CN105728742B - The preparation method of Au nano materials/Au metal oxide nano composite materials - Google Patents
The preparation method of Au nano materials/Au metal oxide nano composite materials Download PDFInfo
- Publication number
- CN105728742B CN105728742B CN201610090751.6A CN201610090751A CN105728742B CN 105728742 B CN105728742 B CN 105728742B CN 201610090751 A CN201610090751 A CN 201610090751A CN 105728742 B CN105728742 B CN 105728742B
- Authority
- CN
- China
- Prior art keywords
- nano
- ethanol
- metal oxide
- sodium citrate
- preparation
- 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.)
- Expired - Fee Related
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention provides a kind of preparation method of Au nano materials/Au metal oxide nano composite materials.Present invention the characteristics of being insoluble in straight alcohol using sodium citrate, gold chloride is reduced using sodium citrate ethanol colloidal sol, it is narrower, evenly so as to obtain particle diameter distribution, dispersiveness more preferably, and Au nano materials/Au metal oxide nano composite materials of size adjustable.The inventive method effectively overcomes the shortcomings that sodium citrate is insoluble in ethanol, and need not add any stabilizer and protective agent, has the advantages that technique is simple, reaction condition is gentle；Using centrifuging method of purification; sodium citrate ethanol sol particle with different-grain diameter size is separated; the sodium citrate ethanol sol particle reduction gold chloride of particle size needed for selection; particle diameter distribution is narrow, uniform so as to obtaining at low ambient temperatures, and Au nano materials/Au metal oxide nano composite materials of size adjustable.
Description
Technical field
The present invention relates to technical field of nano material, in particular to a kind of Au nano materials/Au- metal oxides
The preparation method of nano composite material.
Background technology
In recent years the small-size effect based on nano material, the Raman of surface plasma body resonant vibration, enhancement effect of fluorescence with
And the Novel Biosensor part that polarization effect of light etc. grows up in optical transport, it can be realized on single molecules level to life
The quick detection of thing molecule (DNA, protein, antibody etc.), there is important application in terms of disease identification and early prediction, draw
Extensive concern is played.The development of wherein biosensing device recent years based on SERS (SERS) effect is outstanding
For protrusion, turn into one important direction of hypersensitivity detection field.
Generally, material raman spectral signal is all very weak.However, research shows that the noble metal nano particles such as Au, Ag are respectively provided with
Very strong local surface plasma resonance effect, it can effectively strengthen Raman light scattering signal intensity.And in core shell structure,
Coupling between core material and Shell Materials can further enhance this SERS effects.SERS effects are applied to sensing
Device field, it is possible to increase the sensitivity of sensor, realize to the highly sensitive, quick of the materials such as microchemistry medicine, biomolecule
Detection.
Therefore compound, and the composite construction center heartwood of research high refractive index nano metal oxide and precious metal material
Coupling between material and Shell Materials has important practical significance to the humidification of surface Raman light scattering signal.
It is more and more on gold nano grain, the research of Au- metal oxide composites in recent years.Such as：Xiamen University
Chemical engineering institute Tanaka group teaches and georgia ,U.S.A Institute of Technology Wang Zhonglin professor's joint study shell isolated nano particles surface
Strengthen the detection (Nature, 464 (2010) 392-395) [5] that Raman spectrum is used for veterinary antibiotics surface residual agricultural chemicals；
Trachta etc. is combined high performance liquid chromatography with surface Raman enhancement scattering method, measures different medicines in human blood and urine
Product and their degraded composition [6]；Nithipatikom etc. [7], which is used, hales graceful scatterer as Raman labels, and with silver
Colloidal sol SERS strengthens the signal of these Raman labels, and it is IC to have detected single ox using confocal Raman fibre technology
Angiotensin II in 12- lipoxygenase and epoxidase and messangial cell.
It is one kind side commonly used at present using reduction of sodium citrate gold chloride in these Au NPs preparation technologies
Method.The advantages that this method has flow simple, and cost is low, and generation Au granular mass is good.Because sodium citrate is practically insoluble in second
Alcohol, thus the restoring method more using the mixed liquor of the aqueous solution, water and ethanol or methanol as solvent, and when using water and
When alcohol mixeding liquid is solvent, the ratio of ethanol is less than 50%.
Preparing Au NPs as solvent using water has some following deficiency.1. water has stronger polarity and surface
Power, Au NPs easily produce reunion in aqueous, therefore generally require the one or more kinds of protective agents of addition and stabilizer, and
It is unfavorable for preserving for a long time.(2. water has of a relatively high fusing point (0 DEG C)), therefore reaction generally requires hot conditions.Particularly,
Solvent is done using water, is not suitable for the environment below 0 degree Celsius and prepares gold nano-material and gold-metal oxide composite.
3. although can generate the Au NPs of particle diameter very little, particle diameter distribution is wider, the more difficult control of size.
Comparatively, ethanol has relatively low surface tension and polarity, is a kind of conventional and excellent organic dispersing agent,
It is widely used in storing nano particle, separated and being purified.Ethanol has lower fusing point (- 114 relative to water simultaneously
℃).If preparing nanometer Au particles as solvent using ethanol, the reunion of nano particle can be effectively prevented, it is scattered to improve it
Property and activity, while be expected to reduce addition protective agent and stabilizer, and be adapted to low temperature environment to prepare.
