CN113210600B - Control method for gold atom deposition on silver nanostructure - Google Patents
Control method for gold atom deposition on silver nanostructure Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 90
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 56
- 239000004332 silver Substances 0.000 title claims abstract description 56
- 230000008021 deposition Effects 0.000 title claims abstract description 40
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 36
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 118
- 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 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000010931 gold Substances 0.000 claims abstract description 27
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 14
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 14
- 238000006722 reduction reaction Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000006073 displacement reaction Methods 0.000 claims abstract description 9
- 239000002073 nanorod Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 229940080262 sodium tetrachloroaurate Drugs 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000000047 product Substances 0.000 description 21
- 239000002211 L-ascorbic acid Substances 0.000 description 12
- 235000000069 L-ascorbic acid Nutrition 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 7
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical group [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- 238000000584 ultraviolet--visible--near infrared spectrum Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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Abstract
The invention discloses a control method for gold atom deposition on a silver nanostructure, which comprises the following steps: step one, taking a gold nanometer bipyramid as a core, epitaxially growing silver to obtain a silver nanometer rod, wherein the high surface energy surface and the tip end position of the silver nanometer rod are distributed in an ectopic way; dispersing silver nanorods serving as a reaction template into a cetyl trimethyl ammonium bromide solution, adding an ascorbic acid solution, and uniformly stirring; regulating the pH value of the mixed solution, further regulating the reducibility of the ascorbic acid solution, and realizing the regulation of the ratio between the displacement reaction and the reduction reaction in the reaction system; and step four, dripping the gold precursor solution into the obtained reaction system, converting the displacement reaction system into a co-reduction reaction system along with the reaction system, and gradually transferring the deposition position of the reduced gold atoms to the tip position of the silver nano-rods from the high surface energy surface. The method can realize the controllable deposition of the atomic gold by adjusting the pH value of the reaction system, and has simple conditions, mild conditions and strong operability.
Description
Technical Field
The invention belongs to a deposition control method, and particularly relates to a control method for gold atom deposition on a silver nanostructure.
Background
Hollow nanostructures have gained wide attention and applications in the fields of catalysis, sensing, imaging, and drug release due to their large specific surface area and internal volume. The displacement reaction is an effective method for realizing the preparation of the hollow nano structure, but the obtained hollow nano structure has a single appearance, and the side wall thickness is difficult to adjust. In recent years, the fine regulation and control of the morphology parameters of the hollow nano structure are further realized by combining a displacement reaction and a co-reduction reaction, so that various hollow structures of a nano shell, a nano box, a nano cage and a nano frame are obtained, and the method has a good application prospect in various fields.
The fine synthesis of hollow nanostructures via complex reaction systems has been reported in many documents (ACS Nano,2016,10, 8019-8025; J.Am.chem.Soc.,2017,139, 13837-13846). However, in these reports, the deposition mode of gold atoms is relatively single, and based on the uniform distribution of high energy surface and tip position in the silver nanostructure in the selected silver nanostructure, the obtained nanostructure is basically a cubic nanostructure with similar structure, so that the deposition mechanism of gold atoms has not been clearly explored so far.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects of the prior art, the invention aims to provide a control method for gold atom deposition on a silver nanostructure, which can clarify the deposition mechanism and realize accurate control of the nanostructure.
The technical scheme is as follows: the invention relates to a control method for gold atom deposition on a silver nanostructure, which comprises the following steps:
step one, taking gold nanometer bipyramids as cores, epitaxially growing silver to prepare silver nanorods, wherein high surface energy surfaces and tip positions of the silver nanorods are in ectopic distribution, and a uniform reaction template is constructed;
step two, dispersing the silver nanorods obtained in the step one into a cetyl trimethyl ammonium bromide solution by taking the silver nanorods as a reaction template, adding a reducing agent ascorbic acid solution, and uniformly stirring;
step three, adjusting the pH value of the mixed solution obtained in the step two, further adjusting the reducibility of the ascorbic acid solution, and realizing the adjustment of the ratio between the shift reaction and the co-reduction reaction in the reaction system, namely the higher the pH value of the mixed solution is, the stronger the reducibility of the ascorbic acid solution is, the higher the ratio of the co-reduction reaction in the reaction system is;
and step four, dropwise adding the gold precursor solution into the reaction system obtained in the step three, changing the reaction system from a displacement reaction system to a co-reduction reaction system along with the reaction system, and gradually moving the deposition position of the reduced gold atoms to the tip position of the silver nanorods from a high surface energy surface to realize the controllable adjustment of the deposition position of the gold atoms.
