CN104674290B - Preparation method of metal oxide nanometer microspheres - Google Patents
Preparation method of metal oxide nanometer microspheres Download PDFInfo
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- CN104674290B CN104674290B CN201510081654.6A CN201510081654A CN104674290B CN 104674290 B CN104674290 B CN 104674290B CN 201510081654 A CN201510081654 A CN 201510081654A CN 104674290 B CN104674290 B CN 104674290B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
Abstract
The invention provides a preparation method of metal oxide nanometer microspheres, belonging to the field of preparation of nano materials. The preparation method comprises the following steps: 1) treating the surface of a metal electrode material; 2) preparing a mixed solution by taking inorganic salt and strong base as solutes and water as a solvent, wherein the total mass concentration of inorganic salt is 80-200g/L and the total mass concentration of strong base is 0-20g/L; and 3) placing an electrode into the mixed solution prepared in the last step, applying a voltage between an anode and a cathode by taking the treated metal electrode material as an anode and an inert electrode or a metal electrode identical with the anode as a cathode, disturbing in a +/-2V range by taking any one of 3-30V as reference to have precipitate in the solution after 20-120min, filtering, washing and drying, to obtain the metal oxide nanometer microspheres. The method is simple in steps and good in controllability, and the metal oxide nanometer microspheres with the uniform shape and size can be obtained.
Description
Technical field
The invention belongs to field of nano material preparation, and in particular to it is micro- that a kind of electrochemical method prepares metal oxide nano
The method of ball.
Background technology
Nano microsphere often claims microballoon, including nanosphere and micron ball, is presently the most one of important nanometer technology product.
And metal oxide nano microballoon, such as ferriferrous oxide nano microballoon, cuprous nano microballoon, stannic oxide nanometer microballoon,
Nickel oxide nano microballoon, cobalt oxide Nano microsphere etc., imitate with less dimensional effect, surface and interfacial effect, quantum size
Should and macro quanta tunnel effect so as to show at aspects such as mechanics, magnetics, thermodynamics, optics, catalysis, biologically actives excellent
Different physics and chemical characteristic.
At present, preparing the method for metal oxide nano microballoon mainly has a sol-gel process, chemical precipitation method, self assembly,
Template etc..Sol-gel process is obtained substantial amounts of metal oxide nano microballoon, and cost is relatively low, but due to sol-gel
The influence factor that method prepares metal oxide nano microballoon is more, it is difficult to prepare shape, uniform Nano microsphere；Chemistry is heavy
The purity of metal oxide nano microballoon prepared by shallow lake method, pattern and size are difficult control；Template preparation technology is relatively complicated,
And template removal is more complicated.Therefore, find a kind of simple controllable, prepare purity height, good stability, pattern size distribution controllable
The method of metal oxide nano microballoon is just particularly important.
Doctor C.Y.Wang is in Materials Research Bulletin 36:A kind of electricity is provided in 2333-2337
The method that chemical method prepares metal oxide and metal hydroxides nano particle, has prepared bar-shaped and spherical nanometer
Ferriferrous oxide particles mixture, the nano zine oxide of elliposoidal, nano-sized magnesium hydroxide particle and nano-hydroxy alumina particle.
The method achieve and nano particle prepared using electrochemical method, but, the voltage applied in its preparation process more than 100V, no
Beneficial to safety in production；The metal oxide nanoparticles shape size for obtaining is uneven, is bar-like the mixture with spherical particle,
Or the particle of elliposoidal；Controllability is poor, and the nano particle for obtaining is probably the nano particle of metal hydroxides.
The content of the invention
A kind of defect that the present invention exists for background technology, it is proposed that preparation method of metal oxide nano microballoon,
The method step is simple, and easy to operate, controllability is good, has obtained the homogeneous metal oxide nano microballoon of shape size.
Technical scheme is as follows：
A kind of preparation method of metal oxide nano microballoon, comprises the following steps：
Step 1：Metal electrode material surface is polished, is cleaned, be dried；
Step 2：Using inorganic salts and highly basic as solute, water is solvent, and preparation obtains mixed solution, wherein, inorganic salts
Total mass concentration is 80～200g/L, and the total mass concentration of highly basic is 0～20g/L；
Step 3：Electrode is placed in the mixed solution that step 2 is prepared, using step 1 process after metal electrode material as
Anode, using inert electrode or with anode identical metal electrode material as negative electrode, applies between the anode and cathode an electricity
Pressure, on the basis of any voltage of the voltage by between 3～30V, disturbs in the range of ± 2V, processes solution after 20～120min
In flocky precipitate occurs, be filtrated to get sediment, washing, be dried, that is, obtain the metal oxide nano microballoon.
