CN102716745A - Preparation method for yolk-eggshell-type organic-inorganic hybrid silicon oxide nanosphere - Google Patents
Preparation method for yolk-eggshell-type organic-inorganic hybrid silicon oxide nanosphere Download PDFInfo
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Abstract
The invention relates to silicon oxide sphere particles, concretely to a preparation method for organic-inorganic hybrid silicon oxide nanospheres with a structure of yolk-eggshell. The invention provides a yolk-eggshell-type organic-inorganic hybrid silicon oxide or a carbon-silicon composite nano-material with adjustable particle size, adjustable core-shell composition and hierarchical pore structure, and the preparation method thereof. In an alkaline system, nanometer silicon oxide spheres with core-shell structures are composed by taking a cationic surfactant as a structure-directing agent. Organosilicon precursor is added to the system. After being stirred, filtered and dried, the organic-inorganic hybrid silicon oxide nanospheres with freely mobile cores and functionalized mesoporous shells are obtained.
Description
Technical field
The present invention relates to organic-inorganic hybrid nanomaterials, specifically a kind of preparation method with hybrid inorganic-organic monox nanometer ball of yolk-eggshell structure (being to be loaded with in the chamber to can move freely nano particle).
Background technology
Inner chamber be loaded with the nano oxidized silicon materials of the yolk-eggshell type that can move freely nano particle since its have unique light, electrical property, with and in potential application prospect aspect catalysis, biological medicine and the imaging, become the research focus of present field of nanometer material technology.The main component of yolk-its shell of eggshell type nano material that has prepared at present comprises: silica, organic polymer, metal oxide and carbon.Wherein, Silica since its have big specific area, high storage capacity, favorable mechanical and heat endurance, cheap and easy to get, bio-compatibility is good etc., and advantage has received extensive concern, be with a wide range of applications in research fields such as nanometer confinement catalysis, targeted drug (gene) slowly-releasing, absorption, insulating materials, photoelectron crystal, dielectric materials and medical diagnosis on disease treatments.At present; Yolk-eggshell type nano silicon oxide preparation methods mainly is divided into: " the selective etch method that template is auxiliary "; " soft template method ", " ship construction method in the bottle ", " Kenny's Dare effect " (Kirkendall effect); " electrification displacement " (galvanic replacement), and " Ostwald maturing process from the inside to the outside ".Wherein the most frequently used a kind of method is: " the selective etch method that template is auxiliary "; Prepared yolk-eggshell type nano material (Jounal of American Chemical Society that a lot of different IPs-shell is formed through this method; 2003, the 125th volume, 2384-2385 page or leaf; Nano Lett, 2002, the 2nd volume, 1383-1387 page or leaf; Chemmcial Communications, the 2009th, the 1653-1654 page or leaf; Small 2007, the 3rd volume, 261-265 page or leaf; Angewandte Chemie International Edition, 2008, the 47th volume, 5806-5811 page or leaf; Chemistry of Materials, 2009, the 21st year, the 3848-3852 page or leaf; Advanced Materials, 2009, the 21st volume, 3804-3807 page or leaf; Chemistry of Materials, 2009, the 21st volume, 2547-2553 page or leaf; Chemistry of Materials
,2006, the 18th volume, 614-619 page or leaf).This method mainly is that the nano particle that will prepare in advance earlier wraps up with one deck or two-layer shell with different component; Optionally optionally etch away middle one deck of part shell, nuclear or two-layer shell through solvent or calcining then, obtain having the nanometer particle material that can move freely in the chamber.But this method step is various, and preparation difficulty mainly comes from the following aspects: optionally partly removing same material, to prepare the cavity that nano particle can move freely be to be difficult to realize; Preparation has the nano particle of two kinds of different component shell parcels and optionally removes the requirement on technological and shell wall composition of tool subshell fully very high, so this method is difficult for implementing the very difficult modulation of shell wall composition.Lu high definition and Xu Dongsheng group has been reported respectively to adopt and has been mixed soft template and nano particle is packaged into has yolk-nanosilica white sphere (Angewandte Chemie International Edition,, the 49th volume, the 4981-4985 page or leaf in 2010 of eggshell structure; Jounal of American Chemical Society, 2009, the 131st page, the 2774-2775 page or leaf.), but this method is not suitable for encapsulating the particle diameter < nano particle of 10 nm; " ship construction method in the bottle " is meant and prepares hollow nano-sphere earlier; Again metal precursor and reducing agent are impregnated into inside, ball chamber; Thereby method (Chemistry of Materials,, the 17th volume in 2005 at hollow ball inside in-situ preparing nano particle; The 3578-3581 page or leaf), this method is difficult to guarantee that the spherical shell outside does not have nano particle; " Kenny's Dare effect " (Kirkendall effect); " electrification displacement " (galvanic replacement); And " Ostwald maturing process from the inside to the outside " only is applicable to metal or the semiconductor (Science with specific composition and structure; 2004, the 304th volume, 711-714 page or leaf; Journal of Physical Chemical B, 2006, the 110th volume, 19162-19167 page or leaf; Jounal of American Chemical Society, 2005, the 127th volume, 12504-12505 page or leaf; Jounal of American Chemical Society, 2007, the 129th volume, 8406-8407 page or leaf; Advanced Materials, 2007, the 19th volume, 3328-3332 page or leaf; ).In addition, the shell wall of the silica-based yolk-eggshell type material of report mainly is made up of pure silica at present, and Shang Weijian has the report of the yolk-eggshell type nanosphere of hybrid inorganic-organic silica shell wall.
