CN102530972A - Method for preparing silicon dioxide hollow sphere with grain size of 30 to 80 nm - Google Patents
Method for preparing silicon dioxide hollow sphere with grain size of 30 to 80 nm Download PDFInfo
- Publication number
- CN102530972A CN102530972A CN2012100023292A CN201210002329A CN102530972A CN 102530972 A CN102530972 A CN 102530972A CN 2012100023292 A CN2012100023292 A CN 2012100023292A CN 201210002329 A CN201210002329 A CN 201210002329A CN 102530972 A CN102530972 A CN 102530972A
- Authority
- CN
- China
- Prior art keywords
- particle diameter
- hollow silica
- preparation
- silica ball
- solution
- 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.)
- Pending
Links
Images
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention discloses a method for preparing a silicon dioxide hollow sphere with the grain size of 30 to 80 nm. The method comprises the following steps: a surface active agent of an anion and alkali liquor are added into the de-ionized water to obtain a solution, and the solution is heated and stirred until the surface active agent of the anion is dissolved; in stirring, a co-structure-directing agent with amido functional groups is added into the solution, and then a silica source is added into the solution to prepare mixed liquor; and after being processed through heating and stationary reaction, the mixed liquor is centrifugally washed, dried and roasted to obtain the silicon dioxide hollow sphere. The mol ratio among of the surface active agent of the anion, the alkali liquor, the de-ionized water and the co-structure-directing agent with the amido functional groups is 1 : (0.2 to 0.6) : (500 to 10,000) : (0.3 to 2) : (3 to 50). In the invention, the surface active agent of the anion is taken as a template, and a path is synthetized through adopting a co-structure-directing method, so that the silicon dioxide hollow sphere with the grain size of 30 to 80 nm, which has controllable grain size and shell thickness, is obtained.
Description
Technical field
The present invention relates to the nano inorganic material technical field, be specifically related to the preparation method of the hollow silica ball of a kind of particle diameter 30～80nm.
Background technology
Silicon dioxide hollow sphere material has big specific surface area and hole, adjustable particle diameter, density is low, heat insulating ability good, in field great prospect such as drug release, catalysis, absorption, separation.
The size of silica spheres is very big to its performance impact.I.A.Rahmana etc. have delivered the article that is entitled as " Size-dependent Physicochemical and Optical Properties of Silica Nanoparticles " (relation of the physical chemistry of nano SiO 2 particle and optical property and size) at " Materials Chemistry and Physics " (material physical chemistry) 2009 the 114th phases the 1st volume 328-332 page or leaf; Physical chemistry and optical property and the size of pointing out nano SiO 2 particle are closely related; Size is more little, and performance is good more.
The preparation method of silicon dioxide hollow sphere material can be divided into hard template method and soft template method mainly based on template.Organic filler, inorganic particulate, polyelectrolyte nanoparticle etc. can be used as hard template.Emulsion, micella, macromole aggregate, bubble etc. can be used as soft template.Though the less particle of size can be synthetic through hard template method; Yet hard template method prepares the complicated steps of template; Spherical shell is unstable even broken in the template removal processes, is inconvenient to load guest molecule in synthetic, the big limitations of these shortcomings the application of hollow ball.Soft template method has higher handiness, obtains the littler structure of size easily.Tensio-active agent can form various structures, and like micella, vesica etc., structure is easy to control.The AS strong detergency, cheap, good stability is widely used.
Shunai Che has delivered at " Nature Materials " (nature material) 2003 the 2nd volume 801-805 page or leaf and has been entitled as " A Novel Anionic Surfactant Templating Route for Synthesizin g Mesoporous Silica with Unique Structure " (a kind of is template with the AS; Be used for synthetic novel method with Metaporous silicon dioxide material of unique texture) article; Utilize AS to be template first; Silane with the band amidine functional group is co-structured directed agents, has successfully synthesized to have mesoporous earth silicon material.Co-structured guiding method synthetic material has specific functional group, and these functional groups can be at the material surface homodisperse.
Lu Han etc. have delivered at " Solid State Sciences " (solid-state science) 2010 the 13rd volumes 721-728 page or leaf and have been entitled as " Anionic Surfactants Templating Route for Synthesizing Silica Hollow Spheres with Different Shell Porosity " (is the synthetic hollow silica ball with different porosities of template with the AS); As template, synthesized the mesoporous silicon oxide hollow ball of particle diameter with several kinds of different ASs at 80～220nm.With the palmitinic acid is the hollow silica ball that template has synthesized 100～200nm particle diameter; Yet this method is not suitable for and prepares the more hollow silica ball of small particle size.
