CN101934378A - High-concentration fast preparation method for silver nanowires - Google Patents
High-concentration fast preparation method for silver nanowires Download PDFInfo
- Publication number
- CN101934378A CN101934378A CN 201010281704 CN201010281704A CN101934378A CN 101934378 A CN101934378 A CN 101934378A CN 201010281704 CN201010281704 CN 201010281704 CN 201010281704 A CN201010281704 A CN 201010281704A CN 101934378 A CN101934378 A CN 101934378A
- Authority
- CN
- China
- Prior art keywords
- ethylene glycol
- nano silver
- silver wire
- glycol solution
- ethanol
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002042 Silver nanowire Substances 0.000 title abstract 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 163
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000012452 mother liquor Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- 239000013049 sediment Substances 0.000 claims description 24
- 239000006228 supernatant Substances 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- UGWRVHSFESMVND-UHFFFAOYSA-N silver;ethane-1,2-diol;nitrate Chemical compound [Ag+].OCCO.[O-][N+]([O-])=O UGWRVHSFESMVND-UHFFFAOYSA-N 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003252 repetitive effect Effects 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract 1
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Images
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a high-concentration fast preparation method for silver nanowires. The method comprises the following steps of: under the protection of inert gas, adding high-concentration silver nitrate glycol solution and polymer glycol solution into pre-heated glycol solution, and adding copper chloride serving as control agent at the same time so as to obtain mother liquor of the silver nanowires; and performing centrifugal separation and purification on the mother liquor so as to obtain pure silver nanowires diffused in ethanol solution. The high-concentration fast preparation method for silver nanowires has the advantages of high efficiency, low cost, simple process, high repeatability, high stability, fast reaction, high yield and adjustable and controllable shape and size of the silver nanowires, and makes the large-scale fast preparation and the application and research of the silver nanowires possible.
Description
Technical field
The present invention relates to the nano material preparation technology, specifically a kind of high concentration fast preparation method of nano silver wire.
Background technology
The one-dimensional metal nano material, comprise nano wire, nanometer rods, nanofiber, nanometer band etc., have physical properties such as unique light, electricity, magnetic with and chemical property and be widely used in fields such as nano electron device, nano-photon device, biology sensor, chemical detection, nano composite material.Receive much concern and be widely used in association area owing to nano silver wire has good heat-conductivity conducting ability and outstanding chemical stability.Especially the high speed development of solar energy industry is increasing to the demand of nano silver wire membrane electrode, and the quick preparation of nano silver wire has critical role in the preparation of nano material and application study for this reason.Topmost method is the polyalcohol method in the preparation of nano silver wire at present.People such as Y.Sun have proposed two step polyalcohol legal systems and have been equipped with nano-silver thread, and they are solvent with ethylene glycol, prepare nano silver wire in the presence of prefabricated crystal seed.[Sun, Y.; Mayers, B.T.; Xia, Y.Nano Lett.2002,2; Wiley, B.; Herricks, T.; Sun, Y.; Xia, Y.Nano Lett.2004,4,1733.] on this basis, developed the fast preparation method of one-step method nano silver wire, carry out the preparation of nano silver wire by adding suitable cation, anion and neutral molecule controlling agent.[Chen, C., et al.Nanotechnology.2007.18,115612-115619; Wiley, B., Y.Sun, and Y.Xia.Langmuir.2005,14,8077-8080] preparation of nano silver wire at present mostly be lower silver ion molar concentration (＜carry out under 0.1M), and the reaction time needs 1～2h.If develop the method that a kind of high concentration prepares nano silver wire fast, in the presence of micro-controlling agent, realize the quick preparation of nano silver wire, obtain product controllable appearance and size, adjustable nano silver wire, this will be expected to be applied to every basic research and practical application.
Summary of the invention
In order to overcome disadvantages of background technology, the purpose of this invention is to provide a kind of high concentration fast preparation method of nano silver wire.
The step of the technical solution used in the present invention is as follows:
Under the protection and magnetic agitation of inert gas, under condensing reflux, the oil bath heating and temperature control is at 140～200 ℃, with a ethylene glycol solution preheating 10～30 minutes, be that the silver nitrate ethylene glycol solution of 0.3～3.0M joins in the ethylene glycol solution of preheating with the molar concentration of volume then with a and ethylene glycol, adding portion and ethylene glycol are the polymer ethylene glycol solution of 0.3～3.0M with the molar concentration of volume simultaneously, contain the copper chloride that molar concentration is 0.05～0.5mM in the polymer ethylene glycol solution, the reaction time is 5～30 minutes; Be cooled to normal temperature and obtain the mother liquor of nano silver wire;
The nano silver wire of gained takes the centrifugation method of purification to separate purification, the mother liquor of nano silver wire is moved to centrifuge container, adding volume is the acetone of 5～10 times of mother liquor volumes and the mixed liquor of ethanol, centrifugation under the rotating speed of 1500～5000rpm, remove supernatant liquor, leave and take the bottom sediment; Repeat 1～2 time this process; In the ethanol that again sediment that obtains is added volume and be 5～10 times of reaction mother liquor volumes and the mixed liquor of deionized water, mix centrifugation under the rotating speed of 1500～4000rpm afterwards, remove supernatant liquor, leave and take the bottom sediment; Repeat this process 2～3 times; At last the nano silver wire that obtains is disperseed to be stored in the ethanolic solution.