But because sodium citrate is almost not easy ethanol, so conventional Au NPs preparation methods, ethanol usually as
Additive, for improving the surface tension of the aqueous solution and polarity, and adding proportion is no more than 50%.Have been reported that or even point out,
In reduction of sodium citrate method prepares Au NPs, generation of the ethanol in itself to Au NPs is harmful.Therefore pure
In ethanol solution, one of Au NPs key is prepared using reduction of sodium citrate gold chloride, exactly solves sodium citrate in ethanol
Problems of dissolution in solution.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of system of Au nano materials/Au- metal oxide nano composite materials
Preparation Method, the preparation methods of described Au nano materials/Au- metal oxide nano composite materials have that technique is simple, reaction
The advantages that mild condition；The present invention uses reduction of sodium citrate gold chloride method, and particle diameter distribution can be prepared in ethanol
Narrow, uniform, size adjustable Au nano materials/Au- metal oxide nano composite materials.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of preparation method of Au nano materials/Au- metal oxide nano composite materials, it is molten using sodium citrate ethanol
Glue reduces chlorauric acid solution or reduces the mixing suspension of gold chloride and nano-metal-oxide, be prepared Au nano particles or
Au- metal oxide nano composite materials.
When prior art uses reduction of sodium citrate gold chloride, the mixing of the aqueous solution or water and ethanol or methanol should be used
For liquid as solvent, and when using water with alcohol mixeding liquid for solvent, the ratio of ethanol is less than 50%.And the present invention overcomes
The shortcomings that sodium citrate is insoluble in ethanol, it is the characteristics of being insoluble in straight alcohol using sodium citrate, using sodium citrate ethanol molten
Glue reduces gold chloride, narrower, evenly so as to obtain particle diameter distribution, and the Au nano materials of size adjustable/Au- metals oxidation
Thing nano composite material, whole course of reaction, sodium citrate serve as reducing agent, gold chloride Jin Yuan, and straight alcohol is dispersant.This
Invention uses ethanol to be beneficial to Au particles in the compound of metal oxide surface for reaction dissolvent, because ethanol polarity is small, with
Nano-particle more has affinity, and the inventive method is also beneficial to compound, the formation Au- metal oxidations of Au and metal oxide
Thing nano composite material.Compared to water, ethanol is with lower than table tension force, polarity and fusing point.Wherein surface tension and polarity
Nanoparticle agglomerates can be effectively prevented, and fusing point is lower, is more suitable for low-temperature insulation operation.In addition, lemon is used in the prior art
Lemon acid sodium aqueous solution needs to add a large amount of stabilizers during preparing Au nano materials/Au- metal oxide nano composite materials
And protective agent, and the inventive method need not add any stabilizer and protective agent, can substantially reduce cost and ensure gained
The purity of Au nano materials/Au- metal oxide nano composite materials, the follow-up stabilizer and protectant of removing can also be saved
Some cumbersome procedures.
Preferably, in the preparation method of Au nano materials/Au- metal oxide nano composite materials of the present invention, water used
Volume gross score be not more than 10%, preferably less than 0.1%, close to water-less environment.
A kind of preparation method of above-mentioned Au nano materials/Au- metal oxide nano composite materials, including following step
Suddenly：
(1) sodium citrate ethanol colloidal sol is centrifuged, controls to obtain the nanoscale lemon of pre-set dimension using centrifugation rate
Sour sodium ethanol colloidal sol；
(2) using the nanoscale sodium citrate ethanol sol solution reduction chlorauric acid solution, or reduction gold chloride with
The mixing suspension of nano-metal-oxide, Au nano materials/Au- metal oxide nano composite materials are prepared.
Using method of purification is centrifuged, the sodium citrate ethanol sol particle with different-grain diameter size is separated, choosing
The sodium citrate ethanol sol particle reduction gold chloride of particle size needed for selecting, it is narrow, uniform so as to obtain particle diameter distribution, and chi
Very little adjustable Au nano materials/Au- metal oxide nano composite materials.
Preferably, the preparation method of the sodium citrate ethanol colloidal sol is：Sodium citrate is dissolved in water, then by gained
Solution is added drop-wise in ethanol is prepared under agitation.
Sodium citrate is insoluble in ethanol, may directly have any problem sodium citrate is scattered in ethanol, now can in advance by
Sodium citrate is dissolved in a small amount of water (water should not be excessive, is preferably close to saturated solution), then by gained sodium citrate solution
Agitation and dropping is so more conducive to be uniformly dispersed in ethanol, obtains sodium citrate ethanol colloidal sol into excess ethyl alcohol.
Preferably, the ethanol is the ethanol solution that volume fraction of ethanol is not less than 80%, preferably absolute ethyl alcohol.
Preferably, the ethanol solution is ethanol water or the mixed solution of ethanol and organic solvent.
Preferably, by controlling centrifugal rotational speed, the sodium citrate that sodium citrate nano particle diameter is required size is obtained
Ethanol colloidal sol.
Using method of purification is centrifuged, by controlling centrifugal rotational speed, by the sodium citrate second with different-grain diameter size
Alcosol particle separates, the sodium citrate ethanol sol particle reduction gold chloride of particle size needed for selection, so as to obtain particle diameter
Narrowly distributing, uniformly, and Au nano materials/Au- metal oxide nano composite materials of size adjustable.
It is further preferred that the nanoscale sodium citrate ethanol for controlling to obtain pre-set dimension using secondary centrifuging mode is molten
Glue, take unprecipitated sodium citrate ethanol colloidal sol to carry out second after centrifuging for the first time and centrifuge, the speed of second of centrifugation
Higher than the speed of first time centrifugation, second of centrifuged pellet is taken, using ethanol as solvent, the citric acid of pre-set dimension is made
Sodium ethanol colloidal sol.
