CN113385687A - Asymmetric gold-silver-platinum-silver multilayer composite material and synthetic method thereof - Google Patents
Asymmetric gold-silver-platinum-silver multilayer composite material and synthetic method thereof Download PDFInfo
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Abstract
The invention discloses an asymmetric gold-silver-platinum-silver multilayer composite material and a synthesis method thereof, which comprises the steps of firstly preparing gold nanorods by using a seed growth method, then adding corresponding amounts of CTAC, silver nitrate and ascorbic acid into the gold nanorods serving as seeds to uniformly mix the gold nanorods, heating the gold nanorods in a water bath at 60 ℃, and growing a layer of thin silver on the periphery of the gold nanorods; adding a corresponding amount of potassium tetrachloroplatinate, heating in a water bath at 60 ℃ to enable platinum to grow at two ends of the gold-silver bimetal; finally, silver nitrate with a corresponding amount is added, so that the final silver grows asymmetrically. The asymmetric gold-silver-platinum-silver multilayer composite material synthesized by the invention has high uniformity in structure, low cost and easy realization.
Description
Technical Field
The invention relates to the field of synthesis of metal nano materials, in particular to an asymmetric gold-silver-platinum-silver multilayer composite material and a synthesis method thereof.
Background
Research in the field of noble metal nanoparticles has been in the field of researchers in recent years, with gold nanorods being the most prominent. Because gold nanorods have very rich chemical and physical properties, it is also popular to select gold nanorods as new seeds to synthesize bimetallic and multi-metal composite materials. Because the bimetal and the polymetal not only have the excellent performance of the gold nanorods, but also have the excellent performance of the second metal and a plurality of metals, the bimetal and the polymetal composite material are more and more widely applied, the bimetal composite materials such as gold-platinum and gold-palladium can greatly enhance the catalytic performance of the original gold nanorods, and the bimetal composite materials such as gold-silver have excellent surface Raman enhancement effect.
When the surface raman enhancement effect is studied, it is found that not only gold-silver bimetal has better effect than gold nanorods, but also asymmetric multi-metal composite material shows stronger performance than symmetric multi-metal composite material. However, the method for synthesizing the asymmetric multi-metal composite material at the present stage is complicated, the reaction temperature is about 80 ℃, the growth of platinum needs at least eight hours, the temperature is not easy to control, the reaction time is long, and meanwhile, the synthesized multi-metal composite material is not uniform.
Disclosure of Invention
The invention aims to provide an asymmetric gold-silver-platinum-silver multilayer composite material and a synthesis method thereof, wherein the reaction condition is water bath heating, the water bath temperature is 60 ℃, and the reaction condition is easy to control; the amount of the needed reactants is small, the cost is low, and the resource waste is not caused; can efficiently synthesize the uniform gold-silver-platinum-silver multilayer composite material with the asymmetric structure.
The invention provides a synthesis method of an asymmetric gold-silver-platinum-silver multilayer composite material, which comprises the following steps:
step S1: preparing gold nanorods by using a seed growth method:
s10: 10mL of 0.1M CTAB (hexadecyltrimethyl bromide)Ammonium) with 0.25mL of 10mM HAuCl4Mixing in a bottle, mixing with ice-water mixture and certain amount of NaBH4Mixing to prepare 0.01M solution, adding 0.6mL of the solution into a bottle, and stirring to obtain seed solution;
s11: 2.5mL of 0.1M CTAB and 0.037g of NaOL were dissolved in 21.25mL of water at 50 ℃; after dissolution, the solution was cooled to 30 ℃ and then 0.9mL of 4m AgNO was added3The solution was allowed to stand at a constant temperature, and then 0.25mL of 10mM HAuCl was added4(tetrachloroauric acid), stirring to obtain a growth solution;
s12: adjusting the pH value of the growth solution, sequentially adding 75 mu L of 64mM AA and 40 mu L of seed solution, stirring, and standing at constant temperature;
s13: centrifuging the solution after growth, removing clear liquid, and dispersing the obtained gold nanorods in 1-2mM CTAB;
step S2: taking 0.1mL of gold nanorods dispersed in CTAB in S13, putting the gold nanorods into a bottle, sequentially adding 3.4mL of 30mM CTAC (cetyltrimethylammonium chloride), 0.04mL of 4mM silver nitrate solution and 0.05mL of 4mM ascorbic acid solution, stirring to mix the gold nanorods uniformly, and then placing the mixture in a water bath at 60 ℃ for heating for 30 minutes;
step S3: adding 0.04mL of 2mL potassium tetrachloroplatinate solution into the solution obtained in the step S2, stirring to mix the solution uniformly, and then heating the mixture in a water bath at 60 ℃ for 20 minutes;
step S4: adding 0.2mL of 4mM silver nitrate solution into the solution obtained in the step S3, and heating the solution in a water bath at 60 ℃ for 40 minutes;
step S5: and (5) centrifuging the product obtained in the step (S4), and removing supernatant to obtain the gold-silver-platinum-silver multilayer composite material with the asymmetric structure.
