CN110076348B - Superfine metal nano frame and preparation method thereof - Google Patents
Superfine metal nano frame and preparation method thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 184
- 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 80
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 43
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 40
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 36
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 36
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052737 gold Inorganic materials 0.000 claims abstract description 23
- 239000010931 gold Substances 0.000 claims abstract description 23
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910001111 Fine metal Inorganic materials 0.000 claims description 5
- 238000005530 etching Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 description 10
- 239000002211 L-ascorbic acid Substances 0.000 description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical group [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- 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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Abstract
The invention discloses an ultrafine metal nano frame and a preparation method thereof, wherein the ultrafine metal nano frame is supported by a nano bipyramid, the metal nano frame comprises silver atoms and reaction atoms, the nano bipyramid comprises gold atoms, and the reaction atoms are gold atoms, palladium atoms or platinum atoms. The preparation method comprises the following steps: a. adding the gold nano bipyramid solution into a hexadecyl trimethyl ammonium chloride solution, then adding a silver nitrate solution and an ascorbic acid solution, shaking the mixed solution uniformly, and putting the mixed solution into a drying oven to obtain silver nanorods; b. centrifugally placing the silver nanorods into a hexadecyl trimethyl ammonium bromide solution, respectively adding a sodium hydroxide solution and an ascorbic acid solution, and slowly dropwise adding a reaction solution at room temperature; c. and c, centrifugally placing the sample obtained in the step b into a hexadecyl trimethyl ammonium bromide solution, respectively adding an ammonia water solution and a hydrogen peroxide solution, and reacting at room temperature. The preparation method has simple preparation conditions, obtains the sample by utilizing the growth and re-etching process of the template, and has mild conditions and strong operability.
Description
Technical Field
The invention relates to a nano material and a preparation method thereof, in particular to an ultrafine metal nano frame and a preparation method thereof.
Background
The noble metal nanoparticles have unique optical, electric field, magnetic field and other characteristics, and thus are widely used in catalysis, electronics, photonics, information storage, energy conversion and biomedicine. Because the content of these metals in the earth crust is extremely low and the price is high, the development of technical means for effectively utilizing the metals is urgently needed. In recent years, researchers have developed strategies to increase the catalytic activity of noble metal nanocrystals, thereby reducing their loading in the catalyst. The ultra-fine metal Nano-frame combines the advantages of hollow and ultra-thin, can greatly improve the utilization efficiency of noble metal, is particularly excellent in a plurality of structures at present, and has related reports in a plurality of literatures (J.Am.chem.Soc.2014, 136, 11594-.
However, because the framework of the ultra-fine nano-frame is very thin (less than 5nm), for various precious metals (gold, silver, palladium, platinum, etc.), the single-metal or multi-metal ultra-fine nano-frame formed by the ultra-fine nano-frame does not have excellent plasmon resonance performance in the visible and near-infrared fields (such as j.am.chem.soc.2011, 133, 8066-.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention aims to provide an ultrafine metal nano frame with plasmon resonance performance, and the invention also aims to provide a preparation method of the ultrafine metal nano frame by using grown silver as a sacrificial template.
The technical scheme is as follows: the superfine metal nanometer frame is supported by a nanometer bipyramid, the metal nanometer frame comprises silver atoms and reaction atoms, the nanometer bipyramid comprises gold atoms, and the reaction atoms are gold atoms, palladium atoms or platinum atoms. The width of the metal nanometer frame is 2-3 nm.
