CN110773748B - Silver shell stripping method and system for gold-silver core-shell nanospheres based on femtosecond laser - Google Patents

Silver shell stripping method and system for gold-silver core-shell nanospheres based on femtosecond laser Download PDF

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CN110773748B
CN110773748B CN201911037878.1A CN201911037878A CN110773748B CN 110773748 B CN110773748 B CN 110773748B CN 201911037878 A CN201911037878 A CN 201911037878A CN 110773748 B CN110773748 B CN 110773748B
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CN110773748A (en
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闫剑锋
梁真为
朱德志
赵玥
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Tsinghua University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F9/00—Making metallic powder or suspensions thereof
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
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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
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    • B22—CASTING; POWDER METALLURGY
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    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F2009/165—Chemical reaction in an Ionic Liquid [IL]

Abstract

The invention relates to a silver shell stripping method and system of gold and silver core-shell nanospheres based on femtosecond laser, and belongs to the technical field of femtosecond laser application. The method adopts a seed liquid growth method, firstly, a gold seed solution is synthesized, a gold ball solution is synthesized by the gold seed liquid growth method, and finally, a gold core silver shell nanosphere solution is synthesized; and irradiating the gold-core-silver-shell nanosphere solution by using a femtosecond laser pulse sequence, and controlling the irradiation time and the flux of laser pulses incident to the gold-core-silver-shell nanosphere solution so as to realize the stripping of the gold-core-silver-shell nanospheres. The method utilizes a reasonably designed femtosecond laser pulse sequence to irradiate the gold-core silver-shell nanosphere solution, so that the silver shell stripping process is relatively simple; the thickness of the release layer can be selectively and precisely controlled. The gold-core silver-shell nanosphere stripping system has a simple device structure, can realize stripping of the gold-core silver-shell nanospheres only by controlling irradiation time and laser flux, and is easy to control the technological process.

Description

Silver shell stripping method and system for gold-silver core-shell nanospheres based on femtosecond laser
Technical Field
The invention relates to a silver shell stripping method and system of gold and silver core-shell nanospheres based on femtosecond laser, and belongs to the technical field of femtosecond laser application.
Background
Gold-core silver-shell nanospheres have gained interest in a wide variety of nanoparticle materials due to their unique physical properties (e.g., bimetallicity, plasmon enhancement, stability, etc.). At present, the gold-core silver-shell nanospheres have good application prospects in the research fields of nano electronics, optics, biomedicine and the like. In the applications, the shell thickness of the gold-core silver-shell nanosphere determines many physical properties of the gold-core silver-shell nanosphere, and how to efficiently regulate the shell thickness of the gold-core silver-shell nanosphere is a difficult problem to be solved urgently. At present, the structure and physical properties of the gold-core silver-shell nanosphere are mainly adjusted and controlled by methods such as a template method, an electrochemical method, a seed growth method, a seedless growth method and the like. However, since the morphology of the gold-core silver-shell nanospheres is influenced by various physical and chemical factors, various surfactants need to be introduced in the process of synthesizing the gold-core silver-shell nanospheres with different shell thicknesses by the existing wet chemical method, and the surfactants are not beneficial to the application of the nanoparticles in the fields of catalysis and biology. And the traditional method has complex preparation conditions and low controllability of the synthesis process.
In order to control the shell thickness of the gold-core silver-shell nanosphere more precisely, the synthesized nanoparticles need to be post-treated. Laser can be used for the plastic of gold core silver-shell nanosphere effectively, moreover under local high temperature effect, can get rid of the surfactant, however, because the photothermal effect of traditional laser is showing for the temperature of whole particle tends to the equilibrium, and gold core and silver shell melt simultaneously, form the gold-silver alloy, can't effectively realize peeling off of silver shell layer, more can't control the thickness of silver shell layer. Therefore, there is a need for a method for simply and efficiently peeling off the shell of the gold-core silver-shell nanosphere.
Disclosure of Invention
The invention aims to provide a silver shell stripping method and a silver shell stripping system for gold and silver core-shell nanospheres based on femtosecond laser.
