CN102794458B - Hollow silver particle and preparation method thereof - Google Patents
Hollow silver particle and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hollow silver particle. The outer diameter of the hollow silver particle is 20-1000nm, the inner diameter of the hollow silver particle is 10-500nm, the wall thickness of the hollow silver particle is 5-250nm, and the specific area of the hollow silver particle is 10-100m<2>/g. A preparation method of the hollow silver particle comprises the following steps of: dissolving silver nitrate and a surface active agent in water, and then adding an alkali solution to react so as to obtain silver oxide particles; and adding a polar solvent dissolved with a reducing agent into a solution containing silver oxide particles, stirring till all Ag2O is reduced into Ag. The invention has the advantages that the process is carried out in the solution, the reaction temperature is low, the preparation process is simple, the yield is high, the hollow silver particles with different particle sizes can be obtained by controlling the reaction conditions; in the range of the technical scheme, the diameter of the hollow silver ball is 20-1000nm; and since the hollow silver structures are narrow in particle size distribution, adjustable in the size and smooth in surface, the application value in the aspects of microelectron, biosensing and catalysis and the like is great.
Description
Technical field
The present invention relates to a kind of hollow silver particle and preparation method thereof, be specifically related to a kind of hydrophilic simple substance Ag hollow bead and preparation method thereof that has, belong to hollow-structure metal particle technical field.
Background technology
Pattern, size and the structure of nano particle depended in the character of noble metal nano particles and nanostructured thereof and application to a great extent.By controlling the size of these nano particles and structure, to obtain desirable physics, chemical property, become the emphasis of people's research.Silver nano-grain is owing to having the performances such as excellent catalysis, optics, electricity and bio-sensing, thereby is widely used in fields such as chemistry, biology, materials.The specific area of hollow silver nano particle is larger, have weak symmetry, at aspects such as microelectronics, bio-sensing, catalysis, has very great application.
The method of synthetic hollow silver particle is generally hard template method or soft template method.Hard template method take template as core, material requested is passed through to absorption, precipitation, the means such as sol-gel are coated in template core, form the microballoon of core/shell structure, then heating, calcining is removed template and is obtained hollow bead, document " Chen Z for example, Zhan P, Wang Z L, et al.[J] .Adv Mater, 2004, 16:417-422. ", document " Zhang D B, Qi L M, Ma J N, et al. [J] .Adv Mater 2002, 14: 1499-1502. " preparation method of hollow Ag ball is all disclosed, these methods are all to adopt template, need afterwards template to remove.Template in soft template method need not heat removes, but need in synthetic, by different chemical molecule or ion, in the aqueous solution, form template, by the method for washing, remove afterwards, in document " Zhang D B, Qi L M; Ma J M; et al. Adv. Mater., 2002,14: 1499-1502 ", disclose the synthetic method of hollow silver, the method hollow core Ag is synthetic in the solution of polymer and surfactant, is a kind of soft template method.
The method of synthetic hollow silver need to just can obtain hollow-core construction by template material now, and process is relatively loaded down with trivial details, and gained silver grain graininess also should not regulate, and can not prepare easily and efficiently as required the hollow silver particle of desired particle size.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of hollow silver particle is provided, this particle has hydrophily, and granularity is adjustable, is convenient to application.
The present invention also provides the preparation method of this hollow silver particle, and the method is simple, convenient and swift, and made hollow silver grain graininess is more easily controlled.
The invention provides a kind of method of hollow silver particle and hollow silver particle of gained prepared simply and easily, described hollow silver particle is called again hollow ping-pong ball, silver-colored hollow ball, hollow silver structure, and concrete technical scheme is as follows:
A hollow silver particle, its performance parameter is: external diameter is 20-1000 nanometer, and internal diameter is 10-500 nanometer, and wall thickness is 5-250nm, and specific area is 10-100 m
2/ g.By adjusting each condition in its preparation method, can obtain the hollow silver particle in above-mentioned scope, can obtain as required particle nanoscale (20-100nm) or micron order (100-1000nm).