Further, in the first step, the silver nanorod comprises a tip, a side face and a side edge, wherein the tip comprises 10 {111} planes, the side face comprises 5 {100} planes, the side edge comprises 5 {110} planes, and the side edge is a high surface energy plane.
Furthermore, in the second step, the concentration of the hexadecyl trimethyl ammonium bromide is 0.05-0.1 mol/L, and the concentration of the ascorbic acid solution is 0.1-1 mol/L. The concentration of hexadecyl trimethyl ammonium bromide is lower than 0.05mol/L, so that the initial position of a displacement reaction in the template can be changed, and the final appearance is further influenced; concentrations higher than 0.1mol/L tend to drive the added precursor solution to the ionic state and reduce the reaction yield. The concentration of the ascorbic acid solution is lower than 0.1mol/L, the overall reducibility is lower, the replacement reaction is dominant, and the ratio between the two reactions cannot be adjusted; the concentration is higher than 1mol/L, the whole reducibility is too high, the co-reduction reaction is dominant, and the adjustment of the ratio between the two reactions cannot be realized.
Further, in the third step, a sodium hydroxide solution with a concentration of 0.1-1 mol/L or a hydrochloric acid solution with a concentration of 0.1mol/L is adopted to adjust the pH value of the mixed solution obtained in the second step. The pH value of the mixed solution is changed within the range of 1.88-12.96. With the increase of the pH value, the reaction system is mainly changed from the replacement reaction to the co-reduction reaction.
Further, in the fourth step, the gold precursor solution is a chloroauric acid solution or a sodium tetrachloroaurate solution. The concentration of the gold precursor solution is 0.1-0.5 mmol/L. The dropping speed of the gold precursor solution is 20 mu L/min, and the reaction time is 1-5 h. The dropping speed is too fast, and the reduced atom deposition position is not controlled; the dropping speed is too slow, and the experimental conditions are difficult to meet.
Further, centrifuging the product obtained in the fourth step, placing the product in a hexadecyl trimethyl ammonium bromide solution with the concentration of 0.005-0.1 mol/L, respectively adding an ammonia water solution with the concentration of 1-14 mol/L and a hydrogen peroxide solution with the concentration of 1-5 mol/L, reacting for 6-24 hours at room temperature, selectively etching silver atoms, and observing the deposition positions of the gold atoms, wherein the rest is the shape of the gold atoms; the volume ratio of the hexadecyl trimethyl ammonium bromide to the ammonia water to the hydrogen peroxide is 100: 1-100: 5 to 200.
The reaction principle is as follows: as shown in fig. 1, the substitution reaction occurs spontaneously when the gold precursor solution is added to the silver nanostructure, and in addition, in the presence of an ascorbic acid reducing agent, a part of the chloroauric acid solution is reduced by the reducing agent, and finally a complex reaction system in which the substitution reaction and the co-reduction reaction coexist is formed. The reducibility of the ascorbic acid can be adjusted through the change of the pH value of the reaction solution, and the reducibility is increased along with the increase of the pH value, so that the controllable adjustment of the reducibility of the ascorbic acid can be realized through the concentrations of the hydrochloric acid solution and the sodium hydroxide solution, and the adjustment mainly based on the reduction reaction and mainly based on the replacement reaction can be further controlled to finish the reaction in a complex reaction system. Based on the requirements of target research, the constructed sacrificial template silver nanorod has a high surface energy surface and a tip position which are distributed in an ectopic mode, and selective deposition of gold atoms on the high surface energy surface and the tip position under different reaction types is convenient to observe. By selecting a uniform template and carrying out the same experiment in different reaction ratio systems, the controllable deposition of the gold atoms on the silver nanorods can be realized.
Has the beneficial effects that: compared with the prior art, the invention has the following remarkable characteristics:
1. the control method is simple, the basic silver nanostructure with the characteristic structure is constructed as the basis, the controllable deposition of the gold atoms on the silver nanostructure can be realized by adjusting the pH value of the reaction system, the overall condition is simple, the condition is mild, and the operability is strong;
2. the prepared product is a silver-gold nanorod structure taking a silver nanorod as a core, the stability of the structure is enhanced by the deposition of gold atoms, the surface plasmon characteristics are excellent, and the preparation method has potential application prospects in the fields of photocatalysis, sensing, Raman and the like.
