CN104550941B - Preparation method of silica @ noble metal nano-composite microspheres - Google Patents
Preparation method of silica @ noble metal nano-composite microspheres Download PDFInfo
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- CN104550941B CN104550941B CN201410704455.1A CN201410704455A CN104550941B CN 104550941 B CN104550941 B CN 104550941B CN 201410704455 A CN201410704455 A CN 201410704455A CN 104550941 B CN104550941 B CN 104550941B
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Abstract
The invention discloses a preparation method of silica @ noble metal nano-composite microspheres. The method comprises the following steps: 1) preparing silica nano microspheres; 2) dispersing the nano microspheres into tri-distilled water, and adding a sodium chloride water solution of polyelectrolyte to obtain polyelectrolyte-modified silica nano microspheres; 3) dispersing the nano microspheres into the tri-distilled water, and dropwise adding a noble metal salt water solution to obtain polyelectrolyte-modified silica nano microspheres stained with noble metal ions; 4) dispersing the silica nano microspheres into the tri-distilled water, and dropwise adding a sodium borohydride water solution to obtain the silica @ noble metal nano-composite microspheres. According to the preparation method, water is taken as a medium under the reaction condition at a room temperature of 25 DEG C; an organic solvent is not required; complicated and tedious modifying processes are not required; the silica @ noble metal nano-composite microspheres with high dispersity and good stability can be rapidly prepared; the method is simple and feasible, good in repeatability, and simple in reaction device; large-scale production can be achieved according to the production requirements.
Description
Technical field
The invention belongs to technical field of composite preparation, is related to a kind of silicon dioxide@noble metal nano complex microspheres
Preparation method, specifically with silicon dioxide as core, polyelectrolyte is modified silicon dioxide, in its area load noble metal nano
Particle and preparation method thereof.
Background technology
Noble metal nano particles are except the small-size effect with nanoparticle, quantum tunneling effect, quantum size effect, table
Beyond the effect of face, due to its unique physical property, chemical property and biological property, chemistry, physicss, electronics, optics,
The ambits such as materialogy, biology, materia medica have important researching value, brilliant in Industrial Catalysis, detection chemistry, photon
Body, surface-enhanced fluorescence spectrum, surface enhanced raman spectroscopy, anti-biotic material, Infrared stealthy materials, biomedicine, biological preparation
Etc. application aspect also has broad application prospects, by researcher extensive concern.But noble metal nano particles are in reality
A problem i.e. nano metal particles are faced with using in there is high specific surface area and high surface energy, be susceptible to due to model
The aggregation that moral China gravitation causes, as noble metal nano particles are reunited, has a strong impact on its application performance.This problem can pass through
Noble metal nano particles are deposited on into monodispersed solid substrate, colloid compound particle are formed, is made noble metal nano particles
Higher stability and activity are kept, and such colloid compound particle application is easy, easily carried out from reaction system point
From reaching the purpose of recycling.
SiO2Nano microsphere synthesis is simple, narrow diameter distribution, size is easily controllable, be easy to be prepared on a large scale, and makees
It is widely used in various nucleocapsid structures for traditional core layer material.These nanoshells structures are improving the chemically stable of colloid
The aspect such as property, the luminescent properties of strengthening system, bio-sensing, drug delivery is respectively provided with important potential using value.By your gold
Category and conventional SiO2The Typical Representative that stratum nucleare combines is SiO2@M nucleocapsid structures, typically by SiO2Core and metal M shell groups
Into nano-complex particle.Because SiO cheap and easy to get can be deposited on by using a small amount of expensive metal material2Core
Layer, reduces the usage amount of noble metal.So, from economy point SiO2@M nucleocapsid structures have very big potentiality.
