Novak, L.C.BrousseauIII, A.B.House, E.M.Edeki, J.C.Feldhaus, D.L.Feldheim, J.Am.Chem.Soc., 1999,121,8518; Z.Wei, M.Wan, Adv.Mater., 2002,14,1314; M.S.Fleming, T.K.Mandal, D.R.Walt, Chem.Mater., 2001,13,2210; D.B.Zhang, L.M.Qi, J.M.Ma, H.M.Cheng, Adv.Mater., 2002,14,1499; S.Eiden, G.Maret, J.Colloid Interface Sci., 2002,250,281; F.Caruso, R.A.Caruso, H.Mohwald, Science, 1998,282,1111; Z.Zhong, Y.Yin, B.Gates, Y.Xia, Adv.Mater., 2000,12,206; A.Bourlinos, N.Boukos, D.Petridis, Adv.Mater., 2002,14,21; Sun, Y.; Xia, Y.Science2002,298,1006; Sun, Y.; Mayers, B.; Xia, Y.Nano.Lett.2002,2,481; Sun, Y.; Xia, Y.Nano.Lett.2003,3,1569).First method is that forerunner's attitude species that will constitute the hollow micro capsule shell component (such as the metal alkoxide of facile hydrolysis etc.) are mixed with the aqueous solution, and by nozzle formation atomizing droplet, because operation is generally carried out under exsiccant atmosphere, solvent in the drop that forms evaporates rapidly, impel the shell structure of difficult evaporable forerunner attitude species at drop surface rapid hydrolysis formation hollow micro capsule, this method can be synthesized hollow micro capsule fast and easily, but relate to high pressure, the use of spraying apparatus of high energy consumption and providing of strict dry atmosphere, the problem of generation security and economy in preparation process; Second method is with the hydrolysis on oil/water termination of formation micro-capsule shell component, form the shell structure of hollow micro capsule, this method is applicable to the synthetic of most shell component micro-capsule, but complicated operating process, poor repeatability, and the strictness of the micro-capsule that obtains size is limited by the size of drop, is difficult to obtain the micro-capsule of size distribution homogeneous.The 3rd method is template with removable microballoon (as polymkeric substance and silicon oxide microsphere), then by approach such as surface chemical reaction or static physical adsorption with desired species layer laminate deposit to the template ball the surface form nucleocapsid structure, by the way of roasting or chemical corrosion template is removed again at last, promptly obtain hollow micro capsule, this method is to use maximum methods for preparing hollow micro capsule, can regulate the thickness and the composition of micro-capsule shell, but often need the multiwalled electroless copper deposition operation in order to form shell with certain intensity, step is comparatively loaded down with trivial details, is not suitable for large-scale synthetic.
Summary of the invention
But the objective of the invention is to find the preparation method of the synthesis of metal oxide hollow micro capsule of a kind of simple and easy to control, economical rationality and shell component modulation.
The method for preparing metal oxide hollow microcapsule involved in the present invention is as follows:
1. the mesopore silicon oxide bead being carried out the modification of alkyl handles, the treatment process that alkyl is modified is that silicon oxide microsphere was stirred in the cyclohexane solution of the alkyl chlorosilane of 1.0～3.0w.t.% 5～7 hours, then with hexanaphthene washing 3 times, sample after filtration, dry back is as the template of synthesis oxide hollow micro capsule.Temperature is 25～35 ℃ among the above-mentioned preparation method, and the solvent and solute weight ratio of silicon oxide microsphere and alkyl silane is 0.1～0.3.
2. the silicon oxide microsphere that alkyl in 1 is modified soaks the deposition regular hour in the cyclohexane solution of the metal alkyl oxide of desired concn, takes out with hexanaphthene washing 1～10 time, then drying at a certain temperature.Product is roasting under certain temperature.
3. the complex microsphere that obtains in 2 is inserted in the certain density polyelectrolyte solution and soak, polyelectrolyte solution concentration is that 0.001～0.05w.t.% soak time is 2～30 minutes, and soaking temperature is 5～80 ℃.
4. the product that obtains in 3 is inserted in the aqueous solution of quaternary ammonium salt that concentration is 0.05～20w.t.% or solubility oxyhydroxide 5～120 ℃ of following stir process 0.5～24 hour to remove the silicon oxide template, through water washing 1～6 time, obtain product metal oxide micro-capsule.
