CN105728742A - Preparation method for Au nanometer material/Au-metallic oxide nano-composite material - Google Patents
Preparation method for Au nanometer material/Au-metallic oxide nano-composite material Download PDFInfo
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- CN105728742A CN105728742A CN201610090751.6A CN201610090751A CN105728742A CN 105728742 A CN105728742 A CN 105728742A CN 201610090751 A CN201610090751 A CN 201610090751A CN 105728742 A CN105728742 A CN 105728742A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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Abstract
The invention provides a preparation method for an Au nanometer material/Au-metallic oxide nano-composite material. According to the preparation method, the characteristic that sodium citrate cannot be dissolved into straight alcohol easily is used, and chloroauric acid is restored by sodium citrate ethyl alcohol sol, so that the Au nanometer material/Au-metallic oxide nano-composite material which is narrower in size distribution, more even, better in dispersibility and adjustable in size is obtained. By means of the method, the defect that the sodium citrate cannot be dissolved into the alcohol easily is effectively overcome; in addition, adding of any stabilizer and any protective agent is not needed, and the beneficial effects of being simple in process, soft in reaction condition and the like are achieved; and a centrifugal separation purification method is used, sodium citrate ethyl alcohol sol particles with different particle sizes are separated, the sodium citrate ethyl alcohol sol particles with the needed particle size are selected to restore the chloroauric acid, and therefore the Au nanometer material/Au-metallic oxide nano-composite material which is narrow in size distribution, even and adjustable in size under a lower temperature environment is obtained.
Description
Technical field
The present invention relates to technical field of nano material, in particular to oneAu Nano material /Au- The preparation method of metal oxide nano composite material。
Background technology
In small-size effect based on nano material, the Raman of surface plasma body resonant vibration, enhancement effect of fluorescence and optical transport, the polarization effect etc. of light grew up in recent yearsNovelBiosensing device, it is possible to realize the quick detection to biomolecule (DNA, protein, antibody etc.) on single molecules level, there is in terms of disease identification and early prediction important application, attract wide attention.Wherein the development of biosensing device of based on surface enhanced raman spectroscopy (SERS) effect recent years is especially prominent, becomes one important direction of hypersensitivity detection field.
Generally, material raman spectral signal is the most weak.But, research shows, the noble metal nano particles such as Au, Ag is respectively provided with the strongest local surface plasma resonance effect, it is possible to effectively strengthen Raman light scattering signal intensity.And in nucleocapsid structure, the coupling between core material and Shell Materials can further enhance this SERS effect.SERS effect is applied to sensor field, it is possible to increase the sensitivity of sensor, it is achieved to microchemistry medicine, the material such as biomolecule highly sensitive, quickly detect.
Therefore research high refractive index nano metal-oxide and precious metal material is compound, and in composite construction, the potentiation to surface Raman light scattering signal that couples between core material with Shell Materials has important practical significance.
In recent years about gold nano grain, the research of Au-metal oxide composite gets more and more.As: chemical engineering institute of Xiamen University Tanaka group professor is used for the detection (Nature, 464 (2010) 392-395) [5] of veterinary antibiotics surface residual pesticide with georgia ,U.S.A Institute of Technology Wang Zhonglin professor's joint study shell isolated nano particles surface enhanced raman spectroscopy；High performance liquid chromatography is combined by Trachta etc. with surface Raman enhancement scattering method, measures different medicines and their degraded composition [6] in human blood and urine；Nithipatikom etc. [7] use and hale graceful scatterer as Raman labels, and the signal of these Raman labels is strengthened with silver sol SERS, utilize confocal Raman fibre technology to detect Angiotensin II in single cattle IC 12-lipoxygenase and epoxidase and messangial cell.
In these Au NPs preparation technologies, using reduction of sodium citrate gold chloride is a kind of method being most frequently with at present.It is simple that the method has flow process, low cost, generates the advantages such as Au granular mass is good.Owing to sodium citrate is practically insoluble in ethanol, so the mixed liquor of this method of reducing many employings aqueous solution, water and ethanol or methanol is as solvent, and when employing water is solvent with alcohol mixeding liquid, the ratio of ethanol is less than 50%.
