CN114160802A - Preparation method for obtaining hollow pot-shaped structure of gold nanoparticles by one-step method - Google Patents
Preparation method for obtaining hollow pot-shaped structure of gold nanoparticles by one-step method Download PDFInfo
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- 229910052737 gold Inorganic materials 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 17
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 24
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 19
- 239000012498 ultrapure water Substances 0.000 claims abstract description 19
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 14
- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims abstract description 10
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005530 etching Methods 0.000 claims abstract description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
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- 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
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- 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 preparation method for obtaining a hollow pot-shaped structure of gold nanoparticles by a one-step method, which comprises the following steps: the first step is as follows: TiO22Preparing template balls, adding ultrapure water and dodecylamine into an ethanol/acetonitrile mixed solution, stirring for 5-15min, adding titanium isopropoxide, continuously stirring for 3-6h, centrifuging, washing, and freeze-drying to obtain TiO2A template ball; the second step is that: preparing a gold nano hollow tank, namely preparing the TiO obtained in the first step2Mixing the template ball with ultrapure water, methanol and ethanol, stirring for 10-30min, adding chloroauric acid solution and bis (chloroauric (I)) bis (diphenylphosphino) methane (C)25H22Au2Cl2P2) Stirring for 10-30min, and collectingThe gold nano hollow tank is prepared by coating a gold layer by photocatalytic deposition and a titanium dioxide nuclear etching method. Reducing chloroauric acid to a gold nanoparticle shell layer on the surface of the titanium dioxide nanosphere by a simple in-situ light deposition method. Meanwhile, the titanium dioxide nanospheres are continuously and slowly etched by utilizing hydrochloric acid byproducts generated in the reaction, the preparation method is simple, the conditions are easy to control, and the mass production can be realized.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a preparation method for obtaining a hollow pot-shaped structure of gold nanoparticles by a one-step method.
Background
The gold nanoparticles are a nano material which is earlier researched, and have wide application prospects in the fields of medicines, biosensors, photochemical and electrochemical catalysis, optoelectronic devices and the like. The gold nanoparticles have good chemical stability and good surface modifiability, can enhance the activity of a plurality of antibiotics through a multivalent effect, have no toxicity to human cells, and are good antibiotic drug carriers. And the gold can convert light energy into heat energy, and antibacterial agents can be developed according to different properties of the gold nano materials, so that a new choice is provided for the development of novel low-toxicity and high-efficiency antibacterial materials. In biological research, the gold nanoparticles have very high electron density and very good contrast under an electron microscope, so the gold nanoparticles are very suitable to be used as a marker for electron microscope tests. In addition, the photocatalyst material is loaded with gold, so that the sunlight capturing capability of the photocatalyst can be effectively improved, the transmission and separation efficiency of photoproduction electrons and holes is enhanced, and the reaction rate of reaction substrates on the surface of the photocatalyst is increased, thereby greatly improving the activity of the photocatalytic reaction. However, gold is a noble metal, the content of earth crust is limited, and how to reduce the cost by the nano-shell structure is one of the hot spots of current research. On the other hand, the nanoshell structure may generally exhibit superior properties compared to solid nanomaterials and thus have broader application value. The hollow structure can be used as an inner space, and more possibilities are provided for the superposition, storage, transportation and the like of the magnetic, optical, mechanical, thermal, electrical and catalytic functions of the material.
At present, the method for removing the hard template is one of the simplest and most effective methods for preparing the hollow core-shell material, and is widely applied due to the characteristics of simple method, high repetition rate, good predictability, uniform product form, stable performance and the like. The hard template method generally uses carbon spheres, silicon spheres or PS spheres as templates, a shell structure is coated on the carbon spheres, silicon spheres or PS spheres, and then a core is removed by a certain means, so that a hollow structure is obtained. For example, a patent with application number CN201310121097.7 in the prior art discloses a preparation method of hollow metal microspheres, and relates to a composite material. Provides a preparation method of the hollow metal microsphere with rapidness, environmental protection and simple subsequent treatment process. Preparing gold nanoparticles and titanium dioxide in sequence, functionalizing the surface of the titanium dioxide, preparing Au/TiO2, and finally preparing the hollow metal microspheres. The PtM metal hollow microspheres with controllable sizes are prepared by taking titanium dioxide microspheres as templates and utilizing the pH sensitivity of titanium dioxide. The size of the PtM hollow microspheres can be controlled by adjusting the size of the template titanium dioxide, and the thickness of the PtM hollow microspheres can be changed by changing the concentration of the metal precursor. Titanium dioxide is used as a template to synthesize multi-level PtM hollow microspheres, and the preparation method for preparing the hollow microspheres is widened. However, such methods generally require a large number of steps and are not suitable for mass production.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method for obtaining a gold nano hollow tank-shaped structure by a one-step method, so as to solve the problems that the steps for preparing the gold nano hollow tank-shaped structure are more and large-scale production is not facilitated in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method for obtaining a gold nano hollow tank-shaped structure by a one-step method comprises the following steps:
(1)TiO2preparing template balls, adding ultrapure water and dodecylamine into an ethanol/acetonitrile mixed solution, stirring, adding titanium isopropoxide, continuously stirring, centrifugally washing, and freeze-drying to obtain TiO2A template ball;
(2) preparing hollow gold nano-tank by mixing TiO with water2Template ball and ultrapure waterMixing and stirring methanol and ethanol, adding chloroauric acid solution and bis (chloroauric (I)) bis (diphenylphosphino) methane, stirring, coating a gold layer by photocatalytic deposition after stirring, and preparing a gold nano hollow tank by a titanium dioxide nuclear etching method.