Mesopore silicon oxide microballoon in above-mentioned 1 is to be the template synthetic with cetylamine or cetyl trimethylammonium bromide (CTAB).Alkyl chlorosilane comprises trimethylchlorosilane, chlorotriethyl silane, tripropyl chlorosilane, dimethyldichlorosilane(DMCS), diethyl dichlorosilane, dipropyl dichlorosilane etc.
Said metal alkyl oxide such as isopropyl titanate in 2, titanium ethanolate, tetrabutyl titanate or zirconic acid isopropyl ester, zirconic acid ethyl ester, zirconium-n-butylate etc.During preparation metal oxide/silicon oxide complex microsphere, the concentration of metal alkyl oxide in hexanaphthene is 0.01～1.0M.Soaking depositing time is 30 minutes～24 hours, and drying temperature is 20～100 ℃, and maturing temperature is 200～800 ℃, and roasting time is 0.5-10 hour.
Said polyelectrolyte is a positive polarity in 3, neutral or electronegative superpolymer, Poly Dimethyl Diallyl Ammonium Chloride for example, polypyrrole alkane ketone etc.Polyelectrolyte solution concentration is 0.001～0.05w.t.%, and soak time is 2～30 minutes, and soaking temperature is 5～80 ℃.
Said quaternary ammonium salt is a Tetramethylammonium hydroxide in 4, tetraethyl ammonium hydroxide, TPAOH or TBAH; Solubility oxyhydroxide is sodium hydroxide, potassium hydroxide or hydrated barta.
The present invention's implementation condition preferably is:
Used mesopore silicon oxide microballoon can be various silicon oxide microspheres, but is that template synthetic mesopore silicon oxide microsphere is optimum with the cetylamine, the mesopore silicon oxide microspherulite diameter with 0.2～10 μ m for well.
The metal alkyl oxide is an isopropyl titanate, tetrabutyl titanate or zirconic acid isopropyl ester, zirconic acid ethyl ester.Concentration in hexanaphthene is 0.2～0.7M.Soaking depositing time is 4～12 hours, and drying temperature is 60～80 ℃, and maturing temperature is 400～700 ℃, and roasting time is 3-6 hour, and calcination atmosphere is an air.
Polyelectrolyte is electropositive Poly Dimethyl Diallyl Ammonium Chloride, and strength of solution is 0.01～0.03w.t.%, and soak time is 10～20 minutes, and soaking temperature is 20～60 ℃.
Quaternary ammonium salt is tetraethyl ammonium hydroxide or TPAOH; Solubility oxyhydroxide is sodium hydroxide, potassium hydroxide.Concentration is the aqueous solution of 0.5～5w.t.%, and treatment temp is 70～100 ℃, and the stir process time is 4～10 hours.
The inventive method can prepare metal oxide (titanium oxide, zirconium white etc.), sulfide (Cadmium Sulfide, silver sulfide, indium sulfide etc.) and precious metal (silver, gold, platinum, palladium, ruthenium, rhodium, iridium, osmium etc.) hollow micro capsule, and the percentage of damage of product is less than 5%.
Because but such hollow micro capsule material has the shell component of uniform spherical shell and modulation, can in the assembling of fuel cell, advanced optical, electricity, magnetics material the potential utility value be arranged in design, special catalyst assembling design and the application of the embedding of medicine and slowly-releasing, artificial cell; In addition, because used silicon oxide microsphere has abundant meso-hole structure, the mode of guest species by pre-implantation can be embedded to mesoporous in, handle by the inventive method then, when silicon oxide microsphere consumes, the pre-object species of implanting will be incorporated into metal oxide hollow microcapsule inside easily, thereby with the further functionalization of hollow micro capsule.
The mesoporous micro-capsule that the inventive method obtains has that thickness is adjustable, high-crystallinity and the shell of high porosity and big cavity, as design, special catalyst assembling design and the application of the embedding of medicine and slowly-releasing, artificial cell, in the assembling of fuel cell, advanced optical, electricity, magnetics material utility value is widely arranged in a lot of fields.
The inventive method is simple and easy to control, the shell component of economical rationality, micro-capsule is adjustable, and the preparation efficiency height, good product performance.
Description of drawings
Fig. 1 is mesopore silicon oxide microballoon A
1SEM figure.
Fig. 2 is mesopore silicon oxide microballoon B
1SEM figure.
Fig. 3 is zirconium white hollow micro capsule D
4SEM figure.
Fig. 4 is D
4TEM figure.
Fig. 5 is Cadmium Sulfide hollow micro capsule C
4TEM figure.
Fig. 6 is silver sulfide hollow micro capsule F
1TEM figure.
