CN101293192B - Method for producing multi-layer hollow pellet or stephanoporate pellet with multi-chamber vesicle mould plate method - Google Patents
Method for producing multi-layer hollow pellet or stephanoporate pellet with multi-chamber vesicle mould plate method Download PDFInfo
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Abstract
The present invention relates to a hollow sphere or porous sphere preparation method through vesicle and multi-chamber vesicle template method. The preparation method is characterized in that a surface active agent forms vesicle and multi-chamber as the soft template under certain conditions; inorganic material carries out nucleus growth on the surface of the soft template so as to copy the shapeof the vesicle and multi-chamber vesicle and obtain a single-layer hollow sphere and multi-layer hollow sphere structure; due to different growing ways of crystal, the formed hollow sphere can be single crystal, polycrystal or multiaperture. The surface active agent is anion surface active agent, cation active agent or a mixer of the two surface active agents. The deposited inorganic material includes oxide, sulfide, simple metal substance, selenide, hydroxid or inorganic salts, which form core and grow on the surface of the vesicle and multi-chamber vesicle and finally obtain the single-layer and multi-layer hollow sphere structure and the porous sphere structure. Cu2O and ZnS hollow sphere or porous sphere is taken as the embodiment for detailed description.
Description
Technical field
The present invention relates to utilize multilamellar vesicles to prepare the hollow ball and the porous ball of special construction as soft template method.Hollow ball with this method preparation has the multilayered shell structure.
Background technology
Nano material is subjected to extensive concern owing to having the specific physical chemical property that many block materials do not possess.Nano material also begins to be applied in military and national defense and the real life in recent years.Because pattern, size and the structure etc. of nano material are closely related with its performance and purposes, preparing various different structures and structure and size are effectively regulated and control is one of focus of research.The nano material of hollow ball structure receives much attention because of the wide application prospect that has at aspects such as drug delivery, artificial cell, catalysis, chemical storage, nano-reactors.The method for preparing hollow ball structure has a lot, roughly is divided into template and non-template method.Wherein template is fairly simple efficient, and practical, it can be divided into soft template method and hard template method again.Vesica is owned by France in soft template method, the document of having reported shows, Zhi Bei hollow ball structure all is hollow ball [1. D.H.W.Hubert, the M.Jung of individual layer shell polycrystalline in this way, P.M.Frederik, P.H.H.Bomans, J.Meuldijk, A.L.German, Adv.Mater.2000,12,1286. 2. M.Kepczynski, F.Ganachaud, P.Hemery, Adv.Mater.2004,16,1861. 3. F.Caruso, Chem.Eur.J.2000,6,413], structural intergrity and stability are not very desirable.
Surfactant molecule is the hydrophobic amphiphile, amphiphilic molecule of the hydrophilic end of an a kind of end, makes that it not only can be water-soluble but also can be dissolved in the organic solvent.In aqueous solvent, during low concentration, the hydrophobic side of surfactant is because water insoluble meeting is surfaced, and water-wet side is then below the water surface.Increase along with surfactant concentration, because the water surface space is all occupied by the hydrophobic side of surfactant, remaining surfactant can only form micella in water, vesica even multilamellar vesicles (as shown in Figure 1) etc. make the hydrophobic side avoid contacting with water from poly mode.Micella be monomolecular from poly mode, and vesica be double-deck molecule from poly mode, multilamellar vesicles as its name suggests, has the special vesica structure of plurality of layers of double molecular layer exactly.The bilayer of vesica has intercepted the inside and outside solution of vesica, make and exist the interface in the system, this interface provides the reflecting point and the deposition growing point of inorganic material, makes the final inorganic material that forms can duplicate the shape of vesica and form hollow ball and multilayer hollow ball structure (as shown in Figure 1).According to vesica, multilamellar vesicles surface inorganic material crystals growth pattern difference, can form monocrystalline, polycrystalline multilayer hollow ball and porous spherical structure.The most surfaces activating agent comprises anion surfactant and cationic surfactant, under certain conditions, can form vesica and multilamellar vesicles.Use this vesica and multilamellar vesicles as soft template, deposition growing forms multiple individual layer shell and multilayered shell hollow ball inorganic material on its interface.The size of hollow ball is by the decision of vesica size.In theory, can form the multilayer hollow ball structure as template by it, but before this without any the report of success.
