CN112828284B - Preparation method of mesoporous silica-coated gold nanorod surface-grown silver composite material - Google Patents

Preparation method of mesoporous silica-coated gold nanorod surface-grown silver composite material Download PDF

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CN112828284B
CN112828284B CN202011631700.2A CN202011631700A CN112828284B CN 112828284 B CN112828284 B CN 112828284B CN 202011631700 A CN202011631700 A CN 202011631700A CN 112828284 B CN112828284 B CN 112828284B
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CN112828284A (en
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邓天松
张棋
卫鸣璋
顾伊杰
程知群
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Hangzhou Dianzi University
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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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • 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
    • 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
    • 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 discloses a preparation method of a mesoporous silica-coated gold nanorod surface growth silver composite material. Gold nanorods were first synthesized using cetyltrimethylammonium bromide (CTAB) and sodium oleate (NaOL) as the bi-surfactants using a seed-mediated method. The mesoporous silica-coated gold nanorod surface growth silver composite material prepared by the invention is uniform in growth. The method has the advantages of simple reaction conditions, high reaction rate and low cost.

Description

Preparation method of mesoporous silica-coated gold nanorod surface-grown silver composite material
Technical Field
The invention relates to the field of synthesis of metal nano materials, in particular to a preparation method of a silver composite material growing on the surface of a mesoporous silica-coated gold nanorod.
Background
Research on noble metal nanoparticles has been rapidly developed in recent years, with gold nanorods being the most prominent. Since gold nanorods have very abundant chemical and physical properties, first it can be used in life sciences including in vitro diagnostics, in vivo imaging and in vivo therapy. Secondly, gold nanorods are also widely used in the sensor field, and can be used for trace molecule and ion detection due to the gold nanorods have extremely strong surface raman scattering enhancement and surface plasmon resonance performance. Meanwhile, the gold nanorods can also be made into optical elements, such as: near infrared filters, solar cells, polarizers, and the like. In recent years, the excellent performance of bimetallic structures has become well known and has become the focus of research. Firstly, because silver has excellent surface properties and chemical activity, the silver can show unique thermal, electrical, optical, acoustic, magnetic, mechanical and catalytic properties, and can be widely applied to the fields of superconduction, chemical engineering, medicine, optics, electronics, electrical appliances and the like. Therefore, it is very important to combine the excellent properties of gold and silver. Meanwhile, in recent years, mesoporous silica has relative stability, and the gold nanorods coated by the mesoporous silica have more stable performance.
Therefore, how to combine the excellent properties of gold-silver bimetal into mesoporous silica to enhance its stability becomes the focus of research of researchers. The stable structure can be widely used in the aspects of biological medical treatment, optical catalysis and the like. Therefore, how to efficiently synthesize a uniform mesoporous silica-coated gold nanorod surface growth silver composite material becomes a problem to be solved at present.
Disclosure of Invention
In order to solve the problems that the synthesis efficiency of the mesoporous silica coated gold nanorod surface silver growing composite material is low and the final synthesis result is not uniform, the invention provides a synthesis method of the mesoporous silica coated gold nanorod surface silver growing composite material, which can efficiently synthesize the uniform mesoporous silica coated gold nanorod surface silver growing material, and has the advantages of simple reaction conditions and low cost.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a synthetic method of a mesoporous silica-coated gold nanorod surface silver growth composite material comprises the following steps:
step S1, preparing the gold nanorods by using a seed growth method.
Wherein, the step S1 further comprises the following steps:
s10 mixing 10mL CTAB (0.1M) and 0.25mL HAuCl 4 (10 mM) are mixed in a bottle with an ice-water mixture and a weighed quantity of NaBH 4 Mix 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.
S11 2.5mL CTAB (0.1M) and 0.037g NaOL were dissolved in 21.25mL water at 50 ℃. After dissolution the solution was cooled to 30 ℃ and then 0.9mL of AgNO3 (4 mM) solution was added. Standing at 30 deg.C for 15 min, and adding 0.25mL HAuCl 4 (10 mM). After stirring (400 rpm) for 60-90 minutes, the solution turned from golden yellow to colorless. This is the growth solution.