The preparation method of hollow silver particle of the present invention, is characterized in that comprising the following steps:
(1) preparation of silver oxide particle: silver nitrate and surfactant is soluble in water, then add aqueous slkali to react to obtain silver oxide particle;
(2) preparation of reductant solution: reducing agent is dissolved in polar solvent, obtains reductant solution;
(3) preparation of silver-colored hollow bead (being hollow silver particle): the reductant solution of step (2) is added in the solution that contains silver oxide particle in step (1), be stirred to all Ag
2o is reduced to Ag;
(4) post processing: by step (3) products therefrom centrifugation, washing, obtain hollow silver particle.
In above-mentioned preparation method, the silver oxide particle of step (1) can, partly for reacting with reducing agent, also can, all for reacting with reducing agent, be determined according to the amount of required hollow silver particle.
Surfactant of the present invention is polyvinylpyrrolidone, 1-METHYLPYRROLIDONE, vinyl pyrrolidone or 2-Pyrrolidone.
Aqueous slkali of the present invention is NaOH, KOH, LiOH or NH
3the aqueous solution or their alcoholic solution, described alcohol is general general solvent alcohol, such as methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol etc.
The described polar solvent of step of the present invention (2) is water, methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol or ethylene glycol.
The present invention's reducing agent used is monoborane-tert-butylamine complex compound, TBAB (TBAB), natrium citricum, sodium borohydride or PVP.
In step of the present invention (1), the concentration 10 of aqueous slkali
-3-5 mol/L, can adjust by controlling the concentration of aqueous slkali the performance parameter of hollow silver particle.
In step of the present invention (1), silver nitrate: surfactant: the mol ratio of alkali is 1: 2-100: 5～2000, preferred mol ratio is 1: 2-20: 5～120, and can be by regulating proportionate relationship between this three to adjust the performance parameter of hollow silver particle.
In step of the present invention (1), water plays the effect of reaction medium, and its consumption does not have too much influence, and the concentration that generally keeps silver nitrate is 1mmol/L-5mol/L.
In step of the present invention (1), the temperature that alkali reacts with silver nitrate is 0-25 ℃.
In step of the present invention (2), the concentration of reductant solution is 0.001-2mol/L, can adjust by controlling the concentration of reductant solution the performance parameter of hollow silver particle.
Reducing agent of the present invention and Ag
2the mol ratio of O is 3～1000:1, and preferred mol ratio is 10～300:1, can be by regulating proportionate relationship between the two to adjust the performance parameter of hollow silver particle.
In step of the present invention (3), reaction temperature is 15-40 ℃, is generally preferably room temperature.
In step of the present invention (3), reducing agent is directly poured in silver oxide solution, and stirs.
The present invention adopts two step synthesis hollow silver nano particle, first by silver nitrate and surfactant dissolves in polar solvent, and the aqueous slkali that injects certain volume obtains silver oxide particle and (also claims Ag
2o ball, lower with), then by silver oxide particle and reducing agent at room temperature stirring reaction certain hour obtain hollow silver particle (also claim Ag hollow ball, lower together).The present invention utilize simple reduction reaction synthetic solid silver oxide particle directly in room temperature or approach at the temperature of room temperature and be reduced into hollow Ag particle, reaction condition simply, easily control, other metal oxide be difficult to reducing agent directly in solution, in room temperature or approach room temperature in the situation that, be reduced into hollow metal simple-substance.Hollow-core construction is that the size of hollow silver particle is by Ag because the contraction in reduction process forms
2the size of O particle determines, and Ag
2the conditions such as the size of O particle and the concentration of the amount ratio of reactant, reducing agent, the concentration of aqueous slkali, reaction temperature are relevant, therefore can be by regulating the relation of these reaction conditions to obtain the hollow silver particle of desired particle size.The present invention and existing method for example template, microemulsion method, oersted Wald slaking method are compared, and the inventive method is simple, the favorable repeatability of preparation, and the granule size of hollow silver particle is more easily controlled, narrow particle size distribution.
