CN104353844B - Preparation method of silica/gold/ silica three-layer nano particles - Google Patents
Preparation method of silica/gold/ silica three-layer nano particles Download PDFInfo
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- CN104353844B CN104353844B CN201410659248.9A CN201410659248A CN104353844B CN 104353844 B CN104353844 B CN 104353844B CN 201410659248 A CN201410659248 A CN 201410659248A CN 104353844 B CN104353844 B CN 104353844B
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Abstract
The invention provides a preparation method of silica/gold/ silica three-layer nano particles. The preparation method comprises the following steps: after performing amination modification on silica nuclear particles, absorbing nano gold particles; then putting in a gold hydroxide aqueous solution, adding formaldehyde used as a reducing agent and performing oxidation reduction reaction so as to form a gold shell; performing surface finishing on silica/gold double-layer core-shell particles by use of heavy polymer polyvinyl pyrrolidone; performing centrifugal cleaning, and adding a silicon source for growing a transparent silica layer and a catalyst, thereby preparing the silica/gold/ silica three-layer nano particles. Raw materials used in the preparation method are easily available, required experimental equipment is simple, the technical process is easy to master, and the preparation method can be used for preparing compound particles with favorable dispersibility and uniform light-transmitting layer.
Description
Technical field
The invention belongs to structurized technical field of nano material, particularly to a kind of silicon dioxide
The preparation method of three layers of nanoparticle of/gold/silicon dioxide.
Background technology
Nanoparticle, as zero dimensional nanometer materials, has the characteristics such as the light of uniqueness, heat, electricity,
Have a wide range of applications at aspects such as nano photoelectric, nano biological medicine and solaodes
Prospect.The composite nanoparticle of silicon dioxide/gold/silicon dioxide three layers has physiology wave band photo-thermal
The function of conversion, can be as the thermotherapy material in biological medicine.At present, with chemosynthesis
Method, can synthesize the core-shell nano of the poor double-deck photothermal deformation of chemical inertness, and make
Get everything ready silicon dioxide/gold/silicon dioxide three layers composite nanoparticle of printing opacity silicon dioxide layer
Report also do not have, the most do not prepare the report of this type of 3-layer composite material by the method for chemosynthesis
Road.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of dioxy
The preparation method of SiClx/three layers of nanoparticle of gold/silicon dioxide, it is possible to prepare and there is photo-thermal turn
Change the nanoparticle of the silicon dioxide/gold/silicon dioxide three-layer composite structure of function.
In order to achieve the above object, the technical scheme that invention is taked is:
The preparation method of a kind of silicon dioxide/three layers of nanoparticle of gold/silicon dioxide, including following
Step:
1) preparation of silicon dioxide/gold core-shell particles solution, comprises the following steps:
1.1) preparation of silicon dioxide nuclear particle: add 25mL's in the conical flask of 50mL
Dehydrated alcohol, is stirred 10min under the rotating speed of 500r/min, is added thereto to subsequently
2.5mL concentration is the ammonia spirit of 10%, is followed by stirring for 10min, then turning agitator
Velocity modulation saves to 1000r/min, is meanwhile added thereto to the positive silicic acid of 1.1mL in 5s
Ethyl ester is also followed by stirring for 1min, and rotating speed is finally transferred to 500r/min, sustained response 8h again；
1.2) amination of silicon dioxide nuclear particle is modified: by step 1.1) gained particle use
After washes of absolute alcohol 3 times, it is configured to the ethanol solution of 25mL, adds in this solution
(3-aminopropyl) trimethoxy silane of 20uL, continuously stirred 1h, uses ethanol dilution subsequently
Solution is to 125mL, and 70 DEG C of insulation 2h in water bath, finally centrifugal clear with dehydrated alcohol
Wash 5 times, be dispersed in the ethanol of 25mL；
1.3) preparation of solution of gold nanoparticles: add going of 45mL in the beaker of 50mL
Ionized water, is sequentially added into sodium hydrate aqueous solution and the 1mL concentration of the 1M of 300uL subsequently
It is the THPC aqueous solution of 1%, stirs 2min, subsequently to above-mentioned mixed solution