The mol ratio of described polymer and silver nitrate, promptly the mol ratio of the repetitive of polymer and silver ion is 1～10: 1.
Described polymer is PVP, polyvinyl alcohol or polyoxyethylene.
It is 180～200 ℃ that described oil bath adds the thermal control optimum temperature.
The adding method of described silver nitrate ethylene glycol solution and polymer ethylene glycol solution is: silver nitrate ethylene glycol solution adding speed is controlled at 10～50ml/min, and polymer ethylene glycol solution adding speed is controlled at 1～10ml/min.
In the centrifugation method of purification of described nano silver wire in acetone and alcohol mixeding liquid and ethanol and the deionized water mixed liquor control of two kinds of compound volume ratios as follows:
(1) volume ratio of acetone and ethanol was 1～10: 1 during acetone and alcohol mixeding liquid were washed;
(2) volume ratio of ethanol and deionized water is 1～10: 1 in ethanol and the deionized water mixed liquor.
Described inert gas is argon gas or nitrogen.
The present invention compares the beneficial effect that has with background technology:
1, one-step method is taked in reaction, and is simple to operate.
2, the molar concentration of reaction system was greatly improved relatively in the past, had brought up to 0.3～3.0M by former＜0.1M.
3, the reaction time has shortened to 5～30min, has improved reaction efficiency and utilization rate of equipment and installations.Above 2 for the mass preparation nano silver wire provide may.
4, the nano silver wire diameter that obtains, length homogeneous, the productive rate height.
5, raw material is easy to get, the reaction efficiency height, and technology is simple.
6, the variation fluctuation of the environmental factor of course of reaction permission, the test good reproducibility, stability is high.
7, can regulate the diameter length of nano silver wire by the control process conditions, the average diameter of the nano silver wire that obtains after the purification is 50～220nm, and average length is 10～100 μ m.
In a word, efficient height of the present invention, cost is low, technology is simple, favorable repeatability, good stability.And be swift in response, the appearance and size of productive rate height, nano silver wire is adjustable controlled, for the extensive preparation fast of nano silver wire and application study provide may.
Description of drawings
Fig. 1 is SEM (SEM) picture of the synthetic nano silver wire of the embodiment of the invention 1, and scale is 1 μ m among the figure, and the average diameter of nano silver wire is 50nm, and average length is 80 μ m.
Fig. 2 is the particle powder X-diffracting spectrum of the synthetic nano silver wire of the embodiment of the invention 1.
Fig. 3 is SEM (SEM) picture of the synthetic nano silver wire of the embodiment of the invention 2, and scale is 1 μ m among the figure, and the average diameter of nano silver wire is 55nm, and average length is 70 μ m.
Fig. 4 is SEM (SEM) picture of the synthetic nano silver wire of the embodiment of the invention 3, and scale is 1 μ m among the figure, and the average diameter of nano silver wire is 60nm, and average length is 50 μ m.
Fig. 5 is SEM (SEM) picture of the synthetic nano silver wire of the embodiment of the invention 4, and scale is 1 μ m among the figure, and the average diameter of nano silver wire is 80nm, and average length is 55 μ m.
Fig. 6 is SEM (SEM) picture of the synthetic nano silver wire of the embodiment of the invention 5, and scale is 1 μ m among the figure, and the average diameter of nano silver wire is 120nm, and average length is 50 μ m.
Fig. 7 is SEM (SEM) picture of the synthetic nano silver wire of the embodiment of the invention 6, and scale is 1 μ m among the figure, and the average diameter of nano silver wire is 160nm, and average length is 40 μ m.
Fig. 8 is SEM (SEM) picture of the synthetic nano silver wire of the embodiment of the invention 7, and scale is 1 μ m among the figure, and the average diameter of nano silver wire is 170nm, and average length is 30 μ m.
Fig. 9 is SEM (SEM) picture of the synthetic nano silver wire of the embodiment of the invention 8, and scale is 1 μ m among the figure, and the average diameter of nano silver wire is 180nm, and average length is 20 μ m.
Figure 10 is SEM (SEM) picture of the synthetic nano silver wire of the embodiment of the invention 9, and scale is 2 μ m among the figure, and the average diameter of nano silver wire is 220nm, and average length is 15 μ m.
The specific embodiment
The invention will be further described to enumerate several specific embodiments below.