Preferably, in S11, the constant temperature is 30 ℃ and the standing time is 15 minutes.
Preferably, in S11, the stirring speed is 400rpm, and the stirring time is 60-90 minutes.
Preferably, in S12, the pH value is adjusted to 1.1-1.3 by adding 0.3mL of 37 wt.% HCl to the growth solution.
Preferably, in S12, the constant temperature standing condition is that the water bath is heated for 30 ℃ and the standing is carried out for 12 hours.
Preferably, in S13, the solution after growth is centrifuged 2 times, 7000rpm for the first time, for 30 minutes, and 1-2mM CTAB is added after removing the supernatant, 7000rpm for the second time, for 30 minutes.
The invention also provides an asymmetric gold-silver-platinum-silver multilayer composite material which is synthesized by the method.
The gold nanorods have good physicochemical properties, such as surface plasmon resonance performance, and can be widely applied to the research of surface properties. Therefore, the uniform gold nanorods are synthesized by using a seed growth method, then the gold nanorods are used as seeds, and the uniform gold-silver bimetal can be finally obtained by adding a surfactant CTAC, a silver nitrate solution and ascorbic acid and heating for 30 minutes in a water bath at 60 ℃. And adding a potassium tetrachloroplatinate solution, and heating for 20 minutes in a water bath at the temperature of 60 ℃ to obtain a gold-silver-platinum structure with platinum deposited at two ends of the gold-silver bimetallic structure. And adding a certain amount of silver nitrate to ensure that the deposition amount of silver on two sides is different so as to obtain the gold-silver-platinum-silver multilayer composite material with an asymmetric structure. The reason why the reaction is heated in a water bath at 60 ℃ is to enable the content of the asymmetric structure to be greatly increased and to ensure that the final result has high uniformity; the addition of the reducing agent ascorbic acid is due to the fact that ascorbic acid greatly increases the rate of reaction. The method can be used for efficiently synthesizing the uniform gold-silver-platinum-silver multilayer composite material with the asymmetric structure, and has the advantages of simple reaction condition, easy control and low cost.
The asymmetric gold-silver-platinum-silver multilayer composite material synthesized by the invention is characterized in that a gold nanorod is used as a core, a layer of uniform silver is deposited on the periphery of the gold nanorod, uniform platinum is deposited at two ends of a gold-silver bimetal, silver with different amounts is deposited at two sides of a gold-silver-platinum structure to form an asymmetric gold-silver-platinum-silver multilayer composite material composite structure, the silver in the first step is uniformly grown on the gold nanorod, the platinum in the second step is uniformly grown at two ends, the silver in the last step is asymmetrically deposited at two sides, and the finally synthesized gold-silver-platinum-silver multilayer composite material presents an asymmetric structure and has the characteristic of high uniformity. Wherein, the asymmetry means that the deposition amount of the outermost silver layers is different at two ends, and the uniformity means that the final composite material basically tends to be consistent in size and shape.
The invention has the beneficial effects that:
(1) the synthesis method is simple, the conditions are easy to control, and the finally obtained product gold-silver-platinum-silver multilayer composite material is very stable and has extremely high reliability.
(2) The synthesized asymmetric gold-silver-platinum-silver multilayer metal structure does not completely change the performance of the gold nanorods, but retains the specific properties of the gold nanorods, such as catalytic performance.
(3) The asymmetric gold-silver-platinum-silver multilayer metal structure grows uniformly, has excellent surface Raman enhancement performance and higher stability.
(4) The asymmetric gold-silver-platinum-silver multilayer composite material has certain special properties of gold, silver and platinum, such as surface plasmon effect and catalytic property, and therefore can be widely applied, for example: biomedical, physical, chemical and optical fields.