Though the hollow silica ball that particle diameter is little is in great demand, do not appear in the newspapers as yet with the hollow ball of AS as the silicon-dioxide below the template synthetic 80nm; The preparation method of the hollow ball of the silicon-dioxide of particle diameter below 80nm is still the emphasis of this area research.
Summary of the invention
The objective of the invention is to above-mentioned deficiency, the preparation method of the hollow silica ball of a kind of particle diameter 30～80nm is provided to the prior art existence.This method is a template with the AS, adopts co-structured guiding method synthetic route, obtains the controlled hollow silica ball shape material of particle diameter and shell thickness.
The present invention seeks to realize through following technical scheme:
The present invention relates to the preparation method of the hollow silica ball of a kind of particle diameter 30～80nm, comprise the steps:
Step 1 adds AS and alkali lye in the deionized water, and heated and stirred to AS dissolves;
Step 2 stirs down, in the solution of step 1 gained, adds the co-structured directed agents of amino-contained functional group, adds the silicon source then, processes mixed solution;
Step 3, after the mixed solution that step 2 the is made heating standing and reacting, centrifuge washing, drying, roasting promptly get said hollow silica ball.
Preferably, the mol ratio in the co-structured directed agents of the AS of said adding, alkali lye, deionized water, amino-contained functional group and silicon source is 1: (0.2～0.6): (500～10000): (0.3～2): (3～50).
Preferably, the AS described in the step 1 is hexadecanoic acid [CH
3(CH
2)
14COOH].
Preferably, the heated and stirred described in the step 1 is meant at 50～90 ℃ and stirs down.
Preferably, the alkali lye described in the step 1 is that concentration is sodium hydroxide or the potassium hydroxide aqueous solution of 0.5～5mol/L.
Preferably, the structure of the co-structured directed agents of the amino-contained functional group described in the step 2 is suc as formula shown in (I):
(R
1O)
3Si-R-NR
2R
3Formula (I);
Wherein, R
1, R
2, R
3Be C
1～C
4Straight chain, branched chain alkyl or Wasserstoffatoms; R is C
1～C
4Straight chain or branched chain alkyl.
Preferably; The co-structured directed agents of described amino-contained functional group is 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 4-aminopropyl trimethoxysilane, N-trimethoxy silicon propyl group-N-methylamine, N-trimethoxy silicon propyl group-N, N-dimethyl amine, N-triethoxysilylpropyl-N, N-dipropylamine, N-triethoxysilylpropyl-N-butylamine, N-trimethoxy silicon propyl group-N; N; N-trimethyl ammonium chloride or N-trimethoxy silicon propyl group-N, N, N-tributyl brometo de amonio.
Preferably, the silicon source described in the step 2, its structure is suc as formula shown in (II):
(R
1O)
m-Si-X
nFormula (II);
Wherein, m is the arbitrary integer in 2～4, and n is the arbitrary integer in 0～2, and m+n=4; R
1Be C
1～C
4Straight chain, branched chain alkyl or Wasserstoffatoms; X is straight chain or the branched chain alkyl of C1～C4.
Preferably; Described silicon source is tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, dimethoxy dimethylsilane, dimethyl-diethoxy silane, trimethoxy silicomethane, triethoxy methyl silicane, trimethoxy ethylsilane, triethoxy ethyl silane, trimethoxy vinyl silanes, triethoxy vinyl silanes or dimethoxy di-isopropyl silane.
Preferably, the heating standing and reacting described in the step 3 is that reaction is after 0.5～120 hour down at 50～90 ℃, and the polycondensation of silicon source forms earth silicon material.
Preferably, the roasting described in the step 3 is to washing dried precipitation of silica thing roasting 3～24 hours under 350～550 ℃.
Basic functional principle of the present invention is: AS forms micella in water, and its hydrophobic chain part forms the micella kernel because hydrophobic interaction is assembled mutually, and hydrophilic segment interacts with water molecules outside micella.The co-structured directed agents of amino-contained functional group is made up of two portions, and its amido part can interact through electrostatic force with AS, and its oxyalkylene segment can polycondensation take place with the silicon source, forms the silicon-dioxide wall jointly.The hydrophobicity of the AS of the synthetic hollow ball of existing bibliographical information is strong, and poorly soluble in water, the material particle size that obtains is bigger; And method of the present invention can access the less hollow silica ball of particle diameter, and the committed step of realization is in synthetic system, to add alkali.On the one hand, alkali can make the carboxyl of part surface promoting agent become carboxylic acid ion, and emulsified oil droplet reduces the size of oil droplet, increases the solvability of tensio-active agent.On the other hand, alkali changes the pH value of solution, promotes the hydrolysis and the polycondensation speed in silicon source, influences the assembling process of tensio-active agent/co-structured directed agents/silicon source system simultaneously.Through changing synthesis condition,, can access the hollow silica ball of 30～80nm particle diameter like the amount of the amount of surfactant concentration, alkali, co-structured directed agents, the amount in silicon source etc.
