CN100408483C - Process for preparing nanometer cobalt oxide - Google Patents
Process for preparing nanometer cobalt oxide Download PDFInfo
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- CN100408483C CN100408483C CNB2006100979563A CN200610097956A CN100408483C CN 100408483 C CN100408483 C CN 100408483C CN B2006100979563 A CNB2006100979563 A CN B2006100979563A CN 200610097956 A CN200610097956 A CN 200610097956A CN 100408483 C CN100408483 C CN 100408483C
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Abstract
The invention discloses a preparing method of nanometer cobalt oxide, which comprises the following steps: (1) dissolving bivalent soluble salt in the water or alcohol or composite solvent of water and alcohol; obtaining the solution with bivalent cobalt ion; (2) adding certain quantity of ammonia in the bivalent cobalt ion solution; blending evenly; refluxing and heating in the reactor; or transmitting into autoclave to do close heat; (3) separating sediment; washing; drying; obtaining nanometer material of black cobalt oxide with different size or shape; realizing controllable equipment of nanometer cobalt oxide within certain scale.
Description
Technical field
The invention belongs to inorganic preparation chemistry and field of inorganic nonmetallic material, relate to a kind of preparation method of nanometer cobalt oxide.
Background technology
Cobalt oxide (Co
3O
4) as transition metal oxide, have purposes widely, can be used as catalyzer, magneticsubstance, electrode materials, the air-sensitive sensing material, field emmision materials etc. have caused people's extensive concern.Nano material is meant to have at least one dimension to be in material between the 1-100nm in the three dimension scale, because size that it is less and bigger specific surface area, embody excellent performance in many aspects, since the 1980s, cause global extensive concern, become the focus of Materials science research.
The preparation of nanometer cobalt oxide has important scientific meaning and using value as the prerequisite of its property research and practical application.Early be reported as 1978, Sugimoto, people such as T adopt cobalt acetate solution to obtain nanometer cobalt oxide [Sugimoto, T. about 100nm 100 ℃ of following forced hydrolysis; Matijevic, E.J.Inorg.Nucl.Chem.1978,41,165].After this, the report that a large amount of nanometer cobalt oxide preparations are successively arranged, most for utilizing acting on of tensio-active agent and organic solvent such as polyvinylpyrrolidone, benzene semi-annular jade pendant acid sodium, dodecyl semi-annular jade pendant acid sodium, tween 85, octanol, n-hexyl alcohol etc. to obtain nanometer cobalt oxide [(a) C.Nethravathi, Sonia Sen, N.Ravishankar in the solution, Michael Rajamathi, Clemens Pietzonka, and Bernd Harbrecht, J.Phys.Chem.B 2005,109,11468-11472; (b) Yanglong Hou, Hiroshi Kondoh, Masatsugu Shimojo, Toshihiro Kogure, andToshiakiOhta, J.Phys.Chem.B 2005,109,19094-19098; (c) Marc Verelst, Teyeb Ould Ely, CatherineAmiens, Etienne Snoeck, Pierre Lecante, Alain Mosset, Marc Respaud, Jean Marc Broto, andBruno Chaudret, Chem.Mater.1999,11,2702-2708; (d) Tao He, Dairong Chen, and XiulingJiao, Chem.Mater.2004,16,737-743; (e) Tao He, Dairong Chen, Xiuling Jiao, YinglingWang, and Yongzheng Duan, Chem.Mater.2005,17,4023-4030; (f) Rong Xu and Hua ChunZeng, Langmuir 2004,20,9780-9790; (g) Tao He, Dairong Chen, Xiuling Jiao, Yanyan Xu, and Yuanxiang Gu, Langmuir 2004,20,8404-8408; (h) Xiaohe Liu, Guanzhou Qiu andXingguo Li, Nanotechnology 16 (2005) 3035-3040]; these methods are because above-mentioned organic use; increase production cost, and brought problem of environmental pollution easily, obviously be not easy to large-scale industrial production.
