CN101407332B - Hydro-thermal synthesis method for cupric oxide nano-rod - Google Patents
Hydro-thermal synthesis method for cupric oxide nano-rod Download PDFInfo
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- CN101407332B CN101407332B CN2007101625382A CN200710162538A CN101407332B CN 101407332 B CN101407332 B CN 101407332B CN 2007101625382 A CN2007101625382 A CN 2007101625382A CN 200710162538 A CN200710162538 A CN 200710162538A CN 101407332 B CN101407332 B CN 101407332B
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 9
- 229960004643 cupric oxide Drugs 0.000 title claims description 24
- 239000002073 nanorod Substances 0.000 title claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 150000001879 copper Chemical class 0.000 claims abstract 2
- 239000000843 powder Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000005751 Copper oxide Substances 0.000 abstract 4
- 229910000431 copper oxide Inorganic materials 0.000 abstract 4
- 238000010438 heat treatment Methods 0.000 abstract 3
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000007769 metal material Substances 0.000 abstract 1
- 229910052755 nonmetal Inorganic materials 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical group FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
The invention discloses a hydro-thermal synthesis method of a copper oxide nanometer rod, which belongs to the field of inorganic non-metal materials, and comprises the steps: soluble copper salt such as copper sulphate is dissolved in water and added with an appropriate amount of different auxiliaries to be taken as a composite template agent, NaOH solution is used for regulating the pH value to be 12-14, and precipitate and the solution are heated in a high-pressure autoclave for the growth of the nanometer copper oxide. The heating mode can be microwave heating or resistance wire heating, and copper oxide nanometer rods grow in the solution. The method has the advantages of simple technology and low cost, and uses the composite template agent for controlling the appearance and the size of the copper oxide nanometer rod.
Description
Technical field
The present invention relates to the hydrothermal synthesis method of cupric oxide nano-rod, belong to field of inorganic nonmetallic material.
Background technology
Cupric oxide is a kind of multi-functional meticulous inorganic materials.At catalytic field, it is to the decomposition of ammoniumper chlorate, and the complete oxidation of carbon monoxide, ethanol, ethyl acetate and toluene all has advantages of high catalytic activity, can also be used as the coating film, glass of transmitter and the tinting material of pottery etc.The particle diameter of nano cupric oxide is between 1nm-100nm, owing to have surface effects, quantum size effect, volume effect and macro quanta tunnel effect etc., compare with common cupric oxide, show peculiar physics and chemical property at aspects such as magnetic, photoabsorption, chemically reactive, thermal resistance, catalyzer and fusing points, caused that people pay close attention to widely, and become purposes one of inorganic materials widely.Therefore, the preparation of nano cupric oxide and applied research are subjected to extensive concern in recent years, become one of important research direction of nano material.
Preparation method about nano cupric oxide mainly contains solid phase method, the liquid-phase deposition technique of controlling dual-jet, spray pyrolysis, alcoholysis method harmony chemical method etc.In recent years, the novel method of a lot of preparation nano cupric oxides has appearred again, as: laser steams the method for coagulating, the boiling reflux precipitator method, complex-precipitation method, hydrothermal method, pressure-hydrothermal method, microemulsion method, electrochemical process and template.Wherein one of most important method is exactly a hydrothermal method.The method of the synthetic cupric oxide nano-rod of hydrothermal method needs pattern and the size of auxiliary reagent as template controlled target product usually, and template commonly used has hexadecyl trimethyl ammonium bromide (CTAB), quadrol, polyoxyethylene glycol (PEG) etc.But this single template can not satisfy the needs of controlled oxidation copper pattern and size fully.
The invention provides a kind of novel method for synthesizing of cupric oxide nano-rod, adopt the synthetic cupric oxide nano-rod of composite mould plate agent hydro-thermal.
Summary of the invention
The invention provides a kind of synthetic method of cupric oxide nano-rod, the present invention adopts following technical scheme:
(1) copper sulfate is soluble in water, in addition PEG and urea successively are added to the water, the two is mixed by a certain percentage and stir;
(2) the pH value with NaOH solution regulator solution is between the 12-14, supersound process 10 minutes;
(3) will precipitate and solution join in the autoclave of inner liner polytetrafluoroethylene, in 120 ℃ of following constant temperature 2-6h;
(4) cooled and filtered or centrifuge washing obtain powder with absolute ethanol washing at last; Powder is obtained cupric oxide nanometer power in 60 ℃ of dryings.
Compare with existing additive method and technology, the present invention has following advantage:
(1) the present invention has adopted composite mould plate agent technology, has obtained the rod-like nano cupric oxide;
(2) the hydro-thermal genealogy of law wet chemical method that adopts of the rod-like nano cupric oxide that obtains of the present invention, product size evenly, mean diameter 5-10nm, length is 60-100nm, does not have reunion substantially.
Description of drawings
Fig. 1: the X-ray diffraction of preparation method's of the present invention nano cupric oxide (XRD) collection of illustrative plates;
Fig. 2: the projection electron microscope collection of illustrative plates (TEM) of preparation method's of the present invention rod-like nano cupric oxide;
Can know that from the X diffracting spectrum of Fig. 1 the oxide powder is cupric oxide.
Can find out that from the image of the projection electron microscope of Fig. 2 the diameter of resulting cupric oxide nanometer rod is 5-10nm, length is 60-100nm.
Hence one can see that, by adding an amount of PEG and urea as compound template, can obtain the very cupric oxide nanometer rod structure of homogeneous of shape under relatively mild condition.