According to required particle size, specific secondary centrifuging mode is selected, it is narrower, evenly to be advantageous to obtain particle diameter distribution
Au nano materials/Au- metal oxide nano composite materials.
Preferably, the process of the reduction is：By the mixed of gold chloride ethanol solution or gold chloride and nano-metal-oxide
Close suspension to be added dropwise in sodium citrate ethanol colloidal sol, after -10~10 DEG C of insulations, obtain Au nano materials or Au- metal oxygens
Compound nano composite material.
The mixing suspension of gold chloride ethanol solution or gold chloride and nano-metal-oxide is added dropwise to excessive citric acid
In sodium ethanol colloidal sol, be advantageous to the small Au nano materials of particle diameter and separate out, after low temperature environment is incubated, it is small to be advantageous to obtain particle diameter,
Particle diameter distribution is narrow, uniform Au nano materials or Au- metal oxide nano composite materials.
Preferably, by gold chloride dissolving in ethanol, it is standby to obtain gold chloride ethanol solution；By metal oxide nano powder
Body is scattered to take unprecipitated nano-metal-oxide suspension in ethanol, after centrifugation, adds in gold chloride ethanol solution fully
Mixing, obtains the mixing suspension of gold chloride and nano-metal-oxide.
By gold chloride dissolving in ethanol, metallic oxide nano powder is also dispersed within ethanol, and the two can when mixing
Fully dissolve each other, be uniformly dispersed.
The metal-oxide powder plays Au nanoparticle vectors, the two can carry out it is compound, preferably can be in second
The metal oxide of stable dispersion in alcohol, commercially available nanosize metal oxide powder can be used, or voluntarily prepare nano level metal
Oxide powder.
Preferably, the preparation method of the mixing suspension of the gold chloride and nano-metal-oxide is：By metal nitrate
Salt is dissolved in alcohol, and nano-metal-oxide gel is made in heating, is calcined, is added alcohol after being ground into powder, do not sunk after centrifugation
The suspension of the alcohol of the metal oxide in shallow lake, the suspension of the alcohol of the metal oxide is mixed with gold chloride, obtain chlorine gold
The mixing suspension of acid and nano-metal-oxide.
Preferably, the temperature of the insulation is -5~5 DEG C, more preferably 0~5 DEG C.
Preferably, the time of the insulation is more than 12h, preferably 12-24h, more preferably 12h.
Low temperature contributes to the precipitation of Au nano materials/Au- metal oxide nano composite materials, and can prevent its group
Poly-, it is small to be advantageous to obtain particle diameter, and particle diameter distribution is narrow, uniform Au nano materials/Au- metal oxide nano composite materials.
Au nano materials/Au- metal oxide nano composite materials can be obtained by drying after insulation.
Preferably, the drying temperature is 20-40 DEG C, preferably 25-35 DEG C, more preferably 30 DEG C.
The present invention uses ethanol as solvent, is not required to be dried using excessive temperature, and under normal temperature condition, ethanol can be with
Quick volatilization, is dried using lower temperature, can also prevent that resulting Au nano materials/Au- metal oxide nanos are compound
Material is reunited, and it is small to be advantageous to obtain particle diameter, and particle diameter distribution is narrow, uniform Au nano materials/Au- metal oxide nano composite woods
Material.
Compared with prior art, beneficial effects of the present invention are：
When prior art uses reduction of sodium citrate gold chloride, the mixing of the aqueous solution or water and ethanol or methanol should be used
For liquid as solvent, and when using water with alcohol mixeding liquid for solvent, the ratio of ethanol is less than 50%.And the present invention overcomes
The shortcomings that sodium citrate is insoluble in ethanol, the characteristics of being insoluble in straight alcohol using sodium citrate on the contrary, prepared by sodium citrate
As sodium citrate ethanol colloidal sol, the colloidal sol is recycled to reduce gold chloride, it is narrower, evenly so as to obtain particle diameter distribution, and
Au nano materials/Au- metal oxide nano composite materials of size adjustable.Whole course of reaction, sodium citrate ethanol colloidal sol
Reducing agent, gold chloride Jin Yuan are served as, straight alcohol is dispersant.The present invention uses ethanol to be beneficial to Au particles for reaction dissolvent
In the compound of metal oxide surface, because ethanol polarity is small, more there is affinity with nano-particle, the inventive method also has
Beneficial to Au and compound, the formation Au- metal oxide nano composite materials of metal oxide.Compared to water, ethanol has lower
Than table tension force, polarity and fusing point.Wherein surface tension and polarity can effectively prevent nanoparticle agglomerates, and fusing point more it is low then
It is more suitable for low-temperature insulation operation.In addition, Au nano materials/Au- metal oxygens are prepared using sodium citrate aqueous solution in the prior art
Need to add a large amount of stabilizers and protective agent during compound nano composite material, and the inventive method need not add it is any steady
Determine agent and protective agent, cost can be substantially reduced and ensure gained Au nano materials/Au- metal oxide nano composite materials
Purity, follow-up removal stabilizer and some protectant cumbersome procedures can also be saved.