The preparation method of the superfine metal nano frame comprises the following steps:
a. adding a gold nano-bipyramid solution into a 0.01-0.1 mol/L hexadecyl trimethyl ammonium chloride solution, then adding a 0.01-0.1 mol/L silver nitrate solution and a 0.1-1 mol/L ascorbic acid solution, wherein the volume ratio of the gold nano-bipyramid to the hexadecyl trimethyl ammonium chloride to the silver nitrate to the ascorbic acid is 10: 100-500: 0.1-6: 0.1-3, shaking the obtained mixed solution uniformly, and putting the mixed solution into a drying oven at 40-80 ℃ for reacting for 1-8 hours to obtain silver nanorods;
b. centrifugally dispersing silver nanorods in 0.01-0.05 mol/L hexadecyl trimethyl ammonium bromide solution, respectively adding 0.1-1 mol/L sodium hydroxide solution and 0.1-1 mol/L ascorbic acid solution, slowly dropwise adding 0.1-0.5 mmol/L reaction solution at room temperature, wherein the volume ratio of the hexadecyl trimethyl ammonium bromide, the sodium hydroxide and the ascorbic acid to the reaction solution is 4: 0.1-1: 0.1-2, the dropwise adding speed is 10-30 mu L/min, the reaction time is 1-3 h, and the reaction solution is chloroauric acid solution, chloropalladate solution or chloroplatinic acid solution;
c. and c, centrifugally dispersing the sample obtained in the step b into 0.003-0.1 mol/L hexadecyl trimethyl ammonium bromide solution, respectively adding 1-14 mol/L ammonia water solution and 1-5 mol/L hydrogen peroxide solution, wherein the volume ratio of the hexadecyl trimethyl ammonium bromide to the ammonia water to the hydrogen peroxide solution is 100: 1-100: 5-200, and reacting at room temperature for 3-24 hours to obtain the superfine metal nano frame.
The reaction principle is as follows: the metal precursor and silver atoms on the surface of the gold nanometer bipyramid are subjected to displacement and coreduction reaction under the action of ascorbic acid and sodium hydroxide; due to the difference of crystal surface energy, deposited metal atoms preferentially grow on the edges of the silver nanorods to form superfine metal nano frames; and etching to obtain the superfine metal nanometer frame supported by the bare gold nanometer bipyramid.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics: the preparation condition is simple, the sample is obtained by utilizing the template growth and re-etching process, the condition is mild, and the operability is strong; the prepared superfine metal nano-frame has high purity and good dispersibility, and has potential application in the fields of solar cells, sensing and photocatalysis.
Drawings
FIG. 1 is a schematic diagram of the preparation of the present invention.
FIG. 2 is a transmission electron micrograph of the ultra-fine metal nano-frame of example 1, wherein a is 100nm and b is 5 nm.
Fig. 3 is an energy spectrum of the ultra-fine metallic nano-frame of example 1.
Fig. 4 is a uv-vis absorption spectrum of the ultra-fine metallic nano-frame of example 1.
Detailed Description
The purity of the gold nanometer bipyramid is 99%, and the absorbance is 2.
Example 1
Step 1, adding 1mL of gold nanoparticle bipyramid solution into 10mL of 0.08mol/L hexadecyl trimethyl ammonium chloride solution, adding 250 mu L of 0.01mol/L silver nitrate solution and 125 mu L of 0.1mol/L ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into a 60 ℃ oven for reaction for 5 hours to obtain silver nanorods;
step 2, centrifuging the silver nanorods at 5000rpm for 10min, redispersing the silver nanorods in 4mL of hexadecyl trimethyl ammonium bromide solution and 0.05mol/L of hexadecyl trimethyl ammonium bromide solution, respectively adding 1mL of sodium hydroxide solution and 0.2mol/L of sodium hydroxide solution and 1mL of ascorbic acid solution and 0.1mol/L of ascorbic acid solution, and slowly dropwise adding 1.6mL of chloropalladite reaction solution and 0.1mmol/L of chloropalladite reaction solution at the rate of 20 mu L/min at room temperature, wherein the reaction time is 2 h;
and 3, centrifuging the sample obtained in the step 2 at 6000rpm for 10min, dispersing the sample 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 2mL of hydrogen peroxide solution and 5mol/L of hydrogen peroxide solution, and reacting at room temperature for 12h to obtain the superfine metal nano frame.