Embodiment 1:
The three-necked bottle that the airtight 100ml of condensation reflux unit is housed is full of argon gas, places 180 ℃ of oil baths; Add 10ml ethylene glycol, preheating 30min under magnetic stirrer; The silver nitrate ethylene glycol solution that then with the 10ml molar concentration is 0.3M joins in the ethylene glycol solution of preheating, and control adding speed is 50ml/min; Adding the 10ml molar concentration simultaneously is the PVP ethylene glycol solution of 0.3M, contains the copper chloride that molar concentration is 0.05mM in the PVP ethylene glycol solution, and control adding speed is 1ml/min; Reaction time is 15 minutes; Be cooled to normal temperature and obtain the mother liquor of nano silver wire; After reactant cooled off naturally, the nano silver wire mother liquor was transferred to the centrifuge tube of 3 50ml, and adding acetone and ethanol volume ratio are 10: 1 solution; Ultrasonic 1min mixes back centrifugal 20min under 3000rpm, removes supernatant liquor; Repeat once; The sediment adding ethanol that obtains and the volume ratio of deionized water are 10: 1 solution, and ultrasonic 1min is uniformly dispersed; Removing supernatant liquor behind the centrifugal 30min under the 3000rpm rotating speed; Repeat 2 times; Sediment adds 10ml ethanol, and ultrasonic being uniformly dispersed stores.Fig. 1 is SEM (SEM) photo of the nano silver wire that obtains of present embodiment; Fig. 2 be the nano silver wire that obtains of present embodiment the X-diffracting spectrum.
Embodiment 2:
The three-necked bottle that the airtight 100ml of condensation reflux unit is housed is full of argon gas, places 180 ℃ of oil baths; Add 10ml ethylene glycol, preheating 30min under magnetic stirrer; The silver nitrate ethylene glycol solution that then with the 10ml molar concentration is 0.3M joins in the ethylene glycol solution of preheating, and control adding speed is 50ml/min; Adding the 10ml molar concentration simultaneously is the PVP ethylene glycol solution of 0.5M, contains the copper chloride that molar concentration is 0.05mM in the PVP ethylene glycol solution, and control adding speed is 10ml/min; Reaction time is 30 minutes; Be cooled to normal temperature and obtain the mother liquor of nano silver wire; After reactant cooled off naturally, reaction mother liquor was transferred to the centrifuge tube of 3 50ml, and adding acetone and ethanol volume ratio are 5: 1 solution; Ultrasonic 1min mixes back centrifugal 20min under 3000rpm, removes supernatant liquor; Repeat once; The sediment adding ethanol that obtains and the volume ratio of deionized water are 5: 1 solution, and ultrasonic 1min is uniformly dispersed; Removing supernatant liquor behind the centrifugal 30min under the 3000rpm rotating speed; Repeat 2 times; Sediment adds 10ml ethanol, and ultrasonic being uniformly dispersed stores.Fig. 3 is SEM (SEM) photo of the nano silver wire that obtains of present embodiment.
Embodiment 3:
The three-necked bottle that the airtight 100ml of condensation reflux unit is housed is full of argon gas, places 180 ℃ of oil baths; Add 10ml ethylene glycol, preheating 30min under magnetic stirrer; The silver nitrate ethylene glycol solution that then with the 10ml molar concentration is 0.3M joins in the ethylene glycol solution of preheating, and control adding speed is 50ml/min; Adding the 10ml molar concentration simultaneously is the PVP ethylene glycol solution of 1.5M, contains the copper chloride that molar concentration is 0.05mM in the PVP ethylene glycol solution, and control adding speed is 5ml/min; Reaction time is 15 minutes; Be cooled to normal temperature and obtain the mother liquor of nano silver wire; After reactant cooled off naturally, reaction mother liquor was transferred to the centrifuge tube of 3 50ml, and adding acetone and ethanol volume ratio are 10: 1 solution; Ultrasonic 1min mixes back centrifugal 20min under 3000rpm, removes supernatant liquor; Repeat once; The sediment adding ethanol that obtains and the volume ratio of deionized water are 5: 1 solution, and ultrasonic 1min is uniformly dispersed; Removing supernatant liquor behind the centrifugal 30min under the 3000rpm rotating speed; Repeat 3 times; Sediment adds 10ml ethanol, and ultrasonic being uniformly dispersed stores.Fig. 4 is SEM (SEM) photo of the nano silver wire that obtains of present embodiment.
Embodiment 4:
The three-necked bottle that the airtight 100ml of condensation reflux unit is housed is full of argon gas, places 180 ℃ of oil baths; Add 10ml ethylene glycol, preheating 30min under magnetic stirrer; The silver nitrate ethylene glycol solution that then with the 10ml molar concentration is 0.3M joins in the ethylene glycol solution of preheating, and control adding speed is 50ml/min; Adding the 10ml molar concentration simultaneously is the PVP ethylene glycol solution of 3.0M, contains the copper chloride that molar concentration is 0.15mM in the PVP ethylene glycol solution, and control adding speed is 1ml/min; Reaction time is 15 minutes; Be cooled to normal temperature and obtain the mother liquor of nano silver wire; After reactant cooled off naturally, reaction mother liquor was transferred to the centrifuge tube of 3 50ml, and adding acetone and ethanol volume ratio are 5: 1 solution; Ultrasonic 1min mixes back centrifugal 20min under 1500rpm, removes supernatant liquor; Repeat 2 times; The sediment adding ethanol that obtains and the volume ratio of deionized water are 10: 1 solution, and ultrasonic 1min is uniformly dispersed; Removing supernatant liquor behind the centrifugal 30min under the 1500rpm rotating speed; Repeat 2 times; Sediment adds 10ml ethanol, and ultrasonic being uniformly dispersed stores.Fig. 5 is SEM (SEM) photo of the nano silver wire that obtains of present embodiment.