Summary of the invention
The object of the present invention is to provide the multilamellar vesicles template to prepare the method for multilayer hollow ball or porous ball, provide the synthetic method of a kind of vesicle mold method.Not only successfully prepare the multilamellar vesicles template, and synthesized multilayer hollow ball and porous spherical structure thus.Wherein the shell wall of multilayer hollow ball is polycrystalline even monocrystalline form, and this will improve the structural stability of hollow ball greatly.Simultaneously, this multilayered shell hollow ball structure also will improve the specific area of material greatly, for practical application creates conditions.This structure of hollow ball is expected to be used for fields such as medicine, catalysis, as by load different medicine or catalysis material in different hollow chambers, plays the effect of medicament slow release or multi-functional catalysis material.Utilize this multilamellar vesicles mould plate technique, the multilayer hollow ball structure that can synthesize multiple material is a kind of simple, quick, manageable soft template method, synthesize have individual layer, bilayer, three layers even four layers the monocrystalline or the inorganic material of polycrystalline hollow ball and porous spherical structure.
Particular content of the present invention is as follows:
1) as the vesica of soft template, the preparation of multilamellar vesicles
Prepare certain density surfactant solution, concentration range is between 0.01～0.5 mol, and temperature is between 0-200 ℃.Make and form surface-active dose of vesica and multilamellar vesicles in the solution.
Described surfactant is an anion surfactant, cationic surfactant or both mixing are (as hexadecane trimethyl ammonium bromide CTAB, lauryl sodium sulfate SDS, ten sodium hisbenzene sulfonate SDBS, dodecyl sodium sulfate SLS, DTAB DTAB, two octadecyl dimethyl ammonium bromide DODAB, didodecyldimethylammbromide bromide DDAB, diallylamine alkyl dimethyl ammonium chloride PDADMAC, sapn Span, tween Tween, polyethylene glycol-propane diols-polyethylene glycol triblock polymer P123 etc.) utilize the ultrasonic formation that impels vesica.
That 2) introduces reaction passes through vesica and the multilamellar vesicles soft template surface deposition inorganic material of chemical method at surfactant, be carried out to nucleus growth, the shape of duplicating vesica or multilamellar vesicles obtains individual layer hollow ball or multilayer hollow ball structure, simultaneously can be according to the difference of crystal growth pattern, can obtain monocrystalline multilayer hollow ball respectively, the structure of polycrystalline multilayer hollow ball or porous ball.The inorganic material kind that can deposit comprises oxide, as CuO, and Cu
2O, SiO
2, ZrO
2, MgO, TiO
2, V
2O
5, WO
3, Fe
2O
3, Fe
3O
4, CoO, NiO, MnO
2, Bi
2O
3, ZnO, Al
2O
3, SnO
2, CeO
2Deng; Metal simple-substance such as Ag, Au, Co, Pt, Cu etc.; Sulfide such as MoS
2, MnS
2, CoS, CuS, Cu
2S, Ag
2S, ZnS, CdS, HgS, InS, PbS etc. and some other compound such as CuI, CdSe, ZnSe, Zn
xCd
1-xS, Zn
xCd
1-xSe, CuInS
2, CuInSe
2, AgInS
2, AgInSe
2, PbSe, Ag
2Se, InSe, HgSe, CaCO
3, BaTiO
3, BiVO
4, Bi
2WO
6, Ni (OH)
2, Co (OH)
2, FeOOH etc.
As Cu
2During O single crystal hollow ball, also need add reducing agent, the heating mixed solution is to specified temp, and heating mixed solution temperature is 50-70 ℃.
Advantage of the present invention:
1, simple, quick, the easy control of structure system of preparation process.
2, product structure (referring to individual layer, bilayer, three layers, four layers of shell) can be controlled by regulating surfactant concentrations.
3, the product crystal property is controlled by crystal growth pattern, can obtain monocrystalline, the empty ball in polycrystalline multilayer hollow ball or hole.
Description of drawings
Fig. 1 vesica or multilamellar vesicles form schematic diagram.
Fig. 2 is the Cu of vesica method preparation among the embodiment 1
2The XRD diffracting spectrum that the O hollow ball is nanocrystalline.
Fig. 3 is Cu among the embodiment 1
2The transmission electron microscope photo of O individual layer double-layer hollow ball.