Relevant SiO2The preparation method of@M nucleocapsid structures, including " seed " growth method (Zhang J, Fu Y, Lakowicz J
R.Luminescent silica core/silver shell encapsulated with Eu(III)complex[J]
.The Journal of Physical Chemistry C, 2009.113 (45)：19404), sonochemical method (Ye X Y,
Zhou Y M, Chen J, et al.Deposition of silver nanoparticles on silica spheres
Via ultrasound irradiation [J] .Applied Surface Science, 2007.253 (14)：6264), chemistry
Plating method (Xiu Z L, Wu Y Z, Hao X P, et al.Fabrication of SiO2@Ag@SiO2 core-shell
microspheres and thermal stability investigation[J].Colloids and Surfaces A：
Physicochemical and EngineeringAspects, 2011.386 (1)：135), successively construction from part (Chen G S,
Chen C N, Tseng T T, et al.Synthesis, characterization, and antibacterial
activity of silver-doped silica nanocomposite particles[J].Journal of
Nanoscience and nanotechnology, 2011.11 (1)：90) method such as.Above-mentioned reaction have the shortcomings that it is certain,
I.e. " seed " growth method is needed to SiO2Carry out surface to be modified, modifying process is most using silane couplers such as APTMS, reaction is needed
To carry out in organic solvent system, required time is longer, modified condition is harsh, it is difficult to control；Sonochemical method needs reaction
Carry out under anaerobic, the difficulty of this increase reaction unit；Electroless plating method needs to introduce stannous chloride as sensitizer, finally
Sn4+It is free in reaction system, is unfavorable for environmental protection；Successively construction from part needs repeatedly to carry out using the polyelectrolyte of opposite charges
Cladding, time-consuming, and expends a large amount of polyelectrolyte.
The content of the invention
The technical problem to be solved is had high demands, consumes for existing method modified condition harshness, reaction unit
Duration, organic solvent expend it is many, the problems such as do not meet environmental requirement
In order to solve the above problems, the invention provides a kind of preparation side of silicon dioxide@noble metal nano complex microspheres
Method, it is characterised in that comprise the following steps that：
Step 1)：Using tetraethyl orthosilicate, mechanical agitation is mixed homogeneously as A liquid at room temperature with ethanol, and ethanol, three are steamed
Mechanical agitation mix homogeneously, as B liquid, pours rapidly A liquid into B liquid at room temperature for water, ammonia, and under room temperature, mechanical agitation 6～24 is little
When, prepare silicon dioxide nanosphere；
Step 2)：By step 1) silicon dioxide that obtains receives body microsphere and is scattered in tri-distilled water, forms 2～50mg/mL's
Silicon dioxide emulsion, adds the aqueous solution of 2mg/mL cationic polyelectrolytes, and polyelectrolyte is 1: 5 with the mass ratio of silicon dioxide
～1: 20, under room temperature, ultrasound is modified for 30～120 minutes, Centrifugal dispersion, the washing of Jing tri-distilled waters, obtains polyelectrolyte-modified
Silicon dioxide nanosphere；
Step 3)：By step 2) the polyelectrolyte-modified silicon dioxide nanosphere that obtains is scattered in tri-distilled water, forms 2
The emulsion of～50mg/mL, is added dropwise over the noble metal salt aqueous solution of 10mmol/L, precious metal salt and polyelectrolyte-modified dioxy
The mass ratio of SiClx is 1: 10～100, ultrasound 30～120 minutes under room temperature, Centrifugal dispersion, and the washing of Jing tri-distilled waters is deposited
The polyelectrolyte-modified silicon dioxide nanosphere of precious metal ion；
Step 4)：By step 3) silicon dioxide nanosphere that obtains is scattered in tri-distilled water, forms 2～50mg/mL's
Emulsion, Deca 50mmol/L reducing agent sodium borohydride aqueous solution, sodium borohydride aqueous solution are 5 with noble metal salt aqueous solution mol ratio
: 1～1: 1, it is stirred at room temperature 30～120 minutes, Centrifugal dispersion, the washing of Jing tri-distilled waters obtains silicon dioxide@noble metal nanos
Complex microsphere.
Preferably, the step 1) in the molar concentration of tetraethyl orthosilicate be 0.2mol/L, the molar concentration of tri-distilled water is
18mol/L, the molar concentration of ammonia is 0.2～1.2mol/L.
