CN112828301A - Synthesis method of gold-silver bimetallic material with special structure - Google Patents
Synthesis method of gold-silver bimetallic material with special structure Download PDFInfo
- Publication number
- CN112828301A CN112828301A CN202011640581.7A CN202011640581A CN112828301A CN 112828301 A CN112828301 A CN 112828301A CN 202011640581 A CN202011640581 A CN 202011640581A CN 112828301 A CN112828301 A CN 112828301A
- Authority
- CN
- China
- Prior art keywords
- solution
- gold
- silver
- ctab
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000001308 synthesis method Methods 0.000 title description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 53
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000012010 growth Effects 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 claims abstract description 17
- 239000004332 silver Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 230000035040 seed growth Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 130
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 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 description 36
- 239000006228 supernatant Substances 0.000 claims description 23
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 21
- 229960005070 ascorbic acid Drugs 0.000 claims description 18
- 235000010323 ascorbic acid Nutrition 0.000 claims description 18
- 239000011668 ascorbic acid Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 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 16
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 12
- 230000005540 biological transmission Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000012467 final product Substances 0.000 claims description 9
- 101710134784 Agnoprotein Proteins 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 14
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000004627 transmission electron microscopy Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 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
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a method for synthesizing a gold-silver bimetallic material with a special structure, which comprises a gold nanorod serving as a nuclear structure and silver growing on the surface of the gold nanorod. The invention adopts a seed growth method to grow silver on the gold nanorods. The method mainly comprises the following steps: firstly, growing gold nanorods by using a seed growth method, and then cleaning the successfully grown gold nanorods to obtain gold nanorods with higher purity; and then, taking the gold nanorods as seeds, adding a corresponding amount of surfactant and silver nitrate, uniformly mixing the gold nanorods and the silver nitrate, and controlling the reaction temperature to successfully grow silver on the surfaces of the gold nanorods. The growth was observed by transmission electron microscopy. The gold-silver bimetallic material with a special structure synthesized by the method 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 metal nano materials, in particular to a synthesis method of a gold-silver bimetallic material with a special structure.
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 micro-molecule and ion detection due to the enhanced surface raman scattering and surface plasmon resonance properties of the gold nanorods. 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.
Researchers have successfully synthesized the gold-silver bimetal material, and the gold-silver bimetal synthesized at the present stage has the defects of non-uniformity, complex synthetic method, higher synthetic cost and the like. Therefore, in order to overcome the defects of the synthesis methods, a synthesis method of a gold-silver bimetallic material with a special structure is proposed. The synthesis method has the advantages of uniform synthesis result, low synthesis cost, simplicity and the like, and can be used for certain special optical catalysis and biomedical fields.
Disclosure of Invention
In order to solve the problems of low synthesis efficiency of the gold-silver bimetal and uneven final synthesis result, the invention provides a synthesis method of a gold-silver bimetal material with a special structure, which can efficiently synthesize the gold-silver bimetal material with the special structure, 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-silver bimetallic material with a special structure comprises the following steps:
and step S1, preparing the gold nanorods by using a seed growth method.
Step S2, taking gold nanorods which are cleaned and dispersed in low-concentration CTAB as new seeds, adding corresponding amount of CTAB, silver nitrate solution and ascorbic acid solution on the seeds, and controlling the reaction rate to synthesize the gold-silver bimetallic structure material with special structure.
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 NaBH4After mixing, a 0.01M NaBH4 solution was prepared, and 0.6mL of the solution was added to the flask and stirred 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 30 ℃ for 15 minutes, after which 0.25mL of HAuCl4(10mM) was added. 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 gold nanorods 0.5mL dispersed in CTAB were put in a bottle, and 17mL of 30mM CTAC was added and mixed uniformly. Magnetically stirring at 800rpm in 60 deg.C water bath for 20 min;
s21: 1mL of a 4mM silver nitrate solution and 1mL of a 100mM ascorbic acid solution prepared with 30mM CTAC were each charged with a syringe pump. The addition rates of the two solutions were controlled, i.e., 0.5mL/min. The above steps are all completed under the condition of water bath at 60 ℃, and then the water bath is heated for 2 hours under the magnetic stirring of 400rpm and then taken out. And 7000rpm of the final product obtained is centrifuged for 30 minutes, 1-2mM CTAB is added after supernatant liquid is removed, 7000rpm is centrifuged for the second time and 30 minutes, and a transmission electron microscope sample is prepared, so that the successful synthesis of the symmetric gold-silver bimetallic structure can be observed, and the successful synthesis of the gold-silver bimetallic material with the special structure can be observed.