Drawings
FIG. 1 is a transmission electron microscope image of the silver nanorods of the invention;
FIG. 2 is a schematic representation of a silver nanorod of the present invention;
FIG. 3 is a transmission electron micrograph of a product obtained in example 1 of the present invention;
FIG. 4 is a high resolution TEM image of the top of the product obtained in example 1 of the present invention;
FIG. 5 is a transmission electron micrograph of a product obtained in example 2 of the present invention;
FIG. 6 is a high resolution TEM image of the top of the product obtained in example 2 of the present invention;
FIG. 7 is a transmission electron micrograph of a product obtained in example 3 of the present invention;
FIG. 8 is a high resolution TEM image of the top of the product obtained in example 3 of the present invention;
FIG. 9 is a UV-VISIBLE-NIR absorption spectrum of silver-gold nanorods obtained according to the present invention.
FIG. 10 is a graph showing the UV-vis-NIR absorption spectrum of the resulting nano-frame of the present invention.
Detailed Description
The raw materials and equipment used in the following examples were all purchased and used. The purity of the gold nanometer bipyramid is 99 percent, and the absorbance is 2.
Example 1
A method for controlling the deposition of gold atoms on silver nanostructures, comprising the steps of:
a. adding 5mL of gold nanoparticle bipyramid solution into 20mL of 0.08mol/L hexadecyltrimethylammonium chloride solution, adding 500 muL of 0.01mol/L silver nitrate solution and 250 muL of 0.1mol/L ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into a 65 ℃ oven for reaction for 4.5 hours to obtain a silver nanorod, as shown in FIGS. 1-2, wherein the silver nanorod is provided with a tip, a side face and a side edge, the tip comprises 10 {111} faces, the side face comprises 5 {100} faces, the side edge comprises 5 {110} faces, the side edge is a high surface energy face, and the high surface energy faces and the tip position are in ectopic distribution;
b. taking the silver nanorods obtained in the step a as a reaction template, centrifuging at 5000rpm for 10min, and dispersing into 8mL of 0.05mol/L hexadecyl trimethyl ammonium bromide solution to obtain silver nanorod solution;
c. adding 1mL and 0.1mol/L ascorbic acid solution into 4mL of silver nanorod solution, and uniformly stirring;
d. c, adjusting the pH value of the mixed solution obtained in the step c to be 1.88 by using 1mL and 0.1mol/L hydrochloric acid solution, and uniformly stirring;
e. slowly dropwise adding 1.6mL of 0.1mmol/L chloroauric acid solution into the reaction system obtained in the step d at the speed of 20 mu L/min, and reacting for 1.3 h.
Centrifuging the product obtained in the step e at 6000rpm for 10min, dispersing the product in 3mL of hexadecyl trimethyl ammonium bromide solution of 0.005mol/L, respectively adding 0.1mL of ammonia water solution of 14mol/L and hydrogen peroxide solution of 2mL of 5mol/L, and reacting at room temperature for 12h to obtain the superfine metal nano frame; and selectively etching the silver atoms, keeping the shape of the gold atoms, and observing the deposition positions of the gold atoms.
As shown in FIGS. 3-4, gold atoms are deposited on the high surface energy surface to form an unsealed gold nano-frame.
Example 2
A method for controlling the deposition of gold atoms on silver nanostructures, comprising the steps of:
a. adding 5mL of gold nanoparticle bipyramid solution into 20mL of 0.08mol/L hexadecyltrimethylammonium chloride solution, adding 500 muL of 0.01mol/L silver nitrate solution and 250 muL of 0.1mol/L ascorbic acid solution, shaking uniformly the obtained mixed solution, and placing the mixed solution into a 65 ℃ oven for reaction for 4.5 hours to obtain a silver nanorod, wherein the silver nanorod is provided with a tip, a side face and a side edge, the tip comprises 10 {111} faces, the side face comprises 5 {100} faces, the side edge comprises 5 {110} faces, the side edge is a high surface energy face, and the high surface energy face and the tip position are in ectopic distribution;
b. taking the silver nanorods obtained in the step a as a reaction template, centrifuging at 5000rpm for 10min, and dispersing into 8mL of 0.05mol/L hexadecyl trimethyl ammonium bromide solution to obtain silver nanorod solution;
c. adding 1mL and 0.1mol/L ascorbic acid solution into 4mL of silver nanorod solution, and uniformly stirring;
d. c, adjusting the pH value of the mixed solution obtained in the step c to 6.52 by adopting 1mL and 0.1mol/L sodium hydroxide solution, and uniformly stirring;
e. slowly dropwise adding 1.6mL of 0.1mmol/L chloroauric acid solution into the reaction system obtained in the step d at the speed of 20 mu L/min, and reacting for 1.3 h.