Compared with prior art, the beneficial effect that the present invention has is: the present invention can access the hollow silica ball of 30～80nm particle diameter through changing surfactant concentration, the amount of alkali, the amount of co-structured directed agents, the synthesis conditions such as amount in silicon source.
Description of drawings
Fig. 1 is the electromicroscopic photograph of the hollow silica ball shape material of embodiment 1 preparation;
Fig. 2 is the electromicroscopic photograph of the hollow silica ball shape material of embodiment 3 preparations;
Fig. 3 is the electromicroscopic photograph of the hollow silica ball shape material of embodiment 6 preparations.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
Under 50 ℃ of water-baths, 0.256g CH
3(CH
2)
14The aqueous sodium hydroxide solution of COOH and 0.15g 2mol/L adds in the 25.6g deionized water, is stirred to the AS dissolving and forms solution; Add 0.221g 3-aminopropyl triethoxysilane and 1.456g tetraethoxysilane to this solution, obtain mixing solutions.The reactant molar ratio example is a tensio-active agent: sodium hydroxide: water: the co-structured tensio-active agent of amino-contained functional group: silicon source 1: 0.3: 1422: 1: 7.This system stirred after 10 minutes, put into 80 ℃ of water bath with thermostatic control standing and reacting 24 hours.Reacted silicon dioxde solution is through spinning, and after water and the washing with alcohol, lyophilize obtains solid precipitation.Carry out calcination process under 550 ℃ 6 hours, and can remove organic formwork, obtain having the earth silicon material of functional group.
Through ESEM, transmission electron microscope this material is characterized.Fig. 1-a, Fig. 1-b are respectively stereoscan photograph, the transmission electron microscope photos of this material.Can find out that from ESEM and transmission electron microscope photo the gained material is that hollow, spherical, median size 45nm, shell thickness are the earth silicon material of 8nm.
Embodiment 2
Under 60 ℃ of water-baths, 0.256g CH
3(CH
2)
14The aqueous sodium hydroxide solution of COOH and 0.15g 2mol/L adds in the 25.6g deionized water, is stirred to the AS dissolving and forms solution.Add 0.155g 3-aminopropyl triethoxysilane and 1.456g tetraethoxysilane to this solution, obtain mixing solutions.The reactant molar ratio example is a tensio-active agent: sodium hydroxide: water: the co-structured tensio-active agent of amino-contained functional group: silicon source 1: 0.3: 1422: 0.7: 7.This system stirred after 10 minutes, put into 80 ℃ of water bath with thermostatic control standing and reacting 24 hours.Reacted silicon dioxde solution is through spinning, and after water and the washing with alcohol, lyophilize obtains solid precipitation.Carry out calcination process under 550 ℃ 3 hours, and can remove organic formwork, obtain having the earth silicon material of functional group.
Through ESEM, transmission electron microscope this material is characterized.The gained material is that hollow, spherical, median size 35nm, shell thickness are the earth silicon material of 7nm.
Embodiment 3
Under 70 ℃ of water-baths, 0.256g CH
3(CH
2)
14The aqueous sodium hydroxide solution of COOH and 0.15g 2mol/L adds in the 51.2g deionized water, is stirred to the AS dissolving and forms solution.Add 0.221g 3-aminopropyl triethoxysilane and 1.456g tetraethoxysilane to this solution, obtain mixing solutions.The reactant molar ratio example is a tensio-active agent: sodium hydroxide: water: the co-structured tensio-active agent of amino-contained functional group: silicon source 1: 0.3: 2844: 1: 7.This system stirred after 10 minutes, put into 80 ℃ of water bath with thermostatic control standing and reacting 24 hours.Reacted silicon dioxde solution is through spinning, and after water and the washing with alcohol, lyophilize obtains solid precipitation.Carry out calcination process under 550 ℃ 6 hours, and can remove organic formwork, obtain having the earth silicon material of functional group.