Adopt and use water as solvent and prepare Au NPs and have that following some is not enough.1. water has stronger polarity and surface tension, and Au NPs the most easily produces reunion, therefore it is generally required to add one or more protective agents and stabilizer, and is unfavorable for preserving for a long time.2. (water has of a relatively high fusing point (0 DEG C)), therefore reaction it is generally required to hot conditions.Particularly, use water to make solvent, be not suitable for environment below 0 degree Celsius and prepare gold nano-material and gold-metal oxide composite.3. although the Au NPs that particle diameter is the least can be generated, but particle diameter distribution is relatively wide, the more difficult control of size.
Comparatively speaking, ethanol has relatively low surface tension and polarity, is a kind of conventional and excellent organic dispersing agent, is widely used in storing nano-particle, separate and purifying.Ethanol is relative to water simultaneously, has lower fusing point (-114 DEG C).If using ethanol to prepare nanometer Au granule as solvent, can effectively prevent the reunion of nano-particle, improving its dispersibility and activity, be expected to reduce add protective agent and stabilizer simultaneously, and be prepared by applicable low temperature environment.
But due to sodium citrate easy ethanol hardly, so conventional Au NPs preparation method, ethanol, usually used as additive, is used for improving surface tension and the polarity of aqueous solution, and adding proportion is less than 50%.Having been reported that and even point out, in reduction of sodium citrate method prepares Au NPs, ethanol generation to Au NPs in itself is harmful.Therefore in straight alcohol solution, one of reduction of sodium citrate gold chloride key preparing Au NPs is used, it is simply that solve sodium citrate problems of dissolution in ethanol solution.
In view of this, the special proposition present invention.
Summary of the invention
The first object of the present invention is to provide oneAu Nano material /Au- The preparation method of metal oxide nano composite material, describedAu Nano material /Au- The preparation method of metal oxide nano composite materialThere is the advantages such as technique is simple, reaction condition is gentle；The present invention uses reduction of sodium citrate gold chloride method, it is possible to prepare narrow diameter distribution, uniform, the Au nano material/Au-metal oxide nano composite material of size adjustable in ethanol.
In order to realize the above-mentioned purpose of the present invention, spy by the following technical solutions:
A kind ofAu Nano material /Au- The preparation method of metal oxide nano composite material, utilize sodium citrate ethanol colloidal sol reduction chlorauric acid solution or reduction gold chloride and the mixing suspension of nano-metal-oxide, prepare Au nano-particle or Au-metal oxide nano composite material.
When prior art uses reduction of sodium citrate gold chloride, aqueous solution or the water mixed liquor with ethanol or methanol should be used as solvent, and when to use water and alcohol mixeding liquid be solvent, the ratio of ethanol is less than 50%.And instant invention overcomes the shortcoming that sodium citrate is insoluble in ethanol, sodium citrate is utilized to be insoluble in the feature of straight alcohol, utilize sodium citrate ethanol colloidal sol reduction gold chloride, thus it is narrower, evenly to obtain particle diameter distribution, and the Au nano material/Au-metal oxide nano composite material of size adjustable, whole course of reaction, sodium citrate serves as reducing agent, gold chloride is Jin Yuan, and straight alcohol is dispersant.The present invention uses ethanol to be that reaction dissolvent is beneficial to Au granule being combined at metal oxide surface, because ethanol polarity is little, more have affinity with nanoparticle, the inventive method is also beneficial to the compound of Au and metal-oxide, forms Au-metal oxide nano composite material.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 is the lowest, are more suitable for low-temperature insulation operation.In addition; prior art use sodium citrate aqueous solution need to add a large amount of stabilizer and protective agent during preparing Au nano material/Au-metal oxide nano composite material; and the inventive method need not add any stabilizer and protective agent; cost can be substantially reduced and ensure the purity of gained Au nano material/Au-metal oxide nano composite material, it is also possible to saving follow-up removal stabilizer and protective agent?Some cumbersome procedure.
Preferably, the present inventionAu Nano material /Au- The preparation method of metal oxide nano composite materialIn, the volume gross score of water used is not more than 10%, and preferably less than 0.1%, close to water-less environment.
Above-mentioned oneAu Nano material /Au- The preparation method of metal oxide nano composite material, comprise the steps:
(1) centrifugation sodium citrate ethanol colloidal sol, utilizes centrifugation rate to control to obtain the nanoscale sodium citrate ethanol colloidal sol of pre-set dimension；
(2) utilize described nanoscale sodium citrate ethanol sol solution to reduce chlorauric acid solution, or the mixing suspension of reduction gold chloride and nano-metal-oxide, prepare Au nano material/Au-metal oxide nano composite material.
