CN100506439C - Method for preparing nanometer copper - Google Patents
Method for preparing nanometer copper Download PDFInfo
- Publication number
- CN100506439C CN100506439C CNB2005100946141A CN200510094614A CN100506439C CN 100506439 C CN100506439 C CN 100506439C CN B2005100946141 A CNB2005100946141 A CN B2005100946141A CN 200510094614 A CN200510094614 A CN 200510094614A CN 100506439 C CN100506439 C CN 100506439C
- Authority
- CN
- China
- Prior art keywords
- peg
- tween
- copper
- sdbs
- sds
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Chemically Coating (AREA)
- Materials For Medical Uses (AREA)
Abstract
The present invention relates to a method for preparing nanometer copper in different shapes. A Tween series and a PEG series or compounds of the Tween series, the PEG series, SDS and SDBS are respectThe invention discloses a making method of different-shape nanometer copper, which comprises the following steps: adapting Tween series and PEG series or these and SDS and SDBS built material as ornamively used as modifiers and are dissolved in water when stirred, reducing agents Vc are added and are sufficiently stirred until Vc is completely dissolved, and a reducing agent-modifier premixed systenting agent; dissolving the material in the water and stirring; adding the reducer Vc; stirring until the material is dissolved completely; making the premixing system of reducer-ornamenting agent; aem is prepared. A copper sulphate solution whose concentration is from 0.2 to 0.5 mol/L is prepared, the molar ratio of the modifiers and copper sulfate is (1 to 2.5): 1, and the molar ratio of the rellocating 0.2-0.5mol/L bluestone solution; letting the mole ration of ornamenting agent and bluestone at 1-2.5:1 and reducer Vc and bluestone at 3-5:1; Heating to reflux the premixed solution at 80 deducing agents Vc and the copper sulfate is (3 to 5): 1. The premixed solution is heated and refluxed in a water bath whose temperature is 80 DEG C when stirred, and is dripped in the copper sulphate sg C in the water; dripping bluestone solution at 20-50 drips per min; reacting for 2-5 h to produce fusco-ferruginous deposition; separating centrifugally; washing; separating centrifugally again; dryolution at a speed of 20 to 50 droplet/minute. After dripping ends, reflux reactions are carried out for 2 to 5 hours to obtain brownish red precipitates. The brownish red precipitates are centrifugaling in the vacuum at 50 deg C to make nanometer copper. The invention displays small grain size powder for nanometer copper, whose even grain size is between 4.0 nm and 20.0 nm. ly separated, are washed by water, are centrifugally separated again, and are dried in a vacuum at 50 DEG C to obtain the nanometer copper. The particle size of the particles of the nanometer copper prepared by the method is small, and the average particle size of the particles is from 4.0 to 20.0 nanometers. The method has the advantages of environmental protection, mild reaction conditions, easy control of the reactions, low cost and simple and convenient techniques and process flow.
Description
Technical field
The present invention relates to the nano material preparation technical field, refer in particular to copper sulphate is that raw material, vitamin C (Vc) are reducing agent, with tween (Tween) series, polyethylene glycol (PEG) series, Tween is serial with lauryl sodium sulfate (SDS) composite, PEG is serial with SDS composite, Tween is serial with neopelex (SDBS) composite, PEG is serial and the composite of SDBS is dressing agent, the liquid phase chemical reduction legal system is equipped with the method for nanometer copper.
Background technology
Nanometer copper is widely used in various fields, for example at aspects such as effective catalyst, electrocondution slurry, high conductivity, high specific strength alloy and kollags.The method for preparing at present nanometer copper is a lot, for example gas evaporation method, plasma method, gamma-radiation irradiation one hydrothermal crystallization combination method, mechanochemical reaction, sonochemistry method, electron beam irradiation method, photocatalysis Decomposition method, electrolysis, sol-gel processing, reverse microemulsion process, microwave irradiation synthetic method, supercritical extraction, thermal decomposition method etc.Some specification requirement height of these preparation methods, apparatus expensive, some complex process, environmental pollution are bigger, and prepared nano copper particle particle diameter is bigger, the particle diameter wider distribution.In preparation nanometer copper, dressing agent commonly used is a polyelectrolyte class material, and the cost height has certain toxicity, and environmental pollution is bigger.Lin Ronghui etc. report this in the paper of Langmuir " Convergent Electron Beam Induced Growth of Copper Nanostructures:Evidence of the Importance of a Soft Template " at " chemical reduction method prepares nanometer copper " of chemical journal and MYYen etc.By retrieval, do not have as yet at present utilize non-ionic surface active agent Tween series and PEG series is independent or with the composite method for preparing small particle diameter nanometer copper for the dressing agent hydrothermal synthesis method of SDS, SDBS.