Fig. 4 is Cu among the embodiment 1
2The high resolution electron microscopy and the electronic diffraction photo of O hollow ball ball wall show that hollow ball ball wall is a mono-crystalline structures.
Fig. 5 is Cu among the embodiment 1
2The transmission electron microscope photo of three layers of hollow ball of O.
Fig. 6 is Cu among the embodiment 1
2The transmission electron microscope photo of four layers of hollow ball of O.
Fig. 7 is the nanocrystalline XRD diffracting spectrum of ZnS porous ball of vesica method preparation among the embodiment 2.
Fig. 8 is transmission electron microscope photo (a) the low power overall situation transmission electron microscope photo of ZnS porous ball during low concentration CTAB among the embodiment 2, (b) moderate multiplying factor transmission electron microscope photo and electronic diffraction photo, (c) high magnification transmission electron microscope photo, (d) high explanation transmission electron microscope photo.
Among Fig. 9 embodiment 2, the pattern of porous ZnS hollow ball during high concentration CTAB, wherein (a) and (b) are the hollow ball structure of the porous of different multiplying; (c) and (d) be respectively transmission electron microscope and stereoscan photograph.
The specific embodiment
Embodiment 1
With preparation Cu
2O multilayer hollow ball is an example.3.64g softex kw (CTAB) is dissolved in the 100mL water, adds 0.05g CuSO then
45H
2O adds the 0.18g ascorbic acid again.Mixed solution is heated to 55 ℃, stirred 20 minutes.Again to above-mentioned mixed solution and dripping NaOH solution until Cu
2O precipitates fully.Continue to stir 5-10 minute.With the yellow mercury oxide centrifugation that obtains, respectively give a baby a bath on the third day after its birth five times with deionized water, absolute ethyl alcohol, dry down at 50 ℃ then.Fig. 2 is the XRD figure of product, proves that product is the cuprous oxide of cube phase.Fig. 3 is the pattern of the product under the concentration conditions for this reason, is mainly the individual layer hollow ball, and a spot of bilayer, three layers and four layers of hollow ball are also arranged simultaneously.The individual layer hollow ball is of a size of 100-120nm, and the double-layer hollow ball is of a size of 150-180nm.Fig. 4 is the high resolution electron microscopy photo and the electronic diffraction photo of individual layer hollow ball, illustrates that shell wall is a mono-crystalline structures.Fig. 5 and Fig. 6 are respectively the transmission electron microscope photo of three layers and four layers hollow ball.
Embodiment 2
With preparation ZnS porous ball and porous hollow sphere is example.1-4g softex kw (CTAB) is dissolved in the 100mL water, adds 0.15g Zn (CH then
3COO)
22H
2O.Mixed solution is heated to 60 ℃, stirred 20 minutes.Again to above-mentioned mixed solution and dripping excessive thiocarbamide or thioacetyl amine aqueous solution.Continuing to be warming up to 90 ℃ stirred 2-10 hour.With the white precipitate centrifugation that obtains, respectively give a baby a bath on the third day after its birth five times with deionized water, absolute ethyl alcohol, dry down at 50 ℃ then.Fig. 7 is the XRD figure of product, proves that product is a zinc sulphide.Fig. 8 (a) and (b) be the pattern of the product under the low concentration CTAB condition is mainly the porous spherical structure.This kind porous ball is of a size of 120-180nm.Electron diffraction diagram among Fig. 8 (b) shows that this kind porous spherical structure is a polycrystalline structure.Fig. 8 (c) is the high magnification electromicroscopic photograph and the electronic diffraction photo of porous ball, therefrom can see tangible pore passage structure.The size in hole is approximately 2-3nm.Fig. 8 (d) is the height explanation Electronic Speculum of this kind porous ball, has further proved polycrystalline structure.Along with the increase of surfactant concentration, the hollow ball structure of preparation-obtained porous is as Fig. 9 (a) with (b); High magnification transmission electron microscope and stereoscan photograph (Fig. 9 (c) and (d)) show that the ball wall of this porous hollow sphere is made up of the porous ball among Fig. 8.This is a kind of very special hollow ball structure, and never seeing has report.