Drawings
Fig. 1 is a transmission electron microscope image of an asymmetric gold-silver-platinum-silver multilayer composite material of example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the structures or terms used herein. The description is given for the sake of example only, to illustrate how the invention may be implemented, and does not constitute any limitation on the invention.
Example 1
10mL CTAB (0.1M) and 0.25mL HAuCl4(10mM) are mixed in a bottle with an ice-water mixture and a weighed quantity of NaBH4Mix to make 0.01M solution, and add 0.6mL into the bottle and stir vigorously. The solution changed from golden yellow to brown yellow, which is a seed solution.
2.5mL CTAB (0.1M) and 0.037g NaOL were dissolved in 21.25mL of water at 50 ℃. After dissolution, the solution was cooled to 30 ℃ and then 0.9mL of AgNO was added3(4mM) solutionAnd (4) liquid. And left to stand at a constant temperature of 30 ℃ for 15 minutes, after which 0.25mL of HAuCl was added4(10 mM). After 60-90 minutes of stirring (400rpm), the solution turned from a golden yellow color to a colorless, growth solution.
To the growth solution was added 0.3mL HCl (37 wt.%) to adjust the pH to 1.2. Then 75. mu.L of AA (64mM), 40. mu.L of the seed solution were added in succession and stirred vigorously. The final solution was left to stand for 12 hours in a 30 ℃ water bath. The solution after growth was centrifuged (7000rpm, 30 minutes), the supernatant removed and CTAB (1-2mM) added, and centrifuged a second time (7000rpm, 30 minutes). After removal of the supernatant, it was dispersed in a corresponding volume of CTAB (1-2 mM).
0.1mL of gold nanorods dispersed in CTAB were taken out of a flask, and CTAC (3.4mL of 30mM), a silver nitrate solution (0.04mL of 4mM), and an ascorbic acid solution (0.05mL of 4mM) were added in this order and stirred with a magnetic stirrer (400rpm) for 30 seconds to mix them uniformly. The solution was placed in a water bath at 60 ℃ and heated for 30 minutes, and after 30 minutes, a potassium tetrachloroplatinate solution (0.04mL of 2mM) was added, followed by heating in a water bath at 60 ℃ for 20 minutes. To the resulting solution was added a silver nitrate solution (0.2mL, 4mM) and heated in a water bath at 60 ℃ for 40 minutes.
And finally, centrifuging the finally obtained product twice (7000rpm for 30 minutes), removing supernatant liquid, and preparing a transmission electron microscope sample to obtain the successfully synthesized gold-silver-platinum-silver multilayer composite material with the asymmetric structure.
Referring to fig. 1, a transmission electron microscope image of an asymmetric gold-silver-platinum-silver multilayer composite material with high uniformity at 60 ℃ with the addition of ascorbic acid to improve reaction efficiency is shown. That is, fig. 1 is a transmission electron microscope image of the asymmetric gold-silver-platinum-silver multilayer composite metal material finally prepared by the invention. As can be seen, the Au-Ag-Pt-Ag multilayer composite material has an asymmetric structure, the length is about 96nm, the diameter is 37nm, and the length-diameter ratio is 2.6. Meanwhile, it can be seen from the figure that the gold-silver-platinum-silver multilayer composite material grows uniformly and has the excellent performances of three metals of gold, silver and platinum.
Example 2
This example differs from example 1 in the amount of silver nitrate added in the last step and thus in the asymmetric composite size that is finally grown.
10mL CTAB (0.1M) and 0.25mL HAuCl4(10mM) are mixed in a bottle with an ice-water mixture and a weighed quantity of NaBH4Mix to make 0.01M solution, and add 0.6mL into the bottle and stir vigorously. The solution changed from golden yellow to brown yellow, which is a seed solution.
2.5mL CTAB (0.1M) and 0.037g NaOL were dissolved in 21.25mL of water at 50 ℃. After dissolution, the solution was cooled to 30 ℃ and then 0.9mL of AgNO was added3(4mM) solution. Standing at 30 deg.C for 15 min, adding 0.25mLHAuCl4(10 mM). After 60-90 minutes of stirring (400rpm), the solution turned from a golden yellow color to a colorless, growth solution.
To the growth solution was added 0.3ml hci (37 wt.%) to adjust the pH to 1.1. Then 75. mu.L of AA (64mM), 40. mu.L of the seed solution were added in succession and stirred vigorously. The final solution was left to stand for 12 hours in a 30 ℃ water bath. The solution after growth was centrifuged (7000rpm, 30 minutes), the supernatant removed and CTAB (1-2mM) added, and centrifuged a second time (7000rpm, 30 minutes). After removal of the supernatant, it was dispersed in a corresponding volume of CTAB (1-2 mM).