Summary of the invention
The present invention proposes a kind of with copper sulphate be raw material, Vc be reducing agent, with tween (Tween) series, polyethylene glycol (PEG) series, Tween is serial with lauryl sodium sulfate (SDS) composite, PEG is serial with SDS composite, Tween is serial with the composite or PEG of neopelex (SDBS) serial with the composite of SDBS be dressing agent, the liquid phase chemical reduction legal system is equipped with the method for nanometer copper, to overcome above-mentioned shortcoming.
Its preparation method is as follows:
Preparation copper sulfate solution 0.2～0.5mol/L, again with tween (Tween) series, polyethylene glycol (PEG) series, Tween is serial with lauryl sodium sulfate (SDS) composite, PEG is serial with SDS composite, Tween is serial with the composite or PEG of neopelex (SDBS) serial with the composite of SDBS be dressing agent, under agitation soluble in water, and adding reductant Vc, be stirred well to dissolving fully, make reducing agent-dressing agent premixed solution; Compound proportion is 1:1, and the mol ratio of dressing agent and copper sulphate is 1～2.5:1, and the mol ratio of reductant Vc and copper sulphate is 3～5:1; Add this premixed solution of hot reflux while stirring in 50 ℃～80 ℃ water-bath, the speed with 20～50/min splashes into copper-bath again; After dropwising, back flow reaction 2-5h obtains the maroon precipitation, centrifugation, and water washing, centrifugation again 50 ℃ of following vacuum drying, promptly gets nanometer copper.
Above-mentioned preparation method, it is good should adopting following technological parameter or step:
Preparation copper sulfate solution 0.3mol/L, the mol ratio of dressing agent and copper sulphate is 2～2.5:1 in reducing agent-dressing agent premixed solution, the mol ratio of reductant Vc and copper sulphate is 4～5:1; Add this premixed solution of hot reflux while stirring in 80 ℃ water-bath, the speed with 20～30/min splashes into copper-bath again; After dropwising, back flow reaction 2-3h.
The dressing agent that uses is: Tween-20, Tween-40, Tween-80, PEG-600, PEG-2000, PEG-6000, Tween-20+SDS, Tween-20+SDBS, Tween-40+SDS, Tween-40+SDBS, Tween-80+SDS, Tween-80+SDBS, PEG-600+SDS, PEG-600+SDBS, PEG-2000+SDS, PEG-2000+SDBS, PEG-6000+SDS or PEG-6000+SDBS.
Description of drawings
Fig. 1: Tween-20 is the transmission electron microscope picture of the ball shaped nano copper products of dressing agent
Fig. 2: Tween-80 is the transmission electron microscope picture of the ball shaped nano copper products of dressing agent
Fig. 3: PEG-600 is the transmission electron microscope picture of the ball shaped nano copper products of dressing agent
Fig. 4: PEG-6000 is the transmission electron microscope picture of the ball shaped nano copper products of dressing agent
Fig. 5: SDS+Tween-40 is the transmission electron microscope picture of the ball shaped nano copper products of dressing agent
Fig. 6: SDBS+PEG-600 is the transmission electron microscope picture of the ball shaped nano copper products of dressing agent
Fig. 7: SDBS+PEG-2000 is the transmission electron microscope picture of the monocrystalline two-dimensional nano copper foil product of dressing agent
Fig. 8: SDS+PEG-6000 is the transmission electron microscope picture of the ball shaped nano copper products of dressing agent
Fig. 9: SDS+Tween-40 is the local SEAD figure of the ball shaped nano copper products of dressing agent
Figure 10: SDBS+PEG-2000 is the local SEAD figure of the monocrystalline two-dimensional nano copper foil product of dressing agent
The specific embodiment
The present invention will be further described below in conjunction with concrete embodiment.
Configuration copper sulfate solution 0.2-0.5mol/L.Get Tween series and PEG series or composite for dressing agent, under agitation soluble in water respectively, and add reductant Vc, be stirred well to dissolving fully, make reducing agent-dressing agent premix system with SDS, SDBS.The mol ratio of dressing agent and copper sulphate is 1-2.5:1, and the mol ratio of reductant Vc and copper sulphate is 3-5:1.Stir in following 80 ℃ of water-baths and add this premixed solution of hot reflux.Speed with 30-50/min splashes into copper sulfate solution again.After dropwising, back flow reaction 2.0-5.0h obtains the precipitation of maroon, centrifugation, and water washing, centrifugation again 50 ℃ of following vacuum drying, promptly gets nanometer copper.