Middle addition 2mL concentration is the aqueous solution of chloraurate of 25mM and is stirred continuously until solution colour change
Become sepia；
1.4) preparation of the silicon dioxde solution of gold particle it is modified with: take step 1.2) prepare
Solution 5mL and step 1.3) the solution of gold nanoparticles 50mL phase prepared is mixed and stirred for
2h, stands overnight afterwards, is finally dispersed into 15mL aqueous solution by water eccentric cleaning；
1.5) preparation of gold shell growth solution: be separately added into 25mg in the deionized water of 100mL
Anhydrous potassium carbonate and the aqueous solution of chloraurate that 1.5mL concentration is 25mM continuously stirred, until
Solution becomes to be clarified；
1.6) preparation of gold shell particles solution: take step 1.5) the golden shell growth solution prepared
30mL, adds 0.45mL step 1.4) the solution & stir 10min for preparing, it is subsequently added
120uL concentration is the formaldehyde of 80% and is stirred continuously until solution and becomes aeruginous and i.e. can get two
Silicon oxide/gold core-shell particles solution；
2) synthesis of printing opacity silicon dioxide layer: by step 1) in the titanium dioxide of 30mL of preparation
Silicon/gold core-shell particles solution deionized water cleans 2 times, is dispersed in the deionization of 30mL afterwards
In water, in the environment of ultrasonic, adding 10mL concentration in the solution of gained is 110g/L's
Aqueous povidone solution, the most ultrasonic 20s, subsequently with the stirring speed of 500r/min
Degree stirring 24h, after having reacted, by gained solution centrifugal, is dispersed in the 4.2% of 60mL
In ethanol containing ammonia, after stirring 10min, the positive silicic acid of the 10% of addition 270～810uL
Ethyl ester ethanol solution, continuously stirred 12h.
Advantages of the present invention: raw material used in the present invention is conveniently easy to get, the letter of required experimental facilities
Single, technical process is prone to grasp, it is possible to preparing favorable dispersibility, photic zone is combined uniformly
Particle, can obtain total size 220～260nm, and photic zone silicon dioxide thickness is
The silicon dioxide of 8～20nm/gold/silicon dioxide three layers compound particle.
Accompanying drawing explanation
Fig. 1 is the transmitted electron of embodiment 1 silicon dioxide/three layers of nanoparticle of gold/silicon dioxide
Microphotograph, wherein figure (a) amplification is 40,000 times；Figure (b) amplification is
40000 times.
Fig. 2 is the transmitted electron of embodiment 2 silicon dioxide/three layers of nanoparticle of gold/silicon dioxide
Microphotograph, wherein figure (a) amplification is 50,000 times；Figure (b) amplification is 2
Wan Bei.
Detailed description of the invention
In conjunction with drawings and Examples, the present invention will be further described.
Embodiment 1
The preparation method of a kind of silicon dioxide/three layers of nanoparticle of gold/silicon dioxide, including following
Step:
1) preparation of silicon dioxide/gold core-shell particles solution, comprises the following steps:
1.1) preparation of silicon dioxide nuclear particle: add the nothing of 25mL in the conical flask of 50mL
Water-ethanol, is stirred 10min under the rotating speed of 500r/min, is added thereto to 2.5mL subsequently
Concentration is the ammonia spirit of 10%, is followed by stirring for 10min, then by the rotational speed regulation of agitator
To 1000r/min, in 5s, meanwhile it is added thereto to the tetraethyl orthosilicate of 1.1mL also
It is followed by stirring for 1min, finally rotating speed is transferred to 500r/min, sustained response 8h again；
1.2) amination of silicon dioxide nuclear particle is modified: by step 1.1) gained particle nothing
After water-ethanol cleans 3 times, it is configured to the ethanol solution of 25mL, in this solution, adds 20uL
(3-aminopropyl) trimethoxy silane, continuously stirred 1h, use ethanol dilution solution subsequently
To 125mL, and 70 DEG C of insulation 2h in water bath, finally by dehydrated alcohol eccentric cleaning 5
Secondary, it is dispersed in the ethanol of 25mL；
1.3) preparation of solution of gold nanoparticles: in the beaker of 50mL add 45mL go from
Sub-water, the sodium hydrate aqueous solution and the 1mL concentration that are sequentially added into the 1M of 300uL subsequently are
The THPC aqueous solution of 1%, stirs 2min, subsequently in above-mentioned mixed solution
Add 2mL concentration to be the aqueous solution of chloraurate of 25mM and be stirred continuously until solution colour and become