0.1mL of gold nanorods dispersed in CTAB were taken out of a bottle, and CTAC (3.4mL of 30mM), a silver nitrate solution (0.04mL of 4mM), and an ascorbic acid solution (0.05mL of 4mM) were added in this order and stirred with a magnetic stirrer (400rpm) for 30 seconds to mix them uniformly. The solution was placed in a water bath at 60 ℃ and heated for 30 minutes, and after 30 minutes, a potassium tetrachloroplatinate solution (0.04mL of 2mM) was added, followed by heating in a water bath at 60 ℃ for 20 minutes. To the resulting solution was added a silver nitrate solution (0.1mL, 4mM) and heated in a water bath at 60 ℃ for 40 minutes.
And finally, centrifuging the finally obtained product twice (7000rpm for 30 minutes), removing supernatant liquid, and preparing a transmission electron microscope sample to obtain the successfully synthesized gold-silver-platinum-silver multilayer composite material with the asymmetric structure.
It can be seen from the observation that the synthesized gold-silver-platinum-silver multilayer composite material of the present example exhibits an asymmetric structure, with a length of about 96nm, a diameter of 38nm and an aspect ratio of 2.5. Meanwhile, the gold-silver-platinum-silver multilayer composite material grows uniformly and has the excellent performances of three metals, namely gold, silver and platinum.
Example 3
This example differs from example 1 in the amount of silver nitrate added in the last step.
10mL CTAB (0.1M) and 0.25mL HAuCl4(10mM) are mixed in a bottle with an ice-water mixture and a weighed quantity of NaBH4Mix to make 0.01M solution, and add 0.6mL into the bottle and stir vigorously. The solution changed from golden yellow to brown yellow, which is a seed solution.
2.5mL CTAB (0.1M) and 0.037g NaOL were dissolved in 21.25mL of water at 50 ℃. After dissolution, the solution was cooled to 30 ℃ and then 0.9mL of AgNO was added3(4mM) solution. And left to stand at a constant temperature of 30 ℃ for 15 minutes, after which 0.25mL of HAuCl was added4(10 mM). After stirring (400rpm) for 60-90 minutes, the solution turned from golden yellow to colorless. This is the growth solution.
To the growth solution was added 0.3mL HCl (37 wt.%) to adjust the pH to 1.3. Then 75. mu.L of AA (64mM), 40. mu.L of the seed solution were added in succession and stirred vigorously. The final solution was left to stand for 12 hours in a 30 ℃ water bath. The solution after growth was centrifuged (7000rpm, 30 minutes), the supernatant removed and CTAB (1-2mM) added, and centrifuged a second time (7000rpm, 30 minutes). After removal of the supernatant, it was dispersed in a corresponding volume of CTAB (1-2 mM).
0.1mL of gold nanorods dispersed in CTAB were taken out of a flask, and CTAC (3.4mL of 30mM), a silver nitrate solution (0.04mL of 4mM), and an ascorbic acid solution (0.05mL of 4mM) were added in this order and stirred with a magnetic stirrer (400rpm) for 30 seconds to mix them uniformly. The solution was placed in a water bath at 60 ℃ and heated for 30 minutes, and after 30 minutes, a potassium tetrachloroplatinate solution (0.04mL of 2mM) was added, followed by heating in a water bath at 60 ℃ for 20 minutes. To the resulting solution was added a silver nitrate solution (0.15mL, 4mM) and heated in a water bath at 60 ℃ for 40 minutes.
And finally, centrifuging the finally obtained product twice (7000rpm for 30 minutes), removing supernatant liquid, and preparing a transmission electron microscope sample to obtain the successfully synthesized gold-silver-platinum-silver multilayer composite material with the asymmetric structure.
It can be seen from the observation that the gold-silver-platinum-silver multilayer composite material synthesized in the present example exhibits an asymmetric structure, with a length of about 97nm, a diameter of 38nm and an aspect ratio of 2.6. Meanwhile, the gold-silver-platinum-silver multilayer composite material grows uniformly and has the excellent performances of three metals, namely gold, silver and platinum.
Example 4
This example differs from example 1 in the amount of silver nitrate added in the last step.