The prepared nanoparticles are subjected to morphology analysis, and referring to fig. 1-3, a transmission electron microscope image, a high-resolution transmission electron microscope image and an energy spectrum image of a superfine metal nanometer frame are respectively shown, the structure is a gold nanometer double-cone supported nanometer frame structure, the thickness of the frame is 2-3 nm, and the frame is silver palladium alloy consisting of silver atoms and palladium atoms.
Fig. 4 is a comparison graph of absorption spectra of the synthesized ultra-fine metal nano-frame and the original gold nano-bipyramid, and by means of the gold nano-bipyramid, the characteristic peak of the ultra-fine metal nano-frame and the characteristic peak of the original gold nano-bipyramid are kept consistent, so that the composite nano-structure has both plasmon resonance performance and nano-frame performance.
Example 2
Step 1, adding 1mL of gold nanoparticle bipyramid solution into 50mL of 0.01mol/L hexadecyl trimethyl ammonium chloride solution, then adding 600 mu L of silver nitrate solution, 0.01mol/L of silver nitrate solution and 300 mu L of ascorbic acid solution, and placing the obtained mixed solution into a 40 ℃ drying oven for reaction for 8 hours to obtain silver nanorods;
step 2, centrifuging the silver nanorods at 5000rpm for 10min, redispersing the silver nanorods in 4mL of hexadecyl trimethyl ammonium bromide solution and 0.01mol/L of hexadecyl trimethyl ammonium bromide solution, respectively adding 1mL of sodium hydroxide solution and 0.1mol/L of ascorbic acid solution, and slowly dropwise adding 2mL of chloroauric acid reaction solution and 0.1mmol/L of chloroauric acid reaction solution at the rate of 10 mu L/min at room temperature for 1 h;
and 3, centrifuging the sample obtained in the step 2 at 6000rpm for 10min, dispersing the sample in 10mL of hexadecyl trimethyl ammonium bromide solution of which the concentration is 0.003mol/L, respectively adding 10mL of ammonia water solution of which the concentration is 1mol/L and 20mL of hydrogen peroxide solution of which the concentration is 1mol/L, and reacting at room temperature for 24h to obtain the superfine metal nano frame.
Example 3
Step 1, adding 1mL of gold nanoparticle bipyramid solution into 10mL of 0.1mol/L hexadecyl trimethyl ammonium chloride solution, then adding 10 mu L of silver nitrate solution, 0.1mol/L of silver nitrate solution and 10 mu L of ascorbic acid solution, and placing the obtained mixed solution into an oven at 80 ℃ for reaction for 1h to obtain silver nanorods;
step 2, centrifuging the silver nanorods at 5000rpm for 10min, redispersing the silver nanorods in 4mL and 0.05mol/L cetyl trimethyl ammonium bromide solutions, respectively adding 0.1mL and 1mol/L sodium hydroxide solutions and 0.1mL and 1mol/L ascorbic acid solutions, and slowly dropwise adding 0.1mL and 0.5mmol/L chloropalladite reaction solutions at the rate of 30 mu L/min at room temperature for 3 h;
and 3, centrifuging the sample obtained in the step 2 at 6000rpm for 10min, dispersing the sample in 10mL of hexadecyl trimethyl ammonium bromide solution and 0.1mol/L of hexadecyl trimethyl ammonium bromide solution, respectively adding 0.1mL of ammonia water solution and 14mol/L of ammonia water solution and 0.5mL of hydrogen peroxide solution and 5mol/L of hydrogen peroxide solution, and reacting at room temperature for 24h to obtain the superfine metal nano frame.