Utilize centrifugation method of purification; the sodium citrate ethanol sol particle with different-grain diameter size is separated; select the sodium citrate ethanol sol particle reduction gold chloride of required size; thus obtain narrow diameter distribution, uniformly, and the Au nano material/Au-metal oxide nano composite material of size adjustable.
Preferably, the preparation method of described sodium citrate ethanol colloidal sol is: is dissolved in water by sodium citrate, is more under agitation added drop-wise to prepare in ethanol by gained solution.
Sodium citrate is insoluble in ethanol, directly sodium citrate dispersion may be had any problem in ethanol, now can in advance sodium citrate be dissolved in a small amount of water (water yield is unsuitable too much, it is preferably close to saturated solution), again by gained sodium citrate solution agitation and dropping to excess ethyl alcohol, so it is more conducive to be uniformly dispersed in ethanol, obtains sodium citrate ethanol colloidal sol.
Preferably, described ethanol is the ethanol solution that volume fraction of ethanol is not less than 80%, preferably dehydrated alcohol.
Preferably, described ethanol solution is the mixed solution of ethanol water or ethanol and organic solvent.
Preferably, by controlling centrifugal rotational speed, the sodium citrate ethanol colloidal sol that sodium citrate nano particle diameter is required size is obtained.
Utilize centrifugation method of purification; by controlling centrifugal rotational speed; the sodium citrate ethanol sol particle with different-grain diameter size is separated; select the sodium citrate ethanol sol particle reduction gold chloride of required size; thus obtain narrow diameter distribution, uniformly, and the Au nano material/Au-metal oxide nano composite material of size adjustable.
Further preferably, secondary centrifuging mode is used to control to obtain the nanoscale sodium citrate ethanol colloidal sol of pre-set dimension, take unprecipitated sodium citrate ethanol colloidal sol after the most centrifugal and carry out the most centrifugal, the speed that described second time is centrifuged is higher than the most centrifugal speed, take second time centrifuged pellet, with ethanol as solvent, make the sodium citrate ethanol colloidal sol of pre-set dimension.
According to required size, select specific secondary centrifuging mode, be conducive to obtaining that particle diameter distribution is narrower, evenly Au nano material/Au-metal oxide nano composite material.
Preferably, the process of described reduction is: be added dropwise in sodium citrate ethanol colloidal sol by the mixing suspension of gold chloride ethanol solution or gold chloride and nano-metal-oxide, after being incubated at-10～10 DEG C, obtain Au nano material or Au-metal oxide nano composite material.
Gold chloride ethanol solution or gold chloride are added dropwise in excessive sodium citrate ethanol colloidal sol with the mixing suspension of nano-metal-oxide, the Au nano material that particle diameter is little is conducive to separate out, after low temperature environment is incubated, be conducive to obtaining particle diameter little, narrow diameter distribution, uniform Au nano material or Au-metal oxide nano composite material.
Preferably, gold chloride is dissolved in ethanol, obtains gold chloride ethanol solution standby；Metallic oxide nano powder is disperseed in ethanol, after being centrifuged, takes unprecipitated nano-metal-oxide suspension, add in gold chloride ethanol solution and be sufficiently mixed, obtain the mixing suspension of gold chloride and nano-metal-oxide.
Being dissolved in ethanol by gold chloride, metallic oxide nano powder is also dispersed within ethanol, can fully dissolve each other, be uniformly dispersed during the two mixing.
Described metal-oxide powder plays Au nanoparticle vector effect, and the two can be combined, preferably can the metal-oxide of stable dispersion in ethanol, commercially available nanosize metal oxide powder body can be used, or prepare nanosize metal oxide powder body voluntarily.
Preferably, described gold chloride with the preparation method of the mixing suspension of nano-metal-oxide is: be dissolved in alcohol by metal nitrate, nano-metal-oxide gel is made in heating, roasting, alcohol is added after grinding to form powder body, obtain the suspension of the alcohol of unprecipitated metal-oxide after Li Xin, the suspension of the alcohol of described metal-oxide is mixed with gold chloride, obtain the mixing suspension of gold chloride and nano-metal-oxide.
Preferably, the temperature of described insulation is-5～5 DEG C, more preferably 0～5 DEG C.
