CN112846219A - Preparation method of gold nanorod-palladium composite material - Google Patents
Preparation method of gold nanorod-palladium composite material Download PDFInfo
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 105
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000010931 gold Substances 0.000 title claims abstract description 41
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 148
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000003756 stirring Methods 0.000 claims abstract description 44
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000012010 growth Effects 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 19
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 19
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 19
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims abstract description 19
- 239000003921 oil Substances 0.000 claims abstract description 17
- 239000012467 final product Substances 0.000 claims abstract description 15
- 230000007797 corrosion Effects 0.000 claims abstract description 13
- 238000005260 corrosion Methods 0.000 claims abstract description 13
- 230000005540 biological transmission Effects 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000006228 supernatant Substances 0.000 claims description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 14
- 101710134784 Agnoprotein Proteins 0.000 claims description 7
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 5
- 230000035040 seed growth Effects 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000001000 micrograph Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 3
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011503 in vivo imaging Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
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- 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
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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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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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
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a preparation method of a gold nanorod-palladium composite material. And then placing the gold nanorods coated with the silicon dioxide in an oil bath at 60 ℃ for heating, starting the corrosion process by adding a corresponding amount of hydrochloric acid, and then adding a large amount of cold methanol to finish the corrosion. The product was then centrifuged (8000rpm,10min) and the resulting precipitate dispersed in an aqueous solution. And finally, adding a corresponding amount of sodium tetrachloropalladate solution, adding a corresponding amount of ascorbic acid solution, and stirring for 1 minute to obtain a final product. And observing the growth condition of the strain by a transmission electron microscope image. The gold nanorod-palladium composite material prepared by the invention grows uniformly. The method has the advantages of simple reaction conditions, high reaction rate and low cost.
Description
Technical Field
The invention relates to the field of synthesis of precious metal nano materials, in particular to a preparation method of a gold nanorod-palladium composite material.
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 strong surface raman scattering enhancement and surface plasmon resonance characteristics. 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, the gold-palladium bimetallic structure has super strong catalytic performance, and can provide great development prospect for biological catalysis. Therefore, it is very important to combine the excellent properties of gold and palladium. 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-palladium 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 medicine, optical catalysis and the like. Therefore, how to efficiently synthesize a uniform mesoporous silica-coated gold nanorod-palladium composite material becomes a problem to be solved at present.
Disclosure of Invention
In order to solve the problems of low synthesis efficiency and uneven final synthesis result of the gold nanorod-palladium composite material, the invention provides a synthesis method of the gold nanorod-palladium composite material, which can efficiently synthesize the uniform mesoporous silica-coated gold nanorod-palladium composite material, and has the advantages of simple reaction condition and low cost.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a synthesis method of a gold nanorod-palladium composite material comprises the following steps:
and step S1, preparing the gold nanorods by using a seed growth method.
Wherein the step S1 further includes the following steps:
s10 mixing 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.
S11 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.
S12 pH was adjusted by adding 0.3mL HCl (37 wt.%) to the growth solution. 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.
S13 the solution after growth was centrifuged (7000rpm, 30 minutes), the supernatant removed and CTAB (1-2mM) added, followed by a second centrifugation (7000rpm, 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 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;
s21: the solution was placed in a 60 ℃ oil bath and etched for 10 minutes by adding 0.1mL of concentrated HCl, followed by addition of cold methanol to quench the etching, and then centrifuged (8000rpm,10 min). Dispersing the precipitate in an 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 sodium tetrachloropalladate solution was added, and 0.04mL of a 0.04M ascorbic acid solution was further added, and the mixture was stirred for 1 minute.
S31: and centrifuging the obtained final product at 7000rpm for 30 minutes, removing supernatant, adding an aqueous solution, centrifuging at 7000rpm for 30 minutes twice, and preparing a transmission electron microscope sample to observe the successfully synthesized gold nanorod-palladium composite material.
As a further improvement, the step S2 is carried out under the oil bath heating condition of 60 ℃, 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 adding sodium tetrachloropalladate and ascorbic acid in step S3, stirring for 1 minute, the uniform mesoporous silica-coated gold nanorod-palladium 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 CTAB, centrifugally adding a certain amount of NaOH solution into the gold nanorods, adding TEOS solution into the gold nanorods at intervals of 30 minutes for 6 times, stirring the solution for 2 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, in the regrowth process, the corroded gold nanorods coated by the silicon dioxide are taken out, then the sodium tetrachloropalladate solution and the ascorbic acid solution are added, and the gold nanorod-palladium composite material with uniform growth is finally obtained after stirring for 1 minute; and the reaction condition is simple and the cost is low.