Claims (10)
1. a vesica, multilamellar vesicles template prepare the method for hollow ball or porous ball.It is characterized in that: surfactant is under the condition of finite concentration and temperature, form vesica or multilamellar vesicles, with this as soft template, inorganic material is carried out to nucleus growth on the soft template surface, thereby the shape of duplicating vesica and multilamellar vesicles obtains individual layer hollow ball, multilayer hollow ball structure or porous ball; The concrete steps of method are:
1) preparation of single chamber and multilamellar vesicles: the concentration of the surfactant solution of preparation is the 0.01-0.5 mol, is heated to 0-200 ℃ then, and keeps this temperature, utilizes the ultrasonic formation that impels vesica simultaneously.
2) will introduce reactant in the above-mentioned solution again, chemical reaction takes place, make product be carried out to nucleus growth, thereby duplicate the vesica structure, obtain individual layer, multilayer hollow ball and the porous spherical structure of monocrystalline or polycrystalline in the surface deposition inorganic material of vesica soft template.
2. vesica according to claim 1, multilamellar vesicles template prepare the method for hollow ball or porous ball, it is characterized in that described surfactant is the mixing of anion surfactant, cationic surfactant or two kinds of surfactants.
3. vesica according to claim 1 and 2, how precious vesicle mold legal system are equipped with the method for hollow ball or porous ball, it is characterized in that described surfactant is one or more in hexadecane trimethyl ammonium bromide, lauryl sodium sulfate, ten sodium hisbenzene sulfonates, dodecyl sodium sulfate, DTAB, two octadecyl dimethyl ammonium bromide, didodecyldimethylammbromide bromide, diallylamine alkyl dimethyl ammonium chloride, sapn, tween and the polyethylene glycol-propane diols-polyethylene glycol triblock polymer.
4. vesica according to claim 1, multilamellar vesicles template prepare the method for hollow ball or porous ball, it is characterized in that the inorganic material that deposits is metal oxide, metal sulfide, metal simple-substance, metal selenide, metal hydroxides or metal inorganic salt, in vesica, multilamellar vesicles surface nucleation and growth, finally obtain individual layer, multilayer hollow ball structure and porous spherical structure; Hollow ball shell is not all monocrystalline according to crystal growth pattern, polycrystalline or porous.
5. the method for preparing hollow ball or porous ball according to claim 1 or 4 described vesicas, multilamellar vesicles template, it is characterized in that described multilayer for double-deck, three layers or four layers.
6. prepare the method for hollow ball or porous ball according to claim 1 or 4 described vesicas, multilamellar vesicles template, it is characterized in that formed hollow ball shell is monocrystalline or polycrystalline.
7. prepare the method for hollow ball or porous ball by the described vesica of claim 4, multilamellar vesicles template, it is characterized in that:
1. described metal oxide is CuO, Cu
2O, SiO
2, ZrO
2, MgO, TiO
2, V
2O
5, WO
3, Fe
2O
3, Fe
3O
4, CoO, NiO, MnO
2, Bi
2O
3, ZnO, Al
2O
3, SnO
2Or CeO
2
2. described metal simple-substance is Ag, Au, Co, Pt or Cu;
3. described metal sulfide is MoS
2, MnS
2, CoS, CuS, Cu
2S, Ag
2S, ZnS, CdS, HgS, InS, PbS, Zn
xCd
1-xS, Zn
xCd
1-xSe or CuInS
2
4. described metal selenide is CdSe, ZnSe, CuInSe
2, AgInS
2, AgInSe
2, PbSe, Ag
2Se, InSe or HgSe;
5. described metal inorganic salt is CaCO
3, BaTiO
3, BiVO
4, Bi
2WO
6Or CuI;
6. described metal hydroxides is Ni (OH)
2, Co (OH)
2Or FeOOH.
8. the method for preparing hollow ball or porous ball by the described vesica of claim 7, multilamellar vesicles template is characterized in that the inorganic material that deposits is Cu
2O or ZnS.
9. prepare the method for hollow ball or porous ball by the described vesica of claim 8, multilamellar vesicles template, it is characterized in that the Cu for preparing
2O individual layer hollow ball is of a size of 100-120nm, and the double-layer hollow ball is of a size of 150-180nm; Shell wall is a mono-crystalline structures.
10. the method for preparing hollow ball or porous ball by the described vesica of claim 8, multilamellar vesicles template, it is characterized in that the ZnS porous ball for preparing is of a size of 120-180nm, the structure of porous ball is a polycrystalline structure, and is pore passage structure, and the size in hole is 2-3nm.
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