Sepia；
1.4) preparation of the silicon dioxde solution of gold particle it is modified with: take step 1.2) prepare
Solution 5mL and step 1.3) the solution of gold nanoparticles 50mL phase prepared is mixed and stirred for 2h,
Stand overnight afterwards, be finally dispersed into 15mL aqueous solution by water eccentric cleaning；
1.5) preparation of gold shell growth solution: be separately added into 25mg in the deionized water of 100mL
Anhydrous potassium carbonate and the aqueous solution of chloraurate that 1.5mL concentration is 25mM continuously stirred, until
Solution becomes to be clarified；
1.6) preparation of gold shell particles solution: take step 1.5) the golden shell growth solution prepared
30mL, adds 0.45mL step 1.4) the solution & stir 10min for preparing, it is subsequently added
120uL concentration is the formaldehyde of 80% and is stirred continuously until solution and becomes aeruginous and i.e. can get two
Silicon oxide/gold core-shell particles solution；
2) synthesis of printing opacity silicon dioxide layer: by step 1) in the titanium dioxide of 30mL of preparation
Silicon/gold nucleocapsid solution deionized water cleans 2 times, is dispersed in afterwards in the deionized water of 30mL,
In the environment of ultrasonic, adding 10mL concentration in the solution of gained is the polyethylene of 110g/L
Pyrrolidone solution, the most ultrasonic 20s, stirs with the mixing speed of 500r/min subsequently
24h, after having reacted, by gained solution centrifugal, be dispersed in 60mL 4.2% ammonia second
In alcoholic solution, after stirring 10min, the tetraethyl orthosilicate ethanol of the 10% of addition 270uL is molten
Liquid, continuously stirred 12h.
The silicon dioxide prepared/gold/silicon dioxide three layers compound particle is with reference to Fig. 1, from Fig. 1
Can see that, the silicon dioxide photic zone of one layer of 8nm thickness in silicon dioxide/golden watch face length,
Favorable dispersibility, even particle size distribution.
Embodiment 2
The preparation method of a kind of silicon dioxide/three layers of nanoparticle of gold/silicon dioxide, including following
Step:
1) preparation of silicon dioxide/gold core-shell particles solution, comprises the following steps:
1.1) preparation of silicon dioxide nuclear particle: add the nothing of 25mL in the conical flask of 50mL
Water-ethanol, is stirred 10min under the rotating speed of 500r/min, is added thereto to 2.5mL subsequently
Concentration is the ammonia spirit of 10%, is followed by stirring for 10min, then by the rotational speed regulation of agitator
To 1000r/min, in 5s, meanwhile it is added thereto to the tetraethyl orthosilicate of 1.1mL also
It is followed by stirring for 1min, finally rotating speed is transferred to 500r/min, sustained response 8h again；
1.2) amination of silicon dioxide nuclear particle is modified: by step 1.1) gained particle nothing
After water-ethanol cleans 3 times, it is configured to the ethanol solution of 25mL, in this solution, adds 20uL
(3-aminopropyl) trimethoxy silane, continuously stirred 1h, subsequently with ethanol dilution solution extremely
In 125mL, and water bath, 70 DEG C of insulation 2h, finally use dehydrated alcohol eccentric cleaning 5 times,
It is dispersed in the ethanol of 25mL；
1.3) preparation of solution of gold nanoparticles: in the beaker of 50mL add 45mL go from
Sub-water, the sodium hydrate aqueous solution and the 1mL concentration that are sequentially added into the 1M of 300uL subsequently are
The THPC aqueous solution of 1%, stirs 2min, subsequently in above-mentioned mixed solution
Add 2mL concentration to be the aqueous solution of chloraurate of 25mM and be stirred continuously until solution colour and become
Sepia；
1.4) preparation of the silicon dioxde solution of gold particle it is modified with: take step 1.2) prepare
Solution 5mL and step 1.3) the solution of gold nanoparticles 50mL phase prepared is mixed and stirred for 2h,
Stand overnight afterwards, be finally dispersed into 15mL aqueous solution by water eccentric cleaning；
1.5) preparation of gold shell growth solution: be separately added into 25mg in the deionized water of 100mL
Anhydrous potassium carbonate and the aqueous solution of chloraurate that 1.5mL concentration is 25mM continuously stirred, until
Solution becomes to be clarified；
1.6) preparation of gold shell particles solution: take step 1.5) the golden shell growth solution prepared
30mL, adds 0.45mL step 1.4) the solution & stir 10min for preparing, it is subsequently added