Through ESEM, transmission electron microscope this material is characterized.Fig. 2-a, Fig. 2-b are respectively stereoscan photograph, the transmission electron microscope photos of this material.Can find out that from ESEM and transmission electron microscope photo the gained material is that hollow, spherical, median size 40nm, shell thickness are the earth silicon material of 6nm.
Embodiment 4
Under 80 ℃ of stirring in water bath, 0.256g CH
3(CH
2)
14The aqueous sodium hydroxide solution of COOH and 0.2g 3mol/L adds in the 25.6g deionized water, is stirred to the AS dissolving and forms solution.Add 0.221g 3-aminopropyl triethoxysilane and 1.456g tetraethoxysilane to this solution, obtain mixing solutions.The reactant molar ratio example is a tensio-active agent: sodium hydroxide: water: the co-structured tensio-active agent of amino-contained functional group: silicon source 1: 0.6: 1422: 1: 7.This system stirred after 10 minutes, put into 80 ℃ of water bath with thermostatic control standing and reacting 12 hours.Reacted silicon dioxde solution is through spinning, and after water and the washing with alcohol, lyophilize obtains solid precipitation.Carry out calcination process under 550 ℃ 6 hours, and can remove organic formwork, obtain having the earth silicon material of functional group.
Through ESEM, transmission electron microscope this material is characterized.The gained material is that hollow, spherical, median size 30nm, shell thickness are the earth silicon material of 5nm.
Embodiment 5
Under 90 ℃ of water-baths, 0.256g CH
3(CH
2)
14The aqueous sodium hydroxide solution of COOH and 0.15g 2mol/L adds in the 25.6g deionized water, is stirred to the AS dissolving and forms solution.Add 0.221g 3-aminopropyl triethoxysilane and 3.12g tetraethoxysilane to this solution, obtain mixing solutions.The reactant molar ratio example is a tensio-active agent: sodium hydroxide: water: the co-structured tensio-active agent of amino-contained functional group: silicon source 1: 0.3: 1422: 1: 15.This system stirred after 10 minutes, put into 80 ℃ of water bath with thermostatic control standing and reacting 24 hours.Reacted silicon dioxde solution is through spinning, and after water and the washing with alcohol, lyophilize obtains solid precipitation.Carry out calcination process under 550 ℃ 6 hours, and can remove organic formwork, obtain having the earth silicon material of functional group.
Through ESEM, transmission electron microscope this material is characterized.The gained material is that hollow, spherical, median size 50nm, shell thickness are the earth silicon material of 11nm.
Embodiment 6
Under 65 ℃ of water-baths, 0.256g CH
3(CH
2)
14The aqueous sodium hydroxide solution of COOH and 0.06g 5mol/L adds in the 25.6g deionized water, is stirred to the AS dissolving and forms solution.Add 0.179g 3-aminopropyl trimethoxysilane and 3.952g tetraethoxysilane to this solution, obtain mixing solutions.The reactant molar ratio example is a tensio-active agent: sodium hydroxide: water: the co-structured tensio-active agent of amino-contained functional group: silicon source 1: 0.3: 2844: 1: 19.This system stirred after 10 minutes, put into 80 ℃ of water bath with thermostatic control standing and reacting 24 hours.Reacted silicon dioxde solution is through spinning, and after water and the washing with alcohol, lyophilize obtains solid precipitation.Carry out calcination process under 350 ℃ 6 hours, and can remove organic formwork, obtain having the earth silicon material of functional group.
Through ESEM, transmission electron microscope this material is characterized.Fig. 3-a, Fig. 3-b are respectively stereoscan photograph, the transmission electron microscope photos of this material.Can find out that from ESEM and transmission electron microscope photo the gained material is that hollow, spherical, median size 65nm, shell thickness are the earth silicon material of 11nm.
Embodiment 7
Under 70 ℃ of water-baths, 0.256g CH
3(CH
2)
14The aqueous sodium hydroxide solution of COOH and 0.6g 0.5mol/L adds in the 25.6g deionized water, is stirred to the AS dissolving and forms solution.Add 0.221g 3-aminopropyl triethoxysilane and 1.06g tetramethoxy-silicane to this solution, obtain mixing solutions.The reactant molar ratio example is a tensio-active agent: sodium hydroxide: water: the co-structured tensio-active agent of amino-contained functional group: silicon source 1: 0.3: 1422: 1: 7.This system stirred after 10 minutes, put into 80 ℃ of water bath with thermostatic control standing and reacting 3 hours.Reacted silicon dioxde solution is through spinning, and after water and the washing with alcohol, lyophilize obtains solid precipitation.Carry out calcination process under 550 ℃ 6 hours, and can remove organic formwork, obtain having the earth silicon material of functional group.
