CN102716745B - 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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- CN102716745B CN102716745B CN201110077140.5A CN201110077140A CN102716745B CN 102716745 B CN102716745 B CN 102716745B CN 201110077140 A CN201110077140 A CN 201110077140A CN 102716745 B CN102716745 B CN 102716745B
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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 one has the preparation method of the hybrid inorganic-organic monox nanometer ball of yolk-eggshell structure (being to be loaded with in chamber to can move freely nano particle).
Background technology
Inner chamber be loaded with the nano oxidized silicon materials of yolk-eggshell type that can move freely nano particle due to its have unique optical, electrical character, with and in potential application prospect aspect catalysis, biological medicine and imaging, become the study hotspot of current field of nanometer material technology.The main component of its shell of yolk-eggshell type nano material of having prepared at present comprises: silica, organic polymer, metal oxide and carbon.Wherein, because it has large specific area, high storage capacity, good machinery and heat endurance, cheap and easy to get, bio-compatibility is good etc., advantage has been subject to extensive concern to silica, is with a wide range of applications in research fields such as nanometer confinement catalysis, targeted drug (gene) slowly-releasing, absorption, insulating materials, Opto-Electronics Crystals, dielectric materials and medical diagnosis on disease treatments.At present, the preparation method of the nano oxidized silicon materials of yolk-eggshell type is mainly divided into: " the selective etch method that template is auxiliary ", " soft template method ", " ship construction method in bottle ", " Kenny's Dare effect " (Kirkendall effect), " electrification displacement " (galvanic replacement), and " Ostwald maturing process from the inside to the outside ".Wherein a kind of the most frequently used method is: " the selective etch method that template is auxiliary "; prepared yolk-eggshell type nano material (the Jounal of American Chemical Society of a lot of different IPs-shell composition by the method; 2003, the 125th volume, 2384-2385 page; Nano Lett, 2002, the 2nd volume, 1383-1387 page; Chemmcial Communications, the 2009th, 1653-1654 page; Small 2007, the 3rd volume, 261-265 page; Angewandte Chemie International Edition, 2008, the 47th volume, 5806-5811 page; Chemistry of Materials, 2009, the 21st year, 3848-3852 page; Advanced Materials, 2009, the 21st volume, 3804-3807 page; Chemistry of Materials, 2009, the 21st volume, 2547-2553 page; Chemistry of Materials
,2006, the 18th volume, 614-619 page).The method is mainly first by previously prepared good nano particle one deck or the two-layer shell parcel with different component, then optionally middle one deck of part shell, core or two-layer shell is optionally etched away by solvent or calcining, obtain in chamber, thering is the nanometer particle material can move freely.But the method step is various, 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 technology and shell wall composition of tool subshell completely very high, and therefore the method is difficult for implementing, and shell wall composition is difficult to modulation.Lu high definition and Xu Dongsheng group have been reported respectively and have been adopted mixing soft template nano particle to be packaged into nanosilica white sphere (Angewandte Chemie International Edition,, the 49th volume, the 4981-4985 page in 2010 with yolk-eggshell structure; Jounal of American Chemical Society, 2009, the 131st page, 2774-2775 page.), but this method is not suitable for encapsulating the nano particle of particle diameter <10 nm; " ship construction method in bottle " refers to and first prepares hollow nano-sphere, again metal precursor and reducing agent are impregnated into inside, ball chamber, thereby prepare method (the Chemistry of Materials of nano particle in hollow ball inside original position, 2005, the 17th volume, 3578-3581 page), the method is difficult to guarantee that 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 " is only applicable to have metal or the semiconductor (Science of specific composition and structure, 2004, the 304th volume, 711-714 page; Journal of Physical Chemical B, 2006, the 110th volume, 19162-19167 page; Jounal of American Chemical Society, 2005, the 127th volume, 12504-12505 page; Jounal of American Chemical Society, 2007, the 129th volume, 8406-8407 page; Advanced Materials, 2007, the 19th volume, 3328-3332 page; ).In addition, the shell wall of the silica-based yolk-eggshell shaped material of report is mainly made up of pure silica at present, there is not yet the report of the yolk-eggshell type nanosphere with hybrid inorganic-organic silica shell wall.
Summary of the invention
The object of this invention is to provide a kind of granularity adjustable, core-shell composition is adjustable and have the yolk-eggshell type hybrid inorganic-organic silica of hierarchical porous structure or carbon-silicon compound nano material and preparation method thereof.The shortcomings such as our method can effectively overcome the process complexity in existing technology of preparing, length consuming time, general type is poor, composition adjusting is difficult.