Preferably, the time of described insulation is more than 12h, preferably 12-24h, more preferably 12h.
Low temperature contributes to the precipitation of Au nano material/Au-metal oxide nano composite material, and is prevented from its reunion, is conducive to obtaining particle diameter little, narrow diameter distribution, uniform Au nano material/Au-metal oxide nano composite material.
Au nano material/Au-metal oxide nano composite material can be obtained by drying after insulation.
Preferably, described drying temperature is 20-40 DEG C, preferably 25-35 DEG C, more preferably 30 DEG C.
The present invention uses ethanol to be solvent, it is not required to use excessive temperature to dry, under normal temperature condition, ethanol just can quickly volatilize, employing lower temperature is dried, it also is able to prevent obtained Au nano material/Au-metal oxide nano composite material from reuniting, is conducive to obtaining particle diameter little, narrow diameter distribution, uniform Au nano material/Au-metal oxide nano composite material.
Compared with prior art, the invention have the benefit that
When prior art uses reduction of sodium citrate gold chloride, aqueous solution or the water mixed liquor with ethanol or methanol should be used as solvent, and when to use water and alcohol mixeding liquid be solvent, the ratio of ethanol is less than 50%.And instant invention overcomes the shortcoming that sodium citrate is insoluble in ethanol, sodium citrate is utilized to be insoluble in the feature of straight alcohol on the contrary, sodium citrate preparation is become sodium citrate ethanol colloidal sol, recycle this colloidal sol reduction gold chloride, thus it is narrower, evenly to obtain particle diameter distribution, and the Au nano material/Au-metal oxide nano composite material of size adjustable.Whole course of reaction, sodium citrate ethanol colloidal sol serves as reducing agent, and gold chloride is Jin Yuan, and straight alcohol is dispersant.The present invention uses ethanol to be that reaction dissolvent is beneficial to Au granule being combined at metal oxide surface, because ethanol polarity is little, more have affinity with nanoparticle, the inventive method is also beneficial to the compound of Au and metal-oxide, forms Au-metal oxide nano composite material.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 is the lowest, are more suitable for low-temperature insulation operation.In addition; prior art use sodium citrate aqueous solution need to add a large amount of stabilizer and protective agent during preparing Au nano material/Au-metal oxide nano composite material; and the inventive method need not add any stabilizer and protective agent; cost can be substantially reduced and ensure the purity of gained Au nano material/Au-metal oxide nano composite material, it is also possible to saving follow-up removal stabilizer and protective agent?Some cumbersome procedure.
The present inventionAu Nano material /Au- The preparation method of metal oxide nano composite materialThere is the advantages such as technique is simple, reaction condition is gentle；Utilize centrifugation method of purification; the sodium citrate ethanol sol particle with different-grain diameter size is separated; select the sodium citrate ethanol sol particle reduction gold chloride of required size; thus obtain narrow diameter distribution, uniformly, and the Au nano material/Au-metal oxide nano composite material of size adjustable.At low ambient temperatures, be conducive to obtaining particle diameter little, narrow diameter distribution, uniform nano material.
Accompanying drawing explanation
In order to be illustrated more clearly that the specific embodiment of the invention or technical scheme of the prior art, below by use required in detailed description of the invention or description of the prior artAccompanying drawingIt is briefly described, it should be apparent that, in describing belowAccompanying drawingIt is some embodiments of the present invention, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to theseAccompanying drawingObtain otherAccompanying drawing。
Figure 1-Figure 3It is respectively the embodiment of the present invention 2 gained gold-ZrO2Transmission electron microscope photo under the different scale of nano composite material；
Figure 4-Figure 6It is respectively the embodiment of the present invention 3 gained gold-ZrO2Transmission electron microscope photo under the different scale of nano composite material；
Figure 7-Figure 9It is respectively the embodiment of the present invention 4 gained gold-ZrO2Transmission electron microscope photo under the different scale of nano composite material；
Figure 10For pure ZrO2Transmission and absorption spectrumFigure；
Figure 11For embodiment of the present invention 2-embodiment 4 gained gold-ZrO2The transmission of nano composite material and absorption spectrumFigure。
Detailed description of the invention
Below in conjunction withAccompanying drawingWith detailed description of the invention, technical scheme is clearly and completely described, but it will be understood to those of skill in the art that, following described embodiment is a part of embodiment of the present invention, rather than whole embodiments, it is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, broadly fall into the scope of protection of the invention.Unreceipted actual conditions person in embodiment, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or instrument unreceipted production firm person, being can be by the commercially available conventional products bought and obtain.