Embodiment 5:
The three-necked bottle that the airtight 100ml of condensation reflux unit is housed is full of argon gas, places 180 ℃ of oil baths; Add 10ml ethylene glycol, preheating 30min under magnetic stirrer; The silver nitrate ethylene glycol solution that then with the 10ml molar concentration is 0.5M joins in the ethylene glycol solution of preheating, and control adding speed is 25ml/min; Adding the 10ml molar concentration simultaneously is the PVP ethylene glycol solution of 0.8M, contains the copper chloride that molar concentration is 0.25mM in the PVP ethylene glycol solution, and control adding speed is being 10ml/min; Reaction time is 5 minutes; Be cooled to normal temperature and obtain the mother liquor of nano silver wire; After reactant cooled off naturally, reaction mother liquor was transferred to the centrifuge tube of 3 50ml, and adding acetone and ethanol volume ratio are 10: 1 solution; Ultrasonic 1min mixes back centrifugal 20min under 3000rpm, removes supernatant liquor; Repeat once; The sediment adding ethanol that obtains and the volume ratio of deionized water are 1: 1 solution, and ultrasonic 1min is uniformly dispersed; Removing supernatant liquor behind the centrifugal 30min under the 3000rpm rotating speed; Repeat 2 times; Sediment adds 10ml ethanol, and ultrasonic being uniformly dispersed stores.Fig. 6 is SEM (SEM) photo of the nano silver wire that obtains of present embodiment.
Embodiment 6:
The three-necked bottle that the airtight 100ml of condensation reflux unit is housed is full of argon gas, places 140 ℃ of oil baths; Add 10ml ethylene glycol, preheating 30min under magnetic stirrer; The silver nitrate ethylene glycol solution that then with the 10ml molar concentration is 0.3M joins in the ethylene glycol solution of preheating, and control adding speed is 25ml/min; Adding the 10ml molar concentration simultaneously is the PVP ethylene glycol solution of 0.3M, contains the copper chloride that molar concentration is 0.25mM in the PVP ethylene glycol solution, and control adding speed is being 5ml/min; Reaction time is 15 minutes; Be cooled to normal temperature and obtain the mother liquor of nano silver wire; After reactant cooled off naturally, reaction mother liquor was transferred to the centrifuge tube of 5 50ml, and adding acetone and ethanol volume ratio are 5: 1 solution; Ultrasonic 1min mixes back centrifugal 20min under 3000rpm, removes supernatant liquor; Repeat once; The sediment adding ethanol that obtains and the volume ratio of deionized water are 1: 1 solution, and ultrasonic 1min is uniformly dispersed; Removing supernatant liquor behind the centrifugal 30min under the 3000rpm rotating speed; Repeat 2 times; Sediment adds 10ml ethanol, and ultrasonic being uniformly dispersed stores.Fig. 7 is SEM (SEM) photo of the nano silver wire that obtains of present embodiment.
Embodiment 7:
The three-necked bottle that the airtight 100ml of condensation reflux unit is housed is full of nitrogen, places 180 ℃ of oil baths; Add 10ml ethylene glycol, preheating 30min under magnetic stirrer; The silver nitrate ethylene glycol solution that then with the 10ml molar concentration is 1.5M joins in the ethylene glycol solution of preheating, and control adding speed is 25ml/min; Adding the 10ml molar concentration simultaneously is the polyvinyl alcohol ethylene glycol solution of 3.0M, contains the copper chloride that molar concentration is 0.5mM in the polyvinyl alcohol ethylene glycol solution, and control adding speed is 1ml/min; Reaction time is 15 minutes; Be cooled to normal temperature and obtain the mother liquor of nano silver wire; After reactant cooled off naturally, reaction mother liquor was transferred to the centrifuge tube of 6 50ml, and adding acetone and ethanol volume ratio are 1: 1 solution; Ultrasonic 1min mixes back centrifugal 20min under 4000rpm, removes supernatant liquor; Repeat once; The sediment adding ethanol that obtains and the volume ratio of deionized water are 1: 1 solution, and ultrasonic 1min is uniformly dispersed; Removing supernatant liquor behind the centrifugal 30min under the 3000rpm rotating speed; Repeat 2 times; Sediment adds 10ml ethanol, and ultrasonic being uniformly dispersed stores.Fig. 8 is SEM (SEM) photo of the nano silver wire that obtains of present embodiment.
Embodiment 8:
The three-necked bottle that the airtight 100ml of condensation reflux unit is housed is full of argon gas, places 160 ℃ of oil baths; Add 10ml ethylene glycol, preheating 30min under magnetic stirrer; The silver nitrate ethylene glycol solution that then with the 10ml molar concentration is 0.3M joins in the ethylene glycol solution of preheating, and control adding speed is 10ml/min; Adding the 10ml molar concentration simultaneously is the polyoxyethylene glycol solution of 0.8M, contains the copper chloride that molar concentration is 0.1mM in the polyoxyethylene glycol solution, and control adding speed is 1ml/min; Reaction time is 15 minutes; Be cooled to normal temperature and obtain the mother liquor of nano silver wire; After reactant cooled off naturally, reaction mother liquor was transferred to the centrifuge tube of 4 50ml, and adding acetone and ethanol volume ratio are 10: 1 solution; Ultrasonic 1min mixes back centrifugal 20min under 3000rpm, removes supernatant liquor; Repeat once; The sediment adding ethanol that obtains and the volume ratio of deionized water are 1: 1 solution, and ultrasonic 1min is uniformly dispersed; Removing supernatant liquor behind the centrifugal 30min under the 3000rpm rotating speed; Repeat 2 times; Sediment adds 10ml ethanol, and ultrasonic being uniformly dispersed stores.Fig. 9 is SEM (SEM) photo of the nano silver wire that obtains of present embodiment.
