CN102464304B - Multi-shell-layer metal oxide hollow ball and preparation method thereof - Google Patents
Multi-shell-layer metal oxide hollow ball and preparation method thereof Download PDFInfo
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Abstract
The invention provides a multi-shell-layer metal oxide hollow ball and a preparation method thereof. A hydrothermal method is used for preparing a carbon ball template; metal salts are dissolved in carbon ball suspension liquid, and the gradient distribution, the depth and the number of metal salts entering carbon balls are controlled through regulating adsorption conditions such as metal salt concentration, solution pH value, soaking temperature and time and the like; and the heat treatment is carried out on the carbon balls adsorbing metal ions, and the multi-shell-layer metal oxide hollow ball can be obtained. The shell-layer of the hollow ball prepared by the method is formed by accumulating nanometer crystal particles of metal oxides, the shell layer number can be regulated and changed from two to four, and both the size of the hollow ball and the thickness of the shell layers are controllable. The method provided by the invention is simple and is easy to implement, the controllability is high, the pollution is little, the cost is low, and in addition, the general applicability is realized. The prepared product has a hollow structure and the shell layers with the thickness inthe nanometer level, simultaneously, the internal space can be effectively utilized through the multilayer structure, and the multi-shell-layer metal oxide hollow ball is applied to gas sensitivity and photocatalysis and has the more excellent performance through being compared with the traditional nanometer material and a single-layer hollow ball.
Description
Technical field
The invention belongs to technical field of function materials, specifically, the present invention relates to a kind of many shell-layer metal oxide hollow balls and preparation method thereof.
Background technology
Metal oxide is widely used in lithium cell, gas sensor, ultraviolet detector, medicament transport, catalytic field.The characteristics such as many shells that many shell hollow spheres of nanometer or micro-meter scale have low density, large specific surface, hollow structure and are made of nanoparticle, thereby be widely used in the field relevant with surface properties, such as catalyzer, medicinal slow release agent, gas sensitive, photocatalyst material etc., in addition, it also has potential using value at aspects such as photonic crystal, diagnostics, pharmacology.
At present, the report of preparation metal oxide many shell hollow spheres is less, and its preparation method mainly contains two kinds of hard template method and soft template methods.Hard template method adopts hollow sphere polymer as template usually, will be through the process of a sulfonation processing, at first prepare the polymkeric substance hollow template, then process with the vitriol oil, with at its finishing one layer charge, last on the microballoon after the modification encasement material, and through Overheating Treatment or dissolve away the organism in middle layer with organic solvent, obtain double-deck hollow ball.The bivalve layer hollow balls such as titanium oxide that utilize this method preparation have been reported among document Angewandte Chemie-International Edition 42 (2003) 1943-1945.This method will be through preparation hollow template and finishing step, and technical process is long, preparation process is complicated, and is difficult to realize synthetic more than three layers hollow ball of shell number.Soft template method adopts tensio-active agent, bubble etc. as template usually.Document Chemistry-A European Journal, 14 (2008): reported among the 5346-5352 and utilized two bubble methods to prepare ferrihydrite bivalve layer hollow ball.Document Angewandte Chemie-International Edition, 46 (2007): reported among the 1489-1492 and utilized the tensio-active agent cetyl trimethylammonium bromide to prepare Cu
2The many shell hollow spheres of O.Document Advanced Functional Materials, 17 (2007): reported among the 2766-2771 to prepare many shells Cu take amino acid as template
2The O hollow ball.But above-mentioned these soft template methods are only applicable to the preparation of the specific compound hollow ball that document relates to, and are difficult to be applied to the synthetic of the many shell hollow spheres of other metal oxides.
Summary of the invention
Prepare the deficiency that many shell hollow spheres exist for prior art, the object of the present invention is to provide a kind of simple, controllability is high, cost is low and have the preparation method of the many shell hollow spheres of metal oxide of universality.