Example 4
Step 1, adding 1mL of gold nanoparticle bipyramid solution into 30mL of 0.05mol/L hexadecyl trimethyl ammonium chloride solution, then adding 305 mu L of silver nitrate solution, 0.015mol/L of silver nitrate solution, 155 mu L of ascorbic acid solution and 0.5mol/L of ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into a 60 ℃ drying oven for reaction for 4.5 hours to obtain silver nanorods;
step 2, centrifuging the silver nanorods at 5000rpm for 10min, dispersing the silver nanorods in 4mL of hexadecyl trimethyl ammonium bromide solution and 0.03mol/L of hexadecyl trimethyl ammonium bromide solution, respectively adding 0.5mL of sodium hydroxide solution, 0.5mol/L of sodium hydroxide solution and 0.5mL of ascorbic acid solution, slowly dropwise adding 1mL of chloroplatinic acid reaction solution and 0.3mmol/L chloroplatinic acid reaction solution at the rate of 20 mu L/min at room temperature, and reacting for 2 h;
and 3, centrifuging the sample obtained in the step 2 at 6000rpm for 10min, dispersing the sample in 10mL of 0.052mol/L hexadecyl trimethyl ammonium bromide solution, respectively adding 5mL of ammonia water solution, 7mol/L ammonia water solution and 10mL of hydrogen peroxide solution, 3mol/L hydrogen peroxide solution, and reacting at room temperature for 13.5h to obtain the superfine metal nano frame.
Example 5
Step 1, adding 1mL of gold nanoparticle bipyramid solution into 40mL of 0.03mol/L hexadecyl trimethyl ammonium chloride solution, then adding 500 mu L of silver nitrate solution, 0.03mol/L of silver nitrate solution and 300 mu L of ascorbic acid solution, and placing the obtained mixed solution into a 50 ℃ drying oven for reaction for 2 hours to obtain silver nanorods;
step 2, centrifuging the silver nanorods at 5000rpm for 10min, redispersing the silver nanorods in 4mL of hexadecyl trimethyl ammonium bromide solution and 0.02mol/L of hexadecyl trimethyl ammonium bromide solution, respectively adding 0.9mL of sodium hydroxide solution, 0.2mol/L of sodium hydroxide solution, 0.9mL of ascorbic acid solution and 0.3mol/L of ascorbic acid solution, and slowly dropwise adding 1.8mL of chloroauric acid reaction solution and 0.2mmol/L of chloroauric acid reaction solution at the rate of 15 mu L/min at room temperature, wherein the reaction time is 1.5 h;
and 3, centrifuging the sample obtained in the step 2 at 6000rpm for 10min, dispersing the sample in 10mL of 0.02mol/L hexadecyl trimethyl ammonium bromide solution, respectively adding 9mL of 3mol/L ammonia water solution and 18mL of 2mol/L hydrogen peroxide solution, and reacting at room temperature for 5h to obtain the superfine metal nano frame.
Example 6
Step 1, adding 1mL of gold nanoparticle bipyramid solution into 20mL of 0.08mol/L hexadecyl trimethyl ammonium chloride solution, then adding 100 mu L of silver nitrate solution, 0.08mol/L of silver nitrate solution and 150 mu L of ascorbic acid solution, and placing the obtained mixed solution into a 70 ℃ drying oven for reaction for 6 hours to obtain silver nanorods;
step 2, centrifuging the silver nanorods at 5000rpm for 10min, dispersing the silver nanorods in 4mL of hexadecyl trimethyl ammonium bromide solution and 0.04mol/L of hexadecyl trimethyl ammonium bromide solution, respectively adding 0.2mL of sodium hydroxide solution, 0.8mol/L of sodium hydroxide solution, 0.3mL of ascorbic acid solution and 0.9mol/L of ascorbic acid solution, slowly dropwise adding 0.4mL of chloropalladite reaction solution and 0.4mmol/L of chloropalladite reaction solution at the speed of 25 mu L/min at room temperature, wherein the reaction time is 2.5 h;
and 3, centrifuging the sample obtained in the step 2 at 6000rpm for 10min, dispersing the sample in 10mL of 0.09mol/L hexadecyl trimethyl ammonium bromide solution, respectively adding 1mL of ammonia water solution, 12mol/L ammonia water solution and 2mL of hydrogen peroxide solution, 4mol/L hydrogen peroxide solution, and reacting at room temperature for 20h to obtain the superfine metal nano frame.
