CN101654285B - Method for preparing Co3O4 nano material by Co2O3 powder - Google Patents
Method for preparing Co3O4 nano material by Co2O3 powder Download PDFInfo
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- CN101654285B CN101654285B CN2009101953846A CN200910195384A CN101654285B CN 101654285 B CN101654285 B CN 101654285B CN 2009101953846 A CN2009101953846 A CN 2009101953846A CN 200910195384 A CN200910195384 A CN 200910195384A CN 101654285 B CN101654285 B CN 101654285B
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- alcohol
- solvent
- deionized water
- nano material
- powder
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Abstract
The invention discloses a method for preparing a Co3O4 nano material by a Co2O3 powder, comprising the following steps: taking the Co2O3 powder as a precursor, wherein, if deionized water and alcohol are taken as solvents, the volume ratio of the deionized water to the alcohol of absolute alcohol is 9:1 to 0:10; or when the water solution of glucose is taken as the solvent, the mass fraction of the glucose is between 5-30 percent; mixing and stirring 0.1-0.2mol/L Co2O3 powder and deionized water and alcohol or glucose aqueous solution solvent to form a uniform mixed material, wherein the alcohol may be ethanol, ethylene glycol or glycerol; putting the mixed material in a container, then putting the container in a constant temperature cabinet, raising the temperature at a speed of 8.5-11.5 DEG C/min, and heating the mixed material within the temperature range of 120-160 DEG C for 6-24h; taking the container out for cooling to the room temperature; alternately washing a synthetic product by the deionized water and the absolute alcohol, and drying at low temperature to obtain the Co3O4 nano material. The Co3O4 nano material prepared by the method has easily controlled shape and granularity, high purity, good crystallinity and environment-friendly production process.
Description
Technical field
The present invention relates under a kind of low temperature by Co
2O
3Powder preparation Co
3O
4The method of nano material.
Background technology
The Co of spinel-type
3O
4And composite nano materials is a kind of important multifunctional material, and application is very extensive: such as polytype catalyst, anode lithium ion rechargeable batteries, solid state sensor, magnetic, optical instrument etc.Since the size of nano particle and the performance that pattern all has influence on material, the Co of the different particle sizes of therefore controlled preparation and pattern
3O
4Nano material is the major domain that the researcher pays close attention to.Up to the present multiple synthesis strategy begins to take shape, and wherein hydro-thermal-solvent-thermal method is an important class, and important development is arranged.For example, and Chen etc. (Adv.Mater.2008,20,1205-1209) at first obtain the hollow ball CoOOH (alkali formula cobalt oxide) of nanostructured by hydro-thermal method, the original position thermal decomposition forms by Co then
3O
4The molecular nano-hollow ball of nanoparticle; (Langmuir 2008,24, and 11164-11168) etc. the solvent-thermal method of utilization take n-butanol as the solvent mixture that decomposes cobalt salt and cobalt hydroxide obtains the Co of superparamagnetism for Rajamathi
3O
4Nano particle; Titirici etc. (Chem.Mater.2006,18,3808-3812) obtain Co take carbohydrate and soluble-salt as raw material by water-heat process and rear sintering process
3O
4The molecular Nano microsphere of nanoparticle etc.
Co according to the said method acquisition
3O
4The major defect that nano material exists is: 1) cost of material height.Solubility cobalt ion source and reagent need be provided; 2) part preparation method's complex process.Usually need to divide two stages to finish, obtain earlier the presoma of product by the process of hydro-thermal or solvent heat, and then obtain Co through the mode of thermal decomposition or sintering
3O
4Particle; 3) reaction temperature is higher, the equipment requirement height.Sintering process needs the high temperature more than 200 ℃ usually; 4) preparation cost height.The production cost of reaction scheme complexity, temperature of reaction is higher and equipment is complicated path of preparing product is higher; 5) environmental pollution is big.Because it is raw material that cobalt salt and suitable reactant are adopted in reaction, in producing the process of oxide, can produce many accessory substances, to environment.
Summary of the invention
For the deficiency that exists in the said method, the present invention discloses that a kind of cost of material is cheap, technology is simple, low temperature, economic environmental protection, granularity are controlled, high-purity, be easy to industrialized by Co
2O
3Powder preparation Co
3O
4The method of nano material.
Technical scheme of the present invention is: adopt hydro-thermal-solvent heat synthetic system, directly with water insoluble and pure Co
2O
3Powder is the cobalt source, Co
2O
3Directly be distributed in the mixed solvent of water and alcohol; Again said mixture is placed in airtight withstand voltage, the pasteurising vessel that heated at constant temperature realizes in the temperature range of setting, time range.The temperature of the present invention by conditioned reaction, time, the proportioning of solvent, the kind and the consumption of additive are realized the size and the distribution situation of nanoparticle are controlled.