Through ESEM, transmission electron microscope this material is characterized.The gained material is that hollow, spherical, median size 45nm, shell thickness are the earth silicon material of 8nm.
Embodiment 8
Under 75 ℃ of water-baths, 0.256g CH
3(CH
2)
14The aqueous sodium hydroxide solution of COOH and 0.15g 2mol/L adds in the 25.6g deionized water, is stirred to the AS dissolving and forms solution.Add 0.221g3-aminopropyl triethoxysilane, 0.98g tetraethoxysilane and 0.34g dimethyl-diethoxy silane to this surfactant soln, obtain mixing solutions.The reactant molar ratio example is a tensio-active agent: sodium hydroxide: water: the co-structured tensio-active agent of amino-contained functional group: silicon source 1: 0.3: 1422: 1: 7.This system stirred after 10 minutes, put into 90 ℃ of water bath with thermostatic control standing and reacting 0.5 hour.Reacted silicon dioxde solution is through spinning, and after water and the washing with alcohol, lyophilize obtains solid precipitation.Carry out calcination process under 550 ℃ 6 hours, and can remove organic formwork, obtain having the earth silicon material of functional group.
Through ESEM, transmission electron microscope this material is characterized.The gained material is that hollow, spherical, median size 38nm, shell thickness are the earth silicon material of 7nm.
Embodiment 9
Under 80 ℃ of water-baths, 0.256g CH
3(CH
2)
14The aqueous sodium hydroxide solution of COOH and 0.15g 2mol/L adds in the 25.6g deionized water, is stirred to the AS dissolving and forms solution.Add 0.221g3-aminopropyl triethoxysilane, 0.257g N-trimethoxy silicon propyl group-N to this surfactant soln, N, N-trimethyl ammonium chloride, 2.24g four butoxy silanes obtain mixing solutions.The reactant molar ratio example is a tensio-active agent: sodium hydroxide: water: the co-structured tensio-active agent of amino-contained functional group: silicon source 1: 0.3: 1422: 2: 7.This system stirred after 10 minutes, put into 80 ℃ of water bath with thermostatic control standing and reacting 72 hours.Reacted silicon dioxde solution is through spinning, and after water and the washing with alcohol, lyophilize obtains solid precipitation.Carry out calcination process under 550 ℃ 24 hours, and can remove organic formwork, obtain having the earth silicon material of functional group.
Through ESEM, transmission electron microscope this material is characterized.The gained material is that hollow, spherical, median size 80nm, shell thickness are the earth silicon material of 10nm.
Embodiment 10
Under 80 ℃ of water-baths, 0.256g CH
3(CH
2)
14The potassium hydroxide aqueous solution of COOH and 0.06g 5mol/L adds in the 36.6g deionized water, is stirred to the AS dissolving and forms solution.Add 0.189g 3-aminopropyl trimethoxysilane, 0.79g tetrapropoxysilane to this surfactant soln, obtain mixing solutions.The reactant molar ratio example is a tensio-active agent: sodium hydroxide: water: the co-structured tensio-active agent of amino-contained functional group: silicon source 1: 0.3: 2030: 1: 3.This system stirred after 10 minutes, put into 85 ℃ of water bath with thermostatic control standing and reacting 10 hours.Reacted silicon dioxde solution is through spinning, and after water and the washing with alcohol, lyophilize obtains solid precipitation.Carry out calcination process under 400 ℃ 12 hours, and can remove organic formwork, obtain having the earth silicon material of functional group.
Through ESEM, transmission electron microscope this material is characterized.The gained material is that hollow, spherical, median size 35nm, shell thickness are the earth silicon material of 7nm.
Embodiment 11
Under 80 ℃ of water-baths, 0.256g CH
3(CH
2)
14The aqueous sodium hydroxide solution of COOH and 0.15g 3mol/L adds in the 126g deionized water, is stirred to the AS dissolving and forms solution.Add 0.28g3-aminopropyl trimethoxysilane and 10.4g tetraethoxysilane to this surfactant soln, obtain mixing solutions.The reactant molar ratio example is a tensio-active agent: sodium hydroxide: water: the co-structured tensio-active agent of amino-contained functional group: silicon source 1: 0.45: 7000: 1.5: 50.This system stirred after 10 minutes, put into 50 ℃ of water bath with thermostatic control standing and reacting 120 hours.Reacted silicon dioxde solution is through spinning, and after water and the washing with alcohol, lyophilize obtains solid precipitation.Carry out calcination process under 550 ℃ 6 hours, and can remove organic formwork, obtain having the earth silicon material of functional group.