Fig. 7 is platinum hollow micro capsule A
7TEM figure.
Fig. 8 is a product A
7XRD spectra.
Fig. 9 is a products C
4XRD spectra.
Embodiment
Example 1
1g cetylamine, 100ml Virahol, 90ml distilled water and 1.4ml ammoniacal liquor are mixed, stir under the room temperature, then the 5.8ml tetraethoxy-silicane is injected above-mentioned solution, stop after 30 seconds stirring, room temperature was left standstill 1 day, product is filtered, use the distilled water wash clean, dry back under 600 ℃ in air atmosphere roasting obtained mesopore silicon oxide microballoon A to remove cetylamine in 6 hours
1
Example 2
With 1.96g CTAB, 2.32gNa
2SiO
39H
2O and 17g distilled water mix, stir under the room temperature, then the 1.75ml ethyl acetate is injected above-mentioned solution, stop after 30 seconds stirring, the mixed solution that room temperature was left standstill after 5 hours heated 50 hours in 90 ℃ oil bath, product is filtered and use the distilled water wash clean, dry back under 600 ℃ in air atmosphere roasting obtained mesopore silicon oxide microballoon B with removal CTAB in 6 hours
1
Example 3
With 0.5g A
1Stirred 6 hours in the ethanolic soln of the amino estersil of immersion 30ml 2w.t.%, clean 1～6 time, filter and obtain the amino silicon oxide microsphere of modification in the duct, be designated as A with ethanol
2With 0.5g A
1Stirred 6 hours in the toluene solution of the sulfydryl estersil of immersion 30ml 2w.t.%, clean 1～6 time, filter the silicon oxide microsphere that obtains modification sulfydryl in the duct, be designated as C with toluene
10.5g A1 is immersed in the cyclohexane solution of trimethylchlorosilane of 30ml 2w.t.% and stirred 6 hours,, filter the silicon oxide microsphere that obtains modification methyl in the duct, be designated as D with cyclohexane 1～6 time
1
Example 4
With 0.1g A
2Be soaked in the Platinic chloride that concentration is 0.01～1M, vigorous stirring is 2 hours under room temperature, leaches product, dries under 80oC after water washing 3 times, obtains the mesopore silicon oxide microballoon of Platinic chloride load, is designated as A
3With 0.1g A
3Add in the aqueous solution of POTASSIUM BOROHYDRIDE that l0ml concentration is 0.005～0.04M or sodium borohydride, stirs and dry under 50～120 ℃ after 1 hour, the mesopore silicon oxide microballoon of acquisition reductive Platinic chloride load is designated as A
4With A
4Under air atmosphere in 400 ℃～600 ℃ roasting 3.0-7.0 hour, obtain platinum/silicon oxide complex microsphere, be designated as A
5
Example 5
With 0.1g C
1Be soaked in concentration and be in the aqueous solution of Cadmium chloride fine powder of 0.2～0.6M 2～12 hours, and leached product, dry down in 60～80 ℃ after washing 3 times.Obtain the mesopore silicon oxide microballoon of cadmium load, be designated as C
2, with C
2Under nitrogen atmosphere,, obtain Cadmium Sulfide/silicon oxide complex microsphere, be designated as C in 200～500 ℃ of roasting 3-8 hours
3
Example 6
With 0.1g D
1Be soaked in concentration and be in the cyclohexane solution of zirconic acid isopropyl ester of 0.2～0.7M.Soak time is 4～12 hours, and product is washed 3 times with hexanaphthene after leaching, and is dry under 60～80 ℃, obtains the mesopore silicon oxide microballoon of zirconic acid isopropyl ester load, is designated as D
2With D
2Under air atmosphere,, obtain zirconium white/silicon oxide complex microsphere, be designated as D in 400～700 ℃ of roasting 3-6 hours
3
Example 7
With 0.1g A
5Under 20～60 ℃, be soaked in concentration and be in the aqueous solution of Poly Dimethyl Diallyl Ammonium Chloride of 0.01～0.03w.t.% 10～20 minutes, and obtained to be coated with the platinum/silicon oxide complex microsphere of one deck Poly Dimethyl Diallyl Ammonium Chloride, be designated as A
6With 0.1g A
6Placing concentration is the aqueous solution of the TPAOH of 0.5～5w.t.%, in 70～100 ℃ of following stir process 4～10 hours, washes with water after product leaches 3 times, obtains the platinum hollow micro capsule, is designated as A
7
Example 8
Experimentize with the method identical, but use Cadmium Sulfide/silicon oxide complex microsphere C with example 7
3, obtain Cadmium Sulfide hollow micro capsule C
4
Example 9
Experimentize with the method identical, but use zirconium white/silicon oxide complex microsphere D with example 7
3, obtain zirconium white hollow micro capsule D
4
Example 10
Experimentize with the method identical with example 4, but use Silver Nitrate, hydrochloro-auric acid, chloro-iridic acid, rhodium chloride, ruthenium chloride, Palladous nitrate as the noble metal precursor body, 200～400 ℃ of processing under hydrogen atmosphere before silicon oxide is removed, silver, gold, iridium, rhodium, ruthenium have been obtained, the palladium hollow micro capsule is designated as E respectively
2, E
3, E
4, E
5, E
6, E
7
Example 11
Experimentize with the method identical with example 5, but use Silver Nitrate, indiumchloride solution carries out load, obtains silver sulfide, and the indium sulfide hollow micro capsule is designated as F respectively