A kind of by Co
2O
3Powder preparation Co
3O
4The method of nano material is characterized in that carrying out in accordance with the following steps:
A) with Co
2O
3Powder is presoma, and during as solvent, the volume ratio of deionized water and alcohol is from 9: 1 to the absolute alcohol by 0: 10 take deionized water and alcohol; Or take the aqueous solution of glucose during as solvent, the mass fraction of glucose is 5%-30%; 0.1-0.2mol/L Co
2O
3Form uniform compound after powder mixes with water alcohol or molasses sugar mixed solvent, and compound is placed heatproof, pressure vessel; Described alcohol is ethanol, ethylene glycol or glycerine;
B) with steps A) in compound is housed container place thermostatic drying chamber, with 8.5-11.5 ℃/minute temperature rise rate, in 120 ℃ of-160 ℃ of scopes, thermostatically heating 6-24 hour;
C) take out container, naturally cool to room temperature; Alternately wash synthetic product with deionized water, dehydrated alcohol, after the cryodrying, promptly get desired product.
Described cobalt source Co
2O
3Powder, the purity of its oxide is greater than 95%.
Described solvent contains additive cetyl trimethylammonium bromide (CTAB) or sodium lauryl sulphate (SDS).
Described addition of C TAB massfraction amount less than solvent 3% or or the massfraction of SDS less than 3% of solvent.
Among the present invention, steps A) described solvent is even, can be undertaken by modes such as mechanical stirring or vibration, magnetic agitation, sonic oscillations.
Among the present invention, after finishing, each washing needs with wash again after the centrifuge separator separation next time.
Advantage of the present invention and positively effect are:
1. raw material of the present invention is simple, and raw materials cost is low.Realized utilizing the oxide compound that is insoluble in water under the normal temperature presoma for solvent thermal reaction, used salts reaction thing different from the past has low price, and the high advantage of atom utilization.
2. method used in the present invention is a step hydro-thermal-solvent-thermal method, has saved follow-up sintering or thermal decomposition process.Production process is simplified, and it is more convenient to operate.
3. temperature required for the present invention is 120 ℃-160 ℃, belongs to low-temperature hydrothermal-solvent thermal category, safety coefficient higher temperatures hydro-thermal-solvent thermal height, and equipment requirements is lower.
4. the present invention is applied widely.By changing the temperature and time of reaction, the kind of additive can be regulated and control pattern, the particulate size of product, and the nano level of different-shape is to micron order crystal grain.The inventive method can be prepared the nanoparticle of 20nm to the variable grain size between the 50nm easily, and the product of different size is provided.
5. low production cost of the present invention.Shorten synthesis technique, cost of material is low, and equipment and process is simplified, so that whole preparation system makes up easily, process costs reduces.
6, adopted oxide compound and nontoxic alcohol to do raw material, made that the environmental pollutant that produce in the reaction process are less, the technology greenization.
7, Co among the present invention
3O
4Pattern, the granularity of nano material product are easily controlled, the purity height, and better crystallinity degree, and the product processing is convenient, is suitable for large-scale industrial production, therefore in industrial production certain advantage is arranged.
Description of drawings
Fig. 1: embodiment 2 is 1: 1 in the water-ethanol volume ratio, and temperature of reaction is under the condition of 160 ℃ of following thermostatically heating 6h, the XRD diffraction spectra of the sample of acquisition.
Fig. 2: embodiment 4 is 9: 1 with the water-ethylene glycol volume ratio, and temperature of reaction is under the condition of 160 ℃ of following thermostatically heating 24h, obtains the scanning electron microscopy pattern of sample.
Fig. 3: embodiment 5 is a solvent with the straight alcohol, and temperature of reaction is under the condition of 160 ℃ of following thermostatically heating 24h, obtains the scanning electron microscopy pattern of sample.
Fig. 4: embodiment 7 is 1: 1 with the water-ethanol volume ratio, adds additive SDS, and temperature of reaction is under the condition of 160 ℃ of following thermostatically heating 24h, obtains the scanning electron photomicrograph of product.
Embodiment
The present invention is described in detail below in conjunction with drawings and Examples, but present embodiment is not limited to the present invention, and every employing similarity method of the present invention and similar variation thereof all should be listed protection scope of the present invention in.
Embodiment 1:
Co with 0.5mmol
2O
3, 1g glucose and 16ml deionized water put into reactor after mixing, and is placed on insulating box at 120 ℃ of lower heated at constant temperature 6h, can make Co after cooling, separation, drying
3O
4Nano particle, through scanning electron microscope analysis as can be known, the heterogeneous spherical aggregate that is formed by the particle of particle diameter about 20 nanometers of acquisition.
Embodiment 2:
Co with 1mmol
2O
3, 8ml absolute ethyl alcohol and 8ml deionized water put into reactor after mixing, and is placed on insulating box at 160 ℃ of lower heated at constant temperature 6h, can make Co after cooling, separation, drying
3O
4Nano particle, XRD spectra are seen figure one, demonstrate the XRD spectra peak position of the sample that obtains and the Co in the international standard spectrogram storehouse among the figure
3O
4Material is in full accord, and the average diameter by calculating its nano particle is at 30nm.