In addition, do not use the nanometer cobalt oxide preparation method of tensio-active agent and organic solvent, some reports are also arranged.As HuaChun Zeng etc. in the presence of SODIUMNITRATE and sodium hydroxide, utilize dioxygen oxidation obtain the cobalt oxide nano material [(a) RongXu and Hua Chun Zeng, J.Phys.Chem.B 2003,107,926-930; (b) Ji Feng and Hua ChunZeng, Chem.Mater.2003,15,2829-2835], Xiong Wang etc. utilizes oxalic acid and Cobaltous diacetate elder generation hydro-thermal reaction, 420 ℃ of calcinings obtain cobalt oxide nano material [Xiong Wang again, Xiangying Chen, Lisheng Gao, HuaguiZheng, Zude Zhang and Yitai Qian, J.Phys.Chem.B 2004,108.16401-16404], rose vitriols such as Yang Jiang, ammoniacal liquor, hydrogen peroxide react under hydrothermal condition and have obtained the single cobalt oxide nano material of pattern.[YangJiang, Yue Wu, Bo Xie, Yi Xie, Yitai Qian, Materials Chemistry and Physics 74 (2002) 234-237], Wang Xinxi etc. utilize Xiao Suangu elder generation and ammoniacal liquor to mix, and utilize the effect of oxygen or hydrogen peroxide to obtain Co (NH
3)
6 3+, and then mix by a certain percentage with Xiao Suangu, refluxing down at 50-90 ℃ obtains nanometer cobalt oxide [Wang Xinxi, Lv Guanglie, Ceng Yuewu, Hu Xiurong, Chen Linshen, chemical journal, 2003,61 (11), 1849-1853].Employing hydro-thermal-solid-phase pyrolysis such as Zhang Weimin obtain the nanometer cobalt oxide [Zhang Weimin, Sun Sixiu, Yu Haiyun, Song Xinyu, SCI, 2003,24 (12), 2151-2154] about 100nm.Chinese patent CN200410060127.9 has reported a kind of manufacture method of high purity tricobalt tetroxide, the divalent cobalt aqueous solution and sodium hydroxide solution are reacted under pH value 4.5～13.5,50 ℃～100 ℃ of temperature and violent stirring, and the adding reductive agent, obtain hydroxide cobalt precipitation.Wherein the ratio of amount of substance is 1.00: 2.0～3.0: 0.01～0.1 between cobalt, sodium hydroxide, the reductive agent.Precipitation after filtration, washing gained filter cake is at 80 ℃～125 ℃ dry down, as to enter the adjustable air flow after pulverizing calcining furnaces, 200 ℃～950 ℃ following roastings and calcine 0.5～14h.Obtain high-purity cobaltosic oxide powder through pulverizing, classification.But required reagent type of these technology or step are more, are not easy to operation and actual production.
Therefore, from current nanometer cobalt oxide production technique present situation, be badly in need of easy, the low-cost preparation method of exploitation nanometer cobalt oxide, to adapt to the demand of all trades and professions to nanometer cobalt oxide.
Summary of the invention
The present invention seeks to: propose a kind of industrialized nanometer cobalt oxide preparation method, especially at the significant application value and the great market prospect of nanometer cobalt oxide, a kind of low cost is proposed, pollute little, easy to operate, be convenient to industrialized nanometer cobalt oxide production technique.
The present invention is a raw material with divalence cobalt soluble salt and ammoniacal liquor, can obtain the uniform cobalt oxide nano material of particle diameter by cryogenic relatively reacting by heating.The preparation method of nanometer cobalt oxide of the present invention can be achieved through the following technical solutions:
(1) divalence cobalt soluble salt (as Cobaltous diacetate, rose vitriol, Xiao Suangu, cobalt chloride etc.) in water-soluble or ethanol or the two mixed solvent, is obtained the solution of divalent cobalt ion;
(2) in divalent cobalt ion solution, add certain amount of ammonia water, stir;
(3) with the solution reflux in reactor in (2), perhaps transfer to airtight heating in the reactor, the reaction postcooling, the gained suspension liquid is centrifugal, washing, drying obtain the cobalt oxide nano material of black.
Purpose of the present invention can also be achieved through the following technical solutions:
(1) by changing the concentration of solvent, divalence cobalt soluble salt kind and divalent cobalt ion and ammoniacal liquor, can obtain the nanometer cobalt oxide of different scale size, thereby can realize the controlled preparation of nanometer cobalt oxide within the specific limits.In divalent cobalt ion solution, add the NH in the ammoniacal liquor
3With Co in the cobalt salt
2+Scope effect when 1-100 of mol ratio better.
(2) by changing Heating temperature, nano particle or nano cubic crystal can be obtained respectively, the selectivity of pattern can be realized to a certain extent in differing temps.Consider that from aspects such as the pattern that obtains nanometer cobalt oxide and energy consumptions the temperature of the present invention's heating is preferably between 60-250 ℃, is preferably 1-8 hour heat-up time.
(3) in the process of heating, need a certain amount of oxygen in the system and exist, otherwise cause oxidation incomplete easily, be difficult to obtain highly purified Co
3O
4This operation can feed some oxygen and realize, also can directly utilize oxygen in the air (bubbling air or under the situation that has air to exist).
The black oxidation cobalt nano material that the present invention obtains identifies that through XRD thing is Co mutually
3O
4, have higher purity.