The preparation method of Au nano materials/Au- metal oxide nano composite materials of the present invention has that technique is simple, reaction
The advantages that mild condition；Using method of purification is centrifuged, by the sodium citrate ethanol sol particle with different-grain diameter size
Separation, the sodium citrate ethanol sol particle reduction gold chloride of particle size needed for selection are narrow, equal so as to obtain particle diameter distribution
It is even, and Au nano materials/Au- metal oxide nano composite materials of size adjustable.At low ambient temperatures, be advantageous to obtain
Particle diameter is small, and particle diameter distribution is narrow, uniform nano material.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The required accompanying drawing used is briefly described in embodiment or description of the prior art, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1-Fig. 3 is respectively the gained gold-ZrO of the embodiment of the present invention 22Transmission under the different scale of nano composite material
Electromicroscopic photograph；
Fig. 4-Fig. 6 is respectively the gained gold-ZrO of the embodiment of the present invention 32Transmission under the different scale of nano composite material
Electromicroscopic photograph；
Fig. 7-Fig. 9 is respectively the gained gold-ZrO of the embodiment of the present invention 42Transmission under the different scale of nano composite material
Electromicroscopic photograph；
Figure 10 is pure ZrO2Transmission and abosrption spectrogram, Figure 11 be the gained gold-ZrO of 2- of embodiment of the present invention embodiments 42
The transmission of nano composite material and abosrption spectrogram.
Embodiment
Technical scheme is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that following described embodiment is part of the embodiment of the present invention, it is rather than whole
Embodiment, the present invention is merely to illustrate, and is not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, ability
The every other embodiment that domain those of ordinary skill is obtained under the premise of creative work is not made, belongs to guarantor of the present invention
The scope of shield.Unreceipted actual conditions person in embodiment, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same
Or the unreceipted production firm person of instrument, it is the conventional products that can be obtained by commercially available purchase.
In the description of the invention, it is necessary to explanation, term " " center ", " on ", " under ", "left", "right", " vertical ",
The orientation or position relationship of the instruction such as " level ", " interior ", " outer " be based on orientation shown in the drawings or position relationship, merely to
Be easy to the description present invention and simplify description, rather than instruction or imply signified device or element must have specific orientation,
With specific azimuth configuration and operation, therefore it is not considered as limiting the invention.In addition, term " first ", " second ",
" the 3rd " is only used for describing purpose, and it is not intended that instruction or hint relative importance.
In the description of the invention, it is necessary to illustrate, unless otherwise clearly defined and limited, term " installation ", " phase
Even ", " connection " should be interpreted broadly, for example, it may be being fixedly connected or being detachably connected, or be integrally connected；Can
To be mechanical connection or electrical connection；Can be joined directly together, can also be indirectly connected by intermediary, Ke Yishi
The connection of two element internals.For the ordinary skill in the art, with concrete condition above-mentioned term can be understood at this
Concrete meaning in invention.
Embodiment 1
A kind of preparation method of Au nano materials, comprises the following steps：
1. the preparation of gold chloride ethanol solution：
A. by 1g gold chlorides (HAuCl4·4H2O) it is dissolved in 600mL absolute ethyl alcohols (mass percent 0.21%), it is standby
With.
2. the preparation of sodium citrate ethanol colloidal sol：
B. by 40g Sodium Citrate, usp, Dihydrate Powders (Na3C6H5O7·2H2O) it is dissolved in (quality percentage in 50 DEG C of deionized waters of 20mL
It is standby after being sufficiently stirred 20min than for 66.7%).
C. 50mL absolute ethyl alcohols are prepared with beaker, is stirred vigorously with magnetic stirring apparatus, mixing speed is more than 1000rpm.
D. it is stirred vigorously under state, the sodium citrate aqueous solution that the first step has been configured, is slowly dropped into 3mL droppers anhydrous
In ethanol.10 drops (about 0.2mL) are instilled in per 50mL ethanol solutions, sodium citrate ethanol sol solution is prepared.Weight
It is multiple 4 times, obtain amounting to 200mL sodium citrate ethanol sol solutions.
E. by 200mL sodium citrate ethanol sol solution centrifugal treatings, centrifugal rotational speed control is 8000rpm, centrifugation time
For 8min.
F. after centrifugation terminates, filtering, milky unprecipitated sodium citrate ethanol colloidal sol (sodium citrate ethanol colloidal sol is extracted
Granular size is effectively controlled by rotating speed).
G. concentrate, in vacuum drying chamber, 200mL sodium citrate ethanol sol solutions are concentrated into 20mL at 50 DEG C, it is standby
With.
2. sodium citrate ethanol colloidal sol mixes with gold chloride, nanogold is restored
H. the sodium citrate ethanol sol solution after 2mL steps g concentrations is taken, 2 drops is instilled wherein and (is prepared before 0.04mL
Mass percent be 0.21% chlorauric acid solution).
I. mixed liquor obtained by step h is put into 30 DEG C of baking ovens, constant temperature 1h obtains average grain diameter and is after 5 DEG C are incubated 12h
2nm gold nano grain material.
Embodiment 2
A kind of gold-ZrO2The preparation method of nano composite material, comprises the following steps：
1. the preparation of gold chloride ethanol solution：
A. by 1g gold chlorides (HAuCl4·4H2O) it is dissolved in 600mL absolute ethyl alcohols (mass percent 0.21%), it is standby
With.
2. the preparation of sodium citrate ethanol colloidal sol：
B. by 40g Sodium Citrate, usp, Dihydrate Powders (Na3C6H5O7·2H2O) it is dissolved in (quality percentage in 50 DEG C of deionized waters of 20mL
It is standby after being sufficiently stirred 20min than for 66.7%).