Example 7
Step 1, adding 1mL of gold nanoparticle bipyramid solution into 15mL of 0.05mol/L hexadecyl trimethyl ammonium chloride solution, then adding 350 mu L of silver nitrate solution, 0.02mol/L of silver nitrate solution, 175 mu L of ascorbic acid solution and 0.3mol/L of ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into a 50 ℃ oven for reaction for 6 hours to obtain the silver nanorods.
And 2, centrifuging the silver nanorods at 4000rpm for 10min, dispersing the silver nanorods in 4mL of hexadecyl trimethyl ammonium bromide solution and 0.03mol/L of hexadecyl trimethyl ammonium bromide solution, respectively adding 1mL of sodium hydroxide solution and 0.4mol/L of sodium hydroxide solution and 1mL of ascorbic acid solution and 0.2mol/L of ascorbic acid solution, and slowly dropwise adding 1.4mL of chloropalladate reaction solution and 0.1mmol/L of chloropalladate reaction solution at the speed of 15 mu L/min at room temperature for 1 h.
And 3, centrifuging the sample obtained in the step 2 at 5000rpm for 10min, dispersing the sample in 3mL of hexadecyl trimethyl ammonium bromide solution and 0.008mol/L of hexadecyl trimethyl ammonium bromide solution, respectively adding 0.2mL of ammonia water solution and 12.5mol/L of ammonia water solution and 3mL of hydrogen peroxide solution and 4.5mol/L of hydrogen peroxide solution, and reacting at room temperature for 12h to obtain the superfine metal nano frame.
Example 8
Step 1, adding 1mL of gold nanoparticle bipyramid solution into 15mL of 0.06mol/L hexadecyl trimethyl ammonium chloride solution, then adding 450 mu L of silver nitrate solution, 0.04mol/L of silver nitrate solution, 225 mu L of ascorbic acid solution and 0.2mol/L of ascorbic acid solution, shaking the obtained mixed solution uniformly, and placing the mixed solution into a 70 ℃ oven for reaction for 4 hours to obtain the silver nanorods.
And 2, centrifuging the silver nanorods at 3500rpm for 10min, dispersing the silver nanorods in 4mL of hexadecyl trimethyl ammonium bromide solution and 0.04mol/L of hexadecyl trimethyl ammonium bromide solution, respectively adding 1mL of sodium hydroxide solution and 0.3mol/L of sodium hydroxide solution and 1mL of ascorbic acid solution and 0.1mol/L of ascorbic acid solution, and slowly dropwise adding 1.2mL of chloropalladate reaction solution and 0.1mmol/L of chloropalladate reaction solution at the speed of 25 mu L/min at room temperature for 2 h.
And 3, centrifuging the sample obtained in the step 2 at 5000rpm for 10min, dispersing the sample in 3mL of hexadecyl trimethyl ammonium bromide solution and 0.01mol/L of hexadecyl trimethyl ammonium bromide solution, respectively adding 0.3mL of ammonia water solution and 10mol/L of ammonia water solution and 1.5mL of hydrogen peroxide solution and 2.5mol/L of hydrogen peroxide solution, and reacting at room temperature for 24h to obtain the superfine metal nano frame.
Example 9
Step 1, adding 1mL of gold nanoparticle bipyramid solution into 10mL of 0.07mol/L hexadecyl trimethyl ammonium chloride solution, then adding 500 mu L of silver nitrate solution, 0.01mol/L of silver nitrate solution and 250 mu L of ascorbic acid solution, and placing the obtained mixed solution into an oven at 80 ℃ for reaction for 2 hours to obtain the silver nanorods.
And 2, centrifuging the silver nanorods at 3000rpm for 10min, dispersing the silver nanorods in 4mL of hexadecyl trimethyl ammonium bromide solution and 0.03mol/L of hexadecyl trimethyl ammonium bromide solution, respectively adding 1mL of sodium hydroxide solution and 0.3mol/L of sodium hydroxide solution and 1mL of ascorbic acid solution and 0.15mol/L of ascorbic acid solution, and slowly dropwise adding 1.8mL of chloropalladite reaction solution and 0.1mmol/L of chloropalladite reaction solution at the speed of 30 mu L/min at room temperature for 3 h.