In describing the invention, it should be noted that term the orientation of the instruction such as " " center ", " on ", D score, "left", "right", " vertically ", " level ", " interior ", " outward " or position relationship be based onAccompanying drawing instituteThe orientation shown or position relationship, be for only for ease of describe the present invention and simplify describe rather than instruction or hint indication device or element must have specific orientation, with specific azimuth configuration and operation, be therefore not considered as limiting the invention.Additionally, term " first ", " second ", " the 3rd " are only used for describing purpose, and it is not intended that instruction or hint relative importance.
In describing the invention, it should be noted that unless otherwise clearly defined and limited, term " is installed ", " being connected ", " connection " should be interpreted broadly, and connects for example, it may be fixing, it is also possible to be to removably connect, or be integrally connected；Can be to be mechanically connected, it is also possible to be electrical connection；Can be to be joined directly together, it is also possible to be indirectly connected to by intermediary, can be the connection of two element internals.For the ordinary skill in the art, above-mentioned term concrete meaning in the present invention can be understood with concrete condition.
Embodiment 1
The preparation method of a kind of Au nano material, comprises the steps:
1. the preparation of gold chloride ethanol solution:
A. by 1g gold chloride (HAuCl4·4H2O) it is dissolved in 600mL dehydrated alcohol (mass percent is 0.21%), standby.
2. the preparation of sodium citrate ethanol colloidal sol:
B. by 40g Sodium Citrate, usp, Dihydrate Powder (Na3C6H5O7·2H2O) it is dissolved in (mass percent is 66.7%) in 50 DEG C of deionized waters of 20mL, after being sufficiently stirred for 20min, standby.
C. preparing 50mL dehydrated alcohol with beaker, be 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 is configured, is slowly dropped in dehydrated alcohol with 3mL dropper.Every 50mL ethanol solution instills 10 (about 0.2mL), prepares sodium citrate ethanol sol solution.It is repeated 4 times, obtains amounting to 200mL sodium citrate ethanol sol solution.
E. by 200mL sodium citrate ethanol sol solution centrifugal treating, centrifugal rotational speed controls to be 8000rpm, and centrifugation time is 8min.
F., after centrifugal end, filter, extract milky unprecipitated sodium citrate ethanol colloidal sol (sodium citrate ethanol sol particle size is effectively controlled by rotating speed).
G. concentrate, in vacuum drying oven, at 50 DEG C, 200mL sodium citrate ethanol sol solution is concentrated into 20mL, standby.
2. sodium citrate ethanol colloidal sol mixes with gold chloride, restores nanometer gold
H. take the sodium citrate ethanol sol solution after 2mL step g concentrates, instill 2 (mass percent that 0.04mL above prepares is 0.21% chlorauric acid solution) wherein.
I. step h gained mixed liquor is after 5 DEG C of insulation 12h, puts in 30 DEG C of baking ovens, and constant temperature 1h obtains the gold nano grain material that mean diameter is 2nm.
Embodiment 2
A kind of gold-ZrO2The preparation method of nano composite material, comprises the steps:
1. the preparation of gold chloride ethanol solution:
A. by 1g gold chloride (HAuCl4·4H2O) it is dissolved in 600mL dehydrated alcohol (mass percent is 0.21%), standby.
2. the preparation of sodium citrate ethanol colloidal sol:
B. by 40g Sodium Citrate, usp, Dihydrate Powder (Na3C6H5O7·2H2O) it is dissolved in (mass percent is 66.7%) in 50 DEG C of deionized waters of 20mL, after being sufficiently stirred for 20min, standby.
C. preparing 50mL dehydrated alcohol with beaker, be 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 is configured, is slowly dropped in dehydrated alcohol with 3mL dropper.Every 50mL ethanol solution instills 10 (about 0.2mL), prepares sodium citrate ethanol sol solution.It is repeated 4 times, obtains amounting to 200mL sodium citrate ethanol sol solution.
E. by 200mL sodium citrate ethanol sol solution centrifugal treating, centrifugal rotational speed controls to be 8000rpm, and centrifugation time is 8min.