As a further improvement, the step S2 is carried out under the water bath heating condition of 60 ℃, the reaction time is greatly shortened, namely the gold-silver bimetallic structure can be obtained within 2 hours, and meanwhile, the injection pump is utilized to simultaneously control the dropping speed of silver nitrate and ascorbic acid, so that the gold-silver bimetallic material with a special structure is 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 two parts. In the first part, a seed growing method is firstly utilized to successfully synthesize uniform gold nanorods. And then taking the cleaned gold nanorods as seeds, adding a surfactant CTAC, a silver nitrate solution and an ascorbic acid solution, and magnetically stirring for 2 hours in a water bath at sixty degrees to finally obtain the gold-silver bimetallic material with more deposits on the side surfaces of the gold nanorods and less deposits at two ends and having a special structure. The heating in a sixty degree water bath for this reaction is due to the greatly increased growth rate that can be achieved; the reason why the silver nitrate solution and the ascorbic acid solution are simultaneously added by the syringe pump is that the reaction rate can be controlled to control the uniformity of the final bimetallic structure. Therefore, the method can be used for efficiently synthesizing the gold-silver bimetallic material with a special structure. And the reaction condition is simple and the cost is low.
The invention synthesizes a gold-silver bimetallic material with a special structure, which takes a gold nanorod as a core and silver as a shell, and silver uniformly grows on the side surface of the gold nanorod. The finally synthesized gold-silver bimetallic material has a special structure.
As a further improvement, the material is prepared by the material of claim 1, wherein, the gold nanorods which have successfully grown are used as seeds, and silver nitrate and ascorbic acid are added dropwise by a syringe pump to control the growth of the gold-silver bimetallic structure; the previous reaction rate is changed to control the uniform growth of silver. Finally, the gold-silver bimetallic material with a special structure is formed.
The gold-silver bimetallic material with a special structure is synthesized, and has the following beneficial effects:
(1) the synthesized gold-silver material with a special structure 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 gold-silver material enhances the catalytic performance of the gold nanorods, and the gold-silver material has a bimetallic structure and can enhance the catalytic activity and realize the effect of lower energy.
(3) The synthesis method of the gold-silver material is simple, and the finally obtained product gold-silver is very stable and has extremely high reliability.
(4) Gold-silver materials combine some of the special advantageous properties of gold and silver and can therefore be used more widely. For example: biomedicine, optical catalysis, etc.
Drawings
FIG. 1 is a flow chart of the steps of the gold-silver material synthesis of the present invention;
FIG. 2 is a transmission electron microscope image of gold nanorods synthesized by the present invention;
fig. 3 is a transmission electron micrograph of the gold-silver material of example 1 of the present invention (fig. 2 and 3 are on the same scale).
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, the prepared gold nanorods are used as seeds, and silver is grown on the surfaces, especially the side surfaces, of the gold nanorods to form the gold-silver bimetallic material with a special structure. The gold-silver material can be used as a composite catalyst, can greatly enhance the catalytic efficiency, has higher catalytic activity and has higher stability. Therefore, the invention provides a synthesis method of a gold-silver material with a special structure.
Referring to fig. 1, the method for synthesizing a gold-silver material with a special structure provided by the invention specifically comprises the following steps:
step S1, gold nanorods were prepared using a seed growth method (see fig. 2).
