CN106629812A - Preparation method of cuprous oxide nanowire material - Google Patents
Preparation method of cuprous oxide nanowire material Download PDFInfo
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- CN106629812A CN106629812A CN201611134425.7A CN201611134425A CN106629812A CN 106629812 A CN106629812 A CN 106629812A CN 201611134425 A CN201611134425 A CN 201611134425A CN 106629812 A CN106629812 A CN 106629812A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys
- C22C3/005—Separation of the constituents of alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C45/00—Amorphous alloys
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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Abstract
The invention belongs to the technical field of nano materials and chemical materials and particularly relates to a preparation method of a cuprous oxide nanowire. In the invention, nano porous copper prepared by de-alloying serves as a matrix and is soaked in an organic solvent alcohol for a period of time to obtain a cuprous oxide nanowire of which the length-diameter ratio is greater than 10. In the invention, the technology is simple, and the cost is low. The prepared cuprous oxide nanowire is widely applied to the fields such as photocatalysis and new energy and can be used as a photoelectric conversion material, a photocatalyst, the cathode material of a lithium ion battery and the electrode material of a dye-sensitized solar cell and also can be applied to a supercapacitor and a sensor.
Description
Technical field
The invention belongs to nano material and chemical material technical field, and in particular to the preparation of nano cuprous oxide wire material
Method.
Background technology
Nano cuprous oxide receives pole with its hypotoxicity, inexpensive and excellent characteristic in the energy and environmental area
Big accreditation, is a kind of semi-conducting material of great development prospect.Its energy gap is active between 2.0～2.2eV
Hole-electron pair and good catalysis activity, can absorb the overwhelming majority visible rays, photocatalysis, opto-electronic conversion, sensor,
There is great application prospect in the fields such as ultracapacitor, DSSC, lithium ion battery, sewage disposal.
Nano cuprous oxide material include cuprous oxide nano particle (octahedra including cube, dodecahedron, 14
Face body), nano cuprous oxide wire, cuprous nano pipe, cuprous oxide film etc..Nano cuprous oxide wire is special due to its
Quantum size effect, skin effect that geometry, big draw ratio and nano material have, have caused that people's is extensive
Concern.Its common preparation method main liquid phase synthetic method, Electrochemical Template etc..The nano cuprous oxide wire that great majority are obtained
Draw ratio is relatively low, and pattern is difficult to control to, complicated process of preparation, therefore more difficult a large amount of productions.[(1)[66]Oh J,Tak Y,Lee
J.Electrochemically Deposited NanoColumnar Junctions of Cu2O and ZnO on Ni
Nanowires[J].Electrochemical and Solid-State Letters,2005,8(6):C81-C84. (2) Liu
Pass silver, Hu Junfu, Li Xueqiang. the preparation of nano cuprous oxide and its electrochemical properties [J]. chemical research, 2005,16 (4):
55-57.]
The content of the invention
It is an object of the invention to solve existing cuprous oxide material preparation process complexity, the big problem of technical difficulty is carried
Go out a kind of process is simple, the technology of preparing of nano cuprous oxide wire material with low cost.
The present invention by the way of soaking in organic solvent alcohol, promotes cuprous oxide to determine with nano porous copper as substrate
To growth, the nano cuprous oxide wire material with high catalytic performance is obtained.Concrete preparation process is as described below：
Rich Cu alloy strip steel rolled stocks are added into HF solution, heating water bath prepares nano porous copper to 25-70 degree Celsius；Will
Nano porous copper obtained in de- alloying is immersed in organic solvent alcohol, generates nano cuprous oxide wire.
Further, the concentration of HF solution is in 0.01-0.2M.
Further, nano porous copper is needing to be soaked 1-4 days in organic solvent alcohol.
Further, rich Cu alloy strip steel rolled stocks are to include non-crystaline amorphous metal and crystal alloy.
Further, the atomic fraction of the Cu of rich Cu alloy strip steel rolled stocks is in 20-70%, it is ensured that the formation of nano-porous structure.
Further, the material of rich Cu alloy strip steel rolled stocks is Ti-Cu, Zr-Cu, Al-Cu, Mn-Cu, Ag-Cu machine alloy strip steel rolled stock
Further, rich Cu alloy strip steel rolled stocks preparation process is specific as follows：Electric arc melting is carried out by alloying component, female conjunction is obtained
Ingot.Foundry alloy is heated to molten condition after will be broken, under the protection of inert gas high purity argon, molten alloy is blown to
At a high speed the copper rod surface of rotation, makes molten alloy obtain quick cooled and solidified and obtains alloy strip steel rolled stock.