F., after centrifugal end, filter, extract milky unprecipitated sodium citrate ethanol colloidal sol (sodium citrate ethanol sol particle size is effectively controlled by rotating speed).
G. concentrate, in vacuum drying oven, at 50 DEG C, 200mL sodium citrate ethanol sol solution is concentrated into 20mL, standby.
3.ZrO2The preparation method of alcohol suspending liquid:
H. 10g five water zirconium nitrate is dissolved in 30mL dehydrated alcohol, then 30mL anhydrous nitric acid zirconium ethanol solution is concentrated to 10mL at 50 degree, be heated rapidly to 100 degree of reactions and generate nano zircite gel.
I. step g gained nano zircite gel is sintered in 550 degree of Muffle furnaces and obtain square zirconium oxide.Add in ethanol after finally grinding to form powder body, after being then centrifuged for 5000 turns of purifications, take unprecipitated nanometer ZrO2Alcohol suspending liquid, standby.
4. gold chloride-ZrO2The preparation method of mixing suspension；
J. by step h gained nanometer ZrO2Suspension joins in gold chloride ethanol solution, stirs, and obtains gold chloride-ZrO2Mixing suspension, standby.
5. sodium citrate ethanol colloidal sol mixes with gold chloride, restores nanometer gold:
K. take 2mL step g gained sodium citrate ethanol sol solution, instill 2 (0.04mL) gold chloride-ZrO wherein2Mixed solution.
L. step h gained mixed liquor is after 5 DEG C of insulation 12h, puts in 30 DEG C of baking ovens, and constant temperature 1h obtains the gold-ZrO that gold nano grain mean diameter is 2nm2Nano 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 steps:
1. the preparation of gold chloride ethanol solution:
A. by 1g gold chloride (HAuCl4·4H2O) it is dissolved in 600mL dehydrated alcohol (mass percent is 0.21%), standby.
2. the preparation of sodium citrate ethanol colloidal sol:
B. by 40g Sodium Citrate, usp, Dihydrate Powder (Na3C6H5O7·2H2O) it is dissolved in (mass percent is 66.7%) in 50 DEG C of deionized waters of 20mL, after being sufficiently stirred for 20min, standby.
C. preparing 50mL dehydrated alcohol with beaker, be 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 is configured, is slowly dropped in dehydrated alcohol with 3mL dropper.Every 50mL ethanol solution instills 10 (about 0.2mL), prepares sodium citrate ethanol sol solution.It is repeated 4 times, obtains amounting to 200mL sodium citrate ethanol sol solution.
E. by 200mL sodium citrate ethanol sol solution centrifugal treating twice:
For the first time, first with centrifuge under 6000rpm rotating speed, centrifugal 8min.Unprecipitated sodium citrate ethanol sol solutions is taken after centrifugal end.
For the second time, putting into secondary centrifuging in centrifuge with the sodium citrate ethanol sol solution after the most centrifugal, centrifugal speed is 8000rpm, centrifugal 8min.Extracting waste precipitation after the centrifugal end of second time.
F. white precipitate is dissolved in 20mL dehydrated alcohol again, and sonic oscillation 5min.
3.ZrO2The preparation method of alcohol suspending liquid:
G. 10g five water zirconium nitrate is dissolved in 30mL dehydrated alcohol, then 30mL anhydrous nitric acid zirconium ethanol solution is concentrated to 10mL at 50 degree, be heated rapidly to 100 degree of reactions and generate nano zircite gel.
H. step g gained nano zircite gel is sintered in 550 degree of Muffle furnaces and obtain square zirconium oxide.Add in ethanol after finally grinding to form powder body, after being then centrifuged for 5000 turns of purifications, take unprecipitated nanometer ZrO2Alcohol suspending liquid, standby.
4. gold chloride-ZrO2The preparation method of mixing suspension；
I. by step h gained nanometer ZrO2Suspension joins in gold chloride ethanol solution, stirs, and obtains gold chloride-ZrO2Mixing suspension, standby.
5. sodium citrate ethanol colloidal sol mixes with gold chloride, restores nanometer gold:
J. take 2mL step f gained sodium citrate ethanol sol solution, instill 2 (0.04mL) gold chloride-ZrO wherein2Mixed solution.