Embodiment 9:
The three-necked bottle that the airtight 100ml of condensation reflux unit is housed is full of argon gas, places 198 ℃ of oil baths; Add 10ml ethylene glycol, preheating 30min under magnetic stirrer; The silver nitrate ethylene glycol solution that then with the 10ml molar concentration is 3.0M joins in the ethylene glycol solution of preheating, and control adding speed is 10ml/min; Adding the 10ml molar concentration simultaneously is the PVP ethylene glycol solution of 3.0M, contains the copper chloride that molar concentration is 0.5mM in the PVP ethylene glycol solution, and control adding speed is 1ml/min; Reaction time is 15 minutes; Be cooled to normal temperature and obtain the mother liquor of nano silver wire; After reactant cooled off naturally, reaction mother liquor was transferred to the centrifuge tube of 3 50ml, and adding acetone and ethanol volume ratio are 5: 1 solution; Ultrasonic 1min mixes back centrifugal 20min under 3000rpm, removes supernatant liquor; Repeat once; The sediment adding ethanol that obtains and the volume ratio of deionized water are 10: 1 solution, and ultrasonic 1min is uniformly dispersed; Removing supernatant liquor behind the centrifugal 30min under the 4000rpm rotating speed; Repeat 2 times; Sediment adds 10ml ethanol, and ultrasonic being uniformly dispersed stores.Figure 10 is SEM (SEM) the photo spectrum of the nano silver wire that obtains of present embodiment.
Claims (7)
1. the high concentration fast preparation method of a nano silver wire is characterized in that the step of this method is as follows:
Under the protection and magnetic agitation of inert gas, under condensing reflux, the oil bath heating and temperature control is at 140～200 ℃, with a ethylene glycol solution preheating 10～30 minutes, be that the silver nitrate ethylene glycol solution of 0.3～3.0M joins in the ethylene glycol solution of preheating with the molar concentration of volume then with a and ethylene glycol, adding portion and ethylene glycol are the polymer ethylene glycol solution of 0.3～3.0M with the molar concentration of volume simultaneously, contain the copper chloride that molar concentration is 0.05～0.5mM in the polymer ethylene glycol solution, the reaction time is 5～30 minutes; Be cooled to normal temperature and obtain the mother liquor of nano silver wire;
The nano silver wire of gained takes the centrifugation method of purification to separate purification, the mother liquor of nano silver wire is moved to centrifuge container, adding volume is the acetone of 5～10 times of mother liquor volumes and the mixed liquor of ethanol, centrifugation under the rotating speed of 1500～5000rpm, remove supernatant liquor, leave and take the bottom sediment; Repeat 1～2 time this process; In the ethanol that again sediment that obtains is added volume and be 5～10 times of reaction mother liquor volumes and the mixed liquor of deionized water, mix centrifugation under the rotating speed of 1500～4000rpm afterwards, remove supernatant liquor, leave and take the bottom sediment; Repeat this process 2～3 times; At last the nano silver wire that obtains is disperseed to be stored in the ethanolic solution.
2. the high concentration fast preparation method of a kind of nano silver wire according to claim 1, it is characterized in that: the mol ratio of described polymer and silver nitrate, promptly the mol ratio of the repetitive of polymer and silver ion is 1～10: 1.
3. the high concentration fast preparation method of a kind of nano silver wire according to claim 1, it is characterized in that: described polymer is PVP, polyvinyl alcohol or polyoxyethylene.
4. the high concentration fast preparation method of a kind of nano silver wire according to claim 1, it is characterized in that: it is 180～200 ℃ that described oil bath adds the thermal control optimum temperature.
5. the high concentration fast preparation method of a kind of nano silver wire according to claim 1, it is characterized in that: the adding method of described silver nitrate ethylene glycol solution and polymer ethylene glycol solution is: silver nitrate ethylene glycol solution adding speed is controlled at 10～50ml/min, and polymer ethylene glycol solution adding speed is controlled at 1～10ml/min.
6. the high concentration fast preparation method of a kind of nano silver wire according to claim 1 is characterized in that: in the centrifugation method of purification of described nano silver wire in acetone and alcohol mixeding liquid and ethanol and the deionized water mixed liquor control of two kinds of compound volume ratios as follows:
(1) volume ratio of acetone and ethanol was 1～10: 1 during acetone and alcohol mixeding liquid were washed;
(2) volume ratio of ethanol and deionized water is 1～10: 1 in ethanol and the deionized water mixed liquor.