Technical scheme of the present invention is as follows: a kind of preparation method of many shell-layer metal oxide hollow balls comprises the steps:
A, take glucose, sucrose or starch as raw material, be made into the aqueous solution of 0.25～1.10g/mL, solution is packed in the reactor, under 160～220 ℃ of conditions, heat 50～300min, obtain the carbon ball after filtration, washing, the drying, the carbon ball is scattered in the suspension that forms the carbon ball in the water;
B, a certain amount of metal-salt is dissolved in the carbon ball suspension of steps A, the add-on of metal-salt is 1～5mol/L, regulates the pH value of mixed solution less than 3, soaks 2～20h under 20～60 ℃ of stirrings, and filtration, washing, drying obtain powdered material;
C, the powdered material that step B is obtained are heat-treated, and can obtain having the metallic oxide hollow sphere of many shell structures of different shell structures.
In the preparation method of many shell-layer metal oxide hollow balls of the present invention, described metal-salt is nitrate, muriate, vitriol or the acetate of Fe, Zn, Co, Ni, Cu or Y.Heat-treat condition is preferably under air atmosphere, with the heat-up rate of 1～5 ℃/min, is heated to 400～800 ℃, insulation 0.5～3h.
In the preparation method of many shell-layer metal oxide hollow balls of the present invention, also can before adding metal-salt, carry out supersound process to described carbon ball suspension.Preferably, described ultrasonic time is 3～30min.
Preparation method of the present invention, the synthetic of carbon ball template is a kind of green non-pollution, and adopting glucose, sucrose or starch is raw material, and building-up process need not to use any organic solvent, initiator and tensio-active agent.The size of carbon ball template can be by hydrothermal temperature and time control, and carbon ball surface has kept a large amount of functional groups, is conducive to follow-up adsorption of metal ions.
Preparation method of the present invention is scattered in the suspension that forms the carbon ball in the water with synthetic carbon ball template, metal-salt is dissolved in the above-mentioned carbon ball suspension again, and this mode is conducive to the carbon ball and adsorbs more metal ion.
Preparation method of the present invention, its key is to control the adsorption conditionses such as metal-salt that metal salt concentrations, pH, soaking temperature, soak time and selection have different anions, make metal ion not only be adsorbed in carbon ball surface, and it is inner to enter the carbon ball, for the formation of many shell hollow spheres provides prerequisite.Further, control quantity, the degree of depth and the Gradient distribution that metal-salt enters the carbon ball template by regulating these adsorption conditionses, can realize the control to final product shell number, shell thickness and interlamellar spacing.
Preparation method of the present invention, in the process that effects on surface and the inner carbon ball that has all adsorbed metal-salt are heat-treated, the carbon burning of being heated, the carbon ball shrinks, the absorption oxidized formation metal oxide of metal ion shell thereon, because layering occurs then for the contraction rate of carbon ball and metal oxide shell different, the metal ion of carbon ball inside further forms new shell, is two layers to four layers metallic oxide hollow sphere thereby make the shell number.The heat-up rate of heat treatment process, Heating temperature and soaking time also have material impact to integrity degree, shell thickness and the interlamellar spacing of hollow ball.
Another object of the present invention provides a kind of many shell-layer metal oxide hollow balls.By many shell-layer metal oxide hollow balls of the inventive method preparation, its shell is piled up by the nanocrystal of metal oxide and is formed, and described metal oxide is preferably α-Fe
2O
3, ZnO, Co
3O
4, NiO, CuO or Y
2O
3Add-on by the control metal-salt, selection has the metal-salt of different anions, and pH value, soaking temperature, the soak time of modulation mixed solution, can realize shell number any modulation between two layers to four layers, the size of hollow ball and shell thickness are all controlled.Preferably, the many shell-layer metal oxide hollow balls of the present invention particle diameter be 0.6～2 μ m, shell thickness is 15～80nm.