The present invention adopts chemical reduction method in solution, to prepare hollow silver particle, reaction is carried out in solution, reaction temperature is low, preparation process is simple, output is high, by controlling reaction condition, can obtain the hollow silver particle of different-grain diameter, within the scope of technical solution of the present invention, can be by regulating reaction condition to obtain different-grain diameter, the hollow silver structure of different specific areas, the diameter of hollow ping-pong ball can be 20-1000 nm, narrow diameter distribution due to these hollow silver structures, size is adjustable, make it at microelectronics, bio-sensing, the aspects such as catalysis have great using value.
Accompanying drawing explanation
Fig. 1 is ESEM (SEM) picture of the synthetic hollow ping-pong ball of the embodiment of the present invention 2.
Fig. 2 is ESEM (SEM) picture of the synthetic hollow ping-pong ball of the embodiment of the present invention 3.
Fig. 3 is ESEM (SEM) picture of the synthetic hollow ping-pong ball of the embodiment of the present invention 4.
Fig. 4 is ESEM (SEM) picture of the synthetic hollow ping-pong ball of the embodiment of the present invention 5.
Fig. 5 is ESEM (SEM) picture of the synthetic hollow ping-pong ball of the embodiment of the present invention 9.
The specific embodiment
Below by embodiment, the present invention will be further elaborated, and following explanation only, in order to explain the present invention, does not limit its content.
embodiment 1
1.1 contain 0.5 mM(mmol/L, down together) aqueous solution 10 mL of silver nitrate and 10mM polyvinylpyrrolidone are placed in water-bath, Temperature Setting is at 20 degrees Celsius, adding afterwards 1 mL concentration is 5 M(mol/L, the NaOH aqueous solution down together), stir 20 min and make silver oxide particle, wherein the mol ratio of silver nitrate/polyvinylpyrrolidone/NaOH is 1:20:1000.
1.2 solution that contain silver oxide particle of getting described in appropriate embodiment 1.1 (contain 2.5 μ mol Ag
2o), injecting 0.5 mL concentration is the NaBH of 100 mM
4frozen water solution (temperature is 0 ℃), stirs 1 h at 25 degrees Celsius.Ag wherein
2o/NaBH
4mol ratio be 1:20.
After 1.3 reactions finish, after centrifugation and washing, obtain silver-colored hollow ball, the diameter of silver-colored hollow ball is about 50-100 nm, and ping-pong ball wall thickness is 15-30nm, and specific area is about 80 m
2/ g.
embodiment 2
2.1 aqueous solution 15 mL that contain 1 mM silver nitrate and 2 mM polyvinylpyrrolidones are placed in water-bath, Temperature Setting is at 0 degree Celsius, adding afterwards 1 mL concentration is the NaOH aqueous solution of 75 mM, stir 20 min and obtain silver oxide particle, wherein the mol ratio of silver nitrate/polyvinylpyrrolidone/NaOH is 1:2:5.
2.2 solution that contain silver oxide particle of getting described in appropriate 2.1 (contain 10 μ mol Ag
2o), temperature, be that 25 degrees Celsius, concentration are that ethylene glycol solution 1 mL of the natrium citricum of 1 M injects, at 40 degrees Celsius, stir 2 h.Ag wherein
2the mol ratio of O/ natrium citricum is 1:100.
After 2.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that particle diameter is 100-160 nm, ping-pong ball wall thickness is 30-42nm, and specific area is about 20 m
2/ g, as shown in Figure 1.
embodiment 3
3.1 aqueous solution 13 mL that contain 1.2 mM silver nitrates and 0.12M polyvinylpyrrolidone are placed in water-bath, and Temperature Setting is at 10 degrees Celsius, and adding afterwards 3.12 mL concentration is the KOH aqueous solution of 5 M, stir 20 min and obtain silver oxide particle.Wherein the mol ratio of silver nitrate/polyvinylpyrrolidone/KOH is about 1:100:1000.
3.2 solution that contain silver oxide particle of getting described in appropriate 3.1 (contain 30 nmol Ag
2o), 9 mL temperature, be that 0 degree Celsius, concentration are the NaBH of 1 mM
4ethylene glycol solution injects, and at 10 degrees Celsius, stirs 1.5 hours.Ag wherein
2o/NaBH
4mol ratio be 1:300.