C. 50mL absolute ethyl alcohols are prepared with beaker, is stirred vigorously with magnetic stirring apparatus, mixing speed is more than 1000rpm.
D. it is stirred vigorously under state, the sodium citrate aqueous solution that the first step has been configured, is slowly dropped into 3mL droppers anhydrous
In ethanol.10 drops (about 0.2mL) are instilled in per 50mL ethanol solutions, sodium citrate ethanol sol solution is prepared.Weight
It is multiple 4 times, obtain amounting to 200mL sodium citrate ethanol sol solutions.
E. by 200mL sodium citrate ethanol sol solution centrifugal treatings, centrifugal rotational speed control is 8000rpm, centrifugation time
For 8min.
F. after centrifugation terminates, filtering, milky unprecipitated sodium citrate ethanol colloidal sol (sodium citrate ethanol colloidal sol is extracted
Granular size is effectively controlled by rotating speed).
G. concentrate, in vacuum drying chamber, 200mL sodium citrate ethanol sol solutions are concentrated into 20mL at 50 DEG C, it is standby
With.
3.ZrO2The preparation method of alcohol suspending liquid：
H. the water zirconium nitrates of 10g five are dissolved in 30mL absolute ethyl alcohols, then by 30mL anhydrous nitric acid zirconium ethanol solutions 50
Degree is concentrated to 10mL, is heated rapidly to 100 degree of reaction generation nano zircite gels.
I. nano zircite gel obtained by step g is sintered in 550 degree of Muffle furnaces and obtains square zirconium oxide.Finally grind
Added after wearing into powder in ethanol, unprecipitated nanometer ZrO is taken after being then centrifuged for 5000 turns of purifications2Alcohol suspending liquid, it is standby.
4. gold chloride-ZrO2The preparation method of mixing suspension；
J. by nanometer ZrO obtained by step h2Suspension is added in gold chloride ethanol solution, is stirred, and obtains chlorine gold
Acid-ZrO2Mixing suspension, it is standby.
5. sodium citrate ethanol colloidal sol mixes with gold chloride, nanogold is restored：
K. sodium citrate ethanol sol solution obtained by 2mL steps g is taken, instills 2 drop (0.04mL) gold chloride-ZrO wherein2
Mixed solution.
L. mixed liquor obtained by step h is put into 30 DEG C of baking ovens, constant temperature 1h obtains gold nano grain after 5 DEG C are incubated 12h
Average grain diameter is 2nm gold-ZrO2Nano composite material.Gained gold-ZrO2The transmission electron microscope photo of nano composite material such as Fig. 1-
Fig. 3 (is followed successively by gold-ZrO under 500nm, 20nm, 10nm scale2The transmission electron microscope photo of nano composite material) shown in.
Embodiment 3
A kind of gold-ZrO2The preparation method of nano composite material, comprises the following steps：
1. the preparation of gold chloride ethanol solution：
A. by 1g gold chlorides (HAuCl4·4H2O) it is dissolved in 600mL absolute ethyl alcohols (mass percent 0.21%), it is standby
With.
2. the preparation of sodium citrate ethanol colloidal sol：
B. by 40g Sodium Citrate, usp, Dihydrate Powders (Na3C6H5O7·2H2O) it is dissolved in (quality percentage in 50 DEG C of deionized waters of 20mL
It is standby after being sufficiently stirred 20min than for 66.7%).
C. 50mL absolute ethyl alcohols are prepared with beaker, is stirred vigorously with magnetic stirring apparatus, mixing speed is more than 1000rpm.
D. it is stirred vigorously under state, the sodium citrate aqueous solution that the first step has been configured, is slowly dropped into 3mL droppers anhydrous
In ethanol.10 drops (about 0.2mL) are instilled in per 50mL ethanol solutions, sodium citrate ethanol sol solution is prepared.Weight
It is multiple 4 times, obtain amounting to 200mL sodium citrate ethanol sol solutions.
E. by 200mL sodium citrate ethanol sol solutions centrifugal treating twice：
For the first time, first with centrifuge under 6000rpm rotating speeds, 8min is centrifuged.Centrifugation takes unprecipitated citric acid after terminating
Sodium ethanol sol solutionses.
Second, the sodium citrate ethanol sol solution after being centrifuged with first time is put into secondary centrifuging in centrifuge, centrifuges
Speed is 8000rpm, centrifuges 8min.Second of centrifugation terminates rear extracting waste precipitation.
F. white precipitate is dissolved in 20mL absolute ethyl alcohols again, and sonic oscillation 5min.
3.ZrO2The preparation method of alcohol suspending liquid：
G. the water zirconium nitrates of 10g five are dissolved in 30mL absolute ethyl alcohols, then by 30mL anhydrous nitric acid zirconium ethanol solutions 50
Degree is concentrated to 10mL, is heated rapidly to 100 degree of reaction generation nano zircite gels.
H. nano zircite gel obtained by step g is sintered in 550 degree of Muffle furnaces and obtains square zirconium oxide.Finally grind
Added after wearing into powder in ethanol, unprecipitated nanometer ZrO is taken after being then centrifuged for 5000 turns of purifications2Alcohol suspending liquid, it is standby.
4. gold chloride-ZrO2The preparation method of mixing suspension；
I. by nanometer ZrO obtained by step h2Suspension is added in gold chloride ethanol solution, is stirred, and obtains chlorine gold
Acid-ZrO2Mixing suspension, it is standby.