Preferably, the step 2) in polyelectrolyte be polypropylene amine, polyvinylamine or PIBA.
Preferably, the step 2) in cation polyelectrolyte aqueous solution in Sodium Chloride concentration be 0.5mol/L.
Preferably, described precious metal salt is silver nitrate, gold chloride or chloroplatinic acid.
The invention provides a kind of utilize polyelectrolyte-modified silicon dioxide, prepare silicon dioxide@noble metal nanos and be combined
The simple and easy to do method of microsphere, i.e., with silicon dioxide as core, Jing is polyelectrolyte-modified, in its area load noble metal nano grain
The method of son.The present invention under the reaction condition of 25 DEG C of room temperatures, with water as medium, without using organic solvent, without process
Complicated loaded down with trivial details modifying process, quickly prepares dispersion height, the silicon dioxide@noble metal nano complex microspheres of good stability, should
Method is simple, and favorable reproducibility, and reaction unit is simple, can be accomplished scale production according to the needs of production, and
And, noble metal nano particles particle size dispersion prepared by this patent method is homogeneous, and size is adjustable.This patent can be used for preparing
The silicon dioxide@silver of different-grain diameter, silicon dioxide@gold and the composite nano-microsphere such as silicon dioxide@platinum.
The present invention is interacted by hydrogen bond etc. with amino in polyelectrolyte molecules using silica surface hydroxyl, two
Silicon oxide surface introduces polyelectrolyte, using silver ion and the complexing of amino in polyelectrolyte molecules, silver ion is adsorbed
And silica surface is stable at, by in-situ reducing, prepare the noble metal nano grain of dispersion height, good stability, small particle
The silicon dioxide@noble metal nano complex microspheres of son.
Advantages of the present invention：Under gentle reaction condition, with water as solvent, quickly prepare dispersion height, good stability,
The silicon dioxide@noble metal nano complex microspheres of small particle noble metal nano particles, can be according to the needs of production, flexible
The particle diameter of noble metal nano particles and its cladding degree on silicon dioxide microsphere.The present invention both can apply to different-grain diameter
The preparation of silicon dioxide@silver nanoparticle complex microspheres, it is also possible to be applied to prepare in noble metals such as silica surface gold-supported, platinum
Composite nano-microsphere.The complex microsphere of preparation can be in catalytic chemistry, detection chemistry, photonic crystal, surface-enhanced fluorescence light
The fields such as spectrum, surface enhanced raman spectroscopy, anti-biotic material, Infrared stealthy materials, biomedicine, biopharmaceutics are applied.
Description of the drawings
Fig. 1 is SiO in embodiment 12Transmission electron microscope picture；
Fig. 2 is SiO in embodiment 12The transmission electron microscope picture of@Ag composite nano-microspheres；
Fig. 3 is SiO in embodiment 22Transmission electron microscope picture；
Fig. 4 is SiO in embodiment 22The transmission electron microscope picture of@Ag composite nano-microspheres.
Specific embodiment
To become apparent the present invention, hereby with preferred embodiment, and accompanying drawing is coordinated to be described in detail below.
Embodiment 1
59.20mL tri-distilled waters, 38.00mL dehydrated alcohol, 2.80mL strong aqua ammonia are inserted in 250mL there-necked flasks successively,
1100rpm magnetic agitation 30min.After mix homogeneously, by 9.00mLTEOS and the homogeneous mixture solotion of 91.00mL dehydrated alcohol,
Pour rapidly above-mentioned there-necked flask into, mixing speed is reduced to into 400rpm after 2min, holding reaction 6h under the conditions of 25 DEG C, 10
000rpm is centrifuged 5min, is washed for several times with dehydrated alcohol and tri-distilled water respectively, obtains monodispersed SiO2Nano microsphere, then will
Which is dispersed in water, SiO2Mass fraction is 2mg/ml.Transmission electron microscope observing shows, reacts the SiO for obtaining2Nano-particle is ball
Shape, diameter are about 100nm, and are single dispersing, as shown in Figure 1.