The invention provides a silver shell stripping method of gold and silver core-shell nanospheres based on femtosecond laser, which comprises the following steps:
(1) synthesizing a gold seed solution:
injecting a tetrachloroauric acid solution with the molar concentration of 0.01mol/L into a hexadecyl trimethyl ammonium bromide solution with the molar concentration of 0.1mol/L, mildly mixing, wherein the solution is transparent brown yellow, then adding a sodium borohydride solution with the molar concentration of 0.01mol/L at one time, rapidly stirring for 2 minutes, wherein the solution is whitish brown yellow, standing for 3 hours at 27 ℃ to obtain a gold seed solution, and the molar concentrations of tetrachloroauric acid, hexadecyl trimethyl ammonium bromide and sodium borohydride in the gold seed solution are respectively 0.1-0.3 mmol/L, 0.08-0.10 mol/L and 0.4-0.7 mmol/L;
(2) synthesizing a gold ball solution by a gold seed solution growth method:
injecting a tetrachloroauric acid solution with the molar concentration of 0.01mol/L into water to obtain a diluted tetrachloroauric acid solution, mixing and stirring a hexadecyltrimethylammonium chloride solution with the molar concentration of 0.2mol/L and the diluted tetrachloroauric acid solution at a warm temperature to obtain a transparent brown yellow solution, and then adding an ascorbic acid solution with the molar concentration of 0.1mol/L to obtain a colorless mixed solution, wherein the molar concentrations of the hexadecyltrimethylammonium chloride, the tetrachloroauric acid and the ascorbic acid in the colorless mixed solution are respectively 0.1-0.3 mmol/L, 0.06-0.08 mol/L and 0.02-0.04 mol/L; adding the gold seed solution obtained in the step (1) into the colorless mixed solution, and standing for 1 hour to obtain a gold ball solution, wherein the volume ratio of the gold seed solution to the colorless mixed solution in the gold ball solution is 1 (36-80);
(3) synthesizing a gold-core silver-shell nanosphere solution:
centrifuging the gold ball solution obtained in the step (2), wherein the centrifugal rotating speed is 12000rpm/min, and the centrifugal time is 15min, so as to obtain gold ball particles; the preparation method comprises the steps of mixing a hexadecyltrimethylammonium chloride solution with the molar concentration of 0.1mol/L and ascorbic acid with the molar concentration of 0.1mol/L (the solution and a silver nitrate solution with the molar concentration of 0.01 mol/L) to obtain a first mixed solution, adding gold ball particles into the first mixed solution to obtain a second mixed solution, wherein the molar concentrations of the hexadecyltrimethylammonium chloride, the ascorbic acid and the silver nitrate in the first mixed solution are respectively 0.08mol/L, 0.4mmol/L and 0.08mmol/L, and the adding proportion of the gold ball particles is that the volume ratio of the gold ball solution before centrifugal treatment to the first mixed solution is 1 (5-7);
(4) irradiating the gold-core silver-shell nanosphere solution obtained in the step (3) by using a femtosecond laser pulse sequence, wherein the flux of the femtosecond laser is (0.2-2.1) mJ/cm2The irradiation time is 5-15 min, and the gold-core silver-shell nanospheres are stripped by changing the laser flux and the irradiation time.
The invention provides a silver shell stripping system of gold and silver core-shell nanospheres based on femtosecond laser, which comprises a femtosecond laser, an attenuation sheet, a first reflecting mirror, a second reflecting mirror, an electric control shutter, a dichroic mirror, a glassware filled with a gold-core silver-shell nanosphere solution, a magnetic stirrer, a beam splitter, a lighting lamp and a camera; wherein:
the femtosecond laser generated by the femtosecond laser passes through the second reflecting mirror and the dichroic mirror in sequence, the electric control shutter is arranged between the second reflecting mirror and the dichroic mirror, one side of the dichroic mirror is provided with a magnetic stirrer, a glassware filled with gold-core silver-shell nanosphere solution is placed on the magnetic stirrer, the other side of the dichroic mirror is provided with an observation system consisting of a beam splitter, an illuminating lamp and a camera, after the energy of the femtosecond laser pulse generated by the femtosecond laser is adjusted by the attenuation plate, the transmission direction is changed by the first reflector and the second reflector respectively, the transmission direction is changed by the dichroic mirror after passing through the electric control shutter, and finally the transmission direction is irradiated into a glass vessel filled with the gold-core-silver-shell nanosphere solution, the gold-core silver-shell nanosphere solution is stirred by a magnetic stirrer to realize the stripping of the gold-core silver-shell nanospheres.
The silver shell stripping method and the silver shell stripping system of the gold-silver core-shell nanospheres based on the femtosecond laser have the advantages that:
1. compared with the existing chemical method for finishing the stripping of the gold-core silver-shell nanospheres, the femtosecond laser-based gold-core silver-shell nanosphere stripping method provided by the invention utilizes a reasonably designed femtosecond laser pulse sequence to irradiate the gold-core silver-shell nanosphere solution, so that the silver-shell stripping process is relatively simple.
