CN105562715A - Low-temperature water-phase preparation method for porous gold nanocrystals - Google Patents
Low-temperature water-phase preparation method for porous gold nanocrystals Download PDFInfo
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- CN105562715A CN105562715A CN201610139284.1A CN201610139284A CN105562715A CN 105562715 A CN105562715 A CN 105562715A CN 201610139284 A CN201610139284 A CN 201610139284A CN 105562715 A CN105562715 A CN 105562715A
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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 discloses a low-temperature water-phase preparation method for porous gold nanocrystals, and belongs to the technical field of synthesis methods for porous nanostructures of precious metals. The low-temperature water-phase preparation method comprises the following steps: pouring sodium citrate solution, sodium carbonate solution and deionized water into a beaker, and placing the beaker in an ice-water mixed water bath environment at 0 DEG C and stirring for 1 hour; dripping chloroauric acid, and continuing to stir for 4 hours; then settling in the ice-water mixed water bath environment at 0 DEG C for 2-72 hours, and carrying out centrifuging and sample washing at a room temperature to obtain the gold nanocrystals. The porous gold nanocrystals prepared by the preparation method disclosed by the invention are of a porous structure, large in specific surface area, high in activity, high in permeability, capable of greatly improving the various physicochemical properties thereof, and adjustable in morphology. The method disclosed by the invention is green and environment-friendly, and simple and efficient.
Description
Technical field
The invention belongs to the technical field of noble metal porous nanometer structure synthetic method, relate to the method that a kind of low temperature simple environmental protection sustainable development site of an exhibition aqueous phase prepares high-quality porous gold nanocrystals.
Background technology
For a long time, porous nanometer structure always is a heat subject of field of scientific study, because it has larger specific area, the permeability that relatively little density is become reconciled, in catalysis, sensor, drug delivery and energy conversion and storage aspect cause extensive concern.Many reports are by preparing porous noble metal nanometer material with the form of template or de-alloy before.Because the post-processed of template and de-alloy adds the complexity of building-up process and is filled with the risk introducing impurity, also certain impact can be brought to the effect after it.
Gold is typical precious metal material, in catalysis, surface Raman enhancement (SERS), thermoelectric material, photoelectric device, Fluorescence Increasing, there is potential application the aspects such as antibiotic property, and gold nano-material has excellent biocompatibility, in immune labeled, cell dyeing, DNA detection, medicine and genophore, biology sensor etc., have fine prospect.Therefore, people are seeking a kind of preparation of aqueous phase preparation method realization to gold nano-material of more effective environmental protection always.The method (Turkevich and Frens method) of well-known two kinds of typical reduction of sodium citrate gold chloride synthesis golden nanometer particles, the golden nanometer particle that high-quality particle diameter is 8-150 nanometer can not only be synthesized, and synthetic method is also fairly simple, but whole building-up process is all need to carry out heat treatment, when gold chloride could being reduced to golden nanometer particle higher than when room temperature.And other the method that at room temperature gold chloride can be reduced to golden nanometer particle also has a lot; such as can obtain with sodium borohydride reduction gold chloride the golden nanometer particle being about 4 nanometers; but have employed the strong reductant sodium borohydride of welding in building-up process; worthless under the theme of current protection of the environment; and the colloidal sol of the golden nanometer particle synthesized is unstable; be unfavorable for practical application, more can not give full play to its biocompatibility.On the other hand in order to keep the stability of aurosol, everybody usually adds some surfactants or stabilizing agent when synthesizing gold nano-material, such as CTAB, mercaptan or hydrogen phosphide, with some organic surface active agents, although can effectively improve its stability, still destroy its biocompatibility.So under room temperature even low temperature, Green Water is combined to out the gold nano-material with biocompatibility and stability and is filled with challenge.Up to now, the report preparing the gold nanocrystals of loose structure about low temperature simple environmental protection method aqueous phase does not almost have.
Summary of the invention
The technical problem to be solved in the present invention is, overcome background technology Problems existing, the green simple aqueous phase of a kind of low temperature is provided to prepare the method for porous gold, this preparation method prepares the gold nanocrystals of loose structure under can be implemented in low temperature (0 DEG C) environment, and the morphology controllable of gold nanocrystals.On the other hand green simple aqueous phase preparation method overcomes the shortcoming of template in background technology and some pernicious reducing agents to the disagreeableness weakness of environment, designs a kind of method being simply easy to the controlled synthesis porous gold nanocrystals operated.