Furthermore, the addition amount of the dodecylamine in the step (1) is 0.5-3 parts by weight, and the addition amount of ultrapure water is 0.15-4.5 parts by weight.
Further, the adding amount of the ethanol/acetonitrile mixed solution in the step (1) is 250 parts by weight, and the volume ratio of ethanol/acetonitrile is 3: 1.
Further, in the step (2), in the preparation process of the gold nano hollow tank, a chloroauric acid solution and bis (chloroauric (I)) bis (diphenylphosphino) methane (C) are added25H22Au2Cl2P2) After stirring, irradiating for 7-14 days under 100-500W ultraviolet light, centrifuging and precipitating, and washing the precipitate to obtain the gold nano hollow tank.
Further, the precipitate is washed with ethanol and deionized water in step (2).
Further, reducing chloroauric acid to a gold nanoparticle shell layer on the surface of the titanium dioxide nanospheres by adopting an in-situ photo-deposition method.
Further, the titanium dioxide nanospheres are etched by utilizing hydrochloric acid which is a byproduct generated by the reaction of titanium dioxide and the chloroauric acid solution.
Further, in the step (2), 2 to 15 parts by weight of TiO is added2And mixing and stirring the template ball, 3-60ml of ultrapure water, 2.4-10 parts of methanol solution and 3.2-13 parts of ethanol solution for 10-30min to obtain solution a.
Further, in the step (2), 0.5-25 parts of chloroauric acid solution and 0.5-25 parts of bis (chloroauric (I)) bis (diphenylphosphino) methane are added into the solution a, stirred for 10-30min, and after stirring, the solution is irradiated under 100-500W ultraviolet light for 7-14 days, and then centrifugal precipitation is carried out, and after washing and precipitation are carried out for 3 times by using ethanol and deionized water, the gold nano hollow tank can be obtained.
Further, the concentration of the chloroauric acid solution is 1g/10 ml.
Compared with the prior art, the preparation method for obtaining the hollow pot-shaped structure of the gold nanoparticles by the one-step method has the following advantages:
the method utilizes the photoreduction characteristic of titanium dioxide and reduces chloroauric acid to a gold nanoparticle shell layer on the surface of the titanium dioxide nanosphere by a simple in-situ light deposition method. Meanwhile, the titanium dioxide nanospheres are continuously and slowly etched by utilizing hydrochloric acid byproducts generated by the reaction, and citric acid or other etching aids are not required to be additionally added, so that the gold nano hollow open tank-shaped structure without the titanium dioxide nanospheres is finally obtained in one step.
The structure saves precious metal resources and reduces the cost.
The obtained hollow tank can well bear other functional substances, the application value and range are widened, and the practical application prospect is good.
The preparation method is simple, the conditions are easy to control, and the preparation method can be used for mass production and is beneficial to industrial production and application.
Drawings
FIG. 1 is a scanning electron microscope photograph of a hollow pot-shaped gold nanoparticle structure according to an embodiment of the present invention, with a scale of 200 nm;
FIG. 2 is a scanning electron microscope photograph of a hollow gold nanostructure according to an embodiment of the present invention, with a scale of 200 nm;
FIG. 3 is a scanning electron microscope photograph of a hollow canister-like gold nanoparticle structure according to an embodiment of the present invention, with a scale of 500 nm;
FIG. 4 is a scanning electron microscope photograph of the hollow gold nano-tube structure according to the embodiment of the present invention, with a scale of 1 μm.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
A preparation method for obtaining a gold nano hollow tank-shaped structure by a one-step method comprises the following steps:
(1)TiO2preparing template balls, adding ultrapure water and dodecylamine into an ethanol/acetonitrile mixed solution, stirring, adding titanium isopropoxide, continuously stirring, and separatingWashing the heart, and freeze-drying to obtain TiO2A template ball;
(2) preparing hollow gold nano-tank by mixing TiO with water2Mixing and stirring the template ball, ultrapure water, methanol and ethanol, adding chloroauric acid solution and bis (chloroauric (I)) bis (diphenylphosphino) methane, stirring, coating a gold layer by photocatalytic deposition after stirring, and preparing a gold nano hollow tank by a titanium dioxide nuclear etching method.