5mL 2mg/mL PAH aqueous solutions (NaCl 0.5M pH 5～6) are added to into 50mL SiO2In dispersion liquid, room temperature
After ultrasonic 60min, 8000rpm centrifugation 5min are washed with tri-distilled water 2 times, are then dispersed in 40mL water.5.25mL 10mM
AgNO3Aqueous solution is added dropwise over above-mentioned solution, and after ultrasonic 60min, 8000rpm centrifugation 5min, tri-distilled water are washed 3 times, be dispersed in
In 40ml water.5.25mL 50mM NaBH4Under 11000rpm intense agitations, above-mentioned solution is added, after stirring 30min,
Rotating speed is reduced to 600rpm, then reacts 30min.8000rpm is centrifuged 5min, is washed 3 times with dehydrated alcohol and tri-distilled water respectively, is removed
Impurity therein is removed, SiO is obtained2@Ag composite nano-microspheres.Jing transmission electron microscope observings show that product is that silver nano-grain is uniform
It is deposited on SiO2The nano composite material of microsphere surface, the particle diameter of silver nano-grain is 2～4nm, as shown in Figure 2.
Embodiment 2
55.10mL tri-distilled waters, 36.50mL dehydrated alcohol, 8.40mL strong aqua ammonia are inserted in 250mL there-necked flasks successively,
1100rpm magnetic agitation 30min.After mix homogeneously, by 9.00mLTEOS and the homogeneous mixture solotion of 91.00mL dehydrated alcohol,
Pour rapidly above-mentioned there-necked flask into, mixing speed be reduced to into 400rpm after 2min, under the conditions of 25 DEG C, keep reaction 6h,
10000rpm is centrifuged 5min, is washed for several times with dehydrated alcohol and tri-distilled water respectively, obtains monodispersed SiO2Nano microsphere, so
After be dispersed in water, SiO2Mass fraction is 2mg/ml.Transmission electron microscope observing shows, reacts the SiO for obtaining2Nano-particle
For spherical, diameter is about 300nm, and is single dispersing, as shown in Figure 3.
5mL 2mg/mL PAH aqueous solutions (NaCl 0.5M pH 5-6) are added to into 50mL SiO2In dispersion liquid, room temperature
After ultrasonic 60min, 8000rpm centrifugation 5min are washed with tri-distilled water 2 times, are then dispersed in 40mL water.
5.25mL 10mM AgNO3Aqueous solution is added dropwise over above-mentioned solution, after ultrasonic 60min, 8000rpm centrifugation 5min,
Tri-distilled water is washed 3 times, is dispersed in 40ml water.5.25mL 50mM NaBH4Under 11000rpm intense agitations, in addition
Solution is stated, and after stirring 30min, rotating speed is reduced to 600rpm, then is reacted 30min.8000rpm is centrifuged 5min, uses anhydrous second respectively
Alcohol and tri-distilled water are washed 3 times, are removed impurity therein, are obtained SiO2@Ag composite nano-microspheres.Jing transmission electron microscope observings show,
Product is silver nano-grain uniform deposition in SiO2The nano composite material of microsphere surface, the particle diameter of silver nano-grain is 2～
4nm, as shown in Figure 4.