Through ESEM, transmission electron microscope this material is characterized.The gained material is that hollow, spherical, median size 70nm, shell thickness are the earth silicon material of 13nm.
Embodiment 12
Under 80 ℃ of water-baths, 0.256g CH
3(CH
2)
14The aqueous sodium hydroxide solution of COOH and 0.1g 2mol/L adds in the 180g deionized water, is stirred to the AS dissolving and forms solution.Add 0.221g3-aminopropyl triethoxysilane and 3.12g tetraethoxysilane to this surfactant soln, obtain mixing solutions.The reactant molar ratio example is a tensio-active agent: sodium hydroxide: water: the co-structured tensio-active agent of amino-contained functional group: silicon source 1: 0.2: 10000: 1: 15.This system stirred after 10 minutes, put into 50 ℃ of water bath with thermostatic control standing and reacting 24 hours.Reacted silicon dioxde solution is through spinning, and after water and the washing with alcohol, lyophilize obtains solid precipitation.Carry out calcination process under 550 ℃ 6 hours, and can remove organic formwork, obtain having the earth silicon material of functional group.
Through ESEM, transmission electron microscope this material is characterized.The gained material is that hollow, spherical, median size 55nm, shell thickness are the earth silicon material of 10nm.
Embodiment 13
Under 80 ℃ of water-baths, 0.256g CH
3(CH
2)
14The aqueous sodium hydroxide solution of COOH and 0.15g 2mol/L adds in the 9g deionized water, is stirred to the AS dissolving and forms solution.Add 0.066g3-aminopropyl triethoxysilane and 1.456g tetraethoxysilane to this surfactant soln, obtain mixing solutions.The reactant molar ratio example is a tensio-active agent: sodium hydroxide: water: the co-structured tensio-active agent of amino-contained functional group: silicon source 1: 0.3: 500: 0.3: 7.This system stirred after 10 minutes, put into 50 ℃ of water bath with thermostatic control standing and reacting 24 hours.Reacted silicon dioxde solution is through spinning, and after water and the washing with alcohol, lyophilize obtains solid precipitation.Carry out calcination process under 550 ℃ 6 hours, and can remove organic formwork, obtain having the earth silicon material of functional group.
Through ESEM, transmission electron microscope this material is characterized.The gained material is that hollow, spherical, median size 48nm, shell thickness are the earth silicon material of 9nm.
The foregoing description is through ESEM, transmission electron microscope this material to be characterized.Sem photograph has provided pattern, size and the size distribution situation of earth silicon material; Can obtain internal structure, size and the size distribution situation of material from transmission electron microscope picture.Selecting 50 ball statistics particle diameters from electromicroscopic photograph, promptly is median size.Can know the physical chemistry sign/component content of the hollow silica ball shape material that the present invention obtains by above each embodiment: particle diameter 30～80nm, silica shell layer thickness 7～13nm.
Claims (11)
1. the preparation method of the hollow silica ball of particle diameter a 30～80nm is characterized in that, comprises the steps:
Step 1 adds AS and alkali lye in the deionized water, and heated and stirred to AS dissolves;
Step 2 stirs down, in the solution of step 1 gained, adds the co-structured directed agents of amino-contained functional group, adds the silicon source then, processes mixed solution;
Step 3, after the mixed solution that step 2 the is made heating standing and reacting, centrifugal, washing, dry, roasting promptly get said hollow silica ball.
2. the preparation method of the hollow silica ball of particle diameter 30～80nm according to claim 1; It is characterized in that the co-structured directed agents of the AS of said adding, alkali lye, deionized water, amino-contained functional group and the mol ratio in silicon source are 1: (0.2～0.6): (500～10000): (0.3～2): (3～50).
3. the preparation method of the hollow silica ball of particle diameter 30～80nm according to claim 1 and 2 is characterized in that, the AS described in the step 1 is a hexadecanoic acid.
4. the preparation method of the hollow silica ball of particle diameter 30～80nm according to claim 1 and 2 is characterized in that, the heated and stirred described in the step 1 is meant at 50～90 ℃ and stirs down.
5. the preparation method of the hollow silica ball of particle diameter 30～80nm according to claim 1 and 2 is characterized in that, the alkali lye described in the step 1 is that concentration is sodium hydroxide or the potassium hydroxide aqueous solution of 0.5～5mol/L.