Further, metal electrode material described in step 1 be pure tin, pure titanium, pure cobalt, pure nickel, pure iron, fine copper, pure tungsten,
Pure molybdenum etc..
Further, inorganic salts described in step 2 are sodium fluoride, sodium sulphate, sodium chloride, potassium fluoride, potassium sulfate and chlorination
One or more in potassium, the total mass concentration of inorganic salts is 80～200g/L.
Further, the highly basic described in step 2 be NaOH, potassium hydroxide in one or two, its gross mass
Concentration is 0～20g/L.
Further, inert electrode described in step 3 is graphite electrode or platinum electrode etc..
Beneficial effects of the present invention are：The present invention has prepared metal oxide nano microballoon using electrochemical method,
Using method it is simple, easy to operate, controllability is good, prepares that voltage is low, and the metal oxide nano microballoon for obtaining is uniform ball
Shape, size uniformity, purity are high, have broad application prospects in fields such as mechanics, magnetics, thermodynamics, optics, catalysis.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of the tin oxide nano-microspheres that the embodiment of the present invention 1 is obtained.
Fig. 2 is the X ray diffracting spectrum (XRD) of the tin oxide nano-microspheres that the embodiment of the present invention 1 is obtained.
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of the ferriferrous oxide nano microballoon that the embodiment of the present invention 2 is obtained.
Fig. 4 is the X ray diffracting spectrum of the ferriferrous oxide nano microballoon that the embodiment of the present invention 2 is obtained.
Fig. 5 is the scanning electron microscope (SEM) photograph (SEM) of the nickel oxide nano microballoon that the embodiment of the present invention 3 is obtained.
Fig. 6 is the X ray diffracting spectrum (XRD) of the nickel oxide nano microballoon that the embodiment of the present invention 3 is obtained.
Fig. 7 is the scanning electron microscope (SEM) photograph (SEM) of the cobalt oxide Nano microsphere that the embodiment of the present invention 4 is obtained.
Fig. 8 is the X ray diffracting spectrum (XRD) of the cobalt oxide Nano microsphere that the embodiment of the present invention 4 is obtained.
Fig. 9 is the scanning electron microscope (SEM) photograph (SEM) of the cuprous nano microballoon that the embodiment of the present invention 5 is obtained.
Figure 10 is the X ray diffracting spectrum (XRD) of the cuprous nano microballoon that the embodiment of the present invention 5 is obtained.
Specific embodiment
Embodiment 1
A kind of preparation method of tin oxide nano-microspheres, comprises the following steps：Metal sheet tin is polished using sand paper
Descale, then cleans in distilled water, and drying for standby；Take 120g sodium fluorides to be dissolved in 1L distilled water, prepare sodium fluoride
Solution；Metal sheet tin and platinum electrode after grinding process is placed in the Fluorinse that upper step is prepared, to polish and cleans dry
Metal sheet tin after dry, using platinum electrode as negative electrode, applies between the anode and cathode a voltage, the voltage as anode
On the basis of 20V, the shock wave in the range of ± 2V to be processed and flocculent deposit occur in solution after 60min, is filtrated to get precipitation
Thing, is cleaned with distilled water, and is dried, that is, obtain the tin oxide nano-microspheres of white.
Fig. 1 is the SEM figures of the tin oxide nano-microspheres that embodiment 1 is obtained, as shown in Figure 1, the tin oxide that embodiment 1 is obtained
Nano particle is spherical, and microballoon shape size is homogeneous, and the diameter of microballoon is about 100nm.Fig. 2 is the tin oxide that embodiment 1 is obtained
The XRD spectrum of Nano microsphere, as shown in Figure 2, the nano particle that embodiment 1 is obtained is tin oxide nanoparticles.
Embodiment 2
A kind of preparation method of ferriferrous oxide nano microballoon, comprises the following steps：Metal iron wire is carried out using sand paper
Polishing descale, then cleans in distilled water, and drying for standby；Take 180g sodium sulphate and 15g NaOH adds 1L to steam
In distilled water, preparation obtains mixed solution；The mixing that metal iron wire and graphite electrode after grinding process is placed in into upper step preparation is molten
In liquid, to polish and metal iron wire after cleaning-drying is used as anode, using graphite electrode as negative electrode, between the anode and cathode
Apply a voltage, on the basis of 30V, the shock wave in the range of ± 2V processed and go out in solution after 120min the voltage
Existing flocculent deposit, is filtrated to get sediment, is cleaned with distilled water, and is dried, and obtains the ferriferrous oxide nano microballoon of black.