Step S2, taking gold nanorods which are cleaned and dispersed in low-concentration CTAB as new seeds, adding corresponding amount of CTAC, silver nitrate solution and ascorbic acid solution on the seeds, and controlling the reaction temperature to synthesize the gold-silver bimetallic material with special structure.
Wherein the step S1 further includes the following steps:
s10 mixing 10mL CTAB (0.1M) and 0.25mL HAuCl4(10mM) in a bottle, mixing a weighed certain mass of NaBH4 with an ice-water mixture to prepare a 0.01M solution, adding 0.6mL into the bottle, and stirring 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 30 ℃ for 15 minutes, after which 0.25mL of HAuCl4(10mM) was added. 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 gold nanorods 0.5mL dispersed in CTAB were put in a bottle, and 17mL of 30mM CTAC was added and mixed uniformly. Magnetically stirring at 800rpm in 60 deg.C water bath for 20 min;
s21: 1mL of a 4mM silver nitrate solution and 1mL of a 100mM ascorbic acid solution prepared with 30mM CTAC were each charged with a syringe pump. The addition rates of the two solutions were controlled, i.e., 0.5mL/min. The above steps are all completed under the condition of water bath at 60 ℃, and then the water bath is heated for 2 hours under the magnetic stirring of 400rpm and then taken out. And 7000rpm of the final product obtained is centrifuged for 30 minutes, 1-2mM CTAB is added after supernatant liquid is removed, 7000rpm is centrifuged for the second time for 30 minutes, and a transmission electron microscope sample is prepared, so that the structure of the gold-silver bimetal successfully synthesized into the special structure can be observed.
The existing synthesis method mainly can realize a symmetrical gold-silver structure and an asymmetrical gold-silver structure, and the structure synthesized by the method is a special structure between the two structures. And the proportion of the special structure of the finally synthesized gold-silver bimetal can reach 99 percent. Meanwhile, the reaction rate of the method is very fast, and the reaction conditions are relatively simple. Referring to fig. 3, a transmission electron microscope image showing that silver is finally grown on the surface, especially the side surface, of gold nanorods by adding silver nitrate solution and ascorbic acid solution using a syringe pump under the condition of 60 ℃. That is, fig. 3 is a transmission electron microscope image of the gold-silver bimetallic material with a special structure finally prepared by the present invention. As can be seen from the figure, the length of the gold-silver bimetallic material is 89nm, the diameter is 45nm, and the aspect ratio is 2.0. Meanwhile, it can be seen from the figure that silver in the gold-silver bimetallic material with the special structure uniformly grows on the surface of the gold nanorod, so that the stability of the gold nanorod is greatly enhanced, and the gold nanorod has the excellent performances of gold and silver.
Example 1:
10mL of CTAB (0.1M) and 0.25mL of HAuCl4(10mM) were mixed in a bottle, a weighed amount of NaBH4 was mixed with an ice-water mixture to prepare a 0.01M solution, and 0.6mL of the solution was added to the bottle and stirred 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 30 ℃ for 15 minutes, after which 0.25mL of HAuCl4(10mM) was added. 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). 0.5mL of gold nanorods dispersed in CTAB was taken out of the flask, and CTAC (17mL of 30mM) was added thereto, followed by magnetic stirring at 800rpm in a water bath at 60 ℃ for 20 min. A silver nitrate solution (1mL of 4mM) was added by a syringe pump, and an ascorbic acid solution (1mL of 100mM) prepared with 30mM CTAC was stirred for 2 hours with a magnetic stirrer (400rpm) in a water bath at 60 ℃. The final product obtained above was centrifuged (7000rpm, 30 minutes), the supernatant removed and CTAB (1-2mM) added, followed by a second centrifugation (7000rpm, 30 minutes). The transmission electron microscope sample is prepared, and the successful synthesis of the gold-silver bimetallic material with the special structure can be observed.