S12 pH was adjusted by adding 0.3mL HCl (37 wt.%) to the growth solution. Then 75. Mu.L of AA (64 mM), 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.
S13-centrifuge the solution after growth (7000 rpm,30 minutes), remove the supernatant, add CTAB (1-2 mM), centrifuge again (7000 rpm,30 minutes). After removal of the supernatant, it was dispersed in a corresponding volume of CTAB (1-2 mM).
The step S2 further includes the steps of:
s20, putting gold nanorods dispersed in CTAB into a bottle, adding 0.4mL of 0.1M NaOH solution, adding 0.05mL of TEOS, stirring for 30 minutes, then repeatedly adding the same amount of TEOS 6 times and stirring for 30 minutes, and stirring the final solution for 2 days after the sixth time;
s21: the solution was put in a 60 ℃ oil bath, and it was subjected to etching for 10 minutes by adding 0.2mL of concentrated hydrochloric acid, and then cooled methanol was added to terminate the etching, followed by centrifugation (8000rpm, 10min). Dispersing the precipitate in 2mL of aqueous solution;
the step S3 further comprises the steps of:
s30: 0.8mL of the product dispersed in the aqueous solution was taken out, 0.02mL of a 0.02M silver nitrate solution and 0.04mL of a 0.04M ascorbic acid solution were added thereto, and the mixture was stirred for 2 minutes.
S31: centrifuging the final product at 7000rpm for 30 minutes, removing supernatant, adding 1-2mM CTAB, centrifuging at 7000rpm for 30 minutes twice, and preparing a transmission electron microscope sample, thus observing the successfully synthesized silver composite material grown on the surface of the mesoporous silica-coated gold nanorod.
As a further improvement, the step S2 is carried out under the heating condition of 60 ℃ oil bath, so that the time of the corrosion reaction is greatly shortened, and the corrosion rate can be controlled by controlling the amount of the added hydrochloric acid. Meanwhile, after silver nitrate and ascorbic acid are added in the step S3, the mixture is stirred for 2 minutes, and then the uniform mesoporous silica coated gold nanorod surface silver growing composite material can be obtained.
In the technical scheme of the invention, the synthesis is carried out by adopting a seed growth method, and the whole process can be divided into three parts. In the first part, a seed growing method is firstly utilized to successfully synthesize uniform gold nanorods. And secondly, a corrosion process, namely, taking gold nanorods which are cleaned and dispersed in low-concentration Cetyl Trimethyl Ammonium Bromide (CTAB), adding a certain amount of NaOH solution in a centrifugal mode, adding TEOS solution for 6 times at intervals of 30 minutes, stirring for two days to obtain the gold nanorods coated by the mesoporous silica, adding methanol into the gold nanorods coated by the mesoporous silica, placing the gold nanorods in an oil bath at the temperature of 60 ℃, controlling the amount of added hydrochloric acid, and corroding the gold nanorods. Thirdly, taking out the corroded gold nanorods coated by the silicon dioxide, adding a silver nitrate solution and an ascorbic acid solution, and stirring for 2 minutes to finally obtain the uniformly-grown silver composite material on the surfaces of the mesoporous silicon dioxide coated gold nanorods; and the reaction condition is simple and the cost is low.
The invention synthesizes a mesoporous silica-coated gold nanorod surface silver-growing composite material, which takes a gold nanorod as a core and mesoporous silica as a shell, and silver is grown on the surface of the gold nanorod by corroding the mesoporous silica-coated gold nanorod and adding a silver nitrate solution and an ascorbic acid solution. Finally, the uniform mesoporous silica-coated gold nanorod surface-grown silver composite material can be obtained.