Fig. 3 is the SEM figures of the ferriferrous oxide nano microballoon that obtains of embodiment 2, from the figure 3, it may be seen that embodiment 2 obtain four
Fe 3 O nano particle is spherical, and microballoon shape size is homogeneous, and the diameter of microballoon is about 40nm.Fig. 4 is what embodiment 2 was obtained
The XRD spectrum of ferriferrous oxide nano microballoon, as shown in Figure 4, the nano particle that embodiment 2 is obtained is ferriferrous oxide nano
Grain.
Embodiment 3
A kind of preparation method of nickel oxide nano microballoon, comprises the following steps：Metal nickel plate is polished using sand paper
Descale, then cleans in distilled water, and drying for standby；Take 100g sodium fluorides and 5g potassium hydroxide adds 1L distilled water
In, preparation obtains mixed solution；Metal nickel plate after grinding process is placed in the mixed solution that upper step is prepared, anode and negative electrode
Using the metal nickel plate after polishing simultaneously cleaning-drying, a voltage is applied between the anode and cathode, the voltage is with 10V
Benchmark, the shock wave in the range of ± 2V to be processed and flocculent deposit occur in solution after 20min, sediment is filtrated to get, with steaming
Distilled water is cleaned, and is dried, and obtains the nickel oxide nano microballoon of green.
Fig. 5 is the SEM figures of the nickel oxide nano microballoon that embodiment 3 is obtained, as shown in Figure 5, the nickel oxide that embodiment 3 is obtained
Nano particle is spherical, and microballoon shape size is homogeneous, and the diameter of microballoon is about 100nm.Fig. 6 is the nickel oxide that embodiment 3 is obtained
The XRD spectrum of Nano microsphere, it will be appreciated from fig. 6 that the nano particle that embodiment 3 is obtained is nickel oxide nanoparticle.
Embodiment 4
A kind of preparation method of cobalt oxide Nano microsphere, comprises the following steps：Metallic cobalt plate is polished using sand paper
Descale, then cleans in distilled water, and drying for standby；Take 200g sodium chloride and 20g NaOH adds 1L distilled water
In, preparation obtains mixed solution；Metallic cobalt plate and platinum electrode after grinding process is placed in the mixed solution that upper step is prepared, with
Metallic cobalt plate after polishing and cleaning-drying, using platinum electrode as negative electrode, applies between the anode and cathode one as anode
Voltage, on the basis of 5V, the shock wave in the range of ± 2V to be processed and flocculent deposit occur in solution after 40min the voltage,
Sediment is filtrated to get, is cleaned with distilled water, and be dried, obtain the cobalt oxide Nano microsphere of grey.
Fig. 7 is the SEM figures of the cobalt oxide Nano microsphere that embodiment 4 is obtained, as shown in Figure 7, the cobalt oxide that embodiment 4 is obtained
Nano particle is spherical, and microballoon shape size is homogeneous, and the diameter of microballoon is about 30nm.Fig. 8 is that the cobalt oxide that embodiment 4 is obtained is received
The XRD spectrum of meter Wei Qiu, as shown in Figure 8, the nano particle that embodiment 4 is obtained is oxidation cobalt nano-particle.
Embodiment 5
A kind of preparation method of cuprous oxide nano particle, comprises the following steps：Metal copper wire is carried out using sand paper beating
Oxide skin is ground off, is then cleaned in distilled water, and drying for standby；Take 150g sodium chloride and 10g potassium hydroxide adds 1L distillations
In water, preparation obtains mixed solution；Metal copper wire after grinding process is placed in the mixed solution that upper step is prepared, anode and the moon
Extremely a voltage is applied between the anode and cathode using the metal copper wire after polishing simultaneously cleaning-drying, the voltage is with 25V
On the basis of, the shock wave in the range of ± 2V to be processed and flocculent deposit occur in solution after 80min, is filtrated to get sediment, is used
Distilled water is cleaned, and is dried, and obtains bolarious cuprous nano microballoon.
Fig. 9 is the SEM figures of the cuprous nano microballoon that embodiment 5 is obtained, as shown in Figure 9, the oxidation that embodiment 5 is obtained
Cuprous Nano microsphere is spherical, and microballoon shape size is homogeneous, and the diameter of microballoon is about 50nm.Figure 10 is the oxygen that embodiment 5 is obtained
Change the XRD spectrum of cuprous Nano microsphere, as shown in Figure 10, the nano particle that embodiment 5 is obtained is cuprous oxide nano particle.