Concrete technical scheme is as follows:
A low temperature aqueous phase preparation method for porous gold nanocrystals, has following steps:
Sodium citrate solution and sodium carbonate liquor and deionized water to be poured in beaker and be placed in 0 DEG C of frozen water mixing water bath and stir 1 hour; Instillation gold chloride, continue stirring 4 hours, whole process is all carried out in 0 DEG C of frozen water mixing water bath; Subsequently above mixed solution to be statically placed in 0 DEG C of frozen water mixing water bath precipitation 2 hours-72 hours, centrifugal under room temperature, wash sample and obtain gold nanocrystals; Wherein the mol ratio of natrium citricum and sodium carbonate is 37:0-60, and the mol ratio of natrium citricum and gold chloride is 37:34.
In the low temperature aqueous phase preparation method of a kind of porous gold nanocrystals of the present invention, described sodium citrate solution concentration is preferably 0.74mol/L; Described sodium carbonate liquor concentration is preferably 1.2mol/L; Described gold chloride concentration is preferably 0.68mol/L; The consumption of described deionized water preferably makes the concentration of natrium citricum in whole system be 40-50mmol/L.
In the low temperature aqueous phase preparation method of a kind of porous gold of the present invention, when the synthetic environment of 0 DEG C of frozen water mixing water-bath is constant, can by changing the effective control of precipitation time realization to gold nano pattern, realize by golden nanometer particle to porous gold-nano-piece finally to the transformation of sheet atresia gold nanocrystals different morphologies, can also by regulating the gold nanocrystals measuring different-shape of the sodium carbonate added.
In sum, the low temperature aqueous phase preparation method of a kind of porous of the present invention gold has following beneficial effect:
1, high-quality porous gold nano structure can be prepared.This porous gold nanocrystals is owing to having loose structure, and large, active high, the good penetrability of its specific area, can increase its various physicochemical property greatly.
2, gold nanocrystals pattern is adjustable.
3, this preparation method's environmental protection, simply efficient.Be conducive to its optics, electricity, catalysis, surface Raman enhancement, antibacterial/antibacterial etc. in application, be more conducive to some practical applications relevant to biology; Greatly reduce preparation cost, for industrial mass production preparation provides larger possibility simultaneously.
Accompanying drawing illustrates:
Fig. 1 is the stereoscan photograph of porous gold nanocrystals prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo of porous gold nanocrystals prepared by embodiment 1.
The stereoscan photograph of the porous gold nanocrystals of Fig. 3 to be the embodiment 2 precipitation time be preparation in 2 hours.
The stereoscan photograph of the porous gold nanocrystals of Fig. 4 to be the embodiment 2 precipitation time be preparation in 8 hours.
The stereoscan photograph of the porous gold nanocrystals of Fig. 5 to be the embodiment 2 precipitation time be preparation in 18 hours.
The stereoscan photograph of the porous gold nanocrystals of Fig. 6 to be the embodiment 2 precipitation time be preparation in 26 hours.
The stereoscan photograph of the porous gold nanocrystals of Fig. 7 to be the embodiment 2 precipitation time be preparation in 36 hours.
The stereoscan photograph of the porous gold nanocrystals of Fig. 8 to be the embodiment 2 precipitation time be preparation in 72 hours.
Fig. 9 is the X-ray electron diffraction pattern of the gold nanocrystals prepared by the embodiment 2 different precipitation time.
Figure 10 is the stereoscan photograph of the porous gold nanocrystals that embodiment 3 obtains when sodium carbonate liquor use amount is 0.33ml.
Figure 11 is the stereoscan photograph of the porous gold nanocrystals that embodiment 3 obtains when sodium carbonate liquor use amount is 0.25ml.
Figure 12 is the stereoscan photograph of the porous gold nanocrystals that embodiment 3 obtains when sodium carbonate liquor use amount is 0.16ml.
Figure 13 is the stereoscan photograph of the porous gold nanocrystals that embodiment 3 obtains when sodium carbonate liquor use amount is 0.08ml.
Figure 14 is the stereoscan photograph of the porous gold nanocrystals that embodiment 3 obtains when sodium carbonate liquor use amount is 0ml.
Figure 15 is the X-ray electron diffraction pattern of the gold nanocrystals that embodiment 3 obtains when using the sodium carbonate liquor of different volumes.
Detailed description of the invention
Embodiment 1:
First, the mixed solution of the natrium citricum of 0.33ml0.74mol/L and the sodium carbonate of 0.165ml1.2mol/L and 5ml deionized water are poured in beaker, is placed in 0 DEG C of frozen water mixing water bath magnetic agitation 1h;
Then, the gold chloride of instillation 0.33ml0.68mol/L, continue to stir 4h, originally first two hours solution present golden yellow always and are not any change, after two hours, solution starts by golden yellow blackening gradually, along with the prolongation of time, solution colour is deepened gradually, and whole process is all carried out in 0 DEG C of frozen water mixing water bath;
Finally, to be statically placed in 0 DEG C of frozen water mixing water bath precipitation 30 hours, centrifugal under room temperature, wash sample and obtain porous gold nanocrystals.As depicted in figs. 1 and 2, field emission scanning electron microscope photo and the transmission electron microscope photo of porous gold nanocrystals is respectively.