1, F
2
Example 12
Experimentize with the method identical, but use the cyclohexane solution of isopropyl titanate to carry out load, obtain the titanium oxide hollow micro capsule, be designated as G with example 6
1
Example 13
Experimentize with the method identical, but use mesopore silicon oxide microballoon B with example 3
1, obtained amido modified mesopore silicon oxide microballoon B
2
Example 14
Experimentize with the method identical, but use amido modified mesopore silicon oxide microballoon B2, obtained the platinum hollow micro capsule, be designated as B as synthetic template with example 4
3
Example 15
Experimentize with the method identical, but the sodium hydroxide that adopts same concentrations is to zirconium white/silicon oxide complex microsphere D with example 9
3Handle, obtain the zirconium white hollow micro capsule, be designated as H
1
Example 15
Experimentize with the method identical, but save calcination steps, obtain discrete nano platinum particle, be designated as I with example 4
1
Example 16
Experimentize with the method identical, handle, obtain platinum/silicon oxide complex microsphere, be designated as J but working concentration is the aqueous solution of the TPAOH of 0.05w.t.% with example 7
1
Example 17
Experimentize with the method identical with example 7, but the aqueous solution treatment time of TPAOH shorten to 5 minutes, obtain platinum/silicon oxide complex microsphere, be designated as K
1
Example 18
Experimentize with the method identical, but the aqueous solution treatment temp of TPAOH is reduced to 30 ℃, obtains platinum/silicon oxide complex microsphere, be designated as L with example 7
1
The stereoscan photograph of the said products (SEM) all absorbs on Philips XL30 D6716 instrument, and lens photo (TEM) absorbs on JEOL JEM-2010 instrument.Fig. 1-the 7th, the electromicroscopic photograph of sample segment, the electromicroscopic photograph of all the other samples is similarly.To the synthetic metal oxide, sulfide and noble metal hollow micro capsule material characterize with XRD (carry out on Rigaku D/Max-IIA type X-ray diffractometer, see Fig. 8-10).From Fig. 8-10 as can be seen, show the characteristic peak of respective material in the XRD of the product that the obtains spectrum, show that product is a pure phase.On SEM photo from Fig. 3-7 and the TEM photo as can be seen product be micro-capsule with hollow structure, size is about 1 micron, shell thickness is about 50nm.Above result has proved with the inventive method not only can make the respond well hollow micro capsule of pattern, and by changing the shell component, can obtain the micro-capsule of different shell structures, to adapt to different application needs.
Claims (12)
1, a kind of preparation method of metal oxide hollow microcapsule is characterized in that:
(1) be template with the mesopore silicon oxide microballoon, alkyl silane is the modifier of mesopore silicon oxide microsphere template, reaction conditions by control alkyl silane and template, alkyl is modified on the duct of mesopore silicon oxide microballoon, the mass percent concentration of alkyl silane in the solution of hexanaphthene is 1.0～3.0w.t.%, and the solid-liquid weight ratio of silicon oxide microsphere and alkyl silane solution is 0.1～0.3, and temperature of reaction is 25～35 ℃, churning time is 5～7 hours, dries then;
(2) be metal oxide source with the metal alkyl oxide, with the hexanaphthene is solvent, by soaking, utilize metal alkyl oxide and the interaction of modifying the alkyl on the mesopore silicon oxide microsphere template of back metal oxide source to be introduced in the duct of mesopore silicon oxide microsphere template, dry then, roasting in air atmosphere, obtain metal oxide/silicon oxide complex microsphere, the concentration of metal alkyl oxide is 0.01～1.0M, soak time is 30 minutes～24 hours, drying temperature is 20～100 ℃, and maturing temperature is 200～800 ℃, and roasting time is 0.5-10 hour;
(3) compound ball of above-mentioned preparation is soaked in the aqueous solution of polyelectrolyte and makes it to form one deck integument on the compound ball surface, polyelectrolyte is a positive polarity, neutral or electronegative superpolymer, polyelectrolyte solution concentration is 0.001～0.05w.t.%, soak time is 2～30 minutes, and soaking temperature is 5～80 ℃;
(4) aqueous solution with quaternary ammonium salt or solubility oxyhydroxide is the etching agent of silicon oxide, the microballoon of above-mentioned parcel polyelectrolyte is immersed this solution-treated, obtain metal oxide hollow microcapsule, the concentration of quaternary ammonium salt or solubility oxyhydroxide is 0.5～5w.t.%, treatment temp is 70～100 ℃, the stir process time is 4～10 hours, and the solid-liquid weight ratio of complex microsphere and quaternary ammonium salt or solubility hydroxide solution is 0.001～0.2.