10mL CTAB (0.1M) and 0.25mL HAuCl4(10mM) are mixed in a bottle with an ice-water mixture and a weighed quantity of NaBH4Mix to make 0.01M solution, and add 0.6mL into the bottle and stir vigorously. The solution changed from golden yellow to brown yellow, which is a seed solution.
2.5mL of LCTAB (0.1M) and 0.037g of NaOL were dissolved in 21.25mL of water at 50 ℃. After dissolution, the solution was cooled to 30 ℃ and then 0.9mL of AgNO was added3(4mM) solution. And left to stand at a constant temperature of 30 ℃ for 15 minutes, after which 0.25mL of HAuCl was added4(10 mM). After 60-90 minutes of stirring (400rpm), the solution turned from a golden yellow color to a colorless, growth solution.
To the growth solution was added 0.3mL HCl (37 wt.%) to adjust the pH to 1.2. Then 75. mu.L of AA (64mM), 40. mu.L of the seed solution were added in succession and stirred vigorously. The final solution was left to stand for 12 hours in a 30 ℃ water bath. The solution after growth was centrifuged (7000rpm, 30 minutes), the supernatant removed and CTAB (1-2mM) added, and centrifuged a second time (7000rpm, 30 minutes). After removal of the supernatant, it was dispersed in a corresponding volume of CTAB (1-2 mM).
0.1mL of gold nanorods dispersed in CTAB were taken out of a bottle, and CTAC (3.4mL of 30mM), a silver nitrate solution (0.04mL of 4mM), and an ascorbic acid solution (0.05mL of 4mM) were added in this order and stirred with a magnetic stirrer (400rpm) for 30 seconds to mix them uniformly. The solution was placed in a water bath at 60 ℃ and heated for 30 minutes, and after 30 minutes, a potassium tetrachloroplatinate solution (0.04mL of 2mM) was added, followed by heating in a water bath at 60 ℃ for 20 minutes. To the resulting solution was added a silver nitrate solution (0.25mL, 4mM) and heated in a water bath at 60 ℃ for 40 minutes.
And finally, centrifuging the finally obtained product twice (7000rpm for 30 minutes), removing supernatant liquid, and preparing a transmission electron microscope sample to obtain the successfully synthesized gold-silver-platinum-silver multilayer composite material with the asymmetric structure.
It can be seen from the observation that the gold-silver-platinum-silver multilayer composite material synthesized in the present example exhibits an asymmetric structure, with a length of about 97nm, a diameter of 39nm, and an aspect ratio of 2.5. Meanwhile, the gold-silver-platinum-silver multilayer composite material grows uniformly and has the excellent performances of three metals, namely gold, silver and platinum.
Example 5
This example differs from example 1 in the amount of silver nitrate added in the last step.
10mL CTAB (0.1M) and 0.25mL HAuCl4(10mM) are mixed in a bottle with an ice-water mixture and a weighed quantity of NaBH4Mix to make 0.01M solution, and add 0.6mL into the bottle and stir vigorously. The solution changed from golden yellow to brown yellow, which is a seed solution.
2.5mL CTAB (0.1M) and 0.037g NaOL were dissolved in 21.25mL of water at 50 ℃. After dissolution, the solution was cooled to 30 ℃ and then 0.9mL of AgNO was added3(4mM) solution. And left to stand at a constant temperature of 30 ℃ for 15 minutes, after which 0.25mL of HAuCl was added4(10 mM). After 60-90 minutes of stirring (400rpm), the solution turned from a golden yellow color to a colorless, growth solution.
To the growth solution was added 0.3mL HCl (37 wt.%) to adjust the pH to 1.2. Then 75. mu.L of AA (64mM), 40. mu.L of the seed solution were added in succession and stirred vigorously. The final solution was left to stand for 12 hours in a 30 ℃ water bath. The solution after growth was centrifuged (7000rpm, 30 minutes), the supernatant removed and CTAB (1-2mM) added, and centrifuged a second time (7000rpm, 30 minutes). After removal of the supernatant, it was dispersed in a corresponding volume of CTAB (1-2 mM).
0.1mL of gold nanorods dispersed in CTAB were taken out of a bottle, and CTAC (3.4mL of 30mM), a silver nitrate solution (0.04mL of 4mM), and an ascorbic acid solution (0.05mL of 4mM) were added in this order and stirred with a magnetic stirrer (400rpm) for 30 seconds to mix them uniformly. The solution was placed in a water bath at 60 ℃ and heated for 30 minutes, and after 30 minutes, a potassium tetrachloroplatinate solution (0.04mL of 2mM) was added, followed by heating in a water bath at 60 ℃ for 20 minutes. To the resulting solution was added a silver nitrate solution (0.3mL, 4mM) and heated in a water bath at 60 ℃ for 40 minutes.