Summary of the invention
It is adjustable to the purpose of this invention is to provide a kind of granularity, and nuclear-shell is formed adjustable and had yolk-eggshell type hybrid inorganic-organic silica or carbon-silicon compound nano material of hierarchical porous structure and preparation method thereof.Our method can effectively overcome shortcomings such as the process complicacy, length consuming time, the general type that have now in the technology of preparing are poor, composition adjusting difficulty.
For realizing above-mentioned purpose; The present invention is under alkaline system; With cationic surfactant (quaternary amine type) is surfactant, and synthetic nanosilica white sphere with nucleocapsid structure adds the organosilicon presoma in above system; Utilize organosilicon forerunner physical efficiency to be deposited on the nanosilica white sphere surface of nucleocapsid structure and can impel the character of inorganic silicon dissolving, obtain having the nuclear that can move freely and the hybrid inorganic-organic monox nanometer ball of functional mesoporous shell wall.Its granularity can be adjustable in 50-200 nm scope; Shell thickness is adjustable in 6-50 nm scope; The nano particle of inner chamber can be Fe
3O
4, monometallic nano particle such as Au, Ag, Pt, Ru, Rh, Pd, also can be the nano particle of bimetallic, many metals and alloy etc.; It can be organosilicon or carbon-silicon compound that shell wall is formed.
Specifically can operate as follows:
1) is scattered in underwater gold and belongs to the perhaps preparation of metal oxide nanoparticles: quaternary amine type surfactant (like CTAB) is dissolved in the deionized water; Concentration 0.55-1mM; Adding 0.1-2 mL is dissolved in and has oleic acid or the stable metal nanoparticle of oleyl amine in the chloroform, and the concentration of metal nanoparticle is 5-50mg/mL, vigorous stirring; Form homogeneous O/W emulsion, in 60-65
OCHeated volatile perhaps vacuumizes and removes organic solvent, obtains being dispersed in the nano particle in the water;
2) preparation of metal (metal oxide) nuclear-silicon oxide mesoporous core/shell nanoparticles: under stirring condition, in above-mentioned solution, add NaOH solution (2 M), add the silicon source subsequently, temperature range 25-80 in the building-up process
oC, mixing time 10 min – 4 h;
3) preparation of yolk-eggshell type nano particle: in above-mentioned nuclear-core/shell nanoparticles system, add organosilicon source presoma, continue at 10-80
oC stirs 0.5-24 h;
The mol ratio of each component is: cationic surfactant: alkali: the inorganic silicon source: organosilicon source: water=1:2.6-5.2:6-33:5-20:400-19455;
4) drying: with the product suction filtration behind step (3) the stirring certain hour, water or washing with alcohol, drying at room temperature;
5) remove surfactant:, make product of the present invention with dried product 1.0 g backflow 15-30 min in containing the ethanolic solution 100-300 mL of 0.1-0.5 g ammonium nitrate.