Example 2:
10mL of CTAB (0.1M) and 0.25mL of HAuCl4(10mM) were mixed in a bottle, a weighed amount of NaBH4 was mixed with an ice-water mixture to prepare a 0.01M solution, and 0.6mL of the solution was added to the bottle and stirred 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 30 ℃ for 15 minutes, after which 0.25mL of HAuCl4(10mM) was added. 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. Will grow afterThe solution of (4) was centrifuged (7000rpm, 30 minutes), and CTAB (1-2mM) was added after removing the supernatant, and centrifuged (7000rpm, 30 minutes) twice. After removal of the supernatant, it was dispersed in a corresponding volume of CTAB (1-2 mM). 0.25mL of gold nanorods dispersed in CTAB was taken out of the flask, and CTAC (8.5mL of 30mM) was added thereto, followed by magnetic stirring at 800rpm in a water bath at 60 ℃ for 20 min. Silver nitrate solution (0.5mL of 4mM), ascorbic acid solution prepared with 30mM CTAC (0.5mL of 100mM), was added by a syringe pump, and stirred with a magnetic stirrer (400rpm) for 2 hours in a water bath at 60 ℃. The final product was taken out for 1mL and the measured spectrum was recorded as the final spectrum. The final product obtained above was centrifuged (7000rpm, 30 minutes), the supernatant removed and CTAB (1-2mM) added, followed by a second centrifugation (7000rpm, 30 minutes). The transmission electron microscope sample is prepared, and the successful synthesis of the gold-silver bimetallic material with the special structure can be observed.
Example 3:
10mL of CTAB (0.1M) and 0.25mL of HAuCl4(10mM) were mixed in a bottle, and a weighed quantity of NaBH was admixed with an ice-water mixture4Mix 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). 1mL of gold nanorods dispersed in CTAB were taken out of a flask, and CTAC (34mL of 30mM) was added to measure the initial spectrum, followed by magnetic stirring at 800rpm in a water bath at 60 ℃ for 20 min. A silver nitrate solution (2mL 4mM) was added by a syringe pump, and an ascorbic acid solution (2mL 100mM) prepared with 30mM CTAC was stirred for 2 hours with a magnetic stirrer (400rpm) in a water bath at 60 ℃.The final product obtained above was centrifuged (7000rpm, 30 minutes), the supernatant removed and CTAB (1-2mM) added, followed by a second centrifugation (7000rpm, 30 minutes). The transmission electron microscope sample is prepared, and the successful synthesis of the gold-silver bimetallic material with the special structure can be observed.
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). 0.4mL of gold nanorods dispersed in CTAB was taken out of the flask, and CTAC (13.6mL of 30mM) was added thereto, followed by magnetic stirring at 800rpm in a water bath at 60 ℃ for 20 min. Silver nitrate solution (0.8mL of 4mM), ascorbic acid solution prepared with 30mM CTAC (0.8mL of 100mM), was added by a syringe pump, and stirred with a magnetic stirrer (400rpm) for 2 hours in a water bath at 60 ℃. The final product obtained above was centrifuged (7000rpm, 30 minutes), the supernatant removed and CTAB (1-2mM) added, followed by a second centrifugation (7000rpm, 30 minutes). The transmission electron microscope sample is prepared, and the successful synthesis of the gold-silver bimetallic material with the special structure can be observed.
Example 5:
10mL CTAB (0.1M) and 0.25mL HAuCl4(10mM) are mixed in a bottle with an ice-water mixture and a weighed quantity of NaBH4Mixing to obtain 0.01M solution, adding 0.6mL, and stirring 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). 0.45mL of gold nanorods dispersed in CTAB was taken out of the flask, and CTAC (15.3mL of 30mM) was added thereto, followed by magnetic stirring at 800rpm in a water bath at 60 ℃ for 20 min. Silver nitrate solution (0.9mL of 4mM), ascorbic acid solution prepared with 30mM CTAC (0.9mL of 100mM), was added by a syringe pump, and stirred with a magnetic stirrer (400rpm) for 2 hours in a water bath at 60 ℃. The final product obtained above was centrifuged (7000rpm, 30 minutes), the supernatant removed and CTAB (1-2mM) added, followed by a second centrifugation (7000rpm, 30 minutes). The transmission electron microscope sample is prepared, and the successful synthesis of the gold-silver bimetallic material with the special structure can be observed.