5. sodium citrate ethanol colloidal sol mixes with gold chloride, nanogold is restored：
J. sodium citrate ethanol sol solution obtained by 2mL steps f is taken, instills 2 drop (0.04mL) gold chloride-ZrO wherein2
Mixed solution.
K. mixed liquor obtained by step h is put into 30 DEG C of baking ovens, constant temperature 1h obtains gold nano grain after 5 DEG C are incubated 12h
Average-size is 40nm or so gold-ZrO2Nano composite material.Gained gold-ZrO2The transmission electron microscope photo of nano composite material
As shown in Fig. 4-Fig. 6 (transmission electron microscope photo for being followed successively by gold-ZrO2 nano composite materials under 500nm, 100nm, 10nm scale).
Embodiment 4
A kind of gold-ZrO2The preparation method of nano composite material, comprises the following steps：
1. the preparation of gold chloride ethanol solution：
A. by 1g gold chlorides (HAuCl4·4H2O) it is dissolved in 600mL absolute ethyl alcohols (mass percent 0.21%), it is standby
With.
2. the preparation of sodium citrate ethanol colloidal sol：
B. by 40g Sodium Citrate, usp, Dihydrate Powders (Na3C6H5O7·2H2O) it is dissolved in (quality percentage in 50 DEG C of deionized waters of 20mL
It is standby after being sufficiently stirred 20min than for 66.7%).
C. 50mL absolute ethyl alcohols are prepared with beaker, is stirred vigorously with magnetic stirring apparatus, mixing speed is more than 1000rpm.
D. it is stirred vigorously under state, the sodium citrate aqueous solution that the first step has been configured, is slowly dropped into 3mL droppers anhydrous
In ethanol.10 drops (about 0.2mL) are instilled in per 50mL ethanol solutions, sodium citrate ethanol sol solution is prepared.Weight
It is multiple 4 times, obtain amounting to 200mL sodium citrate ethanol sol solutions.
E. by 200mL sodium citrate ethanol sol solutions centrifugal treating twice：
For the first time, first with centrifuge under 4000rpm rotating speeds, 8min is centrifuged.Centrifugation takes unprecipitated citric acid after terminating
Sodium ethanol sol solutionses.
Second, the sodium citrate ethanol sol solution after being centrifuged with first time is put into secondary centrifuging in centrifuge, centrifuges
Speed is 6000rpm, centrifuges 8min.Second of centrifugation terminates rear extracting waste precipitation.
F. white precipitate is dissolved in 20mL absolute ethyl alcohols again, and sonic oscillation 5min.
3.ZrO2The preparation method of alcohol suspending liquid：
G. the water zirconium nitrates of 10g five are dissolved in 30mL absolute ethyl alcohols, then by 30mL anhydrous nitric acid zirconium ethanol solutions 50
Degree is concentrated to 10mL, is heated rapidly to 100 degree of reaction generation nano zircite gels.
H. nano zircite gel obtained by step g is sintered in 550 degree of Muffle furnaces and obtains square zirconium oxide.Finally grind
Added after wearing into powder in ethanol, unprecipitated nanometer ZrO is taken after being then centrifuged for 5000 turns of purifications2Alcohol suspending liquid, it is standby.
4. gold chloride-ZrO2The preparation method of mixing suspension；
I. by nanometer ZrO obtained by step h2Suspension is added in gold chloride ethanol solution, is stirred, and obtains chlorine gold
Acid-ZrO2Mixing suspension, it is standby.
5. sodium citrate ethanol colloidal sol mixes with gold chloride, nanogold is restored：
J. sodium citrate ethanol sol solution obtained by 2mL steps f is taken, instills 2 drop (0.04mL) gold chloride-ZrO wherein2
Mixed solution.
K. mixed liquor obtained by step h is put into 30 DEG C of baking ovens, constant temperature 1h obtains gold nano grain after 5 DEG C are incubated 12h
Average-size is 80nm or so gold-ZrO2Nano composite material.Gained gold-ZrO2The transmission electron microscope photo of nano combined material is such as
Fig. 7-Fig. 9 (is followed successively by gold-ZrO under 500nm, 50nm, 10nm scale2The transmission electron microscope photo of nano composite material) shown in.
Experimental example
By the gold-ZrO of the gained of 2- of embodiment of the present invention embodiments 42Nano composite material carries out 250-900nm absorptions respectively
Spectroscopic test, gained abosrption spectrogram is as shown in figure 11, and wherein Sample1, Sample2, Sample3 respectively are embodiment
2nd, embodiment 3, the gold-ZrO corresponding to embodiment 42The abosrption spectrogram of nano composite material；Figure 10 is pure ZrO2250-
900nm absorption and transmission spectrograms；
By Figure 10 and Figure 11, gold-ZrO of the present invention2Nano composite material is by by gold nano grain and ZrO2Carry out
It is compound, it is provided with and pure ZrO2Different property, Sample1, Sample2, Sample3 successively respectively 580nm, 560nm,
There is specific absworption peak, with the increase of gold nano grain particle diameter, gained gold-ZrO at 530nm2Nano composite material is specific
Absworption peak is in blue shift trend.