120uL concentration is the formaldehyde of 80% and is stirred continuously until solution and becomes aeruginous and i.e. can get two
Silicon oxide/gold core-shell particles solution；
2) synthesis of printing opacity silicon dioxide layer: by step 1) in the titanium dioxide of 30mL of preparation
Silicon/gold core-shell particles solution deionized water cleans 2 times, is dispersed in the deionization of 30mL afterwards
In water, in the environment of ultrasonic, adding 10mL concentration in the solution of gained is 110g/L's
Aqueous povidone solution, the most ultrasonic 20s, subsequently with the stirring speed of 500r/min
Degree stirring 24h, after having reacted, by gained solution centrifugal, is dispersed in the 4.2% of 60mL
In ethanol containing ammonia, after stirring 10min, the tetraethyl orthosilicate of the 10% of addition 810uL
Ethanol solution, continuously stirred 12h.
The silicon dioxide prepared/gold/silicon dioxide three layers compound particle is with reference to Fig. 2, from Fig. 2
Can see that, the silicon dioxide printing opacity of one layer of 20nm thickness in silicon dioxide/golden watch face length
Layer, favorable dispersibility, even particle size distribution.
Claims (3)
1. a preparation method for silicon dioxide/three layers of nanoparticle of gold/silicon dioxide, it is special
Levy and be, comprise the following steps:
1) preparation of silicon dioxide/gold core-shell particles solution, comprises the following steps:
1.1) preparation of silicon dioxide nuclear particle: add 25mL's in the conical flask of 50mL
Dehydrated alcohol, is stirred 10min under the rotating speed of 500r/min, is added thereto to subsequently
2.5mL concentration is the ammonia spirit of 10%, is followed by stirring for 10min, then turning agitator
Velocity modulation saves to 1000r/min, is meanwhile added thereto to the positive silicic acid of 1.1mL in 5s
Ethyl ester is also followed by stirring for 1min, and rotating speed is finally transferred to 500r/min, sustained response 8h again；
1.2) amination of silicon dioxide nuclear particle is modified: by step 1.1) gained particle use
After washes of absolute alcohol 3 times, it is configured to the ethanol solution of 25mL, adds in this solution
(3-aminopropyl) trimethoxy silane of 20uL, continuously stirred 1h, uses ethanol dilution subsequently
Solution is to 125mL, and 70 DEG C of insulation 2h in water bath, finally centrifugal clear with dehydrated alcohol
Wash 5 times, be dispersed in the ethanol of 25mL；
1.3) preparation of solution of gold nanoparticles: add going of 45mL in the beaker of 50mL
Ionized water, is sequentially added into sodium hydrate aqueous solution and the 1mL concentration of the 1M of 300uL subsequently
It is the THPC aqueous solution of 1%, stirs 2min, subsequently to above-mentioned mixed solution
Middle addition 2mL concentration is the aqueous solution of chloraurate of 25mM and is stirred continuously until solution colour change
Become sepia；
1.4) preparation of the silicon dioxde solution of gold particle it is modified with: take step 1.2) prepare
Solution 5mL and step 1.3) the solution of gold nanoparticles 50mL phase prepared is mixed and stirred for
2h, stands overnight afterwards, is finally dispersed into 15mL aqueous solution by water eccentric cleaning；
1.5) preparation of gold shell growth solution: be separately added into 25mg in the deionized water of 100mL
Anhydrous potassium carbonate and the aqueous solution of chloraurate that 1.5mL concentration is 25mM continuously stirred, until
Solution becomes to be clarified；
1.6) preparation of gold shell particles solution: take step 1.5) the golden shell growth solution prepared
30mL, adds 0.45mL step 1.4) the solution & stir 10min for preparing, it is subsequently added
120uL concentration is the formaldehyde of 80% and is stirred continuously until solution and becomes aeruginous and i.e. can get two
Silicon oxide/gold core-shell particles solution；
2) synthesis of printing opacity silicon dioxide layer: by step 1) in the titanium dioxide of 30mL of preparation
Silicon/gold core-shell particles solution deionized water cleans 2 times, is dispersed in the deionization of 30mL afterwards
In water, in the environment of ultrasonic, adding 10mL concentration in the solution of gained is 110g/L's
Aqueous povidone solution, the most ultrasonic 20s, subsequently with the stirring speed of 500r/min
Degree stirring 24h, after having reacted, by gained solution centrifugal, is dispersed in the 4.2% of 60mL
In ethanol containing ammonia, after stirring 10min, the positive silicic acid of the 10% of addition 270～810uL
Ethyl ester ethanol solution, continuously stirred 12h.