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 method for synthesizing a gold-silver bimetallic material with a special structure is characterized by comprising the following steps:
step S1, preparing gold nanorods by using a seed growth method;
step S2, taking gold nanorods which are cleaned and dispersed in low-concentration Cetyl Trimethyl Ammonium Bromide (CTAB) as new seeds, adding corresponding amount of Cetyl Trimethyl Ammonium Chloride (CTAC), silver nitrate solution and ascorbic acid solution on the seeds, and controlling reaction temperature to synthesize a bimetallic structure;
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 clear solution, dispersing in a corresponding volume of 1-2mM CTAB;
the step S2 further includes the steps of:
s20, taking 0.5mL of gold nanorods dispersed in CTAB, adding 17mL of 30mM CTAC, and uniformly mixing; magnetically stirring at 800rpm in 60 deg.C water bath for 20 min;
s21: 1mL of a 4mM silver nitrate solution and 1mL of a 100mM ascorbic acid solution prepared with 30mM CTAC were separately filled in a syringe pump; the adding rate of the two solutions is controlled, namely 0.5mL/min, and the two solutions are simultaneously dripped into the product; the steps are all completed under the condition of water bath at 60 ℃, and then the mixture is taken out after being heated for 2 hours in the water bath under the magnetic stirring of 400 rpm; and 7000rpm of the final product obtained is centrifuged for 30 minutes, 1-2mM CTAB is added after supernatant liquid is removed, 7000rpm is centrifuged for the second time for 30 minutes, and a transmission electron microscope sample is prepared, so that the successfully synthesized gold-silver bimetallic material with a special structure can be observed.
2. The method for synthesizing a gold-silver bimetallic material with a special structure as claimed in claim 1, wherein the step S2 is carried out under the water bath heating condition of 60 ℃, the reaction rate is increased, the dropping rate of the silver nitrate solution and the ascorbic acid solution is controlled by an injection pump, so that the silver can uniformly grow on the surface of the gold nanorods; so that the final synthesized bimetal structure has high uniformity.
3. The method for synthesizing gold-silver bimetallic material with special structure as claimed in claim 1, characterized in that the gold nanorods which have been successfully grown are used as seeds, and the rate of adding silver nitrate and ascorbic acid is controlled by using a syringe pump to control the growth condition of the gold-silver bimetallic structure; CTAC is adopted, and the reaction temperature is controlled to greatly shorten the time required by the reaction; finally, the silver can grow on the gold nanorods, namely the silver mainly grows on two sides of the gold nanorods, and two ends of the gold nanorods are fewer.
4. The method for synthesizing gold-silver bimetallic material with special structure as in claim 3, characterized in that the length of the gold-silver material is 89nm, the diameter is 45nm, and the length-diameter ratio is 2.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011640581.7A CN112828301A (en) | 2020-12-31 | 2020-12-31 | Synthesis method of gold-silver bimetallic material with special structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011640581.7A CN112828301A (en) | 2020-12-31 | 2020-12-31 | Synthesis method of gold-silver bimetallic material with special structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112828301A true CN112828301A (en) | 2021-05-25 |
Family
ID=75927041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011640581.7A Pending CN112828301A (en) | 2020-12-31 | 2020-12-31 | Synthesis method of gold-silver bimetallic material with special structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112828301A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113369494A (en) * | 2021-06-11 | 2021-09-10 | 杭州电子科技大学 | Hollow gold-silver-platinum trimetal material and synthesis method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103551586A (en) * | 2013-09-22 | 2014-02-05 | 江苏瑞德新能源科技有限公司 | Preparation method of micron spherical silver powder for electroconductive silver paste |