Embodiment 1
As Fig. 1, get the Tween-20 of 0.05mol, under agitation be dissolved in the 50mL water, and add the Vc of 0.125mol, be stirred well to dissolving fully, make reducing agent-dressing agent premix system.This premixed solution is placed in 50 ℃ the water-bath and adds hot reflux.Speed with 20/min splashes into the copper sulfate solution 50mL that concentration is 0.5mol/L, and after dropwising, back flow reaction 5.0h obtains the precipitation of maroon, centrifugation, and water washing, centrifugation again 50 ℃ of following vacuum drying, obtains nanometer copper.
Embodiment 2
As Fig. 2, get the Tween-80 of 0.025mol, under agitation be dissolved in the 50mL water, and add the Vc of 0.075mol, be stirred well to dissolving fully, make reducing agent-dressing agent premix system.This premixed solution is placed in 60 ℃ the water-bath and adds hot reflux.Speed with 50/min splashes into the copper sulfate solution 100mL that concentration is 0.2mol/L, and after dropwising, back flow reaction 2.0h obtains the precipitation of maroon, centrifugation, and water washing, centrifugation again 50 ℃ of following vacuum drying, obtains nanometer copper.
Embodiment 3
As Fig. 3, get the PEG-600 of 0.0625mol, under agitation be dissolved in the 50mL water, and add the Vc of 0.1mol, be stirred well to dissolving fully, make reducing agent-dressing agent premix system.This premixed solution is placed in 70 ℃ the water-bath and adds hot reflux.Speed with 30/min splashes into the copper sulfate solution 75mL that concentration is 0.3mol/L, and after dropwising, back flow reaction 3.0h obtains the precipitation of maroon, centrifugation, and water washing, centrifugation again 50 ℃ of following vacuum drying, obtains nanometer copper.
Embodiment 4
As Fig. 4, get the PEG-6000 of 0.05mol, under agitation be dissolved in the 50mL water, and add the Vc of 0.1mol, be stirred well to dissolving fully, make reducing agent-dressing agent premix system.This premixed solution is placed in 80 ℃ the water-bath and adds hot reflux.Speed with 30/min splashes into the copper sulfate solution 50mL that concentration is 0.5mol/L, and after dropwising, back flow reaction 5.0h obtains the precipitation of maroon, centrifugation, and water washing, centrifugation again 50 ℃ of following vacuum drying, obtains nanometer copper.
Embodiment 5
As Fig. 5, get the Tween-40 of 0.025mol, get the SDS of 0.0125mol again, under agitation be dissolved in the 50mL water, and add the Vc of 0.125mol, be stirred well to dissolving fully, make reducing agent-dressing agent premix system.This premixed solution is placed in 80 ℃ the water-bath and adds hot reflux.Speed with 30/min splashes into the copper sulfate solution 50mL that concentration is 0.5mol/L, and after dropwising, back flow reaction 5.0h obtains the precipitation of maroon, centrifugation, and water washing, centrifugation again 50 ℃ of following vacuum drying, obtains nanometer copper.
Embodiment 6
As Fig. 6, get the PEG-600 of 0.025mol, get the SDBS of 0.0125mol again, under agitation be dissolved in the 50mL water, and add the Vc of 0.125mol, be stirred well to dissolving fully, make reducing agent-dressing agent premix system.This premixed solution is placed in 80 ℃ the water-bath and adds hot reflux.Speed with 30/min splashes into the copper sulfate solution 50mL that concentration is 0.5mol/L, and after dropwising, back flow reaction 5.0h obtains the precipitation of maroon, centrifugation, and water washing, centrifugation again 50 ℃ of following vacuum drying, obtains nanometer copper.
Embodiment 7
As Fig. 7, get the PEG-2000 of 0.025mol, get the SDBS of 0.0125mol again, under agitation be dissolved in the 50mL water, and add the Vc of 0.125mol, be stirred well to dissolving fully, make reducing agent-dressing agent premix system.This premixed solution is placed in 80 ℃ the water-bath and adds hot reflux.Speed with 30/min splashes into the copper sulfate solution 50mL that concentration is 0.5mol/L, and after dropwising, back flow reaction 5.0h obtains the precipitation of maroon, centrifugation, and water washing, centrifugation again 50 ℃ of following vacuum drying, obtains nanometer copper.
Embodiment 8
As Fig. 8, get the PEG-6000 of 0.025mol, get the SDS of 0.0125mol again, under agitation be dissolved in the 50mL water, and add the Vc of 0.125mol, be stirred well to dissolving fully, make reducing agent-dressing agent premix system.This premixed solution is placed in 80 ℃ the water-bath and adds hot reflux.Speed with 30/min splashes into the copper sulfate solution 50mL that concentration is 0.5mol/L, and after dropwising, back flow reaction 5.0h obtains the precipitation of maroon, centrifugation, and water washing, centrifugation again 50 ℃ of following vacuum drying, obtains nanometer copper.