And 3, centrifuging the sample obtained in the step 2 at 4000rpm for 10min, dispersing the sample in 3mL of hexadecyl trimethyl ammonium bromide solution and 0.015mol/L of hexadecyl trimethyl ammonium bromide solution, respectively adding 0.3mL of ammonia water solution and 9.5mol/L of ammonia water solution and 4mL of hydrogen peroxide solution and 3.7mol/L of hydrogen peroxide solution, and reacting at room temperature for 24h to obtain the superfine metal nano frame.
Claims (8)
1. An ultra-fine metal nanometer frame is characterized in that: the metal nanometer frame comprises silver atoms and reaction atoms, the nanometer bipyramid comprises gold atoms, and the reaction atoms are gold atoms, palladium atoms or platinum atoms; the width of the metal nanometer frame is 2-3 nm;
the preparation method of the superfine metal nano frame comprises the following steps:
(a) adding the gold nano bipyramid solution into a hexadecyl trimethyl ammonium chloride solution, then adding a silver nitrate solution and an ascorbic acid solution, shaking the obtained mixed solution uniformly, and putting the mixed solution into a drying oven to obtain silver nanorods;
(b) centrifugally placing the silver nanorods into a hexadecyl trimethyl ammonium bromide solution, respectively adding a sodium hydroxide solution and an ascorbic acid solution, and slowly dropwise adding a reaction solution at room temperature;
(c) and (c) centrifuging the sample obtained in the step (b), placing the sample in a cetyl trimethyl ammonium bromide solution, respectively adding an ammonia water solution and a hydrogen peroxide solution, and reacting at room temperature to obtain the bare gold nano-bipyramid supported superfine metal nano-frame.
2. The ultra-fine metallic nano-frame according to claim 1, wherein: in the step (a), the concentration of hexadecyl trimethyl ammonium chloride is 0.01-0.1 mol/L, the concentration of silver nitrate is 0.01-0.1 mol/L, the concentration of ascorbic acid is 0.1-1 mol/L, and the volume ratio of the gold nano bipyramid to the hexadecyl trimethyl ammonium chloride to the silver nitrate to the ascorbic acid is 10: 100-500: 0.1-6: 0.1 to 3.
3. The ultra-fine metallic nano-frame according to claim 1, wherein: the reaction temperature in the step (a) is 40-80 ℃, and the reaction time is 1-8 h.
4. The ultra-fine metallic nano-frame according to claim 1, wherein: in the step (b), the concentration of hexadecyl trimethyl ammonium bromide is 0.01-0.05 mol/L, the concentration of sodium hydroxide is 0.1-1 mol/L, the concentration of ascorbic acid is 0.1-1 mol/L, the concentration of a reaction solution is 0.1-0.5 mmol/L, and the volume ratio of hexadecyl trimethyl ammonium bromide, sodium hydroxide, ascorbic acid and the reaction solution is 4: 0.1-1: 0.1-1: 0.1 to 2.
5. The ultra-fine metallic nano-frame according to claim 1, wherein: the reaction solution in the step (b) is a chloroauric acid solution, a chloropalladate solution or a chloroplatinic acid solution.
6. The ultra-fine metallic nano-frame according to claim 1, wherein: and (c) dropwise adding the reaction solution in the step (b) at a rate of 10-30 muL/min, and reacting for 1-3 h.
7. The ultra-fine metallic nano-frame according to claim 1, wherein: in the step (c), the concentration of the hexadecyl trimethyl ammonium bromide is 0.003-0.1 mol/L, the mass concentration of the ammonia water is 1-14 mol/L, the mass concentration of the hydrogen peroxide is 1-5 mol/L, and the volume ratio of the hexadecyl trimethyl ammonium bromide to the ammonia water to the hydrogen peroxide is 100: 1-100: 5 to 200.
8. The ultra-fine metallic nano-frame according to claim 1, wherein: the reaction time in the step (c) is 3-24 h.
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