2. The method for stripping the gold-core silver-shell nanospheres based on the femtosecond laser maintains the properties of the respective nanoparticles of the gold core and the silver shell in the stripping process, namely, the gold core and the silver shell are stripped on a physical layer.
3. The gold-core silver-shell nanosphere stripping system based on the femtosecond laser has a simple device structure, can realize stripping of the gold-core silver-shell nanospheres only by controlling irradiation time and laser flux, can observe stripping conditions in real time by an observation system, and is easy to control technological process.
Drawings
Fig. 1 is a schematic structural diagram of a femtosecond laser-based gold-core silver-shell nanosphere stripping system.
FIG. 2 shows the flux used in example 1 of the present invention, which is 2mJ/cm2And a transmission electron microscope image of the gold ball stripped by femtosecond laser with the irradiation time of 8 min. In which fig. 2(a) is a prepared gold core silver shell ball, and fig. 2(b) is a gold ball after the silver shell is stripped after the femtosecond laser treatment.
In fig. 1, 1 is a femtosecond laser, 2 is an attenuation sheet, 3 is a first reflecting mirror, 4 is a second reflecting mirror, 5 is an electrically controlled shutter, 6 is a dichroic mirror, 7 is a glass vessel (in which a gold-core silver-shell nanosphere solution is placed), 8 is a magnetic stirrer, 9 is a beam splitter, 10 is an illumination lamp, and 11 is a camera.
Detailed Description
The invention provides a silver shell stripping method of gold and silver core-shell nanospheres based on femtosecond laser, which comprises the following steps:
(1) synthesizing a gold seed solution:
tetrachloroauric acid (HAucll) with a molar concentration of 0.01mol/L4) The solution is injected into a Cetyl Trimethyl Ammonium Bromide (CTAB) solution with the molar concentration of 0.1mol/L, the mixture is mixed gently, the solution presents transparent brown yellow, and sodium borohydride (NaBH) with the molar concentration of 0.01mol/L is added4) Adding the solution at one time, stirring quickly for 2 minutes to obtain a solution which is white and brown yellow, and standing at 27 ℃ for 3 hours to obtain a gold seed solution, wherein the molar concentrations of tetrachloroauric acid, hexadecyl trimethyl ammonium bromide and sodium borohydride in the gold seed solution are 0.1-0.3 mmol/L, 0.08-0.10 mol/L and 0.4-0.7 mmol/L respectively;
(2) synthesizing a gold ball solution by a gold seed solution growth method:
tetrachloroauric acid (HAucll) with a molar concentration of 0.01mol/L4) The solution is poured into water to obtain diluted tetrachloroauric acid (HAucl)4) Solution of cetyltrimethylammonium chloride (CTAC) solution with a molar concentration of 0.2mol/L and diluted tetrachloroauric acid (HAucl)4) The solution is stirred at a warm state, the solution is transparent and brownish yellow, and then the solution is added with the molar concentration of 0.1mol/LAscorbic acid (C)6H8O6) Obtaining a colorless mixed solution, wherein the molar concentrations of hexadecyl trimethyl ammonium chloride, tetrachloroauric acid and ascorbic acid in the colorless mixed solution are respectively 0.1-0.3 mmol/L, 0.06-0.08 mol/L and 0.02-0.04 mol/L; adding the gold seed solution obtained in the step (1) into the colorless mixed solution, and standing for 1 hour to obtain a gold ball solution, wherein the volume ratio of the gold seed solution to the colorless mixed solution in the gold ball solution is 1 (36-80);
(3) synthesizing a gold-core silver-shell nanosphere solution:
centrifuging the gold ball solution obtained in the step (2), wherein the centrifugal rotating speed is 12000rpm/min, and the centrifugal time is 15min, so as to obtain gold ball particles; mixing 0.1mol/L hexadecyl trimethyl ammonium chloride (CTAC) solution and 0.1mol/L ascorbic acid (C)6H8O6) Solution and silver nitrate (AgNO) with the molar concentration of 0.01mol/L3) Mixing the solutions to obtain a first mixed solution, wherein the molar concentrations of hexadecyl trimethyl ammonium chloride, ascorbic acid and silver nitrate in the first mixed solution are respectively 0.08mol/L, 0.4mmol/L and 0.08 mmol/L; adding the gold ball particles into the first mixed solution to obtain a second mixed solution, wherein the adding proportion of the gold ball particles is as follows: the volume ratio of the gold ball solution to the first mixed solution before the centrifugal treatment is 1 (5-7); standing the second mixed solution at 60 ℃ for 3 hours, and then cooling to room temperature to obtain a gold-core silver-shell nanosphere solution;
(4) irradiating the gold-core silver-shell nanosphere solution obtained in the step (3) by using a femtosecond laser pulse sequence, wherein the flux of the femtosecond laser is 0.2-2.1 mJ/cm2The irradiation time is 5-15 min, and the gold-core silver-shell nanospheres are stripped by changing the laser flux and the irradiation time.