7. the high concentration fast preparation method of a kind of nano silver wire according to claim 1, it is characterized in that: described inert gas is argon gas or nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010281704 CN101934378A (en) | 2010-09-10 | 2010-09-10 | High-concentration fast preparation method for silver nanowires |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010281704 CN101934378A (en) | 2010-09-10 | 2010-09-10 | High-concentration fast preparation method for silver nanowires |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101934378A true CN101934378A (en) | 2011-01-05 |
Family
ID=43388083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010281704 Pending CN101934378A (en) | 2010-09-10 | 2010-09-10 | High-concentration fast preparation method for silver nanowires |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101934378A (en) |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161102A (en) * | 2011-02-12 | 2011-08-24 | 明基材料有限公司 | Nano silver wire and manufacturing method thereof |
| CN102328095A (en) * | 2011-10-14 | 2012-01-25 | 济南大学 | Preparation method of metal silver nanowires with adjustable length and diameter |
| CN102423808A (en) * | 2011-12-14 | 2012-04-25 | 天津工业大学 | Quick high concentration synthesizing method of silver nanometer line |
| CN102689018A (en) * | 2012-06-11 | 2012-09-26 | 清华大学深圳研究生院 | Production method of nanometer silver wire material |
| CN102728848A (en) * | 2011-03-31 | 2012-10-17 | 香港科技大学 | Method of producing silver nanowires in large quantities |
| CN103084584A (en) * | 2013-01-29 | 2013-05-08 | 中国科学院理化技术研究所 | Method for preparing silver nanowires by hydrothermal method |
| CN103157807A (en) * | 2011-12-19 | 2013-06-19 | 财团法人工业技术研究院 | Method for preparing silver nanowires |
| CN103192092A (en) * | 2013-04-27 | 2013-07-10 | 苏州诺菲纳米科技有限公司 | Method for manufacturing silver nanowire |
| CN104985174A (en) * | 2015-05-26 | 2015-10-21 | 江苏大学 | Method for quickly preparing mass gold-silver alloy nanotubes |
| CN105081341A (en) * | 2014-05-12 | 2015-11-25 | 中国科学院大连化学物理研究所 | Preparation method for platinum nanowire net |
| CN105345022A (en) * | 2015-10-22 | 2016-02-24 | 东华大学 | Purification method for silver nanowire |
| CN105397107A (en) * | 2015-12-25 | 2016-03-16 | 蚌埠玻璃工业设计研究院 | Preparation method of ultra-long silver nanowires |
| CN105478793A (en) * | 2015-12-09 | 2016-04-13 | 中国科学院深圳先进技术研究院 | Silver nanowire and preparation method thereof |
| CN106068166A (en) * | 2014-03-07 | 2016-11-02 | 同和控股（集团）有限公司 | The manufacture method of nano silver wire and nano silver wire and use the ink of this nano silver wire |
| CN106238742A (en) * | 2015-06-12 | 2016-12-21 | 陶氏环球技术有限责任公司 | The method manufacturing high aspect ratio nano silver wire |
| CN106735294A (en) * | 2016-12-11 | 2017-05-31 | 浙江大学 | The preparation method of nano silver wire |
| CN107127333A (en) * | 2017-05-22 | 2017-09-05 | 哈尔滨工业大学 | A kind of method by vibrating and settling purification nano silver wire |
| CN107335811A (en) * | 2017-06-21 | 2017-11-10 | 天津宝兴威科技股份有限公司 | A kind of preparation method of high-purity nano silver wires with high length-diameter ratio |
| CN107639236A (en) * | 2017-09-08 | 2018-01-30 | 中国乐凯集团有限公司 | The preparation method and product of a kind of nano silver wire |
| US10081020B2 (en) | 2015-06-12 | 2018-09-25 | Dow Global Technologies Llc | Hydrothermal method for manufacturing filtered silver nanowires |
| CN108746661A (en) * | 2018-06-18 | 2018-11-06 | 南京邮电大学 | A kind of preparation method of the adjustable nano silver wire of draw ratio |
| CN108971510A (en) * | 2018-07-26 | 2018-12-11 | 深圳清华大学研究院 | Silver nanowires and preparation method thereof, silver nanowires film and laminated film |
| CN109021707A (en) * | 2018-06-05 | 2018-12-18 | 沈阳建筑大学 | A kind of compound ink of graphene/silver nanowires and preparation method thereof |
| CN110170644A (en) * | 2019-05-31 | 2019-08-27 | 陕西科技大学 | A method of by being centrifuged and settling purification silver nanowires |
| CN112605380A (en) * | 2020-11-30 | 2021-04-06 | 哈尔滨工业大学 | Filtering and purifying method of silver nanowires |
| CN115194143A (en) * | 2022-06-22 | 2022-10-18 | 深圳先进电子材料国际创新研究院 | Method for separating and purifying nano particles in suspension of polyvinyl pyrrolidone coated nano particles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100342064C (en) * | 2005-09-23 | 2007-10-10 | 浙江大学 | Silver nanometer wire synthesizing process |
-
2010
