CN1281306C - Method for preparing metal oxide hollow microcapsule - Google Patents
Method for preparing metal oxide hollow microcapsule Download PDFInfo
- Publication number
- CN1281306C CN1281306C CN 200510023935 CN200510023935A CN1281306C CN 1281306 C CN1281306 C CN 1281306C CN 200510023935 CN200510023935 CN 200510023935 CN 200510023935 A CN200510023935 A CN 200510023935A CN 1281306 C CN1281306 C CN 1281306C
- Authority
- CN
- China
- Prior art keywords
- silicon oxide
- metal oxide
- oxide
- concentration
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention mainly relates to a preparation method of hollow metal oxide microcapsules. In the preparation method, mesoporous silicon oxide microspheres are used as templates and modified by alkyl, and metal oxides are filled into pore canals of the microspheres; then, the surfaces of the microspheres adsorb one layer of polyelectrolyte; finally, silicon oxide is leached out under the alkaline solution treatment conditions, and the hollow metal oxide microcapsules are prepared. The method is a convenient preparation method of microcapsules with adjustable components of shell layers, and is applicable to the preparation of functional microcapsules. The microcapsules obtained by the present invention can have wide utilization value in many fields such as embedment and slow release of medicines, catalysis, electrochemistry, artificial cell design, design of protective bodies of bioactive reagents, and special optical material packaging design.
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 noble 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 spray-drying (P.J.Bruinsma, 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 atomized drop, because operation is generally carried out under the atmosphere of drying, solvent in the drop that forms evaporates rapidly, impel the shell structurre of forerunner's attitude species of difficult volatilization 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 structurre 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 particle diameter distribution homogeneous.The 3rd method is template with removable microballoon (as polymer and silicon oxide microsphere), then by approach such as surface chemical reaction or static physical absorption with desired species layer laminate deposit to the template ball the surface form nucleocapsid structure, by the way of roasting or chemical attack 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 electroless copper deposition operation of multilayer 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 processing method that alkyl is modified is that silicon oxide microsphere was stirred in the cyclohexane solution of the alkylchlorosilane of 1.0～3.0w.t.% 5～7 hours, then with cyclohexane 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 cyclohexane washing 1～10 time, then drying at a certain temperature.Product is roasting under uniform 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 hydroxide 5～120 ℃ of following stir process 0.5～24 hour to remove the silica template, through water washing 1～6 time, obtain product metal oxide micro-capsule.
Mesopore silicon oxide microballoon in above-mentioned 1 is that the template agent is synthetic with cetylamine or softex kw (CTAB).Alkylchlorosilane comprises trim,ethylchlorosilane, chlorotriethyl silane, tripropyl chlorosilane, dimethyldichlorosilane, diethyl dichlorosilane, dipropyl dichlorosilane etc.
Said metal alkyl oxide such as isopropyl titanate in 2, tetraethyl titanate, tetrabutyl titanate or zirconic acid isopropyl ester, zirconic acid ethyl ester, zirconium-n-butylate etc.During preparation metal oxide/silica complex microsphere, the concentration of metal alkyl oxide in cyclohexane is 0.01～1.0M.Soaking sedimentation time is 30 minutes～24 hours, and baking temperature is 20～100 ℃, and sintering temperature is 200～800 ℃, and roasting time is 0.5-10 hour.
Said polyelectrolyte is an electropositive in 3, neutral or electronegative high polymer, PDDA 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 TMAH in 4, tetraethyl ammonium hydroxide, TPAOH or TBAH; Solubility hydroxide is NaOH, potassium hydroxide or barium hydroxide.
The present invention's implementation condition preferably is:
Used mesopore silicon oxide microballoon can be various silicon oxide microspheres, but optimum for the synthetic mesopore silicon oxide microsphere of template agent 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 cyclohexane is 0.2～0.7M.Soaking sedimentation time is 4～12 hours, and baking temperature is 60～80 ℃, and sintering temperature is 400～700 ℃, and roasting time is 3-6 hour, and calcination atmosphere is an air.
Polyelectrolyte is electropositive PDDA, and solution concentration 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 hydroxide is NaOH, potassium hydroxide.Concentration is the aqueous solution of 0.5～5w.t.%, and treatment temperature is 70～100 ℃, and the stir process time is 4～10 hours.