A kind of silicon dioxide/gold/silicon dioxide three layers nanoparticle the most according to claim 1
The preparation method of son, it is characterised in that described step 2) the middle tetraethyl orthosilicate ethanol added
The amount of solution is 270uL.
A kind of silicon dioxide/gold/silicon dioxide three layers nanoparticle the most according to claim 1
The preparation method of son, it is characterised in that described step 2) the middle tetraethyl orthosilicate ethanol added
The amount of solution is 810uL.
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| CN106914630A (en) * | 2017-03-28 | 2017-07-04 | 运城学院 | A kind of preparation method of Cu/SiO 2 core-shell structure nanometer particle |
| CN110293232A (en) * | 2018-03-23 | 2019-10-01 | 中国人民解放军军事科学院军事医学研究院 | A kind of method that ultrasonic wave added hydroxylamine hydrochloride seed mediated growth method prepares silicon core golden shell nano particle |
| CN111375759B (en) * | 2018-12-28 | 2021-10-01 | 同方威视技术股份有限公司 | Raman nano-reinforcing material and preparation method and application thereof |
| CN110038127B (en) * | 2019-04-18 | 2022-03-22 | 合肥师范学院 | Preparation method and application of polypyrrole/gold composite hollow microsphere structure material |
| CN112730381A (en) * | 2020-12-25 | 2021-04-30 | 南京航空航天大学 | Preparation method of surface-enhanced Raman scattering optical fiber probe |
| CN113181938B (en) * | 2021-03-26 | 2023-08-15 | 大连海事大学 | Magnetizable yolk shell structure composite nanoparticle supported metal chloride catalyst and preparation method and application thereof |
| CN115025052B (en) * | 2022-06-27 | 2023-04-18 | 天津大学 | Calcium peroxide and manganese dioxide based nano particle with oxygen production and oxidation resistance and preparation method thereof |
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| CN101050358A (en) * | 2007-04-30 | 2007-10-10 | 吉林大学 | Method for preparing dyestuff controllable doped Nano particles of silicon dioxide |
| CN101388267B (en) * | 2008-07-09 | 2011-04-13 | 长春市博坤生物科技有限公司 | Silicon dioxide magnetic composite particle and preparation |
| KR101351913B1 (en) * | 2012-05-07 | 2014-02-07 | 중원대학교 산학협력단 | Manufacturing method of iron nano particles using slurry reduction process |
| CN102764618B (en) * | 2012-07-09 | 2014-06-04 | 东南大学 | Method for preparing three-layer core-shell structural gold magnetic nano particles |
| CN103286312A (en) * | 2013-05-08 | 2013-09-11 | 复旦大学 | Surface-common-enhanced fluorescence surface-enhanced Raman multi-layer core-shell structure composite particles and preparation method of particles |
| CN104027814B (en) * | 2014-05-29 | 2016-02-24 | 福州大学 | A kind of mesoporous silicon oxide by amido modified rear dual drug-loading |
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