Contrast prepares SiO2The prior art of@M and the present invention, as a result as shown in table 1：
Table 1
Claims (5)
1. a kind of preparation method of silicon dioxide@noble metal nano complex microspheres, it is characterised in that comprise the following steps that：
Step 1)：Using tetraethyl orthosilicate, mechanical agitation is mixed homogeneously as A liquid at room temperature with ethanol, by ethanol, tri-distilled water, ammonia
Mechanical agitation mix homogeneously, as B liquid, pours rapidly A liquid into B liquid to water at room temperature, mechanical agitation 6～24 hours under room temperature, system
It is standby to obtain silicon dioxide nanosphere；
Step 2)：By step 1) silicon dioxide that obtains receives body microsphere and is scattered in tri-distilled water, forms the dioxy of 2～50mg/mL
SiClx emulsion, adds the aqueous solution of 2mg/mL cationic polyelectrolytes, and polyelectrolyte is 1: 5～1 with the mass ratio of silicon dioxide:
20, under room temperature, ultrasound is modified for 30～120 minutes, Centrifugal dispersion, the washing of Jing tri-distilled waters, obtains polyelectrolyte-modified dioxy
SiClx Nano microsphere；
Step 3)：By step 2) the polyelectrolyte-modified silicon dioxide nanosphere that obtains is scattered in tri-distilled water, form 2～
The emulsion of 50mg/mL, is added dropwise over the noble metal salt aqueous solution of 10mmol/L, precious metal salt and polyelectrolyte-modified titanium dioxide
The mass ratio of silicon is 1: 10～100, ultrasound 30～120 minutes under room temperature, Centrifugal dispersion, and the washing of Jing tri-distilled waters obtains deposition expensive
The polyelectrolyte-modified silicon dioxide nanosphere of metal ion；
Step 4)：By step 3) silicon dioxide nanosphere that obtains is scattered in tri-distilled water, forms the emulsion of 2～50mg/mL,
Deca 50mmol/L reducing agent sodium borohydride aqueous solution, sodium borohydride aqueous solution are 5: 1～1 with noble metal salt aqueous solution mol ratio
: 1, it is stirred at room temperature 30～120 minutes, Centrifugal dispersion, the washing of Jing tri-distilled waters obtains silicon dioxide@noble metal nanos and is combined
Microsphere.
2. the preparation method of silicon dioxide@noble metal nano complex microspheres as claimed in claim 1, it is characterised in that described
Step 1) in the molar concentration of tetraethyl orthosilicate be 0.2mol/L, the molar concentration of tri-distilled water is 18mol/L, ammonia it is mole dense
Spend for 0.2～1.2mol/L.
3. the preparation method of silicon dioxide@noble metal nano complex microspheres as claimed in claim 1, it is characterised in that described
Step 2) in polyelectrolyte be polypropylene amine, polyvinylamine or PIBA.
4. the preparation method of silicon dioxide@noble metal nano complex microspheres as claimed in claim 1, it is characterised in that described
Step 2) in cation polyelectrolyte aqueous solution in Sodium Chloride concentration be 0.5mol/L.
5. the preparation method of silicon dioxide@noble metal nano complex microspheres as claimed in claim 1, it is characterised in that described
Precious metal salt be silver nitrate, gold chloride or chloroplatinic acid.
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| CN110461505B (en) * | 2017-03-31 | 2022-07-08 | 东邦钛株式会社 | Method for producing metal powder |
| CN107598184A (en) * | 2017-08-18 | 2018-01-19 | 江西师范大学 | Preparation method of silver nanoparticle coated silicon dioxide microsphere powder |
| CN109390160A (en) * | 2018-11-09 | 2019-02-26 | 江苏大学 | Ag is prepared in situ in one kind2O/Ag/TiO2The method of hollow sphere Z-scheme type optoelectronic pole |
| 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 |
| CN110935454B (en) * | 2019-12-20 | 2022-04-22 | 杭州钦宁科技有限公司 | Preparation method of silicon dioxide/nickel core-shell nano-structure material |
| CN113488651B (en) * | 2020-08-31 | 2022-11-25 | 中南大学 | Titanium oxide @ C hollow composite framework embedded with noble metal silver, and preparation method and application thereof |
| CN116328763A (en) * | 2023-02-28 | 2023-06-27 | 西南交通大学 | Gold-loaded silicon microsphere composite material with three-layer hierarchical structure and preparation method thereof |
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Effective date of registration: 20201216 Address after: No. b429, zone B, 3 / F, innovation building, 315 Changjiang Avenue, hi tech Zone, Shijiazhuang City, Hebei Province Patentee after: Hebei Peiqing Technology Co., Ltd Address before: 201620 No. 2999 North Renmin Road, Shanghai, Songjiang District Patentee before: DONGHUA University |