Embodiment provided by the invention is as follows:
Following Example is to further specify of the present invention, rather than limits the scope of the invention.
Implementation example: 2.5 gram copper sulfate are soluble in water, in addition the 10ml polyoxyethylene glycol is joined in the solution, mix and stirring.Add 10 gram urea, stir.Drip the NaOH solution 30ml of 2M, supersound process 10 minutes.Precipitation and solution are joined in the stainless steel cauldron of inner liner polytetrafluoroethylene, in 120 ℃ of following constant temperature 6h.Cooled and filtered or centrifuge washing obtain powder with absolute ethanol washing at last; Powder is obtained cupric oxide nanometer power in 60 ℃ of dryings.
Claims (1)
1. the synthetic method of a cupric oxide nano-rod is characterized in that utilizing soluble copper salt and sodium hydroxide to be raw material, adds template, make precipitation, through hydro-thermal reaction, can make mean diameter is 5-10nm, length is the cupric oxide nano-rod of 60-100nm, and it may further comprise the steps:
(1) 2.5 gram copper sulfate are soluble in water, 10 milliliters of polyoxyethylene glycol (PEG) and 10 gram urea are added to the water sequentially mix and stirring in addition;
(2) the pH value with NaOH solution regulator solution is between the 12-14, supersound process 10 minutes;
(3) will precipitate and solution join in the autoclave of inner liner polytetrafluoroethylene, in 120 ℃ of following constant temperature 2-6h;
(4) cooled and filtered or centrifuge washing obtain powder with absolute ethanol washing at last; Powder is obtained the cupric oxide nano-rod powder in 60 ℃ of dryings.
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| CN2007101625382A CN101407332B (en) | 2007-10-12 | 2007-10-12 | Hydro-thermal synthesis method for cupric oxide nano-rod |
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| CN2007101625382A CN101407332B (en) | 2007-10-12 | 2007-10-12 | Hydro-thermal synthesis method for cupric oxide nano-rod |
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| CN101407332A CN101407332A (en) | 2009-04-15 |
| CN101407332B true CN101407332B (en) | 2011-04-27 |
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| CN102267714B (en) * | 2010-06-03 | 2013-06-12 | 合肥学院 | Preparation method for hollow silk cocoon-like CuO nanomaterial |
| CN102817078B (en) * | 2011-06-07 | 2015-07-15 | 新疆大学 | Synthesizing method of flower-cluster-shaped structure composed of CuO/ZnO composite oxide porous nano-grade blades |
| CN102491404A (en) * | 2011-12-19 | 2012-06-13 | 天津理工大学 | Copper oxide micro-nano composite structural material and preparation method thereof |
| CN104031273A (en) * | 2013-03-05 | 2014-09-10 | 新疆双龙腐植酸有限公司 | Method for improving yield of humic acid salt prepared from weathered coal |
| CN103408056B (en) * | 2013-08-07 | 2016-01-27 | 江苏大学 | A kind of liquid-phase precipitation method prepares the method for nano cupric oxide |
| CN103979600B (en) * | 2014-05-30 | 2016-08-31 | 上海沃凯生物技术有限公司 | A kind of preparation method of ultrafine copper oxide powder |
| CN105084408B (en) * | 2015-08-07 | 2017-01-25 | 电子科技大学 | Preparing method for copper oxide powder |
| CN105177696B (en) * | 2015-08-26 | 2017-10-17 | 湖北工程学院 | A kind of preparation method of the copper nano structural material of morphology controllable |
| CN105731517B (en) * | 2016-01-15 | 2017-06-13 | 电子科技大学 | A kind of cupric oxide flower-like nanostructure material and preparation method thereof |
| CN105732730B (en) * | 2016-04-25 | 2017-12-01 | 新疆大学 | The method that thermosoling situ catalytic prepares fulvic acid and its salt |
| CN106207148A (en) * | 2016-08-31 | 2016-12-07 | 青海中兴新能源有限公司 | A kind of preparation method of lithium ion battery negative material micro nano structure CuO |
| CN106976903B (en) * | 2017-02-28 | 2019-03-15 | 沈阳化工大学 | A kind of flower-shaped CuO method for preparing microsphere and its in formaldehyde gas sensor application |
| CN107416888B (en) * | 2017-08-23 | 2019-08-13 | 电子科技大学 | A kind of preparation method of nano cupric oxide |
| CN109665557A (en) * | 2019-03-01 | 2019-04-23 | 西北工业大学 | A kind of flower-shaped copper oxide and its preparation method and application |
| CN109761262B (en) * | 2019-03-14 | 2021-04-23 | 东北大学 | Preparation method and application of noble metal impregnation co-doping CuO nano material |
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| US20070140951A1 (en) * | 2003-12-11 | 2007-06-21 | The Trustees Of Columbia University In The City Of New York | Nano-sized particles, processes of making, compositions and uses thereof |
| CN101037228A (en) * | 2007-02-25 | 2007-09-19 | 华中师范大学 | Preparation of graduated nano-structural transition metal oxide by two-phase solvent soft interface process |
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Patent Citations (4)
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| CN1462720A (en) * | 2003-06-10 | 2003-12-24 | 东北师范大学 | Method for preparing nano tube of some metalloid oxides and metals with size and shape being controllable |
| US20070140951A1 (en) * | 2003-12-11 | 2007-06-21 | The Trustees Of Columbia University In The City Of New York | Nano-sized particles, processes of making, compositions and uses thereof |
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