- 2010-09-10 CN CN 201010281704 patent/CN101934378A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100342064C (en) * | 2005-09-23 | 2007-10-10 | 浙江大学 | Silver nanometer wire synthesizing process |
Non-Patent Citations (4)
| Title |
|---|
| 《ACC. CHEM.RES.》 20071231 BENJAMIN WILEY ET AL. SYNTHESIS OF SILVER NANOSTRUCTURES WITH CONTROLLED SHAPES AND PROPERTIES 第1068页Multiply Twinned Pentagonal Nanowires，图2-3，第1075页Photon Transport through Nanowires、Conclusion 1-7 第40卷, 2 * |
| 《CHEM. MATER.》 20071231 LIN FENG GUO ET AL. Convenient,Rapid Synthesis of Ag Nanowires 第1756页EXPERIMENTAL SECTION 1-7 第19卷, 2 * |
| 《ELECTROCHEMISTRY COMMUNICATION》 20080327 KUN NI ET AL. Synthesis of silver nanowires with different aspect ratios as alcohol-tolerant catalysts for oxygen electroreduction 第1027页2.EXPERIMENTAL 1-7 第10卷, 2 * |
| 《JOURNAL OF MATERIALS CHEMISTY》 20081231 Kylee E. Korte ET AL. Rapid synthesis of silver nanowires thourgh a CuCl-or CuCl2-mediated polyol process 第438页EXPERIMENTAL 1-7 第18卷, 2 * |
Cited By (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161102A (en) * | 2011-02-12 | 2011-08-24 | 明基材料有限公司 | Nano silver wire and manufacturing method thereof |
| CN102728848B (en) * | 2011-03-31 | 2015-01-28 | 香港科技大学 | Method of producing silver nanowires in large quantities |
| CN102728848A (en) * | 2011-03-31 | 2012-10-17 | 香港科技大学 | Method of producing silver nanowires in large quantities |
| CN102328095A (en) * | 2011-10-14 | 2012-01-25 | 济南大学 | Preparation method of metal silver nanowires with adjustable length and diameter |
| CN102328095B (en) * | 2011-10-14 | 2013-03-27 | 济南大学 | Preparation method of metal silver nanowires with adjustable length and diameter |
| CN102423808A (en) * | 2011-12-14 | 2012-04-25 | 天津工业大学 | Quick high concentration synthesizing method of silver nanometer line |
| US9073122B2 (en) | 2011-12-19 | 2015-07-07 | Industrial Technology Research Institute | Method for preparing silver nanowire |
| CN103157807A (en) * | 2011-12-19 | 2013-06-19 | 财团法人工业技术研究院 | Method for preparing silver nanowires |
| TWI476160B (en) * | 2011-12-19 | 2015-03-11 | Ind Tech Res Inst | Method for preparing silver nanowire |
| CN102689018B (en) * | 2012-06-11 | 2015-02-25 | 清华大学深圳研究生院 | Production method of nanometer silver wire material |
| CN102689018A (en) * | 2012-06-11 | 2012-09-26 | 清华大学深圳研究生院 | Production method of nanometer silver wire material |
| CN103084584A (en) * | 2013-01-29 | 2013-05-08 | 中国科学院理化技术研究所 | Method for preparing silver nanowires by hydrothermal method |
| CN103192092A (en) * | 2013-04-27 | 2013-07-10 | 苏州诺菲纳米科技有限公司 | Method for manufacturing silver nanowire |
| CN103192092B (en) * | 2013-04-27 | 2015-09-02 | 苏州诺菲纳米科技有限公司 | The manufacture method of nano silver wire |
| CN106068166A (en) * | 2014-03-07 | 2016-11-02 | 同和控股（集团）有限公司 | The manufacture method of nano silver wire and nano silver wire and use the ink of this nano silver wire |
| CN106068166B (en) * | 2014-03-07 | 2018-10-09 | 同和控股（集团）有限公司 | The manufacturing method and nano silver wire of nano silver wire and the ink for using the nano silver wire |
| CN105081341A (en) * | 2014-05-12 | 2015-11-25 | 中国科学院大连化学物理研究所 | Preparation method for platinum nanowire net |
| CN104985174A (en) * | 2015-05-26 | 2015-10-21 | 江苏大学 | Method for quickly preparing mass gold-silver alloy nanotubes |
| US10081020B2 (en) | 2015-06-12 | 2018-09-25 | Dow Global Technologies Llc | Hydrothermal method for manufacturing filtered silver nanowires |
| CN106238742B (en) * | 2015-06-12 | 2018-07-20 | 陶氏环球技术有限责任公司 | The method for manufacturing high aspect ratio nano silver wire |
| CN106238742A (en) * | 2015-06-12 | 2016-12-21 | 陶氏环球技术有限责任公司 | The method manufacturing high aspect ratio nano silver wire |
| US10376898B2 (en) | 2015-06-12 | 2019-08-13 | Dow Global Technologies Llc | Method for manufacturing high aspect ratio silver nanowires |
| CN105345022A (en) * | 2015-10-22 | 2016-02-24 | 东华大学 | Purification method for silver nanowire |
| CN105478793B (en) * | 2015-12-09 | 2018-08-14 | 中国科学院深圳先进技术研究院 | A kind of preparation method of nano silver wire |
| CN105478793A (en) * | 2015-12-09 | 2016-04-13 | 中国科学院深圳先进技术研究院 | Silver nanowire and preparation method thereof |
| CN105397107A (en) * | 2015-12-25 | 2016-03-16 | 蚌埠玻璃工业设计研究院 | Preparation method of ultra-long silver nanowires |
| CN106735294A (en) * | 2016-12-11 | 2017-05-31 | 浙江大学 | The preparation method of nano silver wire |
| CN107127333A (en) * | 2017-05-22 | 2017-09-05 | 哈尔滨工业大学 | A kind of method by vibrating and settling purification nano silver wire |