Prepared yolk-eggshell type nano particle granularity can be adjustable in 50-200 nm scope; Shell thickness is adjustable in 6-50 nm scope, and the aperture is adjustable at 2-4 nm, and specific area is at 500-800 m
2g
-1Between, pore volume is at 0.5-1.5 cm
3g
-1Between.The nano particle of inner chamber can be Fe
3O
4, monometallic nano particle such as Au, Ag, Pt, Ru, Rh, Pd, also can be nano particles such as bimetallic, many metals and alloy; It can be organosilicon or carbon-silicon compound that shell wall is formed.Surfactant can remove through the mode of ethanol extraction, reaches the purpose of economic recovery.
Said metal or metal oxide are Fe
3O
4, monometallic nano particle such as Au, Ag, Pt, Ru, Rh, Pd, also can be bimetallic, many metals and alloy etc.;
Said organosilicon source is 1; 2-bis (trimethoxysilyl) ethane (BTME), 3-aminopropyl-triethoxysilane (APTES), 1; 2-bis (triethoxysilyl) ethane (BTEE) and 1,4-bis (trimethoxysilyl) benzene (BTEB).
Preparation method of the present invention has following advantage:
1. synthetic take " one kettle way " of material, whole process only needs a step to filter, and step is few, weak point consuming time (optimal conditions from the metal nanoparticle to yolk-eggshell type material only need 3 h), energy consumption is low, is suitable for large-scale industrial production;
2. (the alkalescent system pH=10), does not need highly basic or HF acid to dissolve inorganic silicon to the reaction condition gentleness, controls reaction process, environmental friendliness easily;
3. can realize examining the modulation of composition easily through the kind that changes nano particle;
4. can be easy to the composition of the mesoporous shell of modulation through the kind that changes the organosilicon source, there is very application prospects in the functional group of being convenient to introduce difference in functionality;
5. can realize the adjustable continuously of yolk-eggshell type nano particle size and wall thickness through the amount that changes inorganic silicon source and organosilicon source;
The material of the present invention's preparation has following advantage:
1. the material of preparation has favorable mechanical, heat endurance and alkali resistant erosion ability;
2. the material particle size homogeneous and the good dispersion that prepare;
3. the material for preparing all has big specific area and (can reach 634 m
2g
-1) and pore volume (can reach 0.99 cm
3g
-1), high storage capacity, bio-compatibility are good, have on the shell wall to connect inside and outside mesoporous (2-4 nm);
4. the material inner chamber of preparation contains the nano particle of metal or metal oxide, and this nano particle that can move freely has following advantage with respect to the nano particle of traditional embedded type load: nano particle surrounding environment homogeneous; The avtive spot that nano particle exposes is many; Shell wall can stop the gathering of nano particle;
5. the kind of the interior metal nanoparticle of the materials chamber for preparing, the composition of shell wall, wall thickness, particle chi, pore size make things convenient for adjustable, have unique optics, electrical properties;
6. the nano particle confinement of the material inner chamber of preparation has potential application prospect in the confinement nano-catalytic in certain nanometer space;
7. the material inner chamber of preparation also has very big space except that containing nano particle, can be used as functionalization (Fe
3O
4: medicine target) (gene) carrier has wide practical use in fields such as medicament slow release, target administration, imagings;
8. synthesis mechanism is at nuclear-core/shell nanoparticles surface deposition through organosilicon source presoma; And the dissolving of auxiliary inorganic silicon dioxide, thus form have the nuclear that can move freely nano particle, the yolk-eggshell type hybrid inorganic-organic monox nanometer ball of the mesoporous shell of organosilicon functionalization.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) photo of products obtained therefrom among the embodiment 1.
Fig. 2 is the nitrogen adsorption-desorption isothermal curve among the embodiment 1.
Fig. 3 is the electromicroscopic photograph of material among the embodiment 2.
Fig. 4 is the electromicroscopic photograph of material among the embodiment 3.
Fig. 5 is the electromicroscopic photograph of material among the embodiment 6.
Fig. 6 is the electromicroscopic photograph of material among the embodiment 8.
Fig. 7 is the electromicroscopic photograph of material among the embodiment 9.
The specific embodiment
In order to further specify the present invention, enumerate following embodiment, but it does not limit the defined invention scope of each accessory claim.