With respect to the method for the many shell hollow spheres of present preparation, the present invention need not through the preparation of complexity and finishing process, and technique is simple, and can more accurately control shell number, size and the shell thickness of hollow ball by the modulation experiment condition.This hollow ball has the internal structure of hollow, and thickness is at the shell of nanoscale, and multilayered structure can effectively utilize the internal space simultaneously, has improved the specific surface area of material, and has had better structural stability.These many shell-layer metal oxide hollow balls can be widely used in the field of functional materials such as sensor, energy storage material, catalyzer, medicine controlled releasing.Resulting materials has been carried out the test of air-sensitive and photocatalysis performance, all have and compare the more excellent performance of traditional nano material, and the performance of many shell hollow spheres has been better than monoshell layer hollow ball.
Description of drawings
Describe embodiment of the present invention in detail below in conjunction with accompanying drawing, wherein:
Fig. 1 a, 1b and 1c are respectively the α-Fe of the embodiment of the invention 1 preparation
2O
3The transmission electron microscope photo of bivalve layer, three shells and four shell structure hollow balls;
Fig. 2 is the α-Fe of the embodiment of the invention 1 preparation
2O
3The X-ray diffracting spectrum of four shell hollow spheres;
Fig. 3 a, 3b, 3c, 3d are respectively ZnO, the Co of many shell structures of the embodiment of the invention 2,3,4,5 preparations
3O
4, NiO, CuO hollow ball transmission electron microscope photo;
Fig. 4 is the X-ray diffracting spectrum of the hollow ball (respectively corresponding curve a, b, c, d) of the multilayered structure of the embodiment of the invention 2,3,4,5 preparations.
Embodiment
Below in conjunction with specific embodiment the present invention is described in more detail and illustrates, but those skilled in the art will recognize that these embodiment only are used for illustrating the present invention, it does not consist of any restriction to scope of the present invention.
Embodiment 1
At first utilize hydrothermal method to prepare the carbon ball template with sucrose: to get sucrose 5.5g and be dissolved in the 10ml water, this solution is packed in the reactor, at 200 ℃ of lower hydro-thermal 80min, product after filtration, after the washing, drying, with the carbon ball that obtains approximately 0.4g insert in the 10ml deionized water, ultrasonic 3min obtains the suspension of carbon ball.
Dipping: respectively with the Fe (NO of 8g, 16g, 20g
3)
39H
2O adds and mixes (concentration that is metal-salt is respectively 2mol/L, 3mol/L, 5mol/L) in the above-mentioned carbon ball suspension, then ultrasonic 15min, at room temperature continue to stir again 5h, with this suspension filtered washing, then at 100 ℃ of lower dry 12h, the dusty material that obtains is the carbon ball that has adsorbed metal ion.
Thermal treatment: at last the powder that obtains is warming up to 500 ℃ and be incubated 1h with the temperature rise rate of 2 ℃/min under air atmosphere in retort furnace, with except the carbon elimination ball.
The transmission electron microscope photo of product such as Fig. 1 a, 1b and 1c are as seen by modulation Fe (NO
3)
39H
2The O add-on has obtained respectively the hollow ball of bivalve layer, three shells and four shells.Fig. 2 is the X-ray diffracting spectrum of four shell hollow spheres, and analyzing as can be known, product is the α-Fe of pure phase
2O
3
At first utilize hydrothermal method to prepare the carbon ball template with glucose: to get glucose 11g and be dissolved in the 10ml water, this solution is packed in the reactor, at 160 ℃ of lower hydro-thermal 50min, product after filtration, after the washing, drying, with the carbon ball that obtains approximately 0.4g insert in the 10ml deionized water, ultrasonic 30min obtains the suspension of carbon ball.
Dipping: with the Zn (CH of 5.5g
3COO)
26H
2O adds in the above-mentioned carbon ball suspension and mixes (being that metal salt concentrations is 2.5mol/L), then ultrasonic 15min, at room temperature continue to stir again 20h, with this suspension filtered washing, then at 100 ℃ of lower dry 12h, the dusty material that obtains is the carbon ball that has adsorbed metal ion.