After 3.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 153 nm, ping-pong ball wall thickness is about 40nm, and specific area is about 30 m
2/ g, as shown in Figure 2.
embodiment 4
The preparation of 4.1 silver oxide particles is with embodiment 2.1.
4.2 solution that contain silver oxide particle of getting described in appropriate embodiment 4.1 (contain 30 nmol Ag
2o), 1 mL temperature, be that 10 degrees Celsius, concentration are that the methanol solution of the PVP of 30 mM injects wherein, at 15 degrees Celsius, stir 1 h.Ag wherein
2the mol ratio of O/PVP is 1:1000.
After 4.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 85 nm, as shown in Figure 3.Wherein ping-pong ball wall thickness is about 25nm, and specific area is about 50 m
2/ g
embodiment 5
The preparation of 5.1 silver oxide particles is with embodiment 2.1.
5.2 solution that contain silver oxide particle of getting described in appropriate 5.1 (contain 10 mmol Ag
2o), the NaBH that is 1M 40 mL concentration
4ice butanol solution injects, and at 10 degrees Celsius, stirs 1 h.
After 5.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 145 nm, ping-pong ball wall thickness is about 37nm, and specific area is about 32 m
2/ g as shown in Figure 4.
embodiment 6
6.1 aqueous solution 1 mL that contain 5 M silver nitrates and 15M polyvinylpyrrolidone are placed in water-bath, and temperature is 25 degrees Celsius, drips afterwards the LiOH aqueous solution that 10 mL concentration are 5M, stir 30 min and make silver oxide particle.The mol ratio of silver nitrate/polyvinylpyrrolidone/LiOH is 1:3:10.
6.2 solution of getting the silver oxide particle described in appropriate 6.1 (contain 10 μ mol Ag
2o), the NaBH that is 2M 0.5 mL concentration
4ice ethylene glycol solution injects, stirring at room 1.5 h.Ag wherein
2o/NaBH
4mol ratio be 1:100.
After 6.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 20 nm.Wherein ping-pong ball wall thickness is about 5nm, and specific area is about 100 m
2/ g.
embodiment 7
The silver nitrate that 7.1 concentration is 0.25 mM and the polyvinylpyrrolidone of 0.5 mM are dissolved in 10 mL frozen water, temperature is zero degree, adding afterwards 1 mL concentration is the NaOH aqueous solution of 5 M, stir 20 min and obtain silver oxide particle, wherein the mol ratio of silver nitrate/polyvinylpyrrolidone/NaOH is 1:2:2000.
7.2 solution of getting the silver oxide particle described in appropriate 7.1 (contain 10 μ mol Ag
2o), the NaBH that is 2M 0.5 mL concentration
4ice ethylene glycol solution injects, stirring at room 1.5 h.Ag wherein
2o/NaBH
4mol ratio be 1:100.
After 7.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 130 nm.Wherein ping-pong ball wall thickness is about 35nm, and specific area is about 45 m
2/ g.
embodiment 8
The preparation of 8.1 silver oxide particles is with embodiment 7.1.
8.2 solution of getting the silver oxide particle described in appropriate 8.1 (contain 10 μ mol Ag
2o), 10 mL temperature, be that zero degrees celsius, concentration are the NaBH of 100 mM
4propanol solution is injected, stirring at room 4 h.
After 8.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 130 nm.
embodiment 9
9.1 frozen water solution 8 mL that contain 2 mM silver nitrates and 6 mM polyvinylpyrrolidones constant temperature in water-bath, at 10 degrees Celsius, adds the KOH aqueous solution that 4 mL concentration are 0.4M afterwards, stirs 40 min and obtains silver oxide particle.Wherein the mol ratio of silver nitrate/polyvinylpyrrolidone/KOH is 1:3:100.