And finally, centrifuging the finally obtained product twice (7000rpm for 30 minutes), removing supernatant liquid, and preparing a transmission electron microscope sample to obtain the successfully synthesized gold-silver-platinum-silver multilayer composite material with the asymmetric structure.
It can be seen from the observation that the gold-silver-platinum-silver multilayer composite material synthesized in the present example exhibits an asymmetric structure, with a length of about 98nm, a diameter of 40nm and an aspect ratio of 2.5. Meanwhile, the gold-silver-platinum-silver multilayer composite material grows uniformly and has the excellent performances of three metals, namely gold, silver and platinum.
Finally, it should be noted that the above embodiments are only used to help understand the method of the present invention and its core idea, and not to limit it. Those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the present invention's device solution. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A synthetic method of an asymmetric gold-silver-platinum-silver multilayer composite material is characterized by comprising the following steps:
step S1: preparing gold nanorods by using a seed growth method:
s10: 10mL of 0.1M CTAB and 0.25mL of 10mM HAuCl4Mixing in a bottle, mixing with ice-water mixture and certain amount of NaBH4Mixing to prepare 0.01M solution, adding 0.6mL of the solution into a bottle, and stirring to obtain seed solution;
s11: 2.5mL of 0.1M CTAB and 0.037g of NaOL were dissolved in 21.25mL of water at 50 ℃; after dissolution, the solution was cooled to 30 ℃ and then 0.9mL of 4m AgNO was added3The solution was allowed to stand at a constant temperature, and then 0.25mL of the solution was added10mM HAuCl4Stirring to obtain a growth solution;
s12: adjusting the pH value of the growth solution, sequentially adding 75 mu L of 64mM AA and 40 mu L of seed solution, stirring, and standing at constant temperature;
s13: centrifuging the solution after growth, removing clear liquid, and dispersing the obtained gold nanorods in 1-2mM CTAB;
step S2: taking 0.1mL of gold nanorods dispersed in CTAB in S13, adding 3.4mL of 30mM CTAC, 0.04mL of 4mM silver nitrate solution and 0.05mL of 4mM ascorbic acid solution in turn, stirring to mix uniformly, and then placing in a water bath at 60 ℃ for heating for 30 minutes;
step S3: adding 0.04mL of 2mL potassium tetrachloroplatinate solution into the solution obtained in the step S2, stirring to mix the solution uniformly, and then heating the mixture in a water bath at 60 ℃ for 20 minutes;
step S4: adding 0.2mL of 4mM silver nitrate solution into the solution obtained in the step S3, and heating in a water bath at 60 ℃ for 40 minutes;
step S5: and (5) centrifuging the product obtained in the step (S4), and removing supernatant to obtain the gold-silver-platinum-silver multilayer composite material with the asymmetric structure.
2. The method for synthesizing an asymmetric gold-silver-platinum-silver multilayer composite material as claimed in claim 1, wherein in S11, the standing temperature is 30 ℃ and the standing time is 15 minutes.
3. The method for synthesizing an asymmetric gold-silver-platinum-silver multilayer composite material as claimed in claim 1, wherein in S11, the stirring speed is 400rpm and the stirring time is 60-90 minutes.
4. The method for synthesizing the asymmetric gold-silver-platinum-silver multilayer composite material as claimed in claim 1, wherein in S12, the pH value is adjusted to 1.1-1.3 by adding 0.3mL of 37 wt.% HCl into the growth solution.
5. The method for synthesizing an asymmetric gold-silver-platinum-silver multilayer composite material as claimed in claim 1, wherein in S12, the constant temperature standing condition is heating in water bath for 30 ℃, and standing for 12 hours.
6. The method for synthesizing an asymmetric gold-silver-platinum-silver multilayer composite material as claimed in claim 1, wherein in S13, the solution after growth is centrifuged 2 times, the first solution is centrifuged at 7000rpm for 30 minutes, the supernatant is removed, then 1-2mM CTAB is added, and the second solution is centrifuged at 7000rpm for 30 minutes.
7. An asymmetric gold-silver-platinum-silver multilayer composite, characterized by being synthesized by any one of claims 1 to 6.
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