The structure of the silver shell stripping system of the gold and silver core-shell nanosphere based on the femtosecond laser is shown in figure 1, and the silver shell stripping system comprises a femtosecond laser 1, an attenuation sheet 2, a first reflecting mirror 3, a second reflecting mirror 4, an electric control shutter 5, a dichroic mirror 6, a magnetic stirrer 8, a beam splitter 9, an illuminating lamp 10 and a camera 11; wherein:
the femtosecond laser 1, the attenuation sheet 2 and the first reflecting mirror 3 form a common optical axis, the femtosecond laser generated by the femtosecond laser 1 sequentially passes through the second reflecting mirror 4 and the dichroic mirror 6, the electric control shutter 5 is arranged between the second reflecting mirror 4 and the dichroic mirror 6, one side of the dichroic mirror 6 is provided with a magnetic stirrer 8, a glassware 7 filled with gold-core-silver-shell nanosphere solution is placed on the magnetic stirrer 8, the other side of the dichroic mirror 6 is provided with an observation system consisting of a beam splitter 9, an illuminating lamp 10 and a camera 11, the femtosecond laser pulse generated by the femtosecond laser 1 is subjected to energy adjustment by the attenuation sheet 2, the propagation direction is changed by the first reflecting mirror 3 and the second reflecting mirror 4 respectively, the propagation direction is changed by the electric control shutter 5, the dichroic mirror 6 is irradiated into the glassware 7 filled with the gold-core-silver-shell nanosphere solution finally, the gold-core-silver-shell nanosphere solution is stirred by the magnetic stirrer, realize the peeling of the gold-core silver-shell nanospheres.
The operation process of the gold-core silver-shell nanosphere stripping system based on femtosecond laser comprises the following steps:
the femtosecond laser 1 is turned on to generate femtosecond laser pulse, and the laser energy is adjusted through the attenuation sheet 2 to be 0.2-2.1 mJ/cm2And the power requirement required by the stripping of the gold-core silver-shell nanospheres is met. The femtosecond laser pulse sequence is introduced into the gold-core silver-shell nanosphere solution in the glassware 7, the glassware 7 is placed on the magnetic stirrer 8, and the relative position of the femtosecond laser beam and the magnetic stirrer 8 is adjusted, so that the femtosecond laser beam passes through the center of the glassware 7. The stripping of the gold-core silver-shell nanospheres is realized by controlling the irradiation time of the pulse sequence of the incident gold-core silver-shell nanosphere solution. By adjusting the opening time of the electric control shutter 5, the irradiation time of the pulse sequence of the gold-core silver-shell nanosphere solution is controlled to be incident, and the gold-core silver-shell nanosphere solution is uniformly heated by stirring of the magnetic stirrer 8 to complete stripping.