The method of the invention has following advantage:
(1) adopt divalent cobalt class and ammoniacal liquor as reaction raw materials, need not any tensio-active agent, raw material is cheap and easy to get;
(2) can obtain under cryogenic relatively liquid-phase condition reaction, need not through high-temperature heating process, required equipment is simple and easy to operate.
(3) gained nanometer cobalt oxide yardstick is even, and purity is higher, changes the nano material that experiment condition can obtain different scale and pattern, has realized the controlled preparation of nanometer cobalt oxide to a certain extent.
Description of drawings
Fig. 1 is the transmission electron microscope photo of embodiment 1 gained nanometer cobalt oxide;
Fig. 2 is the transmission electron microscope photo of embodiment 2 gained nanometer cobalt oxides;
Fig. 3 is the transmission electron microscope photo of embodiment 3 gained nanometer cobalt oxides;
Fig. 4 is the transmission electron microscope photo of embodiment 4 gained nanometer cobalt oxides;
Fig. 5 is the transmission electron microscope photo of embodiment 5 gained nanometer cobalt oxides;
Fig. 6 is the transmission electron microscope photo of embodiment 6 gained nanometer cobalt oxides;
Fig. 7 is the transmission electron microscope photo of embodiment 7 gained nanometer cobalt oxides;
Fig. 8 is the transmission electron microscope photo of embodiment 8 gained nanometer cobalt oxides;
Fig. 9 is the transmission electron microscope photo of embodiment 9 gained nanometer cobalt oxides;
Figure 10 is the transmission electron microscope photo of embodiment 10 gained nanometer cobalt oxides;
Figure 11 is the transmission electron microscope photo of embodiment 11 gained nanometer cobalt oxides;
Figure 12 is the transmission electron microscope photo of embodiment 12 gained nanometer cobalt oxides;
Figure 13 is the XRD spectra of embodiment 4 gained nanometer cobalt oxides.
Embodiment
Provide several specific embodiment of the present invention below, so that the present invention is described in more details.
Embodiment 1
Get 0.50gCo (CH
3COO)
24H
2O is dissolved in the 20ml water, to wherein adding 25% strong aqua 2.5ml, 70 ℃ of stirring and refluxing reactions 3 hours, solution top keeps a certain amount of air during back flow reaction, the gained suspension liquid is centrifugal, with distilled water wash for several times, can obtain median size at air drying is cobalt oxide nano particle about 15nm.
Embodiment 2
Get 0.56gCoSO
47H
2O is dissolved in the 20ml water, to wherein adding 25% strong aqua 2.5ml, in air, stir, transfer in the closed reactor, solution top keeps a certain amount of air, and is 100 ℃ of reactions 3 hours, that the gained suspension liquid is centrifugal, with distilled water wash for several times, can obtain median size at air drying is cobalt oxide nano particle about 20nm.
Embodiment 3
Get 0.50gCo (CH
3COO)
24H
2O is dissolved in the 20ml water, to wherein adding 25% strong aqua 2.5ml, in air, stir, transfer in the closed reactor, solution top keeps a certain amount of air, and is 200 ℃ of reactions 8 hours, that the gained suspension liquid is centrifugal, with distilled water wash for several times, can obtain median size at air drying is cobalt oxide nano cubic crystal about 25nm.
Embodiment 4
Get 0.50gCo (CH
3COO)
24H
2O is dissolved in the 20ml water, to wherein adding 25% strong aqua 2.5ml, in air, stir, transfer in the closed reactor, solution top keeps a certain amount of air, and is 150 ℃ of reactions 8 hours, that the gained suspension liquid is centrifugal, with distilled water wash for several times, can obtain median size at air drying is cobalt oxide nano particle about 15nm.
Embodiment 5
Get 0.50gCo (NO
3)
26H
2O is dissolved in the 20ml water, to wherein adding 25% strong aqua 2.5ml, in air, stir, transfer in the closed reactor, solution top keeps a certain amount of air, and is 100 ℃ of reactions 3 hours, that the gained suspension liquid is centrifugal, with distilled water wash for several times, can obtain median size at air drying is cobalt oxide nano particle about 50nm.
Embodiment 6
Get 0.50gCoCl
26H
2O is dissolved in the 20ml water, to wherein adding 25% strong aqua 2.5ml, in air, stir, transfer in the closed reactor, solution top keeps a certain amount of air, and is 100 ℃ of reactions 3 hours, that the gained suspension liquid is centrifugal, with distilled water wash for several times, can obtain median size at air drying is cobalt oxide nano particle about 40mm.