Further, the above-mentioned organic solvent alcohol for using is absolute ethyl alcohol.
The present invention is compared relative to prior art, as follows with remarkable advantage：1st, preparation process is simple, it is with low cost；2、
Substantial amounts of chemical agent is not needed, it is pollution-free；3rd, photocatalysis performance is good.4th, there should be the Cu of nano porous copper substrate2O nano wires
Gather around and have wide practical use,
Description of the drawings
Fig. 1 is the XRD spectrum of embodiment nano cuprous oxide wire.
Fig. 2 is the SEM image of embodiment nano cuprous oxide wire.
Fig. 3 is the SEM image of the more high-resolution nano cuprous oxide wire of embodiment.
Specific embodiment
The preparation method of nano cuprous oxide wire proposed by the present invention is further described below by first embodiment.
Block high pure metal is chosen as raw material, wherein, Ti is 99.9% (mass fraction, similarly hereinafter), and Zr is
99.99%, Cu be 99.99%, Ni be 99.99%, Sn be 99.999%.By Ti40.6Zr9.4Cu40.6Ni6.3Sn3.1Atom point
Number dispensing, alleged dispensing then be put into ethanol and cleaned with ultrasonic cleaner 5 minutes.Using arc-melting furnace high-purity
The lower melting of argon gas protection prepares foundry alloy, typically wants composition of the melting 4 times or so to ensure foundry alloy uniform.The mother that will be obtained
Polishing, cleaning, take 5g or so and are put into quartz ampoule after alloy breaks down, by single roller rotation quenching equipment in high-purity argon gas protective atmosphere
Prepare thickness 30 μm, the Ti of width 1mm40.6Zr9.4Cu40.6Ni6.3Sn3.1Amorphous thin ribbon.Take the amorphous thin ribbon immersion of 1mm width 20mm length
In the HF solution of 60mL 0.1mol/L, and 60 DEG C, after 6h are maintained the temperature at by water-bath, you can obtain nano porous copper.Will
Nano porous copper is successively immersed in deionized water and absolute ethyl alcohol and cleans repeatedly, finally soaks 3 days in 25 DEG C of absolute ethyl alcohols,
Cu of the draw ratio more than 10 can be grown in nanoporous copper substrate surfaces2O nano wires.By the shape of XRD, SEM to sample
Looks are characterized.
If Fig. 1 is de- XRD spectrum of the alloy sample Jing after soaked in absolute ethyl alcohol.Research shows not only to contain nanometer in material
Porous Cu substrate, also cuprous oxide.
If Fig. 2 is de- typical SEM images of the alloy sample Jing after soaked in absolute ethyl alcohol, illustrate that nano cuprous oxide wire is tight
The growth of nanoporous Cu interface disorders is attached to, length is more than 1 μm.
Such as the SEM image that Fig. 3 is nano cuprous oxide wire material under higher resolution, the width of nano cuprous oxide wire is shown
Degree only has 20nm or so, and length has exceeded areas imaging.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But above-mentioned detailed process equipment and technological process are the invention is not limited in, that is, does not mean that the present invention has to rely on above-mentioned detailed
Thin process equipment and technological process could be implemented.Person of ordinary skill in the field to any of the present invention it will be clearly understood that change
Enter, equivalence replacement soaked with nano porous copper preparation method and similar organic solvent to virgin alloy of the present invention etc. all falls within
Within the scope of protection scope of the present invention and disclosure.
Claims (8)
1. a kind of preparation method of nano cuprous oxide wire material, it is characterised in that the method is：Rich Cu alloy strip steel rolled stocks are added
Into HF solution, heating water bath prepares nano porous copper to 25-70 degree Celsius；Nano porous copper obtained in de- alloying is soaked
Bubble generates nano cuprous oxide wire in organic solvent alcohol.
2. the preparation method of nano cuprous oxide wire material according to claim 1, it is characterised in that the concentration of HF solution
In 0.01-0.2M.
3. the preparation method of nano cuprous oxide wire material according to claim 1, it is characterised in that nano porous copper exists
Soak 1-4 days in organic solvent alcohol.