As a further improvement scheme, the material is prepared by the method, wherein gold nanorods which have successfully grown are used as seeds, and a certain amount of NaOH solution and TEOS are added to obtain the gold nanorods coated by the mesoporous silica; then, carrying out centrifugation, controlling the reaction temperature and controlling the amount of the added hydrochloric acid, and corroding the gold nanorods coated with the mesoporous silica; finally, silver is grown on the surface of the mesoporous silica coated gold nanorods by adding silver nitrate and ascorbic acid. The existing synthesis method has the defects that the silver grows on the surface of the mesoporous silica-coated gold nanorod unevenly, the silver deposition is not seen on the surface of some gold nanorods, and the ratio of the silver successfully growing on the surface of the silica-coated gold nanorods is very low; too long reaction time and the like. Therefore, the mesoporous silica-coated gold nanorod surface growth silver composite material synthesized by the method has the following beneficial effects:
(1) The synthesized composite material does not completely change the performance of the gold nanorods, but retains the special properties of the gold nanorods.
(2) The uniform growth of the composite material enhances the catalytic performance of the gold nanorods, has two metal structures of gold and silver, and can enhance the catalytic activity, thereby realizing the effect of lower energy.
(3) The composite material has simple synthesis method, and the final product is very stable and has very high reliability.
(4) The composite material has some special excellent properties of both gold and silver, and thus can be widely applied. For example: biomedicine, optical catalysis, etc.
Drawings
FIG. 1 is a flow chart of the synthesis steps of the mesoporous silica coated gold nanorod surface silver composite material of the present invention;
FIG. 2 is a transmission electron microscope (transmission electron microscope of example 1) of a mesoporous silica coated gold nanorod surface grown silver composite synthesized by the present invention;
Detailed Description
The technical solution provided by the present invention will be further explained with reference to the accompanying drawings.
The gold nanorods have good physical and chemical properties, surface plasmon resonance performance and can be widely applied to the field of catalysis, especially photo-thermal conversion. Therefore, naOH and TEOS are added into the prepared gold nanorods to form the gold nanorods coated by the mesoporous silica, and then the gold nanorods are corroded by controlling the amount of the added hydrochloric acid under the condition of oil bath at the temperature of 60 ℃. Finally, silver nitrate solution and ascorbic acid solution with corresponding amount are added into the corroded mesoporous silica-coated gold nanorods, so that silver can uniformly grow on the surfaces of the gold nanorods. Therefore, the finally synthesized mesoporous silica-coated gold nanorod surface-grown silver composite material can greatly enhance the catalytic efficiency, has higher catalytic activity and has higher stability. Therefore, the invention provides a synthetic method of the gold-platinum-silver material with the asymmetric structure.
Referring to fig. 1, the method for synthesizing gold-silver material provided by the present invention specifically comprises the following steps:
step S1, preparing the gold nanorods by using a seed growth method.
And S2, a corrosion process, namely, taking gold nanorods which are cleaned and dispersed in low-concentration Cetyl Trimethyl Ammonium Bromide (CTAB), adding a certain amount of NaOH solution in a centrifugal mode, adding TEOS solution for 6 times at intervals of 30 minutes, stirring for two days to obtain the gold nanorods coated by the mesoporous silica, adding methanol into the gold nanorods coated by the mesoporous silica, placing the gold nanorods in an oil bath at the temperature of 60 ℃, controlling the amount of added hydrochloric acid, and corroding the gold nanorods.
And S3, a regrowing process, namely taking out the corroded gold nanorods coated by the silicon dioxide, then adding a silver nitrate solution and an ascorbic acid solution, and stirring for 2 minutes to finally obtain the mesoporous silicon dioxide coated gold nanorod surface silver-grown composite material (see figure 2).
Wherein, the step S1 further comprises the following steps:
s10 mixing 10mL CTAB (0.1M) and 0.25mL HAuCl 4 (10 mM) are mixed in a bottle with an ice-water mixture and a weighed quantity of NaBH 4 Mix 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.
S11 2.5mL CTAB (0.1M) and 0.037g NaOL were dissolved in 21.25mL water at 50 ℃. After dissolution, the solution was cooled to 30 ℃ and then 0.9mL of AgNO was added 3 (4 mM) solution. And left to stand at a constant temperature of 30 ℃ for 15 minutes, after which 0.25mL of HAuCl was added 4 (10 mM). After stirring (400 rpm) for 60-90 minutes, the solution turned from golden yellow to colorless. This is the growth solution.