The method for peeling the gold-core silver-shell nanospheres of the invention is further described with reference to the accompanying drawings and examples:
example 1
(1) Synthesizing a gold seed solution: tetrachloroauric acid (HAucll) with a molar concentration of 0.01mol/L4) The solution was poured into 0.1mol/L Cetyl Trimethyl Ammonium Bromide (CTAB) solution and was mildly dissolvedMixing, making the solution transparent brown yellow, and adding sodium borohydride (NaBH) with a molar concentration of 0.01mol/L4) The solution is added at one time, rapidly stirred for 2 minutes, the solution is white and brownish yellow, and then is kept stand for 3 hours at the temperature of 27 ℃ to obtain a seed solution. The molar concentrations of the tetrachloroauric acid, the hexadecyl trimethyl ammonium bromide and the sodium borohydride in the gold seed solution are respectively 0.2mmol/L, 0.09mol/L and 0.6 mmol/L;
(2) synthesizing a gold ball solution by a seed solution growth method: tetrachloroauric acid (HAucll) with a molar concentration of 0.01mol/L4) The solution is injected into water to obtain diluted tetrachloroauric acid (HAucl)4) Adding Cetyl Trimethyl Ammonium Chloride (CTAC) solution with molar concentration of 0.2mol/L and the diluted tetrachloroauric acid (HAucl4) solution into a test tube, stirring gently to obtain transparent brown yellow solution, and adding ascorbic acid (C) with molar concentration of 0.1mol/L6H8O6) And (3) solution. And (3) obtaining a colorless mixed solution, wherein the molar concentrations of hexadecyltrimethylammonium chloride, tetrachloroauric acid and ascorbic acid in the mixed solution are respectively 0.2mmol/L, 0.07mol/L and 0.03mol/L, adding the gold seed solution obtained in the step (1) into the mixed solution, and standing for 1 hour to obtain a gold ball solution, wherein the volume ratio of the gold seed solution in the gold ball solution to the mixed solution is 1: 55;
(3) synthesizing a gold-core silver-shell nanosphere solution: centrifuging the gold ball solution obtained in the step (2), wherein the centrifugal rotating speed is 12000rpm/min, and the centrifugal time is 15min, so as to obtain gold ball particles; mixing 0.1mol/L hexadecyl trimethyl ammonium chloride (CTAC) solution and 0.1mol/L ascorbic acid (C)6H8O6) Solution and silver nitrate (AgNO) with the molar concentration of 0.01mol/L3) Mixing the solutions to obtain a first mixed solution, wherein the molar concentrations of hexadecyl trimethyl ammonium chloride, ascorbic acid and silver nitrate in the first mixed solution are respectively 0.08mol/L, 0.4mmol/L and 0.08 mmol/L; adding the gold ball particles into the first mixed solution to obtain a second mixed solution, wherein the adding proportion of the gold ball particles is as follows: the volume ratio of the gold ball solution to the first mixed solution before the centrifugal treatment is 1: 6; standing the second mixed solution at 60 ℃ for 3 hours, and then cooling to room temperature to obtain a gold-core silver-shell nanosphere solution;
(4) irradiating the gold-core silver-shell nanosphere solution obtained in the step (3) by using a femtosecond laser pulse sequence, wherein the femtosecond laser flux is 2mJ/cm2And the irradiation time is 8min, so that the gold-core silver-shell nanospheres are stripped.
In this embodiment, the laser flux is adjusted to 2mJ/cm by adjusting the attenuation sheet 22(ii) a The irradiation time of the incident gold nanorod solution pulse sequence is controlled to be 8min through the electric control shutter 5, namely the stripping of the gold-core silver-shell nanosphere solution is completed, the observation result is shown in figure 2, figure 2(a) is a prepared gold-core silver-shell sphere, and figure 2(b) is a gold sphere after the silver shell is stripped through laser treatment.
Example 2
(1) Synthesizing a gold seed solution: tetrachloroauric acid (HAucll) with a molar concentration of 0.01mol/L4) The solution is injected into a Cetyl Trimethyl Ammonium Bromide (CTAB) solution with the molar concentration of 0.1mol/L, the mixture is mixed gently, the solution presents transparent brown yellow, and sodium borohydride (NaBH) with the molar concentration of 0.01mol/L is added4) The solution is added at one time, rapidly stirred for 2 minutes, the solution is white and brownish yellow, and then is kept stand for 3 hours at the temperature of 27 ℃ to obtain a seed solution. The molar concentrations of the tetrachloroauric acid, the hexadecyl trimethyl ammonium bromide and the sodium borohydride in the gold seed solution are respectively 0.2mmol/L, 0.09mol/L and 0.6 mmol/L;
(2) synthesizing a gold ball solution by a seed solution growth method: tetrachloroauric acid (HAucll) with a molar concentration of 0.01mol/L4) The solution is injected into water to obtain diluted tetrachloroauric acid (HAucl)4) Adding Cetyl Trimethyl Ammonium Chloride (CTAC) solution with molar concentration of 0.2mol/L and the diluted tetrachloroauric acid (HAucl4) solution into a test tube, stirring gently to obtain transparent brown yellow solution, and adding ascorbic acid (C) with molar concentration of 0.1mol/L6H8O6) And (3) solution. And (3) obtaining a colorless mixed solution, wherein the molar concentrations of hexadecyltrimethylammonium chloride, tetrachloroauric acid and ascorbic acid in the mixed solution are respectively 0.2mmol/L, 0.07mol/L and 0.03mol/L, adding the gold seed solution obtained in the step (1) into the mixed solution, and standing for 1 hour to obtain a gold ball solution, wherein the volume ratio of the gold seed solution in the gold ball solution to the mixed solution is 1: 55;