Embodiment 7
Get 0.50gCo (CH
3COO)
24H
2O is dissolved in the 20ml water, to wherein adding 25% strong aqua 2.5ml, in air, stir, transfer in the closed reactor, solution top keeps a certain amount of air, and is 250 ℃ of reactions 3 hours, that the gained suspension liquid is centrifugal, with distilled water wash for several times, can obtain median size at air drying is cobalt oxide nanocrystal about 30nm.
Embodiment 8
Get 0.50gCo (CH
3COO)
24H
2O is dissolved in the 25ml water, to wherein adding 25% strong aqua 5.0ml, in air, stir, transfer in the closed reactor, solution top keeps a certain amount of air, and is 150 ℃ of reactions 8 hours, that the gained suspension liquid is centrifugal, with distilled water wash for several times, can obtain median size at air drying is cobalt oxide nano particle about 20nm.
Embodiment 9
Get 0.50gCo (CH
3COO)
24H
2O is dissolved in the 25ml water, to wherein adding 25% strong aqua 10.0ml, in air, stir, transfer in the closed reactor, solution top keeps a certain amount of air, and is 150 ℃ of reactions 8 hours, that the gained suspension liquid is centrifugal, with distilled water wash for several times, can obtain median size at air drying is cobalt oxide nano particle about 12nm.
Embodiment 10
Get 0.50gCo (CH
3COO)
24H
2O is dissolved in the 25ml dehydrated alcohol, to wherein adding 25% strong aqua 2.5ml, in air, stir, transfer in the closed reactor, solution top keeps a certain amount of air, and is 150 ℃ of reactions 8 hours, that the gained suspension liquid is centrifugal, with distilled water wash for several times, can obtain median size at air drying and be about cobalt oxide nano particle about 2nm.
Embodiment 11
Get 0.10gCo (CH
3COO)
24H
2O is dissolved in the 25ml water, to wherein adding 25% strong aqua 2.5ml, in air, stir, transfer in the closed reactor, solution top keeps a certain amount of air, and is 150 ℃ of reactions 8 hours, that the gained suspension liquid is centrifugal, with distilled water wash for several times, can obtain median size at air drying is cobalt oxide nano particle about 8nm.
Embodiment 12
Get 2.00gCo (CH
3COO)
24H
2O is dissolved in the 17ml water, to wherein adding 25% strong aqua 10.0ml, in air, stir, transfer in the closed reactor, solution top keeps a certain amount of air, and is 150 ℃ of reactions 8 hours, that the gained suspension liquid is centrifugal, with distilled water wash for several times, can obtain median size at air drying is cobalt oxide nano particle about 60nm.
Claims (2)
1. the preparation method of a nanometer cobalt oxide is characterized in that carrying out according to following steps:
(1) divalence cobalt soluble salt in water-soluble or ethanol or the two mixed solvent, is obtained the solution of divalent cobalt ion; Divalence cobalt soluble salt is Cobaltous diacetate, rose vitriol, Xiao Suangu or cobalt chloride;
(2) in divalent cobalt ion solution, add ammoniacal liquor, in divalent cobalt ion solution, add the NH in the ammoniacal liquor
3With Co in the cobalt salt
2+The scope of mol ratio be 1-100; Mix, reflux in reactor is perhaps transferred to airtight reacting by heating in the reactor; The temperature of reacting by heating is 60-250 ℃; Heat-processed is carried out under the situation that oxygen exists;
(3) after reaction finishes,, obtain the cobalt oxide nano material of black with the separation of gained throw out, washing, drying.
2. the preparation method of nanometer cobalt oxide according to claim 1 is characterized in that with 0.56gCoSO
47H
2O is dissolved in the 20ml water, to wherein adding 25% strong aqua 2.5ml, in air, stir, transfer in the closed reactor, solution top keeps a certain amount of air, and is 100 ℃ of reactions 3 hours, that the gained suspension liquid is centrifugal, with distilled water wash for several times, can obtain median size at air drying is cobalt oxide nano particle about 20nm.
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| CN103771543A (en) * | 2014-01-28 | 2014-05-07 | 复旦大学 | Foam-like cobaltous oxide nano material and preparation method thereof |
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| CN107572601A (en) * | 2017-09-04 | 2018-01-12 | 天津大学 | A kind of synthetic method of CoO appearance of nano material regulation and control |
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| CN110890558B (en) * | 2019-11-05 | 2021-05-04 | 中新国际联合研究院 | Supported platinum-based core-shell catalyst and preparation method thereof |
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| CN113244938A (en) * | 2021-05-21 | 2021-08-13 | 华东理工大学 | P-Nb/Co for low-temperature vinyl chloride catalytic combustion3O4Catalyst, preparation method and application thereof |
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| CN1623908A (en) * | 2003-12-02 | 2005-06-08 | 财团法人工业技术研究院 | Process for low temp synthesis of tricobalt tetraoxide |
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