| CN107127333B (en) * | 2017-05-22 | 2019-04-02 | 哈尔滨工业大学 | A method of by vibrating and settling purification silver nanowires |
| CN107335811A (en) * | 2017-06-21 | 2017-11-10 | 天津宝兴威科技股份有限公司 | A kind of preparation method of high-purity nano silver wires with high length-diameter ratio |
| CN107639236A (en) * | 2017-09-08 | 2018-01-30 | 中国乐凯集团有限公司 | The preparation method and product of a kind of nano silver wire |
| CN109021707A (en) * | 2018-06-05 | 2018-12-18 | 沈阳建筑大学 | A kind of compound ink of graphene/silver nanowires and preparation method thereof |
| CN108746661A (en) * | 2018-06-18 | 2018-11-06 | 南京邮电大学 | A kind of preparation method of the adjustable nano silver wire of draw ratio |
| CN108971510A (en) * | 2018-07-26 | 2018-12-11 | 深圳清华大学研究院 | Silver nanowires and preparation method thereof, silver nanowires film and laminated film |
| CN110170644A (en) * | 2019-05-31 | 2019-08-27 | 陕西科技大学 | A method of by being centrifuged and settling purification silver nanowires |
| CN110170644B (en) * | 2019-05-31 | 2021-08-13 | 陕西科技大学 | Method for purifying silver nanowires through centrifugation and sedimentation |
| CN112605380A (en) * | 2020-11-30 | 2021-04-06 | 哈尔滨工业大学 | Filtering and purifying method of silver nanowires |
| CN115194143A (en) * | 2022-06-22 | 2022-10-18 | 深圳先进电子材料国际创新研究院 | Method for separating and purifying nano particles in suspension of polyvinyl pyrrolidone coated nano particles |
| CN115194143B (en) * | 2022-06-22 | 2023-11-14 | 深圳先进电子材料国际创新研究院 | Method for separating and purifying nano particles in suspension of polyvinylpyrrolidone coated nano particles |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101934378A (en) | High-concentration fast preparation method for silver nanowires | |
| CN103451773B (en) | Bismuth ferrite nano fiber material and preparation method thereof | |
| Zhang et al. | Effects of Ag loading on structural and photocatalytic properties of flower-like ZnO microspheres | |
| Li et al. | Controlled growth of metal–organic framework on upconversion nanocrystals for NIR-enhanced photocatalysis | |
| Cheng et al. | Enhanced photoelectrochemical and photocatalytic properties of anatase-TiO2 (B) nanobelts decorated with CdS nanoparticles | |
| Li et al. | Enhanced ultraviolet emission from ZnS-coated ZnO nanowires fabricated by self-assembling method | |
| CN103658675B (en) | Copper nanowire and preparation method thereof | |
| CN103170645B (en) | The preparation method of nano silver wire | |
| Dong et al. | The pn-type Bi5O7I-modified porous C3N4 nano-heterojunction for enhanced visible light photocatalysis | |
| CN103721708B (en) | A kind of Silver/titanium dioxide composite heterostructure and preparation method thereof | |
| Zheng et al. | Core-shell structured α-Fe2O3@ CeO2 heterojunction for the enhanced visible-light photocatalytic activity | |
| CN102423808A (en) | Quick high concentration synthesizing method of silver nanometer line | |
| CN101934377A (en) | Quick and efficient synthesis method for silver nanowires | |
| CN101693196B (en) | Preparation method of silver/titanium dioxide compound | |
| CN105081348A (en) | Method for preparing particle-free and high-purity silver nanowires under atmospheric pressure with one-pot method | |
| Liao et al. | Panax notoginseng powder-assisted preparation of carbon-quantum-dots/BiOCl with enriched oxygen vacancies and boosted photocatalytic performance | |
| CN103408055A (en) | Room temperature preparation method of spherical Cu2O porous adsorbing material | |
| Cui et al. | Heterogeneous semiconductor shells sequentially coated on upconversion nanoplates for NIR-light enhanced photocatalysis | |
| CN102851877A (en) | Method for assembling gold and silver one-dimensional nano-material by adopting electrostatic spinning technology and application thereof | |
| Harish et al. | Functional properties and enhanced visible light photocatalytic performance of V3O4 nanostructures decorated ZnO nanorods | |
| CN105126807A (en) | Nano ZnO/C composite photocatalyst and preparation method thereof | |
| Guo et al. | Enhanced photocatalytic performance of metal silver and carbon dots co-doped BiOI photocatalysts and mechanism investigation | |
| Liu et al. | Ni 2 P/ZnS (CdS) core/shell composites with their photocatalytic performance | |
| CN103084582A (en) | Preparation method for atomic scale precious metal nanoparticle stable colloidal suspension | |
| CN104690293A (en) | Preparation method for silver nanowires of different length-diameter ratios |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110105 |