The invention synthesizes a mesoporous silica-coated gold nanorod-palladium composite material, which takes gold nanorods as a core and mesoporous silica as a shell, corrodes the mesoporous silica-coated gold nanorods, and then adds a sodium tetrachloropalladate solution and an ascorbic acid solution to grow palladium on the surfaces of the gold nanorods. Finally, the uniform mesoporous silica-coated gold nanorod-palladium composite material can be obtained.
As a further improvement, the material is prepared by the material of claim 1, wherein gold nanorods which have been successfully grown are used as seeds, and a certain amount of NaOH solution and TEOS are added to obtain gold nanorods coated with 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, palladium is grown on the surface of the gold nanorods coated with the mesoporous silica by adding sodium tetrachloropalladate and ascorbic acid. The mesoporous silica-coated gold nanorod-palladium composite material synthesized by the invention 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, and the composite material has two metal structures of gold and palladium, so that the catalytic activity can be enhanced, and the effect of lower energy is realized.
(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 performances of both gold and palladium, so that the composite material 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-palladium composite material of the invention;
FIG. 2 is a transmission electron microscope image of a mesoporous silica-coated gold nanorod-palladium composite material synthesized in instantiation 1 of 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, adding a corresponding amount of sodium tetrachloropalladate solution and ascorbic acid solution into the corroded mesoporous silica-coated gold nanorods to enable palladium to uniformly grow on the surfaces of the gold nanorods. Therefore, the finally synthesized mesoporous silica-coated gold nanorod-palladium composite material can greatly enhance the catalytic efficiency, has higher catalytic activity and has higher stability. Therefore, the invention provides a synthesis method of the gold nanorod-palladium composite material.
Referring to fig. 1, the synthesis method of the mesoporous silica-coated gold nanorod-palladium composite material provided by the invention specifically comprises the following steps:
and step S1, preparing the gold nanorods by using a seed growth method.
And step S2, carrying out corrosion and silicon dioxide coating processes, namely, taking gold nanorods which are cleaned and dispersed in 2mM CTAB, centrifugally adding a certain amount of NaOH solution into the gold nanorods, adding TEOS solution into the gold nanorods at intervals of 6 times within 30 minutes, stirring the solution for 2 days to obtain the mesoporous silicon dioxide coated gold nanorods, adding methanol into the mesoporous silicon dioxide coated gold nanorods, 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 step S3, a regrowth process, namely taking out the corroded gold nanorods coated by the silicon dioxide, then adding a sodium tetrachloropalladate solution and an ascorbic acid solution, and stirring for 1 minute to obtain a final product. Finally obtaining the mesoporous silica-coated gold nanorod-palladium composite material (see figure 2).
Wherein the step S1 further includes the following steps:
s10 mixing 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.
S11 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.
S12 pH was adjusted by adding 0.3mL HCl (37 wt.%) to the growth solution. 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.
S13 the solution after growth was centrifuged (7000rpm, 30 minutes), the supernatant removed and CTAB (1-2mM) added, followed by a second centrifugation (7000rpm, 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 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;
s21: the solution was placed in a 60 ℃ oil bath and etched for 10 minutes by adding 0.1mL of concentrated HCl, followed by addition of cold methanol to quench the etching, and then centrifuged (8000rpm,10 min). Dispersing the precipitate in an 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 0.02M sodium tetrachloropalladate solution was added, and 0.04mL of 0.04M ascorbic acid solution was further added, and the mixture was uniformly mixed and stirred for 1 minute to obtain the final product.
S31: centrifuging the final product at 7000rpm for 30 minutes, removing supernatant, adding 1-2mM CTAB, centrifuging at 7000rpm for two times for 30 minutes, and preparing a transmission electron microscope sample, so that the successfully synthesized mesoporous silica-coated gold nanorod-palladium composite material can be observed.
In the existing synthesis method, palladium grows on the surface of the gold nanorod, and the defects of uneven palladium growth, difficult regulation and control of palladium amount, long reaction time and the like exist. The method has the advantages over other methods that: heating in oil bath at 60 ℃, improving the response speed, adding 0.02mL of 0.02M sodium tetrachloropalladate solution, and then adding 0.04mL of 0.04M ascorbic acid solution, wherein the palladium can uniformly grow on the surface of the gold nanorod by the adding of the ratio, and the ratio of more than 99% is the product of the uniformly grown mesoporous silica-coated gold nanorod-palladium. Referring to fig. 2, a transmission electron microscope image of the gold nanorod-palladium composite material coated with mesoporous silica is shown. As can be seen, the length of the composite material is 100nm, the diameter is 50nm, and the aspect ratio is 2.0. It can also be seen from the figure that palladium in the composite material uniformly grows on the surface of gold in a granular shape, and the structure has the excellent properties of the gold and the palladium and has potential application in the fields of biomedicine and photocatalysis.