(3) synthesizing a gold-core silver-shell nanosphere solution: centrifuging the gold ball solution obtained in the step (2), wherein the centrifugal rotating speed is 12000rpm/min, and the centrifugal time is 15min, so as to obtain gold ball particles; mixing 0.1mol/L hexadecyl trimethyl ammonium chloride (CTAC) solution and 0.1mol/L ascorbic acid (C)6H8O6) Solution and silver nitrate (AgNO) with the molar concentration of 0.01mol/L3) Mixing the solutions to obtain a first mixed solution, wherein the molar concentrations of hexadecyl trimethyl ammonium chloride, ascorbic acid and silver nitrate in the first mixed solution are respectively 0.08mol/L, 0.4mmol/L and 0.08 mmol/L; adding the gold ball particles into the first mixed solution to obtain a second mixed solution, wherein the adding proportion of the gold ball particles is as follows: the volume ratio of the gold ball solution to the first mixed solution before the centrifugal treatment is 1: 6; standing the second mixed solution at 60 ℃ for 3 hours, and then cooling to room temperature to obtain a gold-core silver-shell nanosphere solution;
(4) irradiating the gold-core silver-shell nanosphere solution obtained in the step (3) by using a femtosecond laser pulse sequence, wherein the femtosecond laser flux is 2mJ/cm2And the irradiation time is 15min, so that the gold-core silver-shell nanospheres are stripped.
Example 3
(1) Synthesizing a gold seed solution: tetrachloroauric acid (HAucll) with a molar concentration of 0.01mol/L4) The solution is injected into a Cetyl Trimethyl Ammonium Bromide (CTAB) solution with the molar concentration of 0.1mol/L, the mixture is mixed gently, the solution presents transparent brown yellow, and sodium borohydride (NaBH) with the molar concentration of 0.01mol/L is added4) The solution is added at one time, rapidly stirred for 2 minutes, the solution is white and brownish yellow, and then is kept stand for 3 hours at the temperature of 27 ℃ to obtain a seed solution. The molar concentrations of the tetrachloroauric acid, the hexadecyl trimethyl ammonium bromide and the sodium borohydride in the gold seed solution are respectively 0.2mmol/L, 0.09mol/L and 0.6 mmol/L;
(2) synthesizing a gold ball solution by a seed solution growth method: tetrachloroauric acid (HAucll) with a molar concentration of 0.01mol/L4) The solution is injected into water to obtain diluted tetrachloroauric acid (HAucl)4) A solution prepared by diluting a solution of cetyltrimethylammonium chloride (CTAC) having a molar concentration of 0.2mol/L with the above-mentioned diluted tetrachloro chlorideAdding gold acid (HAucl4) solution into test tube, stirring gently to obtain transparent brown yellow solution, and adding ascorbic acid (C) with molar concentration of 0.1mol/L6H8O6) And (3) solution. And (3) obtaining a colorless mixed solution, wherein the molar concentrations of hexadecyltrimethylammonium chloride, tetrachloroauric acid and ascorbic acid in the mixed solution are respectively 0.2mmol/L, 0.07mol/L and 0.03mol/L, adding the gold seed solution obtained in the step (1) into the mixed solution, and standing for 1 hour to obtain a gold ball solution, wherein the volume ratio of the gold seed solution in the gold ball solution to the mixed solution is 1: 70;
(3) synthesizing a gold-core silver-shell nanosphere solution: centrifuging the gold ball solution obtained in the step (2), wherein the centrifugal rotating speed is 12000rpm/min, and the centrifugal time is 15min, so as to obtain gold ball particles; mixing 0.1mol/L hexadecyl trimethyl ammonium chloride (CTAC) solution and 0.1mol/L ascorbic acid (C)6H8O6) Solution and silver nitrate (AgNO) with the molar concentration of 0.01mol/L3) Mixing the solutions to obtain a first mixed solution, wherein the molar concentrations of hexadecyl trimethyl ammonium chloride, ascorbic acid and silver nitrate in the first mixed solution are respectively 0.08mol/L, 0.4mmol/L and 0.08 mmol/L; adding the gold ball particles into the first mixed solution to obtain a second mixed solution, wherein the adding proportion of the gold ball particles is as follows: the volume ratio of the gold ball solution to the first mixed solution before the centrifugal treatment is 1: 6; standing the second mixed solution at 60 ℃ for 3 hours, and then cooling to room temperature to obtain a gold-core silver-shell nanosphere solution;
(4) irradiating the gold-core silver-shell nanosphere solution obtained in the step (3) by using a femtosecond laser pulse sequence, wherein the femtosecond laser flux is 1.5mJ/cm2And the irradiation time is 8min, so that the gold-core silver-shell nanospheres are stripped.