Furthermore, the addition amount of the dodecylamine in the step (1) is 0.5-3 parts by weight, and the addition amount of ultrapure water is 0.15-4.5 parts by weight.
Further, the adding amount of the ethanol/acetonitrile mixed solution in the step (1) is 250 parts by weight, and the volume ratio of ethanol/acetonitrile is 3: 1.
Further, in the step (2), in the preparation process of the gold nano hollow tank, a chloroauric acid solution and bis (chloroauric (I)) bis (diphenylphosphino) methane (C) are added25H22Au2Cl2P2) After stirring, irradiating for 7-14 days under 100-500W ultraviolet light, centrifuging and precipitating, and washing the precipitate to obtain the gold nano hollow tank.
Further, the precipitate is washed with ethanol and deionized water in step (2).
Further, reducing chloroauric acid to a gold nanoparticle shell layer on the surface of the titanium dioxide nanospheres by adopting an in-situ photo-deposition method.
Further, the titanium dioxide nanospheres are etched by utilizing hydrochloric acid which is a byproduct generated by the reaction of titanium dioxide and the chloroauric acid solution.
Further, in the step (2), 2 to 15 parts by weight of TiO is added2And mixing and stirring the template ball, 3-60ml of ultrapure water, 2.4-10 parts of methanol solution and 3.2-13 parts of ethanol solution for 10-30min to obtain solution a.
Further, in the step (2), 0.5-25 parts of chloroauric acid solution and 0.5-25 parts of bis (chloroauric (I)) bis (diphenylphosphino) methane are added into the solution a, stirred for 10-30min, and after stirring, the solution is irradiated under 100-500W ultraviolet light for 7-14 days, and then centrifugal precipitation is carried out, and after washing and precipitation are carried out for 3 times by using ethanol and deionized water, the gold nano hollow tank can be obtained.
Further, the concentration of the chloroauric acid solution is 1g/10 ml.
Example 1
The gold nano hollow tank-shaped structure described in this embodiment is completed by the following technical scheme, and the specific implementation manner is as follows:
1) conventional TiO2Preparation of template balls
Adding 0.15 part of ultrapure water and 0.5 part of dodecylamine into a beaker containing 100 parts of ethanol/acetonitrile mixed solution (ethanol: acetonitrile is 3:1) in parts by weight, stirring for 5-15min, quickly injecting 2.3 parts of titanium isopropoxide, continuously stirring for 3-6h at room temperature, centrifuging, washing, and freeze-drying to obtain the conventional TiO2And (4) template balls.
2) Preparation of gold nano hollow tank
The method for preparing the gold nano hollow tank by coating the gold layer through photocatalytic deposition and titanium dioxide nuclear etching comprises the following specific steps: 2 parts of TiO by weight2The template sphere, 3 parts of ultrapure water, 2.4 parts of methanol solution and 3.2 parts of ethanol solution were mixed and stirred for 10 to 30 minutes, and then 0.5 part of chloroauric acid solution (concentration: 1g/10ml) and 0.5 part of bis (chloroauric (I)) bis (diphenylphosphino) methane (C) were added25H22Au2Cl2P2) Stirring for 10-30 min. After stirring, irradiating for 7-14 days under 100-500W ultraviolet light, centrifuging and precipitating, and cleaning and precipitating for 3 times by using ethanol and deionized water to obtain the gold nano hollow tank.
Example 2
The purpose of the invention is achieved by the following technical scheme, and the specific implementation mode is as follows:
1) preparation of conventional TiO2 template spheres
Adding 0.3 part of ultrapure water and 1.8 parts of dodecylamine into a beaker containing 200 parts of ethanol/acetonitrile mixed solution (ethanol: acetonitrile is 3:1) by weight, stirring for 5-15min, quickly injecting 4.5 parts of titanium isopropoxide, continuously stirring for 3-6h at room temperature, centrifuging, washing, and freeze-drying to obtain the conventional TiO2 template ball.
2) Preparing a gold nano hollow tank by photocatalytic deposition and gold coating and titanium dioxide nuclear etching:
based on the weight portion, 9 portions of TiO2The template sphere, 30 parts of ultrapure water, 6.2 parts of a methanol solution and 8.2 parts of an ethanol solution were mixed and stirred for 10 to 30 minutes, and then 13 parts of a chloroauric acid solution (concentration: 1g/10ml) and 13 parts of bis (chloroauric (I)) bis (diphenylphosphino) methane (C) were added25H22Au2Cl2P2) Stirring for 10-30 min. After stirring, irradiating for 7-14 days under 100-500W ultraviolet light, centrifuging and precipitating, and cleaning and precipitating for 3 times by using ethanol and deionized water to obtain the gold nano hollow tank.