For achieving the above object, the present invention is under alkaline system, take cationic surfactant (quaternary amine type) as surfactant, the synthetic nanosilica white sphere with nucleocapsid structure, in above system, add organosilicon presoma, the character of utilizing organosilicon forerunner physical efficiency to be deposited on the nanosilica white sphere surface of nucleocapsid structure and can to impel inorganic silicon to dissolve, obtains having the core that can move freely and the hybrid inorganic-organic monox nanometer ball of functional mesoporous shell wall.Its granularity can be adjustable within the scope of 50-200 nm; Shell thickness is adjustable within the scope of 6-50 nm; The nano particle of inner chamber can be Fe
3o
4, Au, Ag, Pt, Ru, the monometallic nano particle such as Rh, Pd, can be also the nano particle of bimetallic, many metals and alloy etc.; Shell wall composition can be organosilicon or carbon-silicon compound.
Specifically can operate as follows:
1) being scattered in underwater gold belongs to or the preparation of metal oxide nanoparticles: quaternary amine type surfactant (as CTAB) is dissolved in deionized water, concentration 0.55-1mM, add 0.1-2 mL to be dissolved in and in chloroform, there is oleic acid or the stable metal nanoparticle of oleyl amine, the concentration of metal nanoparticle is 5-50mg/mL, vigorous stirring, form homogeneous O/W emulsion, in 60-65
oCheating is volatilized or is vacuumized and removes organic solvent, obtains being dispersed in the nano particle in water;
2) preparation of metal (metal oxide) core-silicon oxide mesoporous core/shell nanoparticles: under stirring condition, add NaOH solution (2 M) in above-mentioned solution, add subsequently silicon source, temperature range 25-80 in building-up process
oc, mixing time 10 min – 4 h;
3) preparation of yolk-eggshell type nano particle: add organosilicon source presoma in above-mentioned core-core/shell nanoparticles system, continue at 10-80
oc stirs 0.5-24 h;
The mol ratio of each component is: cationic surfactant: alkali: inorganic silicon source: organosilicon source: water=1:2.6-5.2:6-33:5-20:400-19455;
4) dry: step (3) to be stirred to the product suction filtration after certain hour, water or ethanol washing, drying at room temperature;
5) remove surfactant: dried product 1.0 g, containing the 15-30 min that refluxes in the ethanolic solution 100-300 mL of 0.1-0.5 g ammonium nitrate, are made to product of the present invention.
Prepared yolk-eggshell type nano particle granularity can be adjustable within the scope of 50-200 nm; Shell thickness is adjustable within the scope of 6-50 nm, and 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, Au, Ag, Pt, Ru, the monometallic nano particle such as Rh, Pd, can be also the nano particles such as bimetallic, many metals and alloy; Shell wall composition can be organosilicon or carbon-silicon compound.Surfactant can remove by the mode of ethanol extraction, reaches the object of economic recovery.
Described metal or metal oxide are Fe
3o
4, Au, Ag, Pt, Ru, the monometallic nano particle such as Rh, Pd, can be also bimetallic, many metals and alloy etc.;
Described organosilicon source is 1,2-bis (trimethoxysilyl) ethane (BTME), 3-aminopropyl-triethoxysilane (APTES), 1,2-bis (triethoxysilyl) ethane (BTEE) and Isosorbide-5-Nitrae-bis (trimethoxysilyl) benzene (BTEB).
Preparation method's tool of the present invention has the following advantages:
1. synthetic " one kettle way ", whole process taked of material only needs a step to filter, and step is few, and consuming time short (optimal conditions only needs 3 h) from metal nanoparticle to yolk-eggshell shaped material, and energy consumption is low, is suitable for large-scale industrial production;
2. reaction condition gentleness (alkalescent system, pH=10), does not need highly basic or HF acid to dissolve inorganic silicon, easily controls reaction process, environmental friendliness;
3. can easily realize the modulation of core composition by changing the kind of nano particle;
4. the composition that can be easy to the mesoporous shell of modulation by changing the kind in organosilicon source,, there is application prospect very widely in the functional group of being convenient to introduce difference in functionality;
5. can realize the adjustable continuously of yolk-eggshell type Nanoparticle Size and wall thickness by the amount that changes inorganic silicon source and organosilicon source;
Material tool prepared by the present invention has the following advantages:
1. the material of preparation has good machinery, heat endurance and alkali resistant erosion ability;
2. material particle size homogeneous and the good dispersion of preparation;
3. the material of preparing all has large 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 and connect inside and outside mesoporous (2-4 nm) on shell wall;
4. the nano particle that the material inner chamber of preparation contains metal or metal oxide, this nano particle can move freely has the following advantages with respect to the nano particle tool 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. kind, the composition of shell wall, wall thickness, particle chi, the pore size of the interior metal nanoparticle of materials chamber of preparing facilitates adjustable, has unique optics, electrical properties;
6. the nano particle confinement of the material inner chamber of preparation, in certain nano-space, has potential application prospect in confinement nano-catalytic;
7. the material inner chamber of preparation also has very large space except containing nano particle, can be used as functionalization (Fe
3o
4: target) medicine (gene) carrier, have wide practical use in fields such as medicament slow release, target administration, imagings;
8. synthesis mechanism is at core-core/shell nanoparticles surface deposition by organosilicon source presoma, and the dissolving of auxiliary inorganic silicon dioxide, thereby form the yolk-eggshell type hybrid inorganic-organic monox nanometer ball of the mesoporous shell with the core, the organosilicon functionalization that can move freely nano particle.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) photo of products obtained therefrom in embodiment 1.