Thermal treatment: at last the powder that obtains is warming up to 800 ℃ and be incubated 3h with the temperature rise rate of 5 ℃/min under air atmosphere in retort furnace, with except the carbon elimination ball.
The transmission electron microscope photo of product is the hollow ball of four shell structures shown in Fig. 3 a.The c curve of Fig. 4 is its X-ray diffracting spectrum, and analyzing as can be known, product is the ZnO of pure phase.
Embodiment 3
At first utilize hydrothermal method to prepare the carbon ball template with sucrose: to get sucrose 5.5g and be dissolved in the 10ml water, this solution is packed in the reactor, at 200 ℃ of lower hydro-thermal 80min, product after filtration, after the washing, drying, with the carbon ball that obtains approximately 0.4g insert in the 10ml deionized water, ultrasonic 15min obtains the suspension of carbon ball.
Dipping: with the Co (NO of 8.7g
3)
26H
2O adds in the above-mentioned carbon ball suspension and mixes (being that metal salt concentrations is 3mol/L), then ultrasonic 15min at room temperature continues to stir 10h again, with this suspension filtered washing, then at 100 ℃ of lower dry 12h, the dusty material that obtains is the carbon ball that has adsorbed metal ion.
Thermal treatment: at last the powder that obtains is warming up to 400 ℃ and be incubated 0.5h with the temperature rise rate of 1 ℃/min under air atmosphere in retort furnace, with except the carbon elimination ball.
The transmission electron microscope photo of product is the hollow ball of three shell structures shown in Fig. 3 b.The a curve of Fig. 4 is its X-ray diffracting spectrum, and analyzing as can be known, product is the Co of pure phase
3O
4
Embodiment 4
At first utilize hydrothermal method to prepare the carbon ball template with sucrose: to get sucrose 5.5g and be dissolved in the 10ml water, this solution is packed in the reactor, at 200 ℃ of lower hydro-thermal 80min, product after filtration, after the washing, drying, with the carbon ball that obtains approximately 0.4g insert in the 10ml deionized water, ultrasonic 5min obtains the suspension of carbon ball.
Dipping: with the NiCl of 9.5g
26H
2O adds in the above-mentioned carbon ball suspension and mixes (being that metal salt concentrations is 4mol/L), then ultrasonic 15min at 40 ℃ of lower stirring 2h that continue, washs this suspension filtered again, then at 100 ℃ of lower dry 12h, the dusty material that obtains is the carbon ball that has adsorbed metal ion.
Thermal treatment: at last the powder that obtains is warming up to 600 ℃ and be incubated 2h with the temperature rise rate of 2 ℃/min under air atmosphere in retort furnace, with except the carbon elimination ball.
The transmission electron microscope photo of product is the hollow ball of four shell structures shown in Fig. 3 c.The d curve of Fig. 4 is its X-ray diffracting spectrum, and analyzing as can be known, product is the NiO of pure phase.
Embodiment 5
At first utilize hydrothermal method to prepare the carbon ball template with starch: to get starch 2.5g and be dissolved in the 10ml water, this solution is packed in the reactor, at 220 ℃ of lower hydro-thermal 300min, product after filtration, after the washing, drying, with the carbon ball that obtains approximately 0.4g insert in the 10ml deionized water, ultrasonic 5min obtains the suspension of carbon ball.
Dipping: with the CuSO of 7.5g
45H
2O adds in the above-mentioned carbon ball suspension and mixes (being that metal salt concentrations is 3mol/L), then ultrasonic 15min at 60 ℃ of lower stirring 2h that continue, washs this suspension filtered again, then at 100 ℃ of lower dry 12h, the dusty material that obtains is the carbon ball that has adsorbed metal ion.
Thermal treatment: at last the powder that obtains is warming up to 600 ℃ and be incubated 2h with the temperature rise rate of 2 ℃/min under air atmosphere in retort furnace, with except the carbon elimination ball.