S12 pH was adjusted by adding 0.3mL HCl (37 wt.%) to the growth solution. Then 75. Mu.L of AA (64 mM), 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.
S13-centrifuge the solution after growth (7000 rpm,30 minutes), remove the supernatant, add CTAB (1-2 mM), centrifuge again (7000 rpm,30 minutes). After removal of the supernatant, it was dispersed in a corresponding volume of CTAB (1-2 mM).
The step S2 further includes the steps of:
s20, putting gold nanorods dispersed in CTAB into a bottle, adding 0.4mL of 0.1M NaOH solution, adding 0.05mL of TEOS, stirring for 30 minutes, then repeatedly adding the same amount of TEOS 6 times and stirring for 30 minutes, and stirring the final solution for 2 days after the sixth time;
s21: the solution was put in a 60 ℃ oil bath, and it was subjected to etching for 10 minutes by adding 0.2mL of concentrated hydrochloric acid, and then cooled methanol was added to terminate the etching, followed by centrifugation (8000rpm, 10min). Dispersing the precipitate in 2mL of aqueous solution;
the step S3 further includes the steps of:
s30: 0.8mL of the product dispersed in the aqueous solution was taken out, 0.02mL of a 0.02M silver nitrate solution and 0.04mL of a 0.04M ascorbic acid solution were added thereto, and the mixture was stirred for 2 minutes.
S31: centrifuging the final product at 7000rpm for 30 minutes, removing supernatant, adding 1-2mM CTAB, centrifuging at 7000rpm for 30 minutes twice, and preparing a transmission electron microscope sample, thus observing the successfully synthesized silver composite material grown on the surface of the mesoporous silica-coated gold nanorod.
In the existing synthesis method, silver grows on the surface of the gold nanorod coated by the mesoporous silica, and the defects of uneven silver growth, difficult regulation and control of silver amount, long reaction time and the like exist. The method has the advantages over other methods that: heating in an oil bath at 60 ℃, improving the rate of reaction, adding 0.02mL of 0.02M silver nitrate solution and then 0.04mL of 0.04M ascorbic acid solution according to the proportion, enabling silver to grow uniformly on the surface of the gold nanorod, wherein the proportion of more than 99% is the product of silver growth on the surface of the gold nanorod coated with the mesoporous silica with uniform growth. Referring to fig. 2, a transmission electron microscope image of silver grown on the surface of the gold nanorods coated with mesoporous silica is shown. As can be seen, the length of the composite material is 92nm, the diameter is 49nm, and the aspect ratio is 1.9. It can also be seen from the figure that the silver in the composite material grows uniformly on the surface of gold, the structure greatly enhances the stability, and the composite material has the excellent performance of the gold and the silver.
Example 1:
10mL of CTAB (0.1M) and 0.25mL of HAuCl 4 (10 mM) are mixed in a bottle with an ice-water mixture and a weighed quantity of NaBH 4 Mix 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 added 3 (4 mM) solution. And left to stand at a constant temperature of 30 ℃ for 15 minutes, after which 0.25mL of HAuCl was added 4 (10 mM). After stirring (400 rpm) 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. Then 75. Mu.L of AA (64 mM), 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 (7000 rpm,30 minutes), and CTAB (1-2 mM) was added after removing the supernatant, and centrifuged twice (7000 rpm,30 minutes). After removal of the clear solution, it was dispersed in CTAB (1-2 mM) in the corresponding volume. Taking gold nanorods dispersed in CTAB, adding 0.4mL of 0.1M NaOH solution, adding 0.05mL of TEOS, stirring for 30 minutes, then repeatedly adding the same amount of TEOS 6 times and stirring for 30 minutes, and stirring the final solution for 2 days after the sixth time; the solution was put in a 60 ℃ oil bath, and it was subjected to etching for 10 minutes by adding 0.2mL of concentrated hydrochloric acid, and then cooled methanol was added to terminate the etching, followed by centrifugation (8000rpm, 10min). Then dispersing the precipitate in 2mL of aqueous solution; 0.8mL of the product dispersed in the aqueous solution was taken out, 0.02mL of 0.02M silver nitrate solution was added, 0.04mL of 0.04M ascorbic acid solution was further added, and the mixture was stirred for 2 minutes. Subjecting the obtained product to final treatmentAnd centrifuging the product at 7000rpm for 30 minutes, removing supernatant, adding 1-2mM CTAB, centrifuging at 7000rpm for 30 minutes twice, and preparing a transmission electron microscope sample to observe the successfully synthesized silver composite material grown on the surface of the mesoporous silica-coated gold nanorod.