Fig. 2 is the nitrogen adsorption-desorption isothermal curve in embodiment 1.
Fig. 3 is the electromicroscopic photograph of material in embodiment 2.
Fig. 4 is the electromicroscopic photograph of material in embodiment 3.
Fig. 5 is the electromicroscopic photograph of material in embodiment 6.
Fig. 6 is the electromicroscopic photograph of material in embodiment 8.
Fig. 7 is the electromicroscopic photograph of material in embodiment 9.
The specific embodiment
In order to further illustrate the present invention, enumerate following embodiment, but it does not limit the defined invention scope of each accessory claim.
Embodiment 1
Under stirring at room temperature condition, 0.1 g CTAB is dissolved in 10 mL deionized waters, add 1 mL (10 mg mL
-1) be dissolved in the stable Fe of oleic acid in 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, forms brown clear solution, adds in turn 38 mL water, and 0.35 mL NaOH (2 M), is warming up to 80
oC, add TEOS 0.68 mL, after a few minutes, there is precipitation, in 80
oc stirs 2 h, adds 60 mL water, adds 0.36 mL BTME (being dissolved in 2 mL ethanol) after temperature stabilization, continues at 80
oCstir 1 h.Product after filtration, washing, dry after, with the ethanol solution that is dissolved with ammonium nitrate in 60
oc stirs 0.5 h, product after filtration, washing, dry after, obtain brown color light weight powder.TEM result shows that the product obtaining is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The entirety 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
The preparation process that adopts embodiment 1, is with its difference, add BTEB as silicon source, mixing time is 3 h.Obtain brown color light weight powder.Characterizing method is the same.TEM result shows that the product obtaining is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The entirety size of the nano particle of yolk-eggshell type is 100 nm, and wall thickness is 10nm(Fig. 3).
Embodiment 3
The preparation process that adopts embodiment 1, is with its difference, add APTES as silicon source, mixing time is 5 h.Obtain brown color light weight powder.Characterizing method is the same.TEM result shows that the product obtaining is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The entirety size of the nano particle of yolk-eggshell type is 120 nm, and wall thickness is 13 nm(Fig. 4).
Embodiment 4
The preparation process that adopts embodiment 1, is with its difference, contains 0.4 g FC-4 and 0.8 g CTAB in the aqueous solution adding, and obtains brown color light weight powder.Characterizing method is the same.TEM result shows that the product obtaining 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 aperture is 2.4 nm.
Embodiment 5
The preparation process that adopts embodiment 4, is in chamber, there is no metal nanoparticle with its difference, adds BTME and PMMA (10% mol ratio) as silicon source, and mixing time is 4 h.Obtain white light weight powder.Characterizing method is the same.TEM result shows that the product obtaining is the nano particle with hollow-core construction, uniform particle diameter, good dispersion; The entirety size of nano particle is 200 nm, and wall thickness is 35 nm.
Embodiment 6
The preparation process that adopts embodiment 4, is with its difference, nano particle used is the Au of 6 nm, obtains light violet magenta light weight powder.Characterizing method is the same.TEM result shows that the product obtaining is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The entirety 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
The preparation process that adopts embodiment 4, is with its difference, nano particle used is the Pt of 8 nm, obtains light grey light weight powder.Characterizing method is the same.TEM result shows that the product obtaining is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The entirety size of the nano particle of yolk-eggshell type is 100 nm, and wall thickness is 13 nm.
Embodiment 8
The preparation process that adopts embodiment 6, is with its difference, resulting materials is through 550 degree N
2atmosphere carbonization, obtains light grey light weight powder.Characterizing method is the same.TEM result shows that the product obtaining is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The entirety size of the nano particle of yolk-eggshell type is 100 nm, and wall thickness is 40 nm, and aperture is 2 nm(Fig. 6).