Embodiment 3:
Co with 1mmol
2O
3, 1.6ml absolute ethyl alcohol and 14.4ml deionized water put into reactor after mixing, and is placed on insulating box at 160 ℃ of lower heated at constant temperature 24h, can make Co after cooling, separation, drying
3O
4Nano particle.Learn that through the projection electronic microscope photos product is the Co of average grain diameter about 40nm
3O
4Nano particle.
Embodiment 4:
Co with 1mmol
2O
3, 1.6ml ethylene glycol and 14.4ml deionized water put into reactor after mixing, and is placed on insulating box at 160 ℃ of lower heated at constant temperature 24h, can make Co after cooling, separation, drying
3O
4Nano particle, the microstructure of sample is seen figure two.As can be seen from the figure, the diameter of nanoparticle and has the irregular coacervate that small-particle is gathered into about 27nm.
Embodiment 5:
Co with 1mmol
2O
3, the 16ml absolute ethyl alcohol puts into reactor after mixing, and is placed on insulating box at 160 ℃ of lower heated at constant temperature 24h, can make Co after cooling, separation, drying
3O
4Nano particle, the microstructure of sample is seen figure three.As can be seen from the figure, particle is the comparatively Co of granularity about 25nm of homogeneous that distribute
3O
4Nano particle
Embodiment 6:
Co with 1mmol
2O
3, 8ml glycerine and 8ml deionized water put into reactor after mixing, and is placed on insulating box at 160 ℃ of lower heated at constant temperature 24h, can make Co after cooling, separation, drying
3O
4Nano particle.Through the XRD diffraction analysis, learn that the mean particle size of the product of acquisition is about 20nm.
Embodiment 7:
Co with 1mmol
2O
3, 0.2gSDS, 8ml absolute ethyl alcohol and 8ml deionized water put into reactor after mixing, and is placed on insulating box at 160 ℃ of lower heated at constant temperature 24h, can make Co after cooling, separation, drying
3O
4Nano particle, scanning electron micrograph are seen figure four.As can be seen from the figure nanoparticle is better dispersed, and average particle diameter is about 25nm.
Embodiment 8:
Co with 1mmol
2O
3, 0.2g CTAB, 8ml absolute ethyl alcohol and 8ml deionized water put into reactor after mixing, and is placed on insulating box at 160 ℃ of lower heated at constant temperature 24h, can make Co after cooling, separation, drying
3O
4Nano particle.Record its average particle diameter greatly about 30nm by the projection Electronic Speculum.
Claims (4)
1. one kind by Co
2O
3Powder preparation Co
3O
4The method of nano material is characterized in that carrying out in accordance with the following steps:
A) with Co
2O
3Powder is presoma, and during as solvent, the volume ratio of deionized water and alcohol is from 9: 1 to the absolute alcohol by 0: 10 take deionized water and alcohol; Or take the aqueous solution of glucose during as solvent, the mass fraction of glucose is 5%-30%; 0.1-0.2mol/L Co
2O
3Form uniform compound after powder mixes with water alcohol or molasses sugar mixed solvent, and compound is placed heatproof, pressure vessel; Described alcohol is absolute ethyl alcohol, ethylene glycol or glycerine;
B) with steps A) in compound is housed container place thermostatic drying chamber, with 8.5-11.5 ℃/minute temperature rise rate, in 120 ℃ of-160 ℃ of scopes, thermostatically heating 6-24 hour;
C) take out container, naturally cool to room temperature; Alternately wash synthetic product with deionized water, dehydrated alcohol, after the cryodrying, promptly get desired product.
2. according to claim 1 by Co
2O
3Powder preparation Co
3O
4The method of nano material is characterized in that: the Co A)
2O
3The purity of the oxide of powder is greater than 95%.
3. according to claim 1 by Co
2O
3Powder preparation Co
3O
4The method of nano material is characterized in that: contain additive softex kw or lauryl sodium sulfate in the solvent A).
4. according to claim 3 by Co
2O
3Powder preparation Co
3O
4The method of nano material is characterized in that: the mass fraction amount that described additive softex kw adds less than the mass fraction of 3% or lauryl sodium sulfate addition of solvent less than 3% of solvent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101953846A CN101654285B (en) | 2009-09-09 | 2009-09-09 | Method for preparing Co3O4 nano material by Co2O3 powder |
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|---|---|---|---|
| CN2009101953846A CN101654285B (en) | 2009-09-09 | 2009-09-09 | Method for preparing Co3O4 nano material by Co2O3 powder |
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| CN101654285B true CN101654285B (en) | 2011-06-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531070B (en) * | 2011-12-30 | 2013-09-25 | 郑州轻工业学院 | Co3O4 nanometer material for supercapacitor and preparation method thereof |
| CN106315691A (en) * | 2016-08-26 | 2017-01-11 | 天津大学 | Nanometer Co 3O4 with cobalt defects and preparation method thereof, and application thereof in oxygen production through electro-catalysis water decomposition |
| CN111072073A (en) * | 2019-12-20 | 2020-04-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of Ni monatomic doped cobaltosic oxide nano material, product and application thereof |
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