Table 1 is that particle diameter, the particle diameter of part nanometer copper distributes.
The particle diameter of table 1 nanometer copper, particle diameter distribute
Claims (4)
1, a kind of method for preparing nanometer copper is characterized in that:
Preparation copper sulfate solution 0.2～0.5mol/L, following surfactant is a dressing agent: Tween series, PEG series, Tween series and SDS composite, PEG is serial with SDS composite, Tween is serial and serial composite with SDBS of the composite or PEG of SDBS, dressing agent is soluble in water, and adding reductant Vc, be stirred well to dissolving fully, make reducing agent-dressing agent premixed solution; The mol ratio of dressing agent and copper sulphate is 1～2.5:1, and the mol ratio of reductant Vc and copper sulphate is 3～5:1; Add this premixed solution of hot reflux while stirring in 50 ℃～80 ℃ water-bath, the speed with 20～50/min splashes into copper-bath again; After dropwising, back flow reaction 2-5h obtains the maroon precipitation, centrifugation, and water washing, centrifugation again, 50 ℃ of vacuum drying promptly get nanometer copper.
2, a kind of method for preparing nanometer copper according to claim 1, it is characterized in that: Tween series is 1:1 with the compound proportion of SDS, PEG series is 1:1 with the compound proportion of SDS, and Tween series is 1:1 with the compound proportion of SDBS, and PEG series is 1:1 with the compound proportion of SDBS.
3, according to claim 1 or the described a kind of method for preparing nanometer copper of claim 2, it is characterized in that: the dressing agent of use is: Tween-20, Tween-40, Tween-80, PEG-600, PEG-2000, PEG-6000, Tween-20+SDS, Tween-20+SDBS, Tween-40+SDS, Tween-40+SDBS, Tween-80+SDS, Tween-80+SDBS, PEG-600+SDS, PEG-600+SDBS, PEG-2000+SDS, PEG-2000+SDBS, PEG-6000+SDS or PEG-6000+SDBS.
4, a kind of method for preparing nanometer copper according to claim 1, it is characterized in that: preparation copper sulfate solution 0.3mol/L, the mol ratio of dressing agent and copper sulphate is 2～2.5:1 in reducing agent-dressing agent premixed solution, and the mol ratio of reductant Vc and copper sulphate is 4～5:1; Add this premixed solution of hot reflux while stirring in 80 ℃ water-bath, the speed with 20～30/min splashes into copper-bath again; After dropwising, back flow reaction 2-3h obtains the maroon precipitation, and centrifugation washes with water, 50 ℃ of following vacuum drying, promptly gets nanometer copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100946141A CN100506439C (en) | 2005-09-29 | 2005-09-29 | Method for preparing nanometer copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100946141A CN100506439C (en) | 2005-09-29 | 2005-09-29 | Method for preparing nanometer copper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1803352A CN1803352A (en) | 2006-07-19 |
| CN100506439C true CN100506439C (en) | 2009-07-01 |
Family
ID=36865573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100946141A Expired - Fee Related CN100506439C (en) | 2005-09-29 | 2005-09-29 | Method for preparing nanometer copper |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100506439C (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101835555B (en) * | 2007-11-05 | 2012-08-22 | 住友金属矿山株式会社 | Copper fine particle, method for producing the same, and copper fine particle dispersion |
| CN101319357B (en) * | 2008-06-20 | 2012-04-04 | 江苏大学 | Preparation of copper nano-wire with microwave auxiliary liquid phase reduction |
| CN101607317B (en) * | 2009-07-16 | 2012-10-17 | 复旦大学 | Preparation method of nano-copper |
| CN101890504B (en) * | 2010-07-07 | 2012-06-27 | 江苏技术师范学院 | Preparation method of flaky nano copper powder |
| CN102114545B (en) * | 2011-03-01 | 2013-01-30 | 宁波大学 | Method for preparing copper nanometer granules |
| CN103056383B (en) * | 2013-01-04 | 2015-06-24 | 中国科学院宁波材料技术与工程研究所 | Preparation method for high-performance conducting copper slurry |
| CN103088371B (en) * | 2013-01-25 | 2015-03-11 | 重庆大学 | Method for preparing nano-copper cubic particles |
| CN103219065B (en) * | 2013-03-28 | 2016-04-06 | 山西森达源科技有限公司 | A kind of environmental-friendly conductive sizing agent based on carbon nanotube-nano copper powder |