The inventive method can prepare metal oxide (titanium oxide, zirconia etc.), sulfide (cadmium sulfide, silver sulfide, indium sulfide etc.) and noble 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 potential 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 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 zirconia 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.
The specific embodiment
Example 1
1g cetylamine, 100ml isopropyl alcohol, 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, 2.32g Na
2SiO
39H
2O and 17g distilled water mix, stir under the room temperature, then 1.75ml ethyl acetate is injected above-mentioned solution, stop after 30 seconds stirring, the mixed liquor 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 solution 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 trim,ethylchlorosilane 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 chloroplatinic acid that concentration is 0.01～1M, vigorous stirring is 2 hours under room temperature, leaches product, dries under 80 ℃ after water washing 3 times, obtains the mesopore silicon oxide microballoon of chloroplatinic acid load, is designated as A
3To O.1g A
3Add in the aqueous solution of potassium borohydride that 10ml concentration is 0.005～0.04M or sodium borohydride, stirs and under 50～120 ℃, dry after 1 hour, obtain the mesopore silicon oxide microballoon of the chloroplatinic acid load of reducing, be designated as A
4With A
4Under air atmosphere in 400 ℃～600 ℃ roasting 3.0-7.0 hour, obtain platinum/silica complex microsphere, be designated as A
5
Example 5
With 0.1g C
1Be soaked in concentration and be in the aqueous solution of caddy 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/silica 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 cyclohexane 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 zirconia/silica 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 PDDA of 0.01～0.03w.t.% 10～20 minutes, and obtained to be coated with the platinum/silica complex microsphere of one deck PDDA, 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/silica complex microsphere C with example 7
3, obtain cadmium sulfide hollow micro capsule C
4
Example 9
Experimentize with the method identical, but use zirconia/silica complex microsphere D with example 7
3, obtain zirconia hollow micro capsule D
4
Example 10
Experimentize with the method identical with example 4, but use silver nitrate, gold chloride, chloro-iridic acid, radium chloride, ruthenic chloride, palladium nitrate as the noble metal precursor body, 200～400 ℃ of processing under hydrogen atmosphere before silica 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 NaOH that adopts same concentrations is to zirconia/silica complex microsphere D with example 9
3Handle, obtain the zirconia 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/silica 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 processing time of TPAOH shorten to 5 minutes, obtain platinum/silica complex microsphere, be designated as K
1
Example 18
Experimentize with the method identical, but the aqueous solution treatment temperature of TPAOH is reduced to 30 ℃, obtains platinum/silica complex microsphere, be designated as L with example 7
1
The stereoscan photograph of the said goods (SEM) all absorbs on Philips XL30 D6716 instrument, and lens photo (TEM) absorbs on the JEOLJEM-2010 instrument.Fig. 1-the 7th, the electromicroscopic photograph of sample segment, the electromicroscopic photograph of all the other samples is similarly.To 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-core construction, 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 structurres, to adapt to different application needs.
Claims (11)
1, a kind of preparation method of metal oxide hollow microcapsule is characterized in that:
(1) be template with the mesopore silicon oxide microballoon, alkylchlorosilane is the dressing agent of mesopore silicon oxide microsphere template, reaction condition by control alkylchlorosilane and template, alkyl is modified on the duct of mesopore silicon oxide microballoon, the mass percent concentration of alkylchlorosilane in the solution of cyclohexane is 1.0～3.0w.t.%, and the solid-liquid weight ratio of silicon oxide microsphere and alkylchlorosilane solution is 0.1～0.3, and reaction temperature is 25～35 ℃, mixing time is 5～7 hours, dries then;
(2) be metal oxide source with the metal alkyl oxide, with the cyclohexane 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/silica complex microsphere, the concentration of metal alkyl oxide is 0.01～1.0M, soak time is 30 minutes～24 hours, baking temperature is 20～100 ℃, and sintering temperature is 200～800 ℃, and roasting time is 0.5-10 hour;
(3) composite balls of above-mentioned preparation is soaked in the aqueous solution of polyelectrolyte and makes it to form one deck integument on the composite balls surface, polyelectrolyte is an electropositive, neutral or electronegative high polymer, 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 hydroxide is the etching agent of silica, 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 hydroxide is 0.5～5w.t.%, treatment temperature 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 metal oxide hollow microcapsule according to claim 1 is characterized in that the mesopore silicon oxide microballoon is synthetic for the template agent 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 cyclohexane is 0.2～0.7M when it is characterized in that preparing metal oxide/silica complex microsphere, soak time is 4～12 hours, baking temperature is 60～80 ℃, sintering temperature is 400～700 ℃, and roasting time is 3～6 hours.