Embodiment 1
Under the stirring at room condition, 0.1 g CTAB is dissolved in the 10 mL deionized waters, add 1 mL (10 mg mL
-1) be dissolved in the stable Fe of oleic acid in the chloroform
3O
4Nano-particle solution (Journal of Materials Chemistry2009, the 19th volume, 1811-1815) stirs 0.5 h, forms homogeneous O/W emulsion, is warming up to 60
oC vapors away chloroform under stirring condition, form brown clear solution, adds 38 mL water in order, and 0.35 mL NaOH (2 M) is warming up to 80
OC, adding TEOS 0.68 mL, deposition appearred after a few minutes, in 80
oC stirs 2 h, adds 60 mL water, treats to add 0.36 mL BTME (being dissolved in the 2 mL ethanol) behind the temperature stabilization, continues at 80
OCStir 1 h.Product uses the ethanol solution that is dissolved with ammonium nitrate in 60 after filtration, washing, drying
oC stirs 0.5 h, and product obtains pale brown chromaticness calomel mercurous chloride end after filtration, washing, drying.TEM result shows that the product that obtains is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The whole size of the nano particle of yolk-eggshell type is 100 nm, wall thickness 6 nm (Fig. 1).The BET specific area of material is 538 m
2g
-1, pore volume is 0.99 cm
3g
-1(Fig. 2).
Embodiment 2
Adopt the preparation process of embodiment 1, be with its difference, add BTEB as the silicon source, mixing time is 3 h.Obtain pale brown chromaticness calomel mercurous chloride end.Characterizing method is the same.TEM result shows that the product that obtains is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The whole size of the nano particle of yolk-eggshell type is 100 nm, and wall thickness is 10nm (Fig. 3).
Embodiment 3
Adopt the preparation process of embodiment 1, be with its difference, add APTES as the silicon source, mixing time is 5 h.Obtain pale brown chromaticness calomel mercurous chloride end.Characterizing method is the same.TEM result shows that the product that obtains is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The whole size of the nano particle of yolk-eggshell type is 120 nm, and wall thickness is 13 nm (Fig. 4).
Embodiment 4
Adopt the preparation process of embodiment 1, be, contain 0.4 g FC-4 and 0.8 g CTAB in the aqueous solution that is added, obtain pale brown chromaticness calomel mercurous chloride end with its difference.Characterizing method is the same.TEM result shows that the product that obtains is the nano particle with yolk-eggshell type; The mean size of the nano particle of yolk-eggshell type is 100 nm, and wall thickness is 13 nm, and the aperture is 2.4 nm.
Embodiment 5
Adopt the preparation process of embodiment 4, be there is not metal nanoparticle in the chamber with its difference, add BTME and PMMA (10% mol ratio) as the silicon source, mixing time is 4 h.Obtain white light weight powder.Characterizing method is the same.TEM result shows that the product that obtains is the nano particle with hollow-core construction, uniform particle diameter, good dispersion; The whole size of nano particle is 200 nm, and wall thickness is 35 nm.
Embodiment 6
Adopt the preparation process of embodiment 4, be that with its difference used nano particle is the Au of 6 nm, obtain light violet magenta light weight powder.Characterizing method is the same.TEM result shows that the product that obtains is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The whole size of the nano particle of yolk-eggshell type is 100 nm, and wall thickness is 23 nm, and mesoporous aperture is 2 nm (Fig. 5).
Embodiment 7
Adopt the preparation process of embodiment 4, be that with its difference used nano particle is the Pt of 8 nm, obtain light grey light weight powder.Characterizing method is the same.TEM result shows that the product that obtains is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The whole size of the nano particle of yolk-eggshell type is 100 nm, and wall thickness is 13 nm.
Embodiment 8
Adopt the preparation process of embodiment 6, be with its difference, the gained material is through 550 degree N
2The atmosphere carbonization obtains light grey light weight powder.Characterizing method is the same.TEM result shows that the product that obtains is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The whole size of the nano particle of yolk-eggshell type is 100 nm, and wall thickness is 40 nm, and the aperture is 2 nm (Fig. 6).
Embodiment 9
Adopt the preparation process of embodiment 4, be with its difference, the BTME that is added is that 0.72 mL (being dissolved in the 2 L ethanol) obtains pale brown chromaticness calomel mercurous chloride end.Characterizing method is the same.TEM result shows that the product that obtains is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The whole size of the nano particle of yolk-eggshell type is 100 nm, and wall thickness is 13 nm, and the aperture is 2.4 nm (Fig. 7).