4. the preparation method of nano cuprous oxide wire material according to claim 1, it is characterised in that described rich Cu is closed
Gold includes non-crystaline amorphous metal and crystal alloy.
5. the preparation method of nano cuprous oxide wire material according to claim 1, it is characterised in that rich Cu alloy strip steel rolled stocks
Cu atomic fraction in 20-70%.
6. the preparation method of nano cuprous oxide wire material according to claim 1, it is characterised in that rich Cu alloy strip steel rolled stocks
For TiCu base amorphous thin ribbons, composition is Ti40.6Zr9.4Cu40.6Ni6.3Sn3.1。
7. the preparation method of nano cuprous oxide wire material according to claim 1, it is characterised in that described rich Cu is closed
Gold ribbon material preparation process is specific as follows：Electric arc melting is carried out by alloying component, master alloy ingot is obtained；Will broken rear foundry alloy heating
To molten condition, under the protection of inert gas high purity argon, molten alloy is blown into the copper rod surface of rotation at a high speed, makes melting
Alloy obtains quick cooled and solidified and obtains alloy strip steel rolled stock.
8. the preparation method of nano cuprous oxide wire material according to claim 1, it is characterised in that described is organic molten
Agent alcohol is absolute ethyl alcohol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107892324A (en) * | 2017-11-10 | 2018-04-10 | 西安理工大学 | A kind of preparation method of ZnO nanowire array |
| CN108295854A (en) * | 2018-01-30 | 2018-07-20 | 河北工业大学 | A kind of multi-stage porous nano porous copper load nano cuprous oxide wire composite material and preparation method |
| CN111676498A (en) * | 2020-06-24 | 2020-09-18 | 河北工业大学 | Preparation method of cuprous oxide electrode |
| CN115178270A (en) * | 2022-08-19 | 2022-10-14 | 南京工程学院 | Vascular structure copper-rich bifunctional catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807688A (en) * | 2005-12-20 | 2006-07-26 | 厦门大学 | Process for preparing shape controllable cuprous oxide micro/nano crystal by electrochemical deposition |
| CN101074108A (en) * | 2007-08-14 | 2007-11-21 | 北京科技大学 | Method for producing cuprous nano-column array |
| CN105621474A (en) * | 2015-12-29 | 2016-06-01 | 中国石油化工股份有限公司 | Hyperbranched graded cuprous oxide nanomateiral and preparation method and application thereof |
-
2016
- 2016-12-10 CN CN201611134425.7A patent/CN106629812B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807688A (en) * | 2005-12-20 | 2006-07-26 | 厦门大学 | Process for preparing shape controllable cuprous oxide micro/nano crystal by electrochemical deposition |
| CN101074108A (en) * | 2007-08-14 | 2007-11-21 | 北京科技大学 | Method for producing cuprous nano-column array |
| CN105621474A (en) * | 2015-12-29 | 2016-06-01 | 中国石油化工股份有限公司 | Hyperbranched graded cuprous oxide nanomateiral and preparation method and application thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107892324A (en) * | 2017-11-10 | 2018-04-10 | 西安理工大学 | A kind of preparation method of ZnO nanowire array |
| CN107892324B (en) * | 2017-11-10 | 2019-06-18 | 西安理工大学 | A kind of preparation method of ZnO nanowire array |
| CN108295854A (en) * | 2018-01-30 | 2018-07-20 | 河北工业大学 | A kind of multi-stage porous nano porous copper load nano cuprous oxide wire composite material and preparation method |
| CN108295854B (en) * | 2018-01-30 | 2019-06-14 | 河北工业大学 | A kind of multi-stage porous nano porous copper load nano cuprous oxide wire composite material and preparation method |
| CN111676498A (en) * | 2020-06-24 | 2020-09-18 | 河北工业大学 | Preparation method of cuprous oxide electrode |
| CN111676498B (en) * | 2020-06-24 | 2022-02-18 | 河北工业大学 | Preparation method of cuprous oxide electrode |
| CN115178270A (en) * | 2022-08-19 | 2022-10-14 | 南京工程学院 | Vascular structure copper-rich bifunctional catalyst and preparation method thereof |
| CN115178270B (en) * | 2022-08-19 | 2023-12-19 | 南京工程学院 | Vascular structure copper-rich bifunctional catalyst and preparation method thereof |
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