Example 2:
10mL CTAB (0.1M) and 0.25mL HAuCl 4 (10 mM) are mixed in a bottle with an ice-water mixture and a weighed quantity of NaBH 4 Mix 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 added 3 (4 mM) solution. And left to stand at a constant temperature of 30 ℃ for 15 minutes, after which 0.25mL of HAuCl was added 4 (10 mM). After stirring (400 rpm) 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. Then 75. Mu.L of AA (64 mM), 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 (7000 rpm,30 minutes), and CTAB (1-2 mM) was added after removing the supernatant, and centrifuged twice (7000 rpm,30 minutes). After removal of the clear solution, it was dispersed in CTAB (1-2 mM) in the corresponding volume. Taking gold nanorods dispersed in CTAB, adding 0.4mL0.1M NaOH solution, adding 0.05mL TEOS, stirring for 30 minutes, then repeating 6 times of adding the same amount of TEOS and stirring for 30 minutes, and stirring the final solution for 2 days after the sixth time; the solution was put in a 60 ℃ oil bath, and it was subjected to etching for 10 minutes by adding 0.2mL of concentrated hydrochloric acid, and then cooled methanol was added to terminate the etching, followed by centrifugation (8000rpm, 10min). Dispersing the precipitate in 2mL of aqueous solution; 0.5mL of the product dispersed in the aqueous solution was taken out, 0.0125mL of a 0.02M silver nitrate solution was added, and 0.025mL of a 0.04M ascorbic acid solution was further added, and the mixture was stirred for 2 minutes. 1mL of the above product was taken out and the spectrum was measured, which was taken as the final spectrum. Centrifuging the final product at 7000rpm for 30 min, removing supernatant, adding 1-2mM CTAB, centrifuging at 7000rpm for 30 min, and preparing transmission electron microscopeThe silver composite material can be successfully synthesized by observing the growth of the silver on the surface of the mesoporous silica-coated gold nanorod.
Example 3:
10mL of CTAB (0.1M) and 0.25mL of HAuCl 4 (10 mM) are mixed in a bottle with an ice-water mixture and a weighed quantity of NaBH 4 Mix 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 added 3 (4 mM) solution. And left to stand at a constant temperature of 30 ℃ for 15 minutes, after which 0.25mL of HAuCl was added 4 (10 mM). After stirring (400 rpm) 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 control the pH. Then 75. Mu.L of AA (64 mM), 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 (7000 rpm,30 minutes), and CTAB (1-2 mM) was added after removing the supernatant, and centrifuged twice (7000 rpm,30 minutes). After removal of the supernatant, it was dispersed in a corresponding volume of CTAB (1-2 mM). Taking gold nanorods dispersed in CTAB, adding 0.4mL0.1M NaOH solution, adding 0.05mL TEOS, stirring for 30 minutes, then repeating 6 times of adding the same amount of TEOS and stirring for 30 minutes, and stirring the final solution for 2 days after the sixth time; the solution was placed in a 60 ℃ oil bath, corroded for 10 minutes by the addition of 0.2mL concentrated HCl, quenched by the addition of cold methanol, and centrifuged (8000rpm, 10min). Dispersing the precipitate in 2mL of aqueous solution; 0.6mL of the product dispersed in the aqueous solution was taken out, 0.015mL of a 0.02M silver nitrate solution was added, and 0.03mL of a 0.04M ascorbic acid solution was further added, and the mixture was stirred for 2 minutes. Centrifuging the final product at 7000rpm for 30 minutes, removing supernatant, adding 1-2mM CTAB, centrifuging at 7000rpm for 30 minutes twice, and preparing a transmission electron microscope sample, thus observing the successfully synthesized silver composite material grown on the surface of the mesoporous silica-coated gold nanorod.