The present invention relates to the silicon oxide ball particle, specifically a kind of preparation method with hybrid inorganic-organic monox nanometer ball of yolk-eggshell structure.Under alkaline system; With cationic surfactant (quaternary amine type) is structure directing agent, and synthetic nanosilica white sphere with nucleocapsid structure adds the organosilicon presoma in this system; Stir; Filter, drying obtains having the hybrid inorganic-organic monox nanometer ball of the nuclear that can move freely, functional mesoporous shell.Its big I is adjustable in 50-200 nm scope; Shell thickness is adjustable in 6-50 nm scope; The nano particle of inner chamber can be Fe
3O
4, monometallic nano particle such as Au, Ag, Pt, Ru, Rh, Pd, also can be the nano particle of bimetallic, many metals and alloy etc.; It can be organosilicon or carbon-silicon compound that shell wall is formed.This synthetic method step is few, and the time spent is short, and nano particle and shell wall are formed adjusting easily in the hole, and the hybrid inorganic-organic monox nanometer ball of synthetic yolk-eggshell structure has big specific area and pore volume; Grain graininess homogeneous, good dispersion; Have plurality of advantages such as high mechanical stability and heat endurance.
Claims (6)
1. the preparation method of yolk-eggshell type hybrid inorganic-organic monox nanometer ball, it can move freely the hollow hybrid inorganic-organic monox nanometer ball of nano particle for inner chamber is loaded with preparation method is characterized in that:
(1) under stirring condition, in containing 0.55-1mM aqueous solution of cationic surfactant active, add the chloroformic solution 0.1-2 mL that is dissolved with metal nanoparticle, the concentration of metal nanoparticle is 5-50mg/mL, stabilizing agent is oleic acid or oleyl amine, in 60-65
oC vapors away chloroform, to wherein adding 2 M NaOH solution, adds the inorganic silicon source subsequently, temperature range 25-80 in the building-up process
oC, mixing time 10 min – 4h; In above-mentioned nuclear-core/shell nanoparticles system, add organosilicon source presoma then, continue at 10-80
oC stirs 0.5-24 h;
The mol ratio of each component is: cationic surfactant: NaOH: the inorganic silicon source: organosilicon source: water=1:2.6-5.2:6-33:5-20:400-19455;
(2) drying: the product suction filtration after will stirring, use water washing, drying at room temperature; The mass percentage content of metal nanoparticle is in the product that obtains: 0.1-5%;
(3) remove surfactant:, make yolk-eggshell type hybrid inorganic-organic monox nanometer ball with dried product 1.0 g backflow 15-30 min in containing the ethanolic solution 100-300 mL of 0.1-0.5 g ammonium nitrate.
2. preparation method according to claim 1 is characterized in that: said cationic surfactant is a quaternary amine type surfactant.
3. preparation method according to claim 1 is characterized in that: said metal nanoparticle is metal or metal oxide, and metal or metal oxide are Fe
3O
4, Au, Ag, Pt, Ru, Rh or Pd the monometallic nano particle, or the alloy more than two kinds or three kinds of Au, Ag, Pt, Ru, Rh, Pd.
4. preparation method according to claim 1; It is characterized in that: said organosilicon source is 1; 2-bis (trimethoxysilyl) ethane (BTME), 3-aminopropyl-triethoxysilane (APTES), 1; 4-bis (trimethoxysilyl) benzene (BTEB), 1, a kind of among 2-bis (triethoxysilyl) ethane (BTEE) or the triethoxysilane (APTES) or more than two kinds.
5. preparation method according to claim 1 is characterized in that: said inorganic silicon source is TEOS.
6. preparation method according to claim 1; It is characterized in that: the preparation of the metal nanoparticle aqueous solution of said cationic surfactant and oleic acid or oleyl amine jointly stabilizing: under stirring condition; In containing 0.55-1 mM aqueous solution of cationic surfactant active, add and be dissolved in the metal nanoparticle 0.1-2 mL in the chloroform; The concentration of metal nanoparticle is 5-50mg/mL, and stabilizing agent is oleic acid or oleyl amine, in 60-65
oC vapors away chloroform, obtains being dispersed in the nano particle in the water.
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