6. the preparation method of the hollow silica ball of particle diameter 30～80nm according to claim 1 and 2 is characterized in that, the structure of the co-structured directed agents of the amino-contained functional group described in the step 2 is suc as formula shown in (I):
(R
1O)
3Si-R-NR
2R
3
Formula (I)
Wherein, R
1, R
2, R
3Be C
1～C
4Straight chain, branched chain alkyl or Wasserstoffatoms; R is C
1～C
4Straight chain or branched chain alkyl.
7. the preparation method of the hollow silica ball of particle diameter 30～80nm according to claim 6; It is characterized in that; The co-structured directed agents of described amino-contained functional group is 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 4-aminopropyl trimethoxysilane, N-trimethoxy silicon propyl group-N-methylamine, N-trimethoxy silicon propyl group-N, N-dimethyl amine, N-triethoxysilylpropyl-N, N-dipropylamine, N-triethoxysilylpropyl-N-butylamine, N-trimethoxy silicon propyl group-N; N; N-trimethyl ammonium chloride or N-trimethoxy silicon propyl group-N, N, the mixing of one or more in the N-tributyl brometo de amonio.
8. the preparation method of the hollow silica ball of particle diameter 30～80nm according to claim 1 and 2 is characterized in that, the silicon source described in the step 2, and its structure is suc as formula shown in (II):
(R
1O)
m-Si-X
nFormula (II);
Wherein, m is the arbitrary integer in 2～4, and n is the arbitrary integer in 0～2, and m+n=4; R
1Be C
1～C
4Straight chain, branched chain alkyl or Wasserstoffatoms; X is straight chain or the branched chain alkyl of C1～C4.
9. the preparation method of the hollow silica ball of particle diameter 30～80nm according to claim 8; It is characterized in that; Described silicon source is tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, dimethoxy dimethylsilane, dimethyl-diethoxy silane, the mixing of one or more in trimethoxy silicomethane, triethoxy methyl silicane, trimethoxy ethylsilane, triethoxy ethyl silane, trimethoxy vinyl silanes, triethoxy vinyl silanes or the dimethoxy di-isopropyl silane.
10. the preparation method of the hollow silica ball of particle diameter 30～80nm according to claim 1 and 2 is characterized in that, the heating standing and reacting described in the step 3 is to react 0.5～120 hour down at 50～90 ℃.
11. the preparation method of the hollow silica ball of particle diameter 30～80nm according to claim 1 and 2 is characterized in that, the roasting described in the step 3 is to washing dried precipitation of silica thing roasting 3～24 hours under 350～550 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100023292A CN102530972A (en) | 2012-01-06 | 2012-01-06 | Method for preparing silicon dioxide hollow sphere with grain size of 30 to 80 nm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100023292A CN102530972A (en) | 2012-01-06 | 2012-01-06 | Method for preparing silicon dioxide hollow sphere with grain size of 30 to 80 nm |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102530972A true CN102530972A (en) | 2012-07-04 |
Family
ID=46339193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100023292A Pending CN102530972A (en) | 2012-01-06 | 2012-01-06 | Method for preparing silicon dioxide hollow sphere with grain size of 30 to 80 nm |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102530972A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106396093A (en) * | 2016-11-10 | 2017-02-15 | 成都信息工程大学 | Method for accelerating granulation of activated sludge |
| CN109574023A (en) * | 2018-12-26 | 2019-04-05 | 江苏德鑫新材料科技有限公司 | The technique that one-step method prepares preparing spherical SiO 2 |
| CN111620342A (en) * | 2020-06-03 | 2020-09-04 | 南京特粒材料科技有限公司 | Small-size monodisperse hollow silica microsphere and preparation method and application thereof |
| CN114436270A (en) * | 2020-11-04 | 2022-05-06 | 中国石油天然气股份有限公司 | Double-spherical silicon dioxide and preparation method and application thereof |
| CN115536032A (en) * | 2022-11-09 | 2022-12-30 | 中国计量大学 | Spherical silicon dioxide and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168440A (en) * | 2007-09-27 | 2008-04-30 | 上海交通大学 | Silicon oxide mesoporous material and preparing method thereof |
| CN101391776A (en) * | 2007-09-21 | 2009-03-25 | 中国科学院理化技术研究所 | Preparation method of porous silicon dioxide nanosphere with special structure on surface and porous silicon dioxide nanosphere |
| CN101654253A (en) * | 2009-09-04 | 2010-02-24 | 上海交通大学 | Preparation method of silica mesoporous hollow sphere material |