Embodiment 9
The preparation process that adopts embodiment 4, is with its difference, the BTME adding is that 0.72 mL (being dissolved in 2 L ethanol) obtains brown color light weight powder.Characterizing method is the same.TEM result shows that the product obtaining is the nano particle with yolk-eggshell type, uniform particle diameter, good dispersion; The entirety size of the nano particle of yolk-eggshell type is 100 nm, and wall thickness is 13 nm, and aperture is 2.4 nm(Fig. 7).
The present invention relates to silicon oxide ball particle, specifically a kind of preparation method of the hybrid inorganic-organic monox nanometer ball with yolk-eggshell structure.Under alkaline system, take cationic surfactant (quaternary amine type) as structure directing agent, the synthetic nanosilica white sphere with nucleocapsid structure, in this system, add organosilicon presoma, stir, filter, be dried, obtain having the hybrid inorganic-organic monox nanometer ball of the core can move freely, functional mesoporous shell.Its large I is adjustable within the scope of 50-200 nm; Shell thickness is adjustable within the scope of 6-50 nm; The nano particle of inner chamber can be Fe
3o
4, Au, Ag, Pt, Ru, the monometallic nano particle such as Rh, Pd, can be also the nano particle of bimetallic, many metals and alloy etc.; Shell wall composition can be organosilicon or carbon-silicon compound.This synthetic method step is few, and the used time is short, and in hole, nano particle and shell wall composition easily regulate, and the hybrid inorganic-organic monox nanometer ball of synthetic yolk-eggshell structure has large specific area and pore volume; Grain graininess homogeneous, good dispersion; There is the high plurality of advantages such as mechanical stability and heat endurance.
Claims (4)
1. a preparation method for yolk-eggshell type hybrid inorganic-organic monox nanometer ball, it can move freely the hollow hybrid inorganic-organic monox nanometer ball of nano particle preparation method for inner chamber is loaded with, is characterized in that:
(1) under stirring condition; in 0.55-1mM aqueous solution of cationic surfactant active, add to containing the chloroformic solution 0.1-2mL that is dissolved with metal nanoparticle; the concentration of metal nanoparticle is 5-50mg/mL; stabilizing agent is oleic acid or oleyl amine; vapor away chloroform in 60-65 ℃, add wherein 2M NaOH solution, add subsequently inorganic silicon source; temperature range 25-80 ℃ in building-up process, mixing time 10min – 4h; Then in above-mentioned core-core/shell nanoparticles system, add organosilicon source, continue at 10-80 ℃ and stir 0.5-24h;
The mol ratio of each component is: cationic surfactant: NaOH: inorganic silicon source: organosilicon source: water=1:2.6-5.2:6-33:5-20:400-19455;
(2) dry: by the product suction filtration after stirring, to wash drying at room temperature with water; In the product obtaining, the mass percentage content of metal nanoparticle is: 0.1-5%;
(3) remove surfactant: dried product 1.0g, containing the 15-30min that refluxes in the ethanolic solution 100-300mL of 0.1-0.5g ammonium nitrate, is made to yolk-eggshell type hybrid inorganic-organic monox nanometer ball;
Described organosilicon source is 1,2-bis-(trimethoxy is silica-based) ethane (BTME), 3-aminopropyl triethoxysilane (APTES), 1,4-bis-(triethoxy is silica-based) benzene (BTEB), 1,2-bis-(triethoxy is silica-based) ethane (BTEE) or wherein one or two or more kinds;
Described metal nanoparticle is metal or metal oxide, and metal or metal oxide are Fe
3o
4, Au, Ag, Pt, Ru, Rh or Pd monometallic nano particle, or many metals of Au, Ag, Pt, Ru, Rh, Pd.
2. preparation method according to claim 1, is characterized in that: described cationic surfactant is quaternary amine type surfactant.
3. preparation method according to claim 1, is characterized in that: described inorganic silicon source is TEOS.
4. preparation method according to claim 1, it is characterized in that: the preparation of the metal nanoparticle aqueous solution of described cationic surfactant and oleic acid or oleyl amine jointly stabilizing: under stirring condition, in 0.55-1mM aqueous solution of cationic surfactant active, add to containing the metal nanoparticle 0.1-2mL being dissolved in chloroform, the concentration of metal nanoparticle is 5-50mg/mL, stabilizing agent is oleic acid or oleyl amine, vapor away chloroform in 60-65 ℃, obtain being dispersed in the nano particle in water.
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