Centrifuging the product obtained in the step e at 6000rpm for 10min, dispersing the product in 3mL of hexadecyl trimethyl ammonium bromide solution of 0.005mol/L, respectively adding 0.1mL of ammonia water solution of 14mol/L and hydrogen peroxide solution of 2mL of 5mol/L, and reacting at room temperature for 12h to obtain the superfine metal nano frame; and selectively etching the silver atoms, keeping the shape of the gold atoms, and observing the deposition positions of the gold atoms.
As shown in FIGS. 5-6, gold atoms are deposited on the high surface energy surface and the tip simultaneously to form a gold nano-frame.
Example 3
A method for controlling the deposition of gold atoms on silver nanostructures, comprising the steps of:
a. adding 5mL of gold nanoparticle bipyramid solution into 20mL of 0.08mol/L hexadecyltrimethylammonium chloride solution, then adding 500 muL of 0.01mol/L silver nitrate solution and 250 muL of 0.1mol/L ascorbic acid solution, shaking up the obtained mixed solution, and placing the mixed solution into a 65 ℃ oven for reaction for 4.5 hours to obtain silver nanorods, wherein the silver nanorods are provided with tips, side faces and side edges, the tips comprise 10 {111} faces, the side faces comprise 5 {100} faces, the side edges comprise 5 {110} faces, the side edges are high surface energy faces, and the high surface energy faces and the tip positions are in ectopic distribution;
b. taking the silver nanorods obtained in the step a as a reaction template, centrifuging at 5000rpm for 10min, and dispersing into 8mL of 0.05mol/L hexadecyl trimethyl ammonium bromide solution to obtain silver nanorod solution;
c. adding 1mL and 0.1mol/L ascorbic acid solution into 4mL of silver nanorod solution, and uniformly stirring;
d. c, adjusting the pH value of the mixed solution obtained in the step c to 11.69 by using 1mL and 0.2mol/L sodium hydroxide solution, and uniformly stirring;
e. slowly dropwise adding 1.6mL of 0.1mmol/L chloroauric acid solution into the reaction system obtained in the step d at the speed of 20 mu L/min, and reacting for 1.3 h.
E, centrifuging the product obtained in the step e at 6000rpm for 10min, dispersing the product in 3mL of hexadecyl trimethyl ammonium bromide solution and 0.005mol/L of hexadecyl trimethyl ammonium bromide solution, respectively adding 0.1mL of ammonia water solution and 14mol/L of ammonia water solution and hydrogen peroxide solution with the concentration of 2mL and 5mol/L, and reacting at room temperature for 12h to obtain the superfine metal nano frame; and selectively etching the silver atoms, keeping the shape of the gold atoms, and observing the deposition positions of the gold atoms.
As shown in FIGS. 7-8, most of the gold atoms are deposited at the tip of the silver nanorod to form the gold-sealing nano-frame.
In summary, the characterization electron microscope images of the whole superfine gold nanometer frame and the top end in fig. 3 to 8 show that the deposition position of the gold atom is changed from the high surface energy surface to the tip position of the silver nanorod along with the increase of the co-reduction reaction ratio, so that the controllable deposition of the gold atom on the silver nanometer structure can be realized by controlling the pH value of the solution. As shown in fig. 9, the silver-gold nanorod structures obtained in examples 1 to 3 have strong absorption peaks in the near-infrared region, and have potential application prospects in the aspects of photocatalysis, sensing, medicine and the like. In addition, as shown in fig. 10, the by-product nano-frames obtained in examples 1 to 3 all have strong absorption peaks, narrow half-peak widths, and excellent surface plasmon properties.