The preparation method of Au nano materials/Au- metal oxide nano composite materials of the present invention has that technique is simple, reaction
The advantages that mild condition；Using method of purification is centrifuged, by the sodium citrate ethanol sol particle with different-grain diameter size
Separation, the sodium citrate ethanol sol particle reduction gold chloride of particle size needed for selection are narrow, equal so as to obtain particle diameter distribution
It is even, and Au nano materials/Au- metal oxide nano composite materials of size adjustable.At low ambient temperatures, be advantageous to obtain
Particle diameter is small, and particle diameter distribution is narrow, uniform nano material.Au nano materials/Au- metal oxide nano composite materials of the present invention are fitted
In nano material of the preparation with property.
Claims (12)
1. a kind of preparation method of Au nano materials/Au- metal oxide nano composite materials, it is characterised in that utilize lemon
Sour sodium ethanol colloidal sol reduction chlorauric acid solution or the mixing suspension for reducing gold chloride and nano-metal-oxide, are prepared Au
Nano particle or Au- metal oxide nano composite materials；
Comprise the following steps：
(1) sodium citrate ethanol colloidal sol is centrifuged, controls to obtain the nanoscale sodium citrate of pre-set dimension using centrifugation rate
Ethanol colloidal sol；
(2) nanoscale sodium citrate ethanol sol solution reduction chlorauric acid solution, or reduction gold chloride and nanometer are utilized
The mixing suspension of metal oxide, Au nano materials/Au- metal oxide nano composite materials are prepared.
2. a kind of preparation method of Au nano materials/Au- metal oxide nano composite materials according to claim 1,
Characterized in that, the preparation method of the sodium citrate ethanol colloidal sol is：Sodium citrate is dissolved in water, then by resulting solution
It is added drop-wise in ethanol and is prepared under agitation.
3. a kind of preparation method of Au nano materials/Au- metal oxide nano composite materials according to claim 1,
Characterized in that, control to obtain the nanoscale sodium citrate ethanol colloidal sol of pre-set dimension using secondary centrifuging mode, for the first time from
Take unprecipitated sodium citrate ethanol colloidal sol to carry out second after the heart to centrifuge, the speed of second of centrifugation higher than for the first time from
The speed of the heart, second of centrifuged pellet is taken, using ethanol as solvent, the sodium citrate ethanol colloidal sol of pre-set dimension is made.
4. a kind of preparation method of Au nano materials/Au- metal oxide nano composite materials according to claim 1,
Characterized in that, the process of the reduction is：The mixing of gold chloride ethanol solution or gold chloride and nano-metal-oxide is hanged
Turbid is added dropwise in sodium citrate ethanol colloidal sol, after -10~10 DEG C of insulations, obtains Au nano materials or Au- metal oxides
Nano composite material.
5. a kind of preparation method of Au nano materials/Au- metal oxide nano composite materials according to claim 1,
Characterized in that, the preparation method of the mixing suspension of the gold chloride and nano-metal-oxide is：Metal nitrate is molten
In alcohol, nano-metal-oxide gel is made in heating, is calcined, adds alcohol after being ground into powder, obtained after centrifugation unprecipitated
The suspension of the alcohol of metal oxide, the suspension of the alcohol of the metal oxide is mixed with gold chloride, obtain gold chloride with
The mixing suspension of nano-metal-oxide.
6. a kind of preparation method of Au nano materials/Au- metal oxide nano composite materials according to claim 4,
Characterized in that, the temperature of the insulation is -5~5 DEG C.
7. a kind of preparation method of Au nano materials/Au- metal oxide nano composite materials according to claim 6,
Characterized in that, the temperature of the insulation is 0~5 DEG C.
8. a kind of preparation method of Au nano materials/Au- metal oxide nano composite materials according to claim 4,
Characterized in that, the time of the insulation is more than 12h.
9. a kind of preparation method of Au nano materials/Au- metal oxide nano composite materials according to claim 8,
Characterized in that, the time of the insulation is 12-24h.
10. a kind of preparation method of Au nano materials/Au- metal oxide nano composite materials according to claim 9,
Characterized in that, the time of the insulation is 12h.
11. a kind of preparation method of Au nano materials/Au- metal oxide nano composite materials according to claim 4,
Characterized in that, the ethanol is the ethanol solution that volume fraction of ethanol is not less than 80%.