Claims (5)
1. a kind of preparation method of metal oxide nano microballoon, comprises the following steps：
Step 1：Metal electrode material surface is polished, is cleaned, be dried；
Step 2：Using inorganic salts and highly basic as solute, water is solvent, and preparation obtains mixed solution, wherein, total matter of inorganic salts
Amount concentration is 80～200g/L, and the total mass concentration of highly basic is 0～20g/L；
Step 3：Electrode is placed in the mixed solution that step 2 is prepared, using the metal electrode material after step 1 process as sun
Pole, using inert electrode or with anode identical metal electrode material as negative electrode, applies between the anode and cathode a voltage,
On the basis of any voltage of the voltage by between 3～30V, disturb in the range of ± 2V, after 20～120min of process in solution
Flocky precipitate occurs, is filtrated to get sediment, washing, is dried, that is, obtain the metal oxide nano microballoon.
2. the preparation method of metal oxide nano microballoon according to claim 1, it is characterised in that described in step 1
Metal electrode material is pure tin, pure titanium, pure cobalt, pure nickel, pure iron, fine copper, pure tungsten or pure molybdenum.
3. the preparation method of metal oxide nano microballoon according to claim 1, it is characterised in that described in step 2
Inorganic salts are one or more in sodium fluoride, sodium sulphate, sodium chloride, potassium fluoride, potassium sulfate and potassium chloride, total matter of inorganic salts
Amount concentration is 80～200g/L.
4. the preparation method of metal oxide nano microballoon according to claim 1, it is characterised in that described in step 2
Highly basic is one or two in NaOH, potassium hydroxide, and its total mass concentration is 0～20g/L.
5. the preparation method of metal oxide nano microballoon according to claim 1, it is characterised in that described in step 3
Inert electrode is graphite electrode or platinum electrode.
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Citations (6)
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| US6179987B1 (en) * | 1999-08-11 | 2001-01-30 | Ut Battelle, Llc | Method and apparatus to electrolytically produce high-purity magnetite particles |
| US6676821B1 (en) * | 1998-09-07 | 2004-01-13 | Henkel Kommanditgesellschaft Auf | Electrochemical production of amorphous or crystalline metal oxides with particles sizes in the nanometer range |
| WO2011112153A1 (en) * | 2010-03-08 | 2011-09-15 | Nanyang Technological University | Method of manufacturing layered metal oxide particles and layered metal oxide particles formed thereof |
| CN102712493A (en) * | 2009-08-27 | 2012-10-03 | 康宁股份有限公司 | Zinc oxide and cobalt oxide nanostructures and methods of making thereof |
| CN103097588A (en) * | 2010-07-19 | 2013-05-08 | 莱顿大学 | Process to prepare metal nanoparticles or metal oxide nanoparticles |
| CN103184466A (en) * | 2013-01-10 | 2013-07-03 | 昆明贵千新型材料技术研究有限公司 | Novel process for preparing high purity metal oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100193363A1 (en) * | 2009-01-30 | 2010-08-05 | Shrisudersan Jayaraman | Electrochemical methods of making nanostructures |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6676821B1 (en) * | 1998-09-07 | 2004-01-13 | Henkel Kommanditgesellschaft Auf | Electrochemical production of amorphous or crystalline metal oxides with particles sizes in the nanometer range |
| US6179987B1 (en) * | 1999-08-11 | 2001-01-30 | Ut Battelle, Llc | Method and apparatus to electrolytically produce high-purity magnetite particles |
| CN102712493A (en) * | 2009-08-27 | 2012-10-03 | 康宁股份有限公司 | Zinc oxide and cobalt oxide nanostructures and methods of making thereof |
| WO2011112153A1 (en) * | 2010-03-08 | 2011-09-15 | Nanyang Technological University | Method of manufacturing layered metal oxide particles and layered metal oxide particles formed thereof |
| CN103097588A (en) * | 2010-07-19 | 2013-05-08 | 莱顿大学 | Process to prepare metal nanoparticles or metal oxide nanoparticles |
| CN103184466A (en) * | 2013-01-10 | 2013-07-03 | 昆明贵千新型材料技术研究有限公司 | Novel process for preparing high purity metal oxide |
Non-Patent Citations (1)
| Title |
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| 交流电沉积法制备金属氧化物纳米材料及形貌控制;王翠英等;《化学物理学报》;20010627;第14卷(第3期);第350页最后1段 * |
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