Example 4
A method for controlling the deposition of gold atoms on silver nanostructures, comprising the steps of:
a. adding 5mL of gold nanoparticle bipyramid solution into 20mL of 0.08mol/L hexadecyltrimethylammonium chloride solution, then adding 500 muL of 0.01mol/L silver nitrate solution and 250 muL of 0.1mol/L ascorbic acid solution, shaking up the obtained mixed solution, and placing the mixed solution into a 65 ℃ oven for reaction for 4.5 hours to obtain silver nanorods, wherein the silver nanorods are provided with tips, side faces and side edges, the tips comprise 10 {111} faces, the side faces comprise 5 {100} faces, the side edges comprise 5 {110} faces, the side edges are high surface energy faces, and the high surface energy faces and the tip positions are in ectopic distribution;
b. taking the silver nanorods obtained in the step a as a reaction template, centrifuging at 5000rpm for 10min, and dispersing into 8mL of 0.1mol/L hexadecyl trimethyl ammonium bromide solution to obtain silver nanorod solution;
c. adding 1mL and 1mol/L ascorbic acid solution into 4mL of silver nanorod solution, and uniformly stirring;
d. c, adjusting the pH value of the mixed solution obtained in the step c to 12.96 by using 1mL and 1mol/L sodium hydroxide solution, and uniformly stirring;
e. slowly dropwise adding 1.6mL of 0.5mmol/L sodium tetrachloroaurate solution into the reaction system obtained in the step d at the speed of 20 mu L/min, and reacting for 5 h.
Centrifuging the product obtained in the step e at 6000rpm for 10min, dispersing the product in 3mL of hexadecyl trimethyl ammonium bromide solution of 0.1mol/L, respectively adding 0.1mL of ammonia water solution of 14mol/L and hydrogen peroxide solution of 2mL of 5mol/L, and reacting at room temperature for 24h to obtain the superfine metal nano frame; and selectively etching the silver atoms, wherein the rest is in the shape of gold atoms, and observing that the gold atoms are mainly deposited at the tip positions of the silver nanorods, and the high surface energy surface has no gold atoms deposited, so that a nanometer frame structure is not formed.
Example 5
A method for controlling the deposition of gold atoms on silver nanostructures, comprising the steps of:
a. adding 5mL of gold nanoparticle bipyramid solution into 20mL of 0.08mol/L hexadecyltrimethylammonium chloride solution, then adding 500 muL of 0.01mol/L silver nitrate solution and 250 muL of 0.1mol/L ascorbic acid solution, shaking up the obtained mixed solution, and placing the mixed solution into a 65 ℃ oven for reaction for 4.5 hours to obtain silver nanorods, wherein the silver nanorods are provided with tips, side faces and side edges, the tips comprise 10 {111} faces, the side faces comprise 5 {100} faces, the side edges comprise 5 {110} faces, the side edges are high surface energy faces, and the high surface energy faces and the tip positions are in ectopic distribution;
b. taking the silver nanorods obtained in the step a as a reaction template, centrifuging at 5000rpm for 10min, and dispersing into 8mL of 0.07mol/L hexadecyl trimethyl ammonium bromide solution to obtain silver nanorod solution;
c. adding 1mL and 0.5mol/L ascorbic acid solution into 4mL of silver nanorod solution, and uniformly stirring;
d. c, adjusting the pH value of the mixed solution obtained in the step c to 11.69 by using 1mL and 0.2mol/L sodium hydroxide solution, and uniformly stirring;
e. slowly dropwise adding 1.6mL of 0.3mmol/L sodium chlorotetrachloroaurate solution into the reaction system obtained in the step d at the rate of 20 mu L/min, and reacting for 3 h.
Centrifuging the product obtained in the step e at 6000rpm for 10min, dispersing the product in 3mL of hexadecyl trimethyl ammonium bromide solution of 0.05mol/L, respectively adding 0.1mL of ammonia water solution of 7mol/L and hydrogen peroxide solution of 2mL of hydrogen peroxide solution of 3mol/L, and reacting at room temperature for 16h to obtain the superfine metal nano frame; and selectively etching the silver atoms, wherein the rest is in the shape of gold atoms, and observing to obtain a majority of gold atoms deposited at the tip positions of the silver nanorods to form the sealed gold nanometer frame.
Example 6
A method for controlling the deposition of gold atoms on silver nanostructures, comprising the steps of:
a. adding 5mL of gold nanoparticle bipyramid solution into 20mL of 0.08mol/L hexadecyltrimethylammonium chloride solution, adding 500 muL of 0.01mol/L silver nitrate solution and 250 muL of 0.1mol/L ascorbic acid solution, shaking uniformly the obtained mixed solution, and placing the mixed solution into a 65 ℃ oven for reaction for 4.5 hours to obtain a silver nanorod, wherein the silver nanorod is provided with a tip, a side face and a side edge, the tip comprises 10 {111} faces, the side face comprises 5 {100} faces, the side edge comprises 5 {110} faces, the side edge is a high surface energy face, and the high surface energy face and the tip position are in ectopic distribution;
b. taking the silver nanorods obtained in the step a as a reaction template, centrifuging at 5000rpm for 10min, and dispersing into 8mL of 0.09mol/L hexadecyl trimethyl ammonium bromide solution to obtain silver nanorod solution;
c. adding 1mL and 0.1mol/L ascorbic acid solution into 4mL of silver nanorod solution, and uniformly stirring;
d. c, adjusting the pH value of the mixed solution obtained in the step c to 6.52 by adopting 1mL and 0.1mol/L sodium hydroxide solution, and uniformly stirring;
e. slowly dropwise adding 1.6mL of 0.1mmol/L sodium tetrachloroaurate solution into the reaction system obtained in the step d at the speed of 20 mu L/min, and reacting for 1 h.