| CN103801709B (en) * | 2014-03-17 | 2016-02-10 | 中国科学院新疆理化技术研究所 | A kind of synthetic method of different-shape copper nano particles |
| CN105328204B (en) * | 2015-10-16 | 2017-10-13 | 苏州卫生职业技术学院 | A kind of preparation method of two-dimentional copper nanometer rods |
| CN105838330A (en) * | 2016-01-04 | 2016-08-10 | 浙江海洋学院 | Preparation method of high-crystallization enthalpy value low-temperature phase transition nanometer cold storage material |
| CN105601494B (en) * | 2016-03-04 | 2018-01-16 | 江苏大学 | A kind of method of nanometer of propane diols of copper catalysis 1,2 oxidation |
| CN107159900B (en) * | 2017-05-10 | 2019-05-28 | 上海应用技术大学 | A kind of method of copper nanocube controllable preparation |
| CN111170828B (en) * | 2020-01-17 | 2023-01-03 | 浙江大学宁波理工学院 | Method for preparing methallyl alcohol using in situ generated Cu (I) catalyst |
| CN111421143B (en) * | 2020-04-01 | 2022-09-13 | 中国人民解放军陆军军医大学第一附属医院 | Preparation method of nano-copper particles for treating inflammatory diseases |
-
2005
- 2005-09-29 CN CNB2005100946141A patent/CN100506439C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 还原法制备纳米级铜粉. 肖寒，王瑞，余磊，邹贵田.贵州师范大学学报(自然科学版)，第21卷第1期. 2003 |
| 还原法制备纳米级铜粉. 肖寒，王瑞，余磊，邹贵田.贵州师范大学学报(自然科学版)，第21卷第1期. 2003 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1803352A (en) | 2006-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100506439C (en) | Method for preparing nanometer copper | |
| CN101693297B (en) | Preparation method of copper nanoparticles with different particle diameters | |
| CN101890504B (en) | Preparation method of flaky nano copper powder | |
| CN101563294A (en) | Method for the production of surface-modified, nanoparticulate metal oxides, metal hydroxides and/or metal oxyhydroxides | |
| CN101391786A (en) | Method for preparing high specific surface area nano alumina material | |
| CN105753070B (en) | A kind of controllable method for preparing of Co Mo S ternary metal sulfide | |
| CN102389949B (en) | A kind of preparation method of sea urchin-shaped nanometer copper particles | |
| Zhang et al. | Revisiting the coordination chemistry for preparing manganese oxide nanocrystals in the presence of oleylamine and oleic acid | |
| Yang et al. | A simple way for preparing antioxidation nano-copper powders | |
| Chen et al. | The pH-controlled {040} facets orientation of BiVO4 photocatalysts with different morphologies for enhanced visible light photocatalytic performance | |
| CN108946761A (en) | A kind of preparation method and application of high dispersive ZSM-5 molecular sieve | |
| Wang et al. | Template-free room temperature solution phase synthesis of Cu2O hollow spheres | |
| Yang et al. | Multiply-twinned intermetallic AuCu pentagonal nanorods | |
| Wang et al. | Synthesis of high-quality Ni2P hollow sphere via a template-free surfactant-assisted solvothermal route | |
| Liu et al. | Controlled formation of Ag2S/Ag Janus nanoparticles using alkylamine as reductant surfactants | |
| CN108971513B (en) | Nano copper particle and low-cost green and environment-friendly preparation method thereof | |
| CN107297510B (en) | Method for preparing nano-scale silver particle powder by reducing silver salt intermediate in grading manner | |
| Lin et al. | Copper hydroxide nano and microcrystal: Facile synthesis, shape evolution and their catalytic properties | |
| Marfur et al. | A Review on Recent Progression of Modifications on Titania Morphology and its Photocatalytic Performance. | |
| CN101698515B (en) | Method for preparing alpha-phase ferricoxide nanospheres | |
| Das et al. | Water soluble sodium sulfate nanorods as a versatile template for the designing of copper sulfide nanotubes | |
| US20130015398A1 (en) | Method for preparing modified micronized particles | |
| CN112811450A (en) | Preparation method of spherical nano-micron alumina | |
| Gilanizadeh et al. | Cascade synthesis of fused polycyclic dihydropyridines by Ni–Zn–Fe hydrotalcite (HT) immobilized on silica-coated magnetite as magnetically reusable nanocatalyst | |
| CN102320645B (en) | Preparation method of solid or hollow Cu4O3 microballoons |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090701 Termination date: 20140929 |
|
| EXPY | Termination of patent right or utility model |