Example 4
(1) Synthesizing a gold seed solution: tetrachloroauric acid (HAucll) with a molar concentration of 0.01mol/L4) The solution is injected into a Cetyl Trimethyl Ammonium Bromide (CTAB) solution with the molar concentration of 0.1mol/L, the mixture is mixed gently, the solution presents transparent brown yellow, and sodium borohydride (NaBH) with the molar concentration of 0.01mol/L is added4) The solution is added at one time, rapidly stirred for 2 minutes, the solution is white and brownish yellow, and then is kept still at the temperature of 27 DEG CStanding for 3 hours to obtain a seed solution. The molar concentrations of the tetrachloroauric acid, the hexadecyl trimethyl ammonium bromide and the sodium borohydride in the gold seed solution are respectively 0.2mmol/L, 0.09mol/L and 0.6 mmol/L;
(2) synthesizing a gold ball solution by a seed solution growth method: tetrachloroauric acid (HAucll) with a molar concentration of 0.01mol/L4) The solution is injected into water to obtain diluted tetrachloroauric acid (HAucl)4) Adding Cetyl Trimethyl Ammonium Chloride (CTAC) solution with molar concentration of 0.2mol/L and the diluted tetrachloroauric acid (HAucl4) solution into a test tube, stirring gently to obtain transparent brown yellow solution, and adding ascorbic acid (C) with molar concentration of 0.1mol/L6H8O6) And (3) solution. And (3) obtaining a colorless mixed solution, wherein the molar concentrations of hexadecyltrimethylammonium chloride, tetrachloroauric acid and ascorbic acid in the mixed solution are respectively 0.2mmol/L, 0.07mol/L and 0.03mol/L, adding the gold seed solution obtained in the step (1) into the mixed solution, and standing for 1 hour to obtain a gold ball solution, wherein the volume ratio of the gold seed solution in the gold ball solution to the mixed solution is 1: 45, a first step of;
(3) synthesizing a gold-core silver-shell nanosphere solution: centrifuging the gold ball solution obtained in the step (2), wherein the centrifugal rotating speed is 12000rpm/min, and the centrifugal time is 15min, so as to obtain gold ball particles; mixing 0.1mol/L hexadecyl trimethyl ammonium chloride (CTAC) solution and 0.1mol/L ascorbic acid (C)6H8O6) Solution and silver nitrate (AgNO) with the molar concentration of 0.01mol/L3) Mixing the solutions to obtain a first mixed solution, wherein the molar concentrations of hexadecyl trimethyl ammonium chloride, ascorbic acid and silver nitrate in the first mixed solution are respectively 0.08mol/L, 0.4mmol/L and 0.08 mmol/L; adding the gold ball particles into the first mixed solution to obtain a second mixed solution, wherein the adding proportion of the gold ball particles is as follows: the volume ratio of the gold ball solution to the first mixed solution before the centrifugal treatment is 1: 6; standing the second mixed solution at 60 ℃ for 3 hours, and then cooling to room temperature to obtain a gold-core silver-shell nanosphere solution;
(4) irradiating the gold-core silver-shell nanosphere solution obtained in the step (3) by using a femtosecond laser pulse sequence, wherein the femtosecond laser flux is 1.5mJ/cm2The irradiation time is 6min, thereby realizing the gold-core silver-shell nanospheresAnd (6) stripping.
In one embodiment of the femtosecond laser-based gold-core silver-shell nanosphere stripping system, the femtosecond laser is a titanium sapphire laser produced by Coherent corporation (Coherent), the type of the titanium sapphire laser is Astrella, the center wavelength of the titanium sapphire laser is 800nm, the pulse width of the titanium sapphire laser is 35fs, the repetition frequency is 1000Hz at most, the maximum single pulse energy is 7mJ, and the light intensity distribution is Gaussian distribution.