The transmission electron microscope photo of product is the hollow ball of three shell structures shown in Fig. 3 d.The b curve of Fig. 4 is its X-ray diffracting spectrum, and analyzing as can be known, product is the CuO of pure phase.
Embodiment 6
At first utilize hydrothermal method to prepare the carbon ball template with sucrose: to get sucrose 5.5g and be dissolved in the 10ml water, this solution is packed in the reactor, at 200 ℃ of lower hydro-thermal 80min, product after filtration, after the washing, drying, with the carbon ball that obtains approximately 0.4g insert in the 10ml deionized water, ultrasonic 5min obtains the suspension of carbon ball.
Dipping: with the Y (NO of 3.8g
3)
36H
2O adds in the above-mentioned carbon ball suspension and mixes (being that metal salt concentrations is 1mol/L), then ultrasonic 15min at room temperature continues to stir 15h again, with this suspension filtered washing, then at 100 ℃ of lower dry 12h, the dusty material that obtains is the carbon ball that has adsorbed metal ion.
Thermal treatment: at last the powder that obtains is warming up to 500 ℃ and be incubated 1h with the temperature rise rate of 2 ℃/min under air atmosphere in retort furnace, with except the carbon elimination ball, products therefrom is the Y of bivalve layer structure
2O
3Hollow ball.
Claims (5)
1. the preparation method of shell-layer metal oxide hollow ball more than a kind comprises the steps:
A, take glucose, sucrose or starch as raw material, be made into the aqueous solution of 0.25～1.10g/mL, solution is packed in the reactor, under 160～220 ℃ of conditions, heat 50～300min, obtain the carbon ball after filtration, washing, the drying, the carbon ball is scattered in the suspension that forms the carbon ball in the water;
B, a certain amount of metal-salt is dissolved in the carbon ball suspension of steps A, the add-on of metal-salt is 1～5mol/L, regulates the pH value of mixed solution less than 3, soaks 2～20h under 20～60 ℃ of stirrings, and filtration, washing, drying obtain powdered material;
C, the powdered material that step B is obtained are heat-treated, and thermal treatment temp is 400～800 ℃, and heat-up rate is 1～5 ℃/min, and soaking time is 0.5～3h, can obtain having the metallic oxide hollow sphere of many shell structures of different shell structures.
2. the preparation method of many shell-layer metal oxide hollow balls as claimed in claim 1 is characterized in that, metal-salt is nitrate, muriate, vitriol or the acetate of Fe, Zn, Co, Ni, Cu or Y.
3. the preparation method of many shell-layer metal oxide hollow balls as claimed in claim 1 is characterized in that, can carry out supersound process to carbon ball suspension before adding metal-salt, and ultrasonic time is 3～30min.
4. shell-layer metal oxide hollow ball more than a kind, shell is piled up by the nanocrystal of metal oxide and is formed, it is characterized in that, this hollow ball is prepared by the described method of any one among the claim 1-3, the shell number can be between two layers to four layers any modulation, the size of hollow ball and shell thickness are all controlled, and the particle diameter of hollow ball is 0.6～2 μ m, and shell thickness is 15～80nm.
5. many shell-layer metal oxide hollow balls as claimed in claim 4 is characterized in that, described metal oxide is α-Fe
2O
3, ZnO, Co
3O
4, NiO, CuO or Y
2O
3
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| US20040126354A1 (en) * | 2002-12-27 | 2004-07-01 | Jun-Yeob Song | Nano carbon ball for deodorization |
| EP1496015A1 (en) * | 2003-07-08 | 2005-01-12 | Yazaki Corporation | Method for producing ferrite hollow particles |
| CN101774646A (en) * | 2009-01-12 | 2010-07-14 | 中国科学院过程工程研究所 | Preparation method of spinel ferrite hollow sphere with core-shell structure |
| CN101759146A (en) * | 2010-01-20 | 2010-06-30 | 浙江师范大学 | Method for preparing ZnO/ZnFe2O4 compound nano hollow sphere |
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