K. step h gained mixed liquor is after 5 DEG C of insulation 12h, puts in 30 DEG C of baking ovens, and constant temperature 1h obtains the gold-ZrO that gold nano grain average-size is about 40nm2Nano composite material.Gained gold-ZrO2Shown in the transmission electron microscope photo of nano composite material such as Fig. 4-Fig. 6 (being followed successively by the transmission electron microscope photo of gold-ZrO2 nano composite material under 500nm, 100nm, 10nm scale).
Embodiment 4
A kind of gold-ZrO2The preparation method of nano composite material, comprises the steps:
1. the preparation of gold chloride ethanol solution:
A. by 1g gold chloride (HAuCl4·4H2O) it is dissolved in 600mL dehydrated alcohol (mass percent is 0.21%), standby.
2. the preparation of sodium citrate ethanol colloidal sol:
B. by 40g Sodium Citrate, usp, Dihydrate Powder (Na3C6H5O7·2H2O) it is dissolved in (mass percent is 66.7%) in 50 DEG C of deionized waters of 20mL, after being sufficiently stirred for 20min, standby.
C. preparing 50mL dehydrated alcohol with beaker, be 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 is configured, is slowly dropped in dehydrated alcohol with 3mL dropper.Every 50mL ethanol solution instills 10 (about 0.2mL), prepares sodium citrate ethanol sol solution.It is repeated 4 times, obtains amounting to 200mL sodium citrate ethanol sol solution.
E. by 200mL sodium citrate ethanol sol solution centrifugal treating twice:
For the first time, first with centrifuge under 4000rpm rotating speed, centrifugal 8min.Unprecipitated sodium citrate ethanol sol solutions is taken after centrifugal end.
For the second time, putting into secondary centrifuging in centrifuge with the sodium citrate ethanol sol solution after the most centrifugal, centrifugal speed is 6000rpm, centrifugal 8min.Extracting waste precipitation after the centrifugal end of second time.
F. white precipitate is dissolved in 20mL dehydrated alcohol again, and sonic oscillation 5min.
3.ZrO2The preparation method of alcohol suspending liquid:
G. 10g five water zirconium nitrate is dissolved in 30mL dehydrated alcohol, then 30mL anhydrous nitric acid zirconium ethanol solution is concentrated to 10mL at 50 degree, be heated rapidly to 100 degree of reactions and generate nano zircite gel.
H. step g gained nano zircite gel is sintered in 550 degree of Muffle furnaces and obtain square zirconium oxide.Add in ethanol after finally grinding to form powder body, after being then centrifuged for 5000 turns of purifications, take unprecipitated nanometer ZrO2Alcohol suspending liquid, standby.
4. gold chloride-ZrO2The preparation method of mixing suspension；
I. by step h gained nanometer ZrO2Suspension joins in gold chloride ethanol solution, stirs, and obtains gold chloride-ZrO2Mixing suspension, standby.
5. sodium citrate ethanol colloidal sol mixes with gold chloride, restores nanometer gold:
J. take 2mL step f gained sodium citrate ethanol sol solution, instill 2 (0.04mL) gold chloride-ZrO wherein2Mixed solution.
K. step h gained mixed liquor is after 5 DEG C of insulation 12h, puts in 30 DEG C of baking ovens, and constant temperature 1h obtains the gold-ZrO that gold nano grain average-size is about 80nm2Nano composite material.Gained gold-ZrO2The transmission electron microscope photo of nano combined material 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
Gold-ZrO by embodiment of the present invention 2-embodiment 4 gained2Nano composite material carries out 250-900nm absorption spectrum test respectively, and as shown in figure 11, wherein Sample1, Sample2, Sample3 respectively are the gold-ZrO corresponding to embodiment 2, embodiment 3, embodiment 4 to gained abosrption spectrogram2The abosrption spectrogram of nano composite material；Figure 10 is pure ZrO2250-900nm absorb and transmitted spectrum figure；
By Figure 10 and Figure 11, gold-ZrO of the present invention2Nano composite material is by by gold nano grain and ZrO2It is combined, is provided with and pure ZrO2Different character, Sample1, Sample2, Sample3 have specific absworption peak the most respectively at 580nm, 560nm, 530nm, along with the increase of gold nano grain particle diameter, gained gold-ZrO2Nano composite material specific absorption peak is blue shift trend.