A kind of 12. preparation side of Au nano materials/Au- metal oxide nano composite materials according to claim 11
Method, it is characterised in that the ethanol is absolute ethyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610090751.6A CN105728742B (en) | 2016-02-18 | 2016-02-18 | The preparation method of Au nano materials/Au metal oxide nano composite materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610090751.6A CN105728742B (en) | 2016-02-18 | 2016-02-18 | The preparation method of Au nano materials/Au metal oxide nano composite materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105728742A CN105728742A (en) | 2016-07-06 |
| CN105728742B true CN105728742B (en) | 2018-02-16 |
Family
ID=56245341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610090751.6A Expired - Fee Related CN105728742B (en) | 2016-02-18 | 2016-02-18 | The preparation method of Au nano materials/Au metal oxide nano composite materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105728742B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106735295B (en) * | 2016-12-12 | 2018-11-23 | 中南大学 | A kind of two-dimensional layer Au nanometer sheet material and preparation method thereof |
| CN108240981A (en) * | 2017-12-27 | 2018-07-03 | 中南大学 | One kind is based on AuNP/NS composite construction flexibility SERS substrates and preparation method thereof |
| CN110280778B (en) * | 2019-07-05 | 2021-12-10 | 中国计量大学 | Ag @ ZrO2Core-shell nano material and preparation method and application thereof |
| CN112808272B (en) * | 2020-12-23 | 2023-01-24 | 江苏师范大学 | Nano composite substrate with SERS activity and degradation performance and preparation method thereof |
| CN115541882B (en) * | 2022-12-02 | 2023-03-31 | 南京申基医药科技有限公司 | Preparation method and kit for improving detection test strip of human immunodeficiency virus antibody |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935421A (en) * | 2006-09-30 | 2007-03-28 | 南京大学 | Method for preparing multiple high-purity anisotropic gold nano particle |
| CN101934739A (en) * | 2010-07-01 | 2011-01-05 | 别道平 | Electric power self-supporting process of electric vehicle |
| CN101972855A (en) * | 2010-11-11 | 2011-02-16 | 肇庆市羚光电子化学品材料科技有限公司 | Method for preparing silver micro-powder for high-temperature sintering silver pastes |
| CN103056384A (en) * | 2013-01-07 | 2013-04-24 | 济南大学 | Preparation method of precious metal and magnetic nano particles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4346510B2 (en) * | 1997-07-17 | 2009-10-21 | 日本ペイント株式会社 | Colloidal solution of noble metal or copper, method for producing the same, coating composition and resin molding |
-
2016
- 2016-02-18 CN CN201610090751.6A patent/CN105728742B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935421A (en) * | 2006-09-30 | 2007-03-28 | 南京大学 | Method for preparing multiple high-purity anisotropic gold nano particle |
| CN101934739A (en) * | 2010-07-01 | 2011-01-05 | 别道平 | Electric power self-supporting process of electric vehicle |
| CN101972855A (en) * | 2010-11-11 | 2011-02-16 | 肇庆市羚光电子化学品材料科技有限公司 | Method for preparing silver micro-powder for high-temperature sintering silver pastes |
| CN103056384A (en) * | 2013-01-07 | 2013-04-24 | 济南大学 | Preparation method of precious metal and magnetic nano particles |
Non-Patent Citations (3)
| Title |
|---|
| Heterostructured ZnO/Au Nanoparticles-Based Resonant Raman Scattering for Protein Detection;Guiye Shan等;《J. Phys. Chem. B》;20091201;第113卷(第5期);第1468–1472页 * |
| TiO2复合纳米材料的制备及其在电化学酶传感器中的应用;张佳美;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20150315;B014-742 * |
| 含有金纳米粒子的复合纳米纤维的制备和表征;闫尔云等;《齐齐哈尔大学学报（自然科学版）》;20160131;第32卷(第1期);第44-46页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105728742A (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105728742B (en) | The preparation method of Au nano materials/Au metal oxide nano composite materials | |
| Zhao et al. | Nanocomposites containing gold nanorods and porphyrin-doped mesoporous silica with dual capability of two-photon imaging and photosensitization | |
| Fu et al. | Preparation of multi-functional magnetic–plasmonic nanocomposite for adsorption and detection of thiram using SERS | |
| Xu et al. | Highly photoluminescent nitrogen-doped carbon nanodots and their protective effects against oxidative stress on cells | |
| Liang et al. | Controlled synthesis of uniform silver nanospheres | |
| Ning et al. | Luminescent MOF nanosheets for enzyme assisted detection of H2O2 and glucose and activity assay of glucose oxidase | |
| CN106623967B (en) | A kind of black phosphorus-metal nanometer composite material and its synthetic method and application | |
| Beqa et al. | Gold nano-popcorn attached SWCNT hybrid nanomaterial for targeted diagnosis and photothermal therapy of human breast cancer cells | |
| Lal et al. | Silica nanobubbles containing an organic dye in a multilayered organic/inorganic heterostructure with enhanced luminescence | |
| Jiang et al. | Two-photon induced photoluminescence and singlet oxygen generation from aggregated gold nanoparticles | |
| Zhu et al. | Improve the surface-enhanced Raman scattering from rhodamine 6G adsorbed gold nanostars with vimineous branches | |
| Zhen et al. | Development of optical nanoprobes for molecular imaging of reactive oxygen and nitrogen species | |
| CN106556586B (en) | A kind of compound particle SERS active-substrate of core-shell structure and preparation method thereof | |
| CN103994991A (en) | Preparation method of surface-enhanced raman spectrum (SERS) substrate based on capillary monolithic column | |
| Xiao et al. | Advances and challenges of fluorescent nanomaterials for synthesis and biomedical applications | |
| CN103539205A (en) | Method for preparing controllable-morphology-and-size mixed-valence tungsten-based nanoparticles | |
| CN105478747B (en) | There is fusiformis golden nanometer particle of notable adjustable absorbent properties and preparation method thereof near infrared light | |
| CN104592996A (en) | Nano probe for copper ion fluorescence imaging in cells and preparation method for nano probe | |
| AU2021102201A4 (en) | Polydopamine-platinum granular nanomaterial doped with moo2 and preparation method thereof | |
| WO2022016741A1 (en) | Method for preparing size-adjustable gold nanoparticles | |
| CN105689701A (en) | Rapid preparation method of AU@Cu2O nanocomposite in yolk-shell structure | |
| CN105261932B (en) | A kind of light source based on exciton close coupling in local surface phasmon and quantum dot | |
| Zhang et al. | One-pot synthesis of gold nanostars using plant polyphenols for cancer photoacoustic imaging and photothermal therapy | |
| Zhang et al. | Ultrastable hydrophilic gold nanoclusters protected by sulfonic thiolate ligands | |
| CN109704321A (en) | A kind of nano graphene oxide and its preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180216 Termination date: 20200218 |