The 9.2 silver oxide aqueous solution that contain of getting described in appropriate 11.1 (contain 10 μ mol Ag
2o), 5 mL temperature, be that the TBAB ethanolic solution that zero degrees celsius, concentration are 2M injects, the solution making is at room temperature stirred to 1 h.Ag
2the mol ratio of O/TBAB is 1:1000.
After 9.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 88 nm, as shown in Figure 5.
embodiment 10
The preparation of 10.1 silver oxide particles is with embodiment 9.1.
The 10.2 silver oxide aqueous solution that contain of getting described in appropriate 10.1 (contain 10 μ mol Ag
2o), 10 mL concentration, be the NaBH of 0.9 M
4butanol solution injects, and the solution making is at room temperature stirred to 1 h.Ag
2o/NaBH
4mol ratio be 1:900.
After 10.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 60 nm.
embodiment 11
Polyvinylpyrrolidone frozen water 10 mL of 11.1 silver nitrates that contain 8 μ M and 24 μ M, 0 ℃ of constant temperature in water-bath, adding afterwards 0.4 mL concentration is in the NaOH frozen water solution of 1 mM, stirs 20 min and obtains the silver oxide aqueous solution.Wherein the mol ratio of silver nitrate/polyvinylpyrrolidone/NaOH is 1:3:5.
The 11.2 silver oxide aqueous solution that contain of getting described in appropriate 11.1 (contain 10 μ mol Ag
2o), 10 mL concentration, be the NaBH of 3.5 mM
4frozen water solution injects, stirring at room 1 h.Ag
2o/NaBH
4mol ratio be 1:3.5.
After 11.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 1000 nm.Wherein ping-pong ball wall thickness is about 250nm, and specific area is about 10 m
2/ g.
embodiment 12
The silver nitrate that 12.1 concentration is 0.5 mM and 1-METHYLPYRROLIDONE frozen water solution 10 mL of 5 mM join in the NaOH frozen water solution that 1.5 mL concentration are 0.4 M, and 0 ℃ is stirred the solution that 50 min must contain silver oxide particle.Wherein the mol ratio of silver nitrate/1-METHYLPYRROLIDONE/NaOH is 1:10:120.
The 12.2 silver oxide aqueous solution that contain of getting described in appropriate 12.1 (contain 10 μ mol Ag
2o), 4 mL concentration, be the NaBH of 25 mM
4frozen water solution injects, stirring at room 3 h.Ag
2o/NaBH
4mol ratio be 1:10.
After 12.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 150 nm.
embodiment 13
13.1 contain 0.5 mM silver nitrate and 3 mM vinyl pyrrolidone frozen water solution 10 mL join in the NaOH frozen water solution that 1mL concentration is 0.5 M, and 0 ℃ is stirred the aqueous solution that 10 min obtain silver oxide particle.Wherein the mol ratio of silver nitrate/vinyl pyrrolidone/NaOH is 1:6:100.
The 13.2 silver oxide aqueous solution that contain of getting described in appropriate 13.1 (contain 10 μ mol Ag
2o), 10 mL concentration, be the NaBH of 80 mM
4ice ethylene glycol solution injects, stirring at room 1 h.Ag wherein
2o/NaBH
4mol ratio be 1:80.
After 13.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 170 nm.
embodiment 14
14.1 silver nitrates that contain 4mM and 40 mM2-pyrrolidones frozen water solution 10 mL join in the ice ethylene glycol solution of NaOH that 2 mL concentration are 0.5 M, and 0 ℃ is stirred the solution that 40 min obtain silver oxide particle.Wherein the mol ratio of silver nitrate/2-Pyrrolidone/NaOH is 1:10:25.
The 14.2 silver oxide aqueous solution that contain of getting described in appropriate 14.1 (contain 10 μ mol Ag
2o), the monoborane-tert-butylamine complex compound ice ethylene glycol solution that is 80 mM 10 mL concentration injects and stirs 1 h.Ag wherein
2the mol ratio of O/ monoborane-tert-butylamine complex compound is 1:80.