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) 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. 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,secondary centrifugation (7000rpm, 30 min). After removal of the supernatant, it was dispersed in a corresponding volume of CTAB (1-2 mM). Taking gold nanorods dispersed in CTAB (cetyltrimethyl ammonium bromide) 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; the solution was placed in a 60 ℃ oil bath and etched for 10 minutes by adding 0.1mL of concentrated HCl, followed by addition of cold methanol to quench the etching, and then centrifuged (8000rpm,10 min). Dispersing the precipitate in an aqueous solution; 0.8mL of the product dispersed in the aqueous solution was taken out, 0.02mL of 0.02M sodium tetrachloropalladate solution was added, and 0.04mL of 0.04M ascorbic acid solution was further added, and the mixture was uniformly mixed and stirred for 1 minute to obtain the final product. And centrifuging the final product at 7000rpm for 30 minutes, removing supernatant, adding an aqueous solution, centrifuging at 7000rpm for 30 minutes twice, and preparing a transmission electron microscope sample to observe the successfully synthesized gold nanorod-palladium composite material.
Example 2:
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. 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). Taking gold nanorods dispersed in CTAB (cetyl trimethyl ammonium bromide) into a bottle, adding 0.4mL of 0.1M NaOH solution, adding 0.05mL of TEOS (tetraethyl orthosilicate), and stirring for 30 minutesThen 6 repetitions of adding the same amount of TEOS and stirring for 30 minutes, the final solution being stirred for 2 days after the sixth; the solution was placed in a 60 ℃ oil bath and etched for 10 minutes by adding 0.1mL of concentrated HCl, followed by addition of cold methanol to quench the etching, and then centrifuged (8000rpm,10 min). Dispersing the precipitate in an aqueous solution; 0.8mL of the product dispersed in the aqueous solution was taken out, 0.01mL of 0.02M sodium tetrachloropalladate solution was added, 0.02mL of 0.04M ascorbic acid solution was further added, and the mixture was uniformly mixed and stirred for 1 minute to obtain the final product. And centrifuging the final product at 7000rpm for 30 minutes, removing supernatant, adding an aqueous solution, centrifuging at 7000rpm for 30 minutes twice, and preparing a transmission electron microscope sample to observe the successfully synthesized gold nanorod-palladium composite material.
Example 3:
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. 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). Taking gold nanorods dispersed in CTAB (cetyltrimethyl ammonium bromide) 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; placing the solution in an oil bath at 60 ℃, adding 0.1mL of concentrated hydrochloric acid to corrode the solution for 10 minutes, and then adding cold storageThe corrosion was stopped by methanol and then centrifuged (8000rpm,10 min). Dispersing the precipitate in an aqueous solution; 0.8mL of the product dispersed in the aqueous solution was taken out, 0.015mL of 0.02M sodium tetrachloropalladate solution was added, 0.03mL of 0.04M ascorbic acid solution was further added, and the mixture was uniformly mixed and stirred for 1 minute to obtain the final product. And centrifuging the final product at 7000rpm for 30 minutes, removing supernatant, adding an aqueous solution, centrifuging at 7000rpm for 30 minutes twice, and preparing a transmission electron microscope sample to observe the successfully synthesized gold nanorod-palladium composite material.
Example 4:
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. 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). Taking gold nanorods dispersed in CTAB (cetyltrimethyl ammonium bromide) 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; the solution was placed in a 60 ℃ oil bath and etched for 10 minutes by adding 0.1mL of concentrated HCl, followed by addition of cold methanol to quench the etching, and then centrifuged (8000rpm,10 min). Dispersing the precipitate in an aqueous solution; 0.8mL of the product dispersed in the aqueous solution was taken out, 0.025mL of 0.02M sodium tetrachloropalladate solution was added, and 0.05mL of 0.0.0 was further added4M ascorbic acid solution is evenly mixed and stirred for 1 minute to obtain the final product. And centrifuging the final product at 7000rpm for 30 minutes, removing supernatant, adding an aqueous solution, centrifuging at 7000rpm for 30 minutes twice, and preparing a transmission electron microscope sample to observe the successfully synthesized gold nanorod-palladium composite material.