The main parameters of the femtosecond laser 1 of one embodiment of the system of the present invention are: the central wavelength of the laser is 800nm, the repetition frequency is 1KHz, and the pulse width is 35 fs.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (1)

1. A silver shell stripping method of gold and silver core-shell nanospheres based on femtosecond laser is characterized by comprising the following steps:
(1) the method comprises the following steps of constructing a silver shell stripping system of gold and silver core-shell nanospheres based on femtosecond laser, wherein the system comprises a femtosecond laser, an attenuation sheet, a first reflecting mirror, a second reflecting mirror, an electric control shutter, a dichroic mirror, a glassware filled with gold-core silver shell nanosphere solution, a magnetic stirrer, a beam splitter, a lighting lamp and a camera; the device comprises a femtosecond laser, an attenuation sheet and a first reflector, wherein a common optical axis is formed by the femtosecond laser, the femtosecond laser generated by the femtosecond laser sequentially passes through a second reflector and a dichroic mirror, an electric control shutter is arranged between the second reflector and the dichroic mirror, a magnetic stirrer is arranged on one side of the dichroic mirror, a glassware filled with a gold-core silver-shell nanosphere solution is placed on the magnetic stirrer, and an observation system consisting of a beam splitter, an illuminating lamp and a camera is arranged on the other side of the dichroic mirror;
(2) synthesizing a gold seed solution:
injecting a tetrachloroauric acid solution with the molar concentration of 0.01mol/L into a hexadecyl trimethyl ammonium bromide solution with the molar concentration of 0.1mol/L, mildly mixing, wherein the solution is transparent brown yellow, then adding a sodium borohydride solution with the molar concentration of 0.01mol/L at one time, rapidly stirring for 2 minutes, wherein the solution is whitish brown yellow, standing for 3 hours at 27 ℃ to obtain a gold seed solution, and the molar concentrations of tetrachloroauric acid, hexadecyl trimethyl ammonium bromide and sodium borohydride in the gold seed solution are respectively 0.1-0.3 mmol/L, 0.08-0.10 mol/L and 0.4-0.7 mmol/L;
(3) synthesizing a gold ball solution by a gold seed solution growth method:
injecting a tetrachloroauric acid solution with the molar concentration of 0.01mol/L into water to obtain a diluted tetrachloroauric acid solution, mixing and stirring a hexadecyltrimethylammonium chloride solution with the molar concentration of 0.2mol/L and the diluted tetrachloroauric acid solution at a warm temperature to obtain a transparent brown yellow solution, and then adding an ascorbic acid solution with the molar concentration of 0.1mol/L to obtain a colorless mixed solution, wherein the molar concentrations of the hexadecyltrimethylammonium chloride, the tetrachloroauric acid and the ascorbic acid in the colorless mixed solution are respectively 0.1-0.3 mmol/L, 0.06-0.08 mol/L and 0.02-0.04 mol/L; adding the gold seed solution obtained in the step (1) into the colorless mixed solution, and standing for 1 hour to obtain a gold ball solution, wherein the volume ratio of the gold seed solution to the colorless mixed solution in the gold ball solution is 1 (36-80);
(4) synthesizing a gold-core silver-shell nanosphere solution:
centrifuging the gold ball solution obtained in the step (2), wherein the centrifugal rotating speed is 12000rpm/min, and the centrifugal time is 15min, so as to obtain gold ball particles; mixing a hexadecyl trimethyl ammonium chloride solution with the molar concentration of 0.1mol/L, an ascorbic acid solution with the molar concentration of 0.1mol/L and a silver nitrate solution with the molar concentration of 0.01mol/L to obtain a first mixed solution, wherein the molar concentrations of the hexadecyl trimethyl ammonium chloride, the ascorbic acid and the silver nitrate in the first mixed solution are respectively 0.08mol/L, 0.4mmol/L and 0.08 mmol/L; adding the gold ball particles into the first mixed solution to obtain a second mixed solution, wherein the adding proportion of the gold ball particles is as follows: the volume ratio of the gold ball solution to the first mixed solution before the centrifugal treatment is 1 (5-7); standing the second mixed solution at 60 ℃ for 3 hours, and then cooling to room temperature to obtain a gold-core silver-shell nanosphere solution;
(5) starting procedure (1)) After the femtosecond laser pulse generated by the femtosecond laser passes through the attenuation sheet to adjust energy, the propagation direction is changed through the first reflector and the second reflector respectively, the energy passes through the electric control shutter, the propagation direction is changed through the dichroic mirror, and finally the energy is irradiated into a glassware filled with the gold-core-silver-shell nanosphere solution obtained in the step (4), the gold-core-silver-shell nanosphere solution is stirred by a magnetic stirrer and is irradiated by a femtosecond laser pulse sequence, and the flux of the femtosecond laser is (0.2-2.1) mJ/cm2The irradiation time is 5-15 min, and the gold-core silver-shell nanospheres are stripped by changing the laser flux and the irradiation time.
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