Centrifuging the product obtained in the step e at 6000rpm for 10min, dispersing the product in 3mL of hexadecyl trimethyl ammonium bromide solution with the concentration of 0.005mol/L, respectively adding 0.1mL of ammonia water solution with the concentration of 1mol/L and hydrogen peroxide solution with the concentration of 2mL of hydrogen peroxide solution with the concentration of 1mol/L, and reacting at room temperature for 6h to obtain the superfine metal nano frame; and selectively etching the silver atoms, wherein the rest is in the shape of gold atoms, and observing that the deposition of the gold atoms is uniformly distributed on the high surface energy surface and the tip position of the silver nanorod to form the gold nano frame.
Claims (5)
1. A method for controlling gold atom deposition on a silver nanostructure is characterized by comprising the following steps:
step one, taking a gold nanometer bipyramid as a core, epitaxially growing silver to obtain a silver nanometer rod, wherein the high surface energy surface and the tip end position of the silver nanometer rod are distributed in an ectopic way;
dispersing the silver nanorods obtained in the step one into a cetyl trimethyl ammonium bromide solution by using the silver nanorods as a reaction template, adding an ascorbic acid solution, and uniformly stirring, wherein the concentration of the cetyl trimethyl ammonium bromide is 0.05-0.1 mol/L, and the concentration of the ascorbic acid solution is 0.1-1 mol/L;
adjusting the pH value of the mixed solution obtained in the step two, further adjusting the reducibility of the ascorbic acid solution, and realizing the adjustment of the ratio between the displacement reaction and the co-reduction reaction in the reaction system, wherein the pH value of the mixed solution is changed within the range of 1.88-12.96, the reducibility of the ascorbic acid is increased along with the increase of the pH value, and the displacement reaction in the reaction system is mainly changed into the co-reduction reaction;
step four, dropwise adding a gold precursor solution into the reaction system obtained in the step three, wherein the dropwise adding rate of the gold precursor solution is 20 muL/min, the gold precursor solution is converted from a displacement reaction system to a co-reduction reaction system along with the reaction system, and the deposition positions of reduced gold atoms are gradually moved to the tip positions of silver nanorods from a high surface energy surface, so that the controllable adjustment of the deposition positions of the gold atoms is realized; in the first step, the silver nanorod comprises a tip, a side face and a side edge, wherein the tip comprises 10 {111} planes, the side face comprises 5 {100} planes, the side edge comprises 5 {110} planes, and the side edge is a high surface energy plane.
2. The method of claim 1, wherein the deposition of gold atoms on the silver nanostructures is controlled by: in the third step, a sodium hydroxide solution with the concentration of 0.1-1 mol/L or a hydrochloric acid solution with the concentration of 0.1mol/L is adopted to adjust the pH value of the mixed solution obtained in the second step.
3. The method of claim 1, wherein the deposition of gold atoms on the silver nanostructures is controlled by: in the fourth step, the gold precursor solution is chloroauric acid solution or sodium tetrachloroaurate solution.
4. The method of claim 1, wherein the deposition of gold atoms on the silver nanostructures is controlled by: in the fourth step, the concentration of the gold precursor solution is 0.1-0.5 mmol/L.
5. The method of claim 1, wherein the deposition of gold atoms on the silver nanostructures is controlled by: and centrifugally placing the product obtained in the step four into a hexadecyl trimethyl ammonium bromide solution, respectively adding an ammonia water solution and a hydrogen peroxide solution, reacting for 6-24 hours at room temperature, selectively etching silver atoms, observing the deposition positions of the gold atoms, wherein the concentration of the hexadecyl trimethyl ammonium bromide solution is 0.005-0.1 mol/L, the concentration of the ammonia water solution is 1-14 mol/L, and the concentration of the hydrogen peroxide solution is 1-5 mol/L.
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