CN109422295B - Preparation method of sea urchin-shaped cobaltosic oxide material - Google Patents
Preparation method of sea urchin-shaped cobaltosic oxide material Download PDFInfo
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- CN109422295B CN109422295B CN201710790021.1A CN201710790021A CN109422295B CN 109422295 B CN109422295 B CN 109422295B CN 201710790021 A CN201710790021 A CN 201710790021A CN 109422295 B CN109422295 B CN 109422295B
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Abstract
The invention provides a preparation method of sea urchin-shaped cobaltosic oxide material, which comprises the following steps: (1) adding metal salt and polyethylene glycol (PEG) into deionized water to form a uniform solution A; (2) adding water-soluble organic amine into the solution A obtained in the step (1) under stirring to obtain a mixture B; (3) continuously stirring the mixture B obtained in the step (2) for 5-120min, and transferring the mixture B to a reaction kettle for hydrothermal reaction; (4) and (4) washing, separating, drying and roasting the product obtained in the step (3) to obtain the sea urchin-shaped cobaltosic oxide material. The experimental operation method is simple, the raw materials are low in price, only deionized water is used as a solvent, the environment is friendly, and the large-scale production is easy to realize.
Description
Technical Field
The invention belongs to the field of micro-nano materials, and particularly relates to a preparation method of a sea urchin-shaped cobaltosic oxide material.
Background
Cobaltosic oxide (Co)3O4) Is a black powder having a density of about 6.0-6.2g/m3And the molecular weight is 240.80. Tricobalt tetraoxide is a cubic system, has a lattice parameter of 0.811nm and a space group of Fd3m, and belongs to the normal AB2O4A spinel structure. The cobaltosic oxide has wide application in the fields of photoelectric devices, chemical energy storage, chemical sensors, heterogeneous catalysis and the like. Because of their superior performance and wide application, researchers have now conducted a great deal of research and have prepared cobaltosic oxides of different morphologies, such as nanospheres, nanotubes, nanodiscs, nanocubes, nanorods, nanobelts, nanosheets and the like. Some more complex structures such as flower-like, honeycomb-like, hollow sphere-like, etc. have also been reported. Among them, sea urchin-like cobaltosic oxide attracts the attention of a group of researchers due to its complex structure and unique properties, but reports of related patents are still few.
Li et al prepared sea urchin-like cobaltosic oxide (H.Li, G.T.Fei, M.Fang, P.Cui, X.Guo, P.Yan, L.D.Zhang, Applied Surface Science 257(2011)6527-6530) by hydrothermal method using cobalt sulfate, urea, cetyltrimethylammonium bromide (CTAB) and deionized water as raw materials; rui et al use cobalt nitrate, urea, NH4F, using deionized water as a raw material, and preparing sea urchin-shaped cobaltosic oxide (X.Rui, H.Tan, D.Sim, W.Liu, C.Xu, H.H.Hng, R.Yazami, T.M.Lim, Q.Yan, Journal of Power Sources 222(2013)97-102) by using a hydrothermal method; zhu et al prepared sea urchin-like cobaltosic oxide (C.Zhu, G.Saito, T.Akiyama, Journal of A) by precipitation from cobalt nitrate, ammonium bicarbonate, ammonium sulfate and ethanollloys and Compounds 646(2015) 639-; xiao et al prepared sea urchin-like cobaltosic oxide (y.xiao, s.liu, f.li, a.zhang, j.zhao, s.fang, d.jia, Advanced Functional Materials 22(2012) 4052-; zhang et al prepared sea urchin-like cobaltosic oxide (y.zhang, y.liu, s.fu, f.guo, y.qian, Materials Chemistry and Physics 104(2007)166-171.) by using cobalt salt, surfactant, hydrogen peroxide and deionized water as raw Materials and using a hydrothermal method; chinese patent 201110453871.5 discloses a method for synthesizing sea urchin-shaped cobaltosic oxide by using cobalt nitrate, ethylene glycol, deionized water and glucose as raw materials and utilizing a hydrothermal method; chinese patent 201210360741.1 discloses a method for preparing sea urchin-like hierarchical cobaltosic oxide nanospheres by mixing an aqueous solution of cobalt chloride with glycerol, adding urea for reaction, removing impurities, and calcining. Chinese patent 201610725892.0 discloses a method for synthesizing sea urchin-shaped cobaltosic oxide by using a hydrothermal method, wherein carbon spheres are used as a template, cobalt acetate and urea are used, and polyvinylpyrrolidone is added or not added as raw materials. The related method for preparing sea urchin-shaped cobaltosic oxide has complex process and sensitive and harsh reaction conditions; meanwhile, an organic solvent is also needed as a solvent or a mineralizer is needed as a structure directing agent, so that the cost is high, the environment pollution is easy to cause, and the large-scale production is not suitable. Therefore, the preparation method of the sea urchin-shaped cobaltosic oxide material with simple synthesis method and mild reaction conditions is especially necessary.