Example 4:
10mL CTAB (0.1M) and 0.25mL HAuCl 4 (10 mM) are mixed in a bottle with an ice-water mixture and a weighed quantity of NaBH 4 Mix 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 added 3 (4 mM) solution. And left to stand at a constant temperature of 30 ℃ for 15 minutes, after which 0.25mL of HAuCl was added 4 (10 mM). After stirring (400 rpm) 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. Then 75. Mu.L of AA (64 mM), 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 (7000 rpm,30 minutes), and CTAB (1-2 mM) was added after removing the supernatant, and centrifuged twice (7000 rpm,30 minutes). After removal of the clear solution, it was dispersed in CTAB (1-2 mM) in the corresponding volume. Taking gold nanorods dispersed in CTAB, adding 0.4mL of 0.1M NaOH solution, adding 0.05mL of TEOS, stirring for 30 minutes, then repeatedly adding the same amount of TEOS 6 times and stirring for 30 minutes, and stirring the final solution for 2 days after the sixth time; the solution was put in a 60 ℃ oil bath, and it was subjected to etching for 10 minutes by adding 0.2mL of concentrated hydrochloric acid, and then cooled methanol was added to terminate the etching, followed by centrifugation (8000rpm, 10min). Dispersing the precipitate in 2mL of aqueous solution; 1mL of the product dispersed in the aqueous solution was taken out, 0.025mL of a 0.02M silver nitrate solution was added, and 0.05mL of a 0.04M ascorbic acid solution was further added, and the mixture was stirred for 2 minutes. And (3) centrifuging the obtained final product at 7000rpm for 30 minutes, removing supernatant, adding 1-2mM CTAB, centrifuging at 7000rpm for 30 minutes twice, and preparing a transmission electron microscope sample to observe the successfully synthesized silver composite material grown on the surface of the mesoporous silica-coated gold nanorod.
Example 5:
10mL CTAB (0.1M) and 0.25mL HAuCl 4 (10 mM) are mixed in a bottle with an ice-water mixture and a weighed quantity of NaBH 4 Mix to make 0.01M solution, and add 0.6mL into the bottle and stir vigorously. SolutionThe solution changed from golden yellow to brown yellow, which is the 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 added 3 (4 mM) solution. And left to stand at a constant temperature of 30 ℃ for 15 minutes, after which 0.25mL of HAuCl was added 4 (10 mM). After stirring (400 rpm) 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. Then 75. Mu.L of AA (64 mM), 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 (7000 rpm,30 minutes), and CTAB (1-2 mM) was added after removing the supernatant, and centrifuged twice (7000 rpm,30 minutes). After removal of the clear solution, it was dispersed in CTAB (1-2 mM) in the corresponding volume. Taking gold nanorods dispersed in CTAB, adding 0.4mL of 0.1M NaOH solution, adding 0.05mL of TEOS, stirring for 30 minutes, then repeatedly adding the same amount of TEOS 6 times and stirring for 30 minutes, and stirring the final solution for 2 days after the sixth time; the solution was placed in a 60 ℃ oil bath, corroded for 10 minutes by the addition of 0.2mL concentrated HCl, quenched by the addition of cold methanol, and centrifuged (8000rpm, 10min). Dispersing the precipitate in 2mL of aqueous solution; 0.7mL of the product dispersed in the aqueous solution was taken out, 0.0175mL of 0.02M silver nitrate solution was added, and 0.035mL of 0.04M ascorbic acid solution was further added, and the mixture was stirred for 2 minutes. Centrifuging the final product at 7000rpm for 30 minutes, removing supernatant, adding 1-2mM CTAB, centrifuging at 7000rpm for 30 minutes twice, and preparing a transmission electron microscope sample, thus observing the successfully synthesized silver composite material grown on the surface of the mesoporous silica-coated gold nanorod.