After 14.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 180 nm.
embodiment 15
15.1 contain 3 M silver nitrates and 9 M polyvinylpyrrolidone frozen water solution 1 mL join in the KOH frozen water solution that 6 mL concentration are 3 M, and 0 ℃ is stirred 30 min and makes silver oxide particle.Wherein the mol ratio of silver nitrate/polyvinylpyrrolidone/KOH is 1:3:6.
The 15.2 silver oxide aqueous solution that contain of getting described in appropriate 15.1 (contain 10 μ mol Ag
2o), 10 mL concentration, be the NaBH of 50 mM
4ice methanol solution injects, and at room temperature stirs 1 h.Ag wherein
2o/ NaBH
4/ mol ratio be 1:50.
After 15.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 750 nm.Wherein ping-pong ball wall thickness is about 180nm, and specific area is about 22 m
2/ g.
embodiment 16
16.1 contain 3 M silver nitrates and 9 M polyvinylpyrrolidone frozen water solution 1 mL join in the NaOH frozen water solution that 6 mL concentration are 3 M, and 0 ℃ is stirred 30 min and makes silver oxide particle.Wherein the mol ratio of silver nitrate/polyvinylpyrrolidone/NaOH is 1:3:6.
The 16.2 silver oxide aqueous solution that contain of getting described in appropriate 16.1 (contain 1 mmol Ag
2o), the natrium citricum ice aqueous isopropanol that is 2 M 30 mL concentration injects, and stirs 1 h.Ag wherein
2o/ natrium citricum/mol ratio be 1:60.
After 16.3 reactions finish, after centrifugation and washing, obtain the hollow ping-pong ball that average grain diameter is 1000 nm.
Claims (9)
1. a preparation method for hollow silver particle, is characterized in that comprising the following steps:
(1) preparation of silver oxide particle: silver nitrate and surfactant is soluble in water, then add aqueous slkali to react to obtain silver oxide particle;
(2) preparation of reductant solution: reducing agent is dissolved in polar solvent, obtains reductant solution;
(3) preparation of hollow silver particle: reductant solution is added in the solution that contains silver oxide particle, be stirred to all Ag
2o is reduced to Ag;
(4) post processing: by step (3) products therefrom centrifugation, washing, obtain hollow silver particle;
Gained hollow silver particle external diameter is 20-1000 nanometer, and internal diameter is 10-500 nanometer, and wall thickness is 5-250nm, and specific area is 10-100 m
2/ g.
2. preparation method according to claim 1, is characterized in that: described surfactant is polyvinylpyrrolidone, 1-METHYLPYRROLIDONE, vinyl pyrrolidone or 2-Pyrrolidone; Described aqueous slkali is NaOH, KOH, LiOH and NH
3the aqueous solution or alcoholic solution; The described polar solvent of step (2) is water, methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol or ethylene glycol; Described reducing agent is monoborane-tert-butylamine complex compound, TBAB, natrium citricum, sodium borohydride or PVP.
3. preparation method according to claim 1, is characterized in that: in step (1), and the concentration 10 of aqueous slkali
-3-5 mol/L.
4. preparation method according to claim 1, is characterized in that: in step (1), and silver nitrate: surfactant: the mol ratio of alkali is 1: 2～100: 5～2000.
5. preparation method according to claim 4, is characterized in that: in step (1), and silver nitrate: surfactant: the mol ratio of alkali is 1: 2～20: 5～120.
6. preparation method according to claim 1, is characterized in that: in step (2), the concentration of reductant solution is 0.001-2mol/L.
7. preparation method according to claim 1, is characterized in that: in step (3), and reducing agent and Ag
2the mol ratio of O is 3～1000:1.
8. preparation method according to claim 7, is characterized in that: in step (3), and reducing agent and Ag
2the mol ratio of O is that mol ratio is 10～300:1.
9. preparation method according to claim 1, is characterized in that: in step (1), the temperature that alkali reacts with silver nitrate is 0-25 ℃; In step (3), reaction temperature is 15-40 ℃.
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| CN101905330A (en) * | 2010-08-20 | 2010-12-08 | 上海交通大学 | Hollow silver microballoon and preparation thereof as well as application method thereof in Raman detection |
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