2, the preparation method of a kind of general metal oxide hollow microcapsule according to claim 1 is characterized in that the mesopore silicon oxide microballoon is is the template synthetic with the cetylamine.
3, method according to claim 1, the particle diameter that it is characterized in that the mesopore silicon oxide microballoon are 0.2～10 μ m.
4, method according to claim 1 is characterized in that the metal alkyl oxide is any in isopropyl titanate, tetrabutyl titanate, zirconic acid isopropyl ester, the zirconium-n-butylate.
5, method according to claim 1, the concentration of metal alkyl oxide in hexanaphthene is 0.2～0.7M when it is characterized in that preparing metal oxide/silicon oxide complex microsphere, soak time is 4～12 hours, drying temperature is 60～80 ℃, maturing temperature is 400～700 ℃, and roasting time is 3～6 hours.
6,, it is characterized in that polyelectrolyte is electropositive Poly Dimethyl Diallyl Ammonium Chloride according to the described method of claim 1.
7, method according to claim 1, the concentration that it is characterized in that polyelectrolyte solution is 0.01～0.03w.t.%, and soak time is 10～20 minutes, and soaking temperature is 20～60 ℃.
8, method according to claim 1 is characterized in that quaternary ammonium salt is tetraethyl ammonium hydroxide or TPAOH.
9, method according to claim 1 is characterized in that solubility oxyhydroxide is sodium hydroxide or potassium hydroxide.
10, method according to claim 1, the concentration that it is characterized in that quaternary ammonium salt or solubility oxyhydroxide is 0.5～5w.t.%, and the etching processing temperature is 70～100 ℃, and the stir process time is 4～10 hours.
11, method according to claim 1, the shell component that it is characterized in that micro-capsule is sulfide or precious metal, thereby obtains sulfide hollow micro capsule or noble metal hollow micro capsule.
12, the metal oxide hollow microcapsule that makes of method according to claim 1 gentlely release in the medicine embedding, artificial cell design, catalyzer assembling design, fuel cell, photoelectricity magnetics material assembling aspect are widely used.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157467A (en) * | 2011-12-14 | 2013-06-19 | 中国科学院大连化学物理研究所 | Ru and / or Ir noble metal oxide and application thereof to oxygen evolution electro-catalysis |
| CN103588920A (en) * | 2013-10-31 | 2014-02-19 | 天津工业大学 | Novel preparation method for monodisperse porous polymer nano microcapsule |
| CN113493220A (en) * | 2020-04-02 | 2021-10-12 | 杨洋 | Hollow metal oxide microsphere, preparation method thereof and drug sustained-release application |
-
2005
- 2005-02-13 CN CN 200510023935 patent/CN1281306C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157467A (en) * | 2011-12-14 | 2013-06-19 | 中国科学院大连化学物理研究所 | Ru and / or Ir noble metal oxide and application thereof to oxygen evolution electro-catalysis |
| CN103157467B (en) * | 2011-12-14 | 2014-11-05 | 中国科学院大连化学物理研究所 | Ru and / or Ir noble metal oxide and application thereof to oxygen evolution electro-catalysis |
| CN103588920A (en) * | 2013-10-31 | 2014-02-19 | 天津工业大学 | Novel preparation method for monodisperse porous polymer nano microcapsule |
| CN113493220A (en) * | 2020-04-02 | 2021-10-12 | 杨洋 | Hollow metal oxide microsphere, preparation method thereof and drug sustained-release application |
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