The present inventionAu Nano material /Au- The preparation method of metal oxide nano composite materialThere is the advantages such as technique is simple, reaction condition is gentle；Utilize centrifugation method of purification; the sodium citrate ethanol sol particle with different-grain diameter size is separated; select the sodium citrate ethanol sol particle reduction gold chloride of required size; thus obtain narrow diameter distribution, uniformly, and the Au nano material/Au-metal oxide nano composite material of size adjustable.At low ambient temperatures, be conducive to obtaining particle diameter little, narrow diameter distribution, uniform nano material.Au nano material/Au-metal oxide nano composite material of the present invention is suitable to prepare the nano material with property.
Although illustrate and describing the present invention with specific embodiment, however it will be appreciated that may be made that without departing from the spirit and scope of the present invention many other change and amendment.It is, therefore, intended that include all such changes and modifications belonging in the scope of the invention in the following claims.
Claims (10)
1. the preparation side of Au nano material/Au-metal oxide nano composite material
Method, it is characterised in that utilize sodium citrate ethanol colloidal sol reduction chlorauric acid solution or reduction chlorine
Auric acid and the mixing suspension of nano-metal-oxide, prepare Au nano-particle or Au-
Metal oxide nano composite material.
A kind of Au nano material/Au-metal-oxide the most according to claim 1 is received
The preparation method of nano composite material, it is characterised in that comprise the steps:
(1) centrifugation sodium citrate ethanol colloidal sol, utilizes centrifugation rate to control to be preset
The nanoscale sodium citrate ethanol colloidal sol of size；
(2) described nanoscale sodium citrate ethanol sol solution reduction chlorauric acid solution is utilized,
Or reduction gold chloride and the mixing suspension of nano-metal-oxide, prepare Au and receive
Rice material/Au-metal oxide nano composite material.
A kind of Au nano material/Au-metal-oxide the most according to claim 2 is received
The preparation method of nano composite material, it is characterised in that the system of described sodium citrate ethanol colloidal sol
Preparation Method is: be dissolved in water by sodium citrate, is more under agitation added drop-wise to by gained solution
Ethanol prepares.
A kind of Au nano material/Au-metal-oxide the most according to claim 2 is received
The preparation method of nano composite material, it is characterised in that use secondary centrifuging mode to control to obtain
The nanoscale sodium citrate ethanol colloidal sol of pre-set dimension, takes unprecipitated lemon after being centrifuged for the first time
It is centrifugal that lemon acid sodium ethanol colloidal sol carries out second time, and the speed that described second time is centrifuged is higher than first
Secondary centrifugal speed, takes second time centrifuged pellet, with ethanol as solvent, makes pre-
If the sodium citrate ethanol colloidal sol of size.
A kind of Au nano material/Au-metal-oxide the most according to claim 2 is received
The preparation method of nano composite material, it is characterised in that the process of described reduction is: by chlorine gold
The mixing suspension of acid ethanol solution or gold chloride and nano-metal-oxide is added dropwise to citric acid
In sodium ethanol colloidal sol, after being incubated at-10～10 DEG C, obtain Au nano material or Au-metal oxygen
Compound nano composite material.
A kind of Au nano material/Au-metal-oxide the most according to claim 2 is received
The preparation method of nano composite material, it is characterised in that described gold chloride and nano metal oxide
The preparation method of the mixing suspension of thing is: being dissolved in alcohol by metal nitrate, heating is made
Nano-metal-oxide gel, roasting, add alcohol after grinding to form powder body, obtain not after being centrifuged
The suspension of the alcohol of the metal-oxide of precipitation, by the suspension of the alcohol of described metal-oxide
Mix with gold chloride, obtain the mixing suspension of gold chloride and nano-metal-oxide.
A kind of Au nano material/Au-metal-oxide the most according to claim 5 is received
The preparation method of nano composite material, it is characterised in that the temperature of described insulation is-5～5 DEG C.
A kind of Au nano material/Au-metal-oxide the most according to claim 7 is received
The preparation method of nano composite material, it is characterised in that the temperature of described insulation is 0～5 DEG C.
A kind of Au nano material/Au-metal-oxide the most according to claim 5 is received
The preparation method of nano composite material, it is characterised in that the time of described insulation is more than 12h,
It is preferably 12-24h, more preferably 12h.
A kind of Au nano material/Au-metal-oxide the most according to claim 5 is received
The preparation method of nano composite material, it is characterised in that described ethanol be volume fraction of ethanol not
Ethanol solution less than 80%, preferably dehydrated alcohol.
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