-
2012
- 2012-01-06 CN CN2012100023292A patent/CN102530972A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391776A (en) * | 2007-09-21 | 2009-03-25 | 中国科学院理化技术研究所 | Preparation method of porous silicon dioxide nanosphere with special structure on surface and porous silicon dioxide nanosphere |
| CN101168440A (en) * | 2007-09-27 | 2008-04-30 | 上海交通大学 | Silicon oxide mesoporous material and preparing method thereof |
| CN101654253A (en) * | 2009-09-04 | 2010-02-24 | 上海交通大学 | Preparation method of silica mesoporous hollow sphere material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106396093A (en) * | 2016-11-10 | 2017-02-15 | 成都信息工程大学 | Method for accelerating granulation of activated sludge |
| CN109574023A (en) * | 2018-12-26 | 2019-04-05 | 江苏德鑫新材料科技有限公司 | The technique that one-step method prepares preparing spherical SiO 2 |
| CN111620342A (en) * | 2020-06-03 | 2020-09-04 | 南京特粒材料科技有限公司 | Small-size monodisperse hollow silica microsphere and preparation method and application thereof |
| CN111620342B (en) * | 2020-06-03 | 2021-11-19 | 南京特粒材料科技有限公司 | Small-size monodisperse hollow silica microsphere and preparation method and application thereof |
| CN114436270A (en) * | 2020-11-04 | 2022-05-06 | 中国石油天然气股份有限公司 | Double-spherical silicon dioxide and preparation method and application thereof |
| CN115536032A (en) * | 2022-11-09 | 2022-12-30 | 中国计量大学 | Spherical silicon dioxide and preparation method thereof |
| CN115536032B (en) * | 2022-11-09 | 2023-10-31 | 中国计量大学 | Spherical silicon dioxide and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103880020B (en) | Chirality mesoporous organic silica nanotube or core-shell type nanometer rod and preparation method thereof | |
| CN102530972A (en) | Method for preparing silicon dioxide hollow sphere with grain size of 30 to 80 nm | |
| CN101168440B (en) | Silicon oxide mesoporous material and preparing method thereof | |
| CN103922390B (en) | A kind of preparation method for light-catalysed porous zinc bloom single crystal nanoplate | |
| CN102272239A (en) | A process for preparing silica microparticles | |
| CN101559952A (en) | Preparation method of nano-scale mesoporous silica spheres | |
| CN101688069A (en) | Metal oxide through hydrophobic treatment | |
| CN105800684B (en) | Monodisperse of the size less than 100 nm, porous crystalline TiOx nano ball and preparation method thereof | |
| CN105329905A (en) | Preparation method of hollow mesoporous silica nano-particles | |
| CN106732221B (en) | A kind of preparation method of amphipathic Janus grading-hole micro-capsule having an open structure | |
| CN103833040B (en) | The preparation method of hollow mesopore silicon oxide spheres and hollow mesoporous organosilicon ball | |
| CN101654253A (en) | Preparation method of silica mesoporous hollow sphere material | |
| CN104386699B (en) | Double-template legal system is for the method for many shells mesoporous silicon oxide nanomaterial | |
| CN105110343A (en) | Method for rapid preparation of monodisperse ordered mesoporous silicon oxide hollow sphere | |
| CN108046244B (en) | Method for synthesizing Janus graphene | |
| CN105236417B (en) | Spherical mesoporous silica with controllable particle size and preparation method of spherical mesoporous silica | |
| JP2013542157A (en) | Production of irregular porous silicon dioxide material and application of fatty alcohol polyoxyethylene ether in its production | |
| CN109574507A (en) | A kind of nano-level sphere bioactivity glass and preparation method thereof | |
| CN101704527B (en) | Monodisperse mesoporous silica nano-particle with controllable appearance and synthesis method thereof | |
| CN102936032A (en) | Preparation method of nano-zinc oxide aqueous solution | |
| CN101891211B (en) | Silicon dioxide mesoporous material with multilayer sleeve structure and preparation thereof | |
| CN112978739B (en) | Synthesis method of uniform symmetrical or asymmetrical nanoparticles, large-size and modified nanoparticles | |
| CN110104654A (en) | A kind of Janus type porous silica composite nanoparticle and preparation method thereof | |
| CN105236427B (en) | A kind of nanoscale ordered mesoporous silica dioxide ball and preparation method thereof | |
| CN103601201A (en) | Monodispersed mesoporous silica nanoparticles and synthetic method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120704 |
|
| WD01 | Invention patent application deemed withdrawn after publication |