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 (1)

1. A preparation method of a mesoporous silica coated gold nanorod surface growth silver composite material is characterized by comprising the following steps:
s1, preparing gold nanorods by using a seed growth method;
s2, a corrosion process, namely adding a certain amount of NaOH solution into the washed gold nanorods dispersed in low-concentration hexadecyl trimethyl ammonium bromide, adding TEOS solution into the gold nanorods at intervals of 30 minutes for 6 times, stirring the solution for two days to obtain mesoporous silica-coated gold nanorods, placing the mesoporous silica-coated gold nanorods into a 60-DEG oil bath, adding concentrated hydrochloric acid, controlling the amount of the added concentrated hydrochloric acid, and corroding the gold nanorods;
s3, a regrowing process, namely taking out the corroded gold nanorods coated by the silicon dioxide, adding a silver nitrate solution and an ascorbic acid solution, and stirring for 2 minutes to finally obtain the mesoporous silicon dioxide coated gold nanorod surface growth silver composite material;
wherein, the step S1 specifically comprises the following steps:
s10, mixing 10mL of 0.1M CTAB and 0.25mL of 10mM HAuCl4 in a bottle, mixing an ice-water mixture with a weighed certain mass of NaBH4 to prepare a 0.01M solution, and adding 0.6mL into the bottle for vigorous stirring; the solution turns from golden yellow to brown yellow, which is a seed solution;
s11, 2.5mL of 0.1M CTAB and 0.037g of NaOL were dissolved in 21.25mL water at 50 ℃; after dissolution, cooling the solution to 30 ℃, and then adding 0.9mL of 4mM AgNO3 solution; and left to stand at a constant temperature of 30 ℃ for 15 minutes, after which 0.25mL of 10mM HAuCl4 was added; after stirring at 400rpm for 60-90 minutes, the solution turns from golden yellow to colorless; this is the growth solution;
s12, adding 0.3mL of 37wt.% HCl into the growth solution to regulate the pH value; then 75 μ L of 64mM AA,40 μ L of seed solution are added in turn and stirred vigorously; standing the final solution for 12 hours in a water bath at 30 ℃;
s13, centrifuging the solution after growth at 7000rpm for 30 minutes, removing the supernatant, adding 1-2mM CTAB, centrifuging at 7000rpm again for 30 minutes, removing the supernatant, and dispersing in 1-2mM CTAB in a corresponding volume;
the step S2 specifically includes the following steps:
s20, putting gold nanorods dispersed in CTAB into a bottle, adding 0.4mL of 0.1M NaOH solution, adding 0.05mL of TEOS, stirring for 30 minutes, repeatedly adding the same amount of TEOS 6 times, stirring for 30 minutes, and stirring the final solution for 2 days after the sixth time;
s21: placing the solution in an oil bath at 60 ℃, adding 0.2mL concentrated hydrochloric acid to corrode the solution for 10 minutes, then adding cold methanol to finish corrosion, and then centrifuging the solution at 8000rpm for 10 minutes; dispersing the precipitate in 2mL aqueous solution;
the step S3 further includes the steps of:
s30: the product 0.8mL dispersed in the aqueous solution was taken out, 0.02mL of 0.02M silver nitrate solution was added, 0.04mL of 0.04M ascorbic acid solution was further added, and stirring was carried out for 2 minutes;
s31: centrifuging the obtained final product at 7000rpm for 30 minutes, removing supernatant, adding CTAB of 1-2mM, centrifuging at 7000rpm again for 30 minutes, and preparing a transmission electron microscope sample, so that the successfully synthesized mesoporous silica-coated gold nanorod surface silver-grown composite material can be observed;
the composite material prepared had a length of 92nm, a diameter of 49nm, and an aspect ratio of 1.9.
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