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 (4)
1. A preparation method of a gold nanorod-palladium composite material is characterized by comprising the following steps:
step S1, preparing gold nanorods by using a seed growth method;
step S2, silicon dioxide coating and gold nanorod corrosion process; the method comprises the following steps of 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 mesoporous silica-coated gold nanorods, adding methanol into the mesoporous silica-coated gold nanorods, placing the mesoporous silica-coated gold nanorods in an oil bath at the temperature of 60 ℃, controlling the amount of added hydrochloric acid, and corroding the gold nanorods;
step S3, regrowth process; taking out the corroded gold nanorods coated by silicon dioxide, adding a sodium tetrachloropalladate solution and an ascorbic acid solution, and stirring for 1 minute to finally obtain the gold nanorod-palladium composite material;
wherein the step S1 further includes the following steps:
s10 mixing 10mL of 0.1M CTAB with 0.25mL of 10mM HAuCl4Mixing in a bottle, mixing with ice-water mixture and certain weighed NaBH4Mixing to prepare 0.01M solution, and adding 0.6mL of the solution into a bottle for vigorous stirring; the solution turns from golden yellow to brown yellow, which is a seed solution;
s11 dissolving 2.5mL of 0.1M CTAB and 0.037g of NaOL in 21.25mL of water at 50 ℃; after dissolution, the solution was cooled to 30 ℃ and 0.9mL of 4mM AgNO was added3A solution; and left to stand at a constant temperature of 30 ℃ for 15 minutes, after which 0.25mL of 10mM HAuCl was added4(ii) a 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 37 wt.% 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, 7000rpm of the solution after growth is centrifuged for 30 minutes, 1-2mM CTAB is added after supernatant liquid is removed, 7000rpm is carried out twice, and centrifugation is carried out for 30 minutes; after removing the supernatant, dispersing in a corresponding volume of 1-2mM CTAB;
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 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;
s21: placing the solution in an oil bath at 60 ℃, adding 0.1mL of 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 an aqueous solution;
the step S3 further includes the steps of:
s30: taking out 0.8mL of the product dispersed in the aqueous solution, adding 0.02mL of 0.02M sodium tetrachloropalladate solution, adding 0.04mL of 0.04M ascorbic acid solution, uniformly mixing and stirring for 1 minute;
s31: and centrifuging the obtained final product at 7000rpm for 30 minutes, removing supernatant, adding an aqueous solution, centrifuging at 7000rpm for 30 minutes twice, and preparing a transmission electron microscope sample to observe the successfully synthesized gold nanorod-palladium composite material.
2. The method of preparing a gold nanorod-palladium composite material according to claim 1, wherein the step S2 is performed under the oil bath heating condition of 60 ℃, the reaction rate is increased, and the corrosion rate is controlled by the amount of hydrochloric acid added; step S3, adding a sodium tetrachloropalladate solution and an ascorbic acid solution to enable palladium to uniformly grow on the surface of the gold nanorod; so that the finally synthesized gold nanorod-palladium composite material has high uniformity.
3. The method for preparing a gold nanorod-palladium composite material according to claim 1, wherein the gold nanorods that have successfully grown are used as seeds, and the corrosion rate and the corrosion amount of the gold nanorods coated with silicon dioxide are controlled by controlling the temperature of oil bath heating and the addition amount of hydrochloric acid; then taking the product which is corroded and dispersed in the water solution, adding a sodium tetrachloropalladate solution and ascorbic acid to grow palladium on the gold nanorods wrapped by the silicon dioxide; the reaction temperature is controlled by adopting oil bath heating to greatly shorten the time required by the corrosion process; and adding a sodium tetrachloropalladate solution and an ascorbic acid solution, and stirring for 1 minute to finally enable the palladium to uniformly grow on the gold nanorods.
4. The method of preparing a gold nanorod-palladium composite material according to claim 1, wherein the prepared composite material has a length of 100nm and a diameter of 50 nm.
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| CN113681021A (en) * | 2021-08-20 | 2021-11-23 | 杭州电子科技大学 | Gold nanorod purification method based on micelle deposition |
| CN114012086A (en) * | 2021-10-29 | 2022-02-08 | 杭州苏铂科技有限公司 | Preparation method of polyethylene glycol gold nanorod |
| CN114748621A (en) * | 2022-05-05 | 2022-07-15 | 山西医科大学 | Crown gold-palladium nano heterogeneous material and preparation method and application thereof |
| CN114799190A (en) * | 2022-06-20 | 2022-07-29 | 杭州电子科技大学富阳电子信息研究院有限公司 | Gold nanorod film and synthesis method thereof |
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| CN113681021A (en) * | 2021-08-20 | 2021-11-23 | 杭州电子科技大学 | Gold nanorod purification method based on micelle deposition |
| CN114012086A (en) * | 2021-10-29 | 2022-02-08 | 杭州苏铂科技有限公司 | Preparation method of polyethylene glycol gold nanorod |
| CN114748621A (en) * | 2022-05-05 | 2022-07-15 | 山西医科大学 | Crown gold-palladium nano heterogeneous material and preparation method and application thereof |
| CN114748621B (en) * | 2022-05-05 | 2023-09-26 | 山西医科大学 | Crown gold-palladium nano heterogeneous material and preparation method and application thereof |
| CN114799190A (en) * | 2022-06-20 | 2022-07-29 | 杭州电子科技大学富阳电子信息研究院有限公司 | Gold nanorod film and synthesis method thereof |
| CN114799190B (en) * | 2022-06-20 | 2023-04-28 | 杭州电子科技大学富阳电子信息研究院有限公司 | Gold nanorod film and synthesis method thereof |
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