Embodiment 2:
First, by the natrium citricum of 0.33ml0.74mol/L and the sodium carbonate of 0.165ml1.2mol/L mix cushioning liquid and 5ml deionized water is poured in beaker, be placed in 0 DEG C of frozen water mixing water bath magnetic agitation 1h;
Then, the gold chloride of instillation 0.33ml0.68mol/L, continue to stir 4h, originally first two hours solution present golden yellow always and are not any change, after two hours, solution starts by golden yellow blackening gradually, along with the prolongation of time, solution colour is deepened gradually, and whole process is all carried out in 0 DEG C of frozen water mixing water bath;
Finally, to be statically placed in 0 DEG C of frozen water mixing water bath precipitation 72 hours, make full use of the effective control of effective dynamics Controlling realization to gold nano pattern, gold nanocrystals is realized by golden nanometer particle to porous gold nanocrystals finally to the transformation of sheet atresia gold nanocrystals different morphologies.As shown in figures 3-8, be respectively not in the same time to the field emission scanning electron microscope photo of the gold nanocrystals of the different-shape recorded after product sampling.The X-ray electron diffraction pattern of the gold nanocrystals of the different-shape that Fig. 9 obtained for the different precipitation time.
Embodiment 3:
First, the natrium citricum of 0.33ml0.74mol/L is respectively added in 5 beakers, add the sodium carbonate liquor of 0.33ml1.2mol/L, the sodium carbonate liquor of 0.25ml1.2mol/L, the sodium carbonate liquor of 0.16ml1.2mol/L, the sodium carbonate liquor of 0.08ml1.2mol/L, the sodium carbonate liquor (namely not adding sodium carbonate liquor) of 0ml1.2mol/L more respectively, respectively add 5ml deionized water respectively again, be placed in 0 DEG C of frozen water mixing water bath magnetic agitation 1h;
Then, in 5 beakers, the gold chloride of difference each instillation 0.33ml0.68mol/L, continues magnetic agitation 4 hours;
Finally, to be statically placed in 0 DEG C of frozen water mixing water bath precipitation 4 hours, centrifugal under room temperature, wash the gold nanocrystals that sample obtains different-shape.When the use amount of sodium carbonate liquor is 0.33ml, the golden nanometer particle that size is less can be formed; When the use amount of sodium carbonate liquor is 0ml and other condition is constant, sheet gold nanocrystals can be formed.As shown in figures 10-14, being respectively when the precipitation time is 4h, the field emission scanning electron microscope photo of different-shape gold nanocrystals corresponding when the use amount of sodium carbonate liquor is respectively 0.33ml, 0.25ml, 0.16ml, 0.08ml and 0ml.Figure 15 is the X-ray electron diffraction pattern of the gold nanocrystals of corresponding different-shape.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection domain that all should be included in the claims in the present invention.
Claims (2)
1. a low temperature aqueous phase preparation method for porous gold nanocrystals, is characterized in that, sodium citrate solution and sodium carbonate liquor and deionized water to be poured in beaker and is placed in frozen water mixing water bath and stir 1 hour; Instillation gold chloride, continues stirring 4 hours; Subsequently above mixed solution is statically placed in precipitation 2-72 hour in frozen water mixing water bath, centrifugal under room temperature, wash sample and obtain gold nanocrystals; Wherein the mol ratio of natrium citricum and sodium carbonate is 37:0-60, and the mol ratio of natrium citricum and gold chloride is 37:34.
2. the low temperature aqueous phase preparation method of a kind of porous gold nanocrystals according to claim 1, is characterized in that, described sodium citrate solution concentration is 0.74mol/L; Described sodium carbonate liquor concentration is 1.2mol/L; Described gold chloride concentration is 0.68mol/L; The consumption of described deionized water makes the concentration of natrium citricum in whole system be 40-50mmol/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106891018A (en) * | 2017-03-05 | 2017-06-27 | 北京化工大学 | A kind of nanoporous gold grain and preparation method thereof |
| CN110153439A (en) * | 2019-05-13 | 2019-08-23 | 鲁东大学 | The low temperature aqueous phase preparation method and its glucose electrocatalytic oxidation of icosahedron gold |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106891018A (en) * | 2017-03-05 | 2017-06-27 | 北京化工大学 | A kind of nanoporous gold grain and preparation method thereof |
| CN106891018B (en) * | 2017-03-05 | 2019-10-18 | 北京化工大学 | A kind of nanoporous gold particle and preparation method thereof |
| CN110153439A (en) * | 2019-05-13 | 2019-08-23 | 鲁东大学 | The low temperature aqueous phase preparation method and its glucose electrocatalytic oxidation of icosahedron gold |
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