| CN107096916A (en) * | 2017-05-14 | 2017-08-29 | 蒋春霞 | A kind of preparation method of silver-coated copper powder |
| CN108672716A (en) * | 2018-05-23 | 2018-10-19 | 厦门斯贝克科技有限责任公司 | A kind of preparation method of silver gold-covered nano stick |
| CN109128211A (en) * | 2018-08-16 | 2019-01-04 | 山东大学 | The method of micro-nano silver particle is prepared in water solution system |
-
2020
- 2020-12-31 CN CN202011640581.7A patent/CN112828301A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103551586A (en) * | 2013-09-22 | 2014-02-05 | 江苏瑞德新能源科技有限公司 | Preparation method of micron spherical silver powder for electroconductive silver paste |
| CN107096916A (en) * | 2017-05-14 | 2017-08-29 | 蒋春霞 | A kind of preparation method of silver-coated copper powder |
| CN108672716A (en) * | 2018-05-23 | 2018-10-19 | 厦门斯贝克科技有限责任公司 | A kind of preparation method of silver gold-covered nano stick |
| CN109128211A (en) * | 2018-08-16 | 2019-01-04 | 山东大学 | The method of micro-nano silver particle is prepared in water solution system |
Non-Patent Citations (1)
| Title |
|---|
| ISRAA HAIDAR，等: ""Tailoring the Shape of Anisotropic Core–Shell Au–Ag Nanoparticles in Dimethyl Sulfoxide"" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113369494A (en) * | 2021-06-11 | 2021-09-10 | 杭州电子科技大学 | Hollow gold-silver-platinum trimetal material and synthesis method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112828284B (en) | Preparation method of mesoporous silica-coated gold nanorod surface-grown silver composite material | |
| CN112846218A (en) | Preparation method of gold-platinum-silver material with asymmetric structure | |
| Gómez-Graña et al. | Au@ Ag nanoparticles: Halides stabilize {100} facets | |
| CN102554258B (en) | Method for preparing metal silver nanostructure in water solution | |
| Gao et al. | Templated synthesis of metal nanorods in silica nanotubes | |
| CN104209533B (en) | Method for rapidly preparing gold nanorod | |
| Yang et al. | Controlled growth of Ag/Au bimetallic nanorods through kinetics control | |
| CN112846219A (en) | Preparation method of gold nanorod-palladium composite material | |
| CN103056384B (en) | Preparation method of precious metal and magnetic nano particles | |
| CN112809016B (en) | Preparation method of thickness-adjustable silicon dioxide material grown on surface of gold nanorod | |
| CN112846217A (en) | Preparation method of nano gold-platinum composite material in mesoporous silica | |
| CN108723385B (en) | Single crystal silver nanosphere water phase preparation method | |
| CN104907578A (en) | Method for preparing gold nanorods | |
| CN112974829A (en) | Method for preparing gold nanorod material by reducing hydroquinone under double surfactants | |
| CN112756622B (en) | Preparation method of gold nanorod material under low surfactant concentration | |
| CN112756623A (en) | Synthesis method of gold-platinum material with special structure | |
| CN112775435A (en) | Preparation method of gold nanorod surface-grown mesoporous silica material | |
| CN112809018B (en) | Synthesis method of gold-platinum bimetallic structural material | |
| CN112620646A (en) | Preparation method of large length-diameter ratio gold nanorod with platinum particles growing at two ends and product thereof | |
| CN112828301A (en) | Synthesis method of gold-silver bimetallic material with special structure | |
| Zhang et al. | Synthesis and growth mechanism of pentagonal bipyramid-shaped gold-rich Au/Ag alloy nanoparticles | |
| Liu et al. | Activation of Oxygen-Mediating Pathway Using Copper Ions: Fine-Tuning of Growth Kinetics in Gold Nanorod Overgrowth | |
| CN112846215A (en) | Synthetic method of symmetric gold-silver bimetallic material | |
| CN113231632B (en) | Gold-palladium asymmetric heterogeneous nano structure and synthesis method thereof | |
| CN112743099A (en) | Preparation method of gold nanorod material with length-diameter ratio regulated and controlled by hydrochloric acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210525 |
|
| RJ01 | Rejection of invention patent application after publication |