6,, it is characterized in that polyelectrolyte is electropositive PDDA 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 hydroxide is NaOH or potassium hydroxide.
10, method according to claim 1, the concentration that it is characterized in that quaternary ammonium salt or solubility hydroxide is 0.5～5w.t.%, and the etching processing temperature is 70～100 ℃, and the stir process time is 4～10 hours.
11, the metal oxide hollow microcapsule that makes of the described method of claim 1 is in medicine embedding and slowly-releasing, artificial cell design, catalyst assembling design, the application of fuel cell, photoelectricity magnetics material assembling aspect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510023935 CN1281306C (en) | 2005-02-13 | 2005-02-13 | Method for preparing metal oxide hollow microcapsule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510023935 CN1281306C (en) | 2005-02-13 | 2005-02-13 | Method for preparing metal oxide hollow microcapsule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1683068A CN1683068A (en) | 2005-10-19 |
| CN1281306C true CN1281306C (en) | 2006-10-25 |
Family
ID=35262673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510023935 Expired - Fee Related CN1281306C (en) | 2005-02-13 | 2005-02-13 | Method for preparing metal oxide hollow microcapsule |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1281306C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103588920B (en) * | 2013-10-31 | 2017-01-25 | 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
Also Published As
| Publication number | Publication date |
|---|---|
| CN1683068A (en) | 2005-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1683066A (en) | Method for preparing noble metal hollow micro capsule | |
| Chen et al. | Electrospun polymer nanofibers decorated with noble metal nanoparticles for chemical sensing | |
| CN103803643B (en) | Spherical titanium dioxide of a kind of monodisperse mesoporous hollow Nano and preparation method thereof | |
| CN102716745B (en) | Preparation method for yolk-eggshell-type organic-inorganic hybrid silicon oxide nanosphere | |
| CN102795786B (en) | Super hydrophobic self-cleaning coating and preparation method thereof | |
| CN104707542B (en) | A kind of photochemical catalyst/SiO2aerogel composite and preparation method thereof | |
| CN104986724A (en) | Flexible film surface micro/nano-structure and application thereof | |
| CN1986724A (en) | Preparing process of nano ZnO line array coated with nano TiO2 particles | |
| CN102198929A (en) | Hollow silicon dioxide sub-microsphere with nanoscale precious metal and silicon dioxide kernel and preparation method thereof | |
| CN101028653A (en) | Chemical production of metal nickel nano-line | |
| CN107416898A (en) | A kind of titanium dioxide hollow micro-nano ball, its preparation method and application | |
| CN109465017A (en) | A kind of seven bronze medals-eight of four vulcanization vulcanize controllable method for preparing and the application of nine bronze medal heterojunction structure hollow cubic body catalysts | |
| CN1281306C (en) | Method for preparing metal oxide hollow microcapsule | |
| CN103526539A (en) | Preparation method of functional gold-silver core-shell nanoparticle/electrostatic spun composite nano-fiber felt | |
| CN1233466C (en) | Method for gqually distributing liquid phase method prepared metal atomic cluster with active composition smaller than 5 nm on porous oxide carrier | |
| CN1923354A (en) | Method for preparing nano hollow inorganic microsphere | |
| CN103272592A (en) | Preparation method of one-dimensional silver-loaded titanium dioxide nanorod photocatalyst | |
| CN103272487B (en) | Method for preparing nano-porous gold film through treating graphene as template | |
| CN102389787B (en) | Carbon-doped titanium dioxide hollow spherical photocatalyst and preparation method thereof | |
| CN108640149B (en) | Titanium dioxide nano hollow ball and preparation method thereof | |
| CN102774885B (en) | Porous submicron sphere, porous film electrode and preparation method and application in dye sensitized solar cells thereof | |
| CN106571240A (en) | Preparation method and application of in in-situ carbon doped hierarchically structured hollow silicon dioxide/titanium dioxide microspheres | |
| CN1923355A (en) | Method for preparing nano hollow inorganic microsphere | |
| CN1329109C (en) | Method for preparing metal sulfide hollow micro capsule | |
| CN1698954A (en) | Method for in situ assembly of highly dispersible nano silver particle on silicon base material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061025 |