The scanning electron microscope pictures of the gold nano hollow tank obtained in the embodiment are shown in fig. 1-4. The hollow tank-shaped microspheres obtained by the embodiment are uniform in size, hollow inside, have an opening structure, are convenient for loading substances, and are beneficial to application in the aspect of photocatalytic degradation of organic matters.
Example 3
The purpose of the invention is achieved by the following technical scheme, and the specific implementation mode is as follows:
1) preparation of conventional TiO2 template spheres
Adding 4.5 parts by weight of ultrapure water and 3 parts by weight of dodecylamine into a beaker filled with 250 parts by weight of ethanol/acetonitrile mixed solution (ethanol: acetonitrile is 3:1), stirring for 5-15min, quickly injecting 6.8 parts by weight of titanium isopropoxide, continuously stirring for 3-6h at room temperature, centrifuging, washing, and freeze-drying to obtain the conventional TiO2 template ball.
2) Preparing a gold nano hollow tank by photocatalytic deposition and gold coating and titanium dioxide nuclear etching:
mixing and stirring 15 parts of TiO2 template ball, 60 parts of ultrapure water, 10 parts of methanol solution and 13 parts of ethanol solution for 10-30min, and adding 25 parts of chloroauric acid solution (with the concentration of 1g/10ml) and 25 parts of bis (chloroauric (I)) bis (diphenylphosphino) methane (C)25H22Au2Cl2P2) Stirring for 10-30 min. After stirring, irradiating for 7-14 days under 100-500W ultraviolet light, centrifuging and precipitating, and cleaning and precipitating for 3 times by using ethanol and deionized water to obtain the gold nano hollow tank.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method for obtaining a gold nano hollow tank-shaped structure by a one-step method is characterized by comprising the following steps:
(1)TiO2preparing template balls, adding ultrapure water and dodecylamine into an ethanol/acetonitrile mixed solution, stirring, adding titanium isopropoxide, stirring, centrifugally washing, and freeze-drying to obtain TiO2A template ball;
(2) preparing hollow gold nano-tank by mixing TiO with water2Mixing and stirring the template ball, ultrapure water, methanol and ethanol, adding chloroauric acid solution and bis (chloroauric (I)) bis (diphenylphosphino) methane, stirring, coating a gold layer by photocatalytic deposition after stirring, and preparing a gold nano hollow tank by a titanium dioxide nuclear etching method.
2. The method according to claim 1, wherein the dodecylamine is added in the step (1) in an amount of 0.5 to 3 parts by weight, and the ultrapure water is added in an amount of 0.15 to 4.5 parts by weight.
3. The production method according to claim 2, wherein the ethanol/acetonitrile mixed solution in the step (1) is added in an amount of 100 parts by weight and 250 parts by weight, and the volume ratio of ethanol/acetonitrile is 3: 1.
4. The preparation method according to claim 1, wherein in the step (2), in the preparation process of the gold nano hollow tank, a chloroauric acid solution and bis (chloroauric (I)) bis (diphenylphosphino) methane are added, stirred, irradiated under ultraviolet light for 7-14 days, centrifugally precipitated, and washed to obtain the gold nano hollow tank.
5. The method according to claim 4, wherein the precipitate is washed with ethanol and deionized water in the step (2).
6. The preparation method according to claim 4, wherein the chloroauric acid is reduced to the gold nanoparticle shell layer on the surface of the titanium dioxide nanospheres by an in-situ photo-deposition method.
7. The method of claim 4, wherein the titanium dioxide nanospheres are etched using hydrochloric acid produced as a by-product of the reaction of titanium dioxide with the chloroauric acid solution.
8. The production method according to claim 4, wherein in the step (2), 2 to 15 parts by weight of TiO is added2And mixing and stirring the template ball, 3-60ml of ultrapure water, 2.4-10 parts of methanol solution and 3.2-13 parts of ethanol solution for 10-30min to obtain solution a.
9. The preparation method according to claim 8, wherein in the step (2), 0.5-25 parts of chloroauric acid solution and 0.5-25 parts of bis (chloroauric (I)) bis (diphenylphosphino) methane are added into the solution a, stirred for 10-30min, and after the stirring, the solution is irradiated under 100-500W ultraviolet light for 7-14 days, and then centrifugally precipitated, and washed and precipitated with ethanol and deionized water for 3 times, so that the gold nano hollow tank is obtained.
10. The method according to claim 9, wherein in the step (2), the concentration of the chloroauric acid solution is 1g/10 ml.
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