Disclosure of Invention
The invention aims to disclose a preparation method of a sea urchin-shaped cobaltosic oxide material, the sea urchin-shaped cobaltosic oxide material is prepared by a hydrothermal method, and the material is simple in preparation method, low in cost and easy for large-scale production.
A preparation method of sea urchin-shaped cobaltosic oxide material comprises the following steps:
1) adding metal salt and polyethylene glycol (PEG) into deionized water to form a uniform solution A;
2) adding water-soluble organic amine into the solution A obtained in the step 1) under stirring to obtain a mixture B;
3) continuously stirring the mixture B obtained in the step 2) for 5-120min, and transferring the mixture B to a reaction kettle for hydrothermal reaction;
4) washing, separating, drying and roasting the product obtained by the reaction in the step 3) to obtain sea urchin-shaped cobaltosic oxide.
Wherein: the metal salt in the step 1) is nitrate, sulfate, acetate or chloride of cobalt.
The concentration of the metal salt in the step 1) is 0.01-5 mol/L; the preferred concentration is 0.02-3 mol/L; the optimal concentration is 0.02-1 mol/L.
The polyethylene glycol in the step 1) comprises polyethylene glycol (PEG) with different molecular weights, and specifically comprises polyethylene glycol with different molecular weights such as PEG-200, PEG-400, PEG-600, PEG-800, PEG-1000, PEG-1500, PEG-2000, PEG-4000, PEG-6000, PEG-8000, PEG-10000, PEG-20000 and the like; based on the mass of the deionized water, the mass concentration range of the polyethylene glycol is 0.1-40%; preferably 1% to 20%.
Wherein the water-soluble organic amine used in the step 2) comprises one or a mixture of more than two of n-butylamine, cyclohexylamine, tert-butylamine, propylamine, hexamethylenediamine, ethylenediamine, 1, 2-propylenediamine, 1, 4-butanediamine, ethanolamine, diethanolamine and triethanolamine.
The concentration of the water-soluble organic amine in the step 2) is 5-300 g/L; the preferred concentration is 10-250 g/L; the optimal concentration is 20-200 g/L.
Stirring the mixed solution B in the step 3) for 5-120 min; preferably, the stirring time is 15-90 min; the optimal stirring time is 30-60 min.
The hydrothermal reaction temperature in the step 3) is 100-220 ℃, the preferable reaction temperature is 100-200 ℃, and the hydrothermal reaction time is 5-48 h; the reaction time is preferably 12 to 48 hours.
The washing liquid in the washing process in the step 4) is one or more than two of deionized water, ethanol and isopropanol.
The roasting temperature in the step 4) is 300-600 ℃, and the preferable roasting temperature is 350-500 ℃; the roasting time is 1-6h, and the preferable roasting time is 2-5 h.
The sea urchin-shaped cobaltosic oxide material prepared by the invention has high product purity and the yield is up to more than 95%. The result is highly consistent with the standard spectrum (42-1467) of the cobaltosic oxide through XRD diffraction analysis, which shows that the product is pure-phase cobaltosic oxide without other impurities. Meanwhile, Scanning Electron Microscope (SEM) observation is carried out on different products, and the diameter of the sea urchin-shaped cobaltosic oxide is about 8-10 mu m.
The invention has the following beneficial effects:
1) the invention realizes that the sea urchin-shaped cobaltosic oxide is obtained without adding an organic solvent as a solvent or salts as a mineralizer in the hydrothermal reaction.
2) The invention has mild preparation conditions, simple process and little pollution, and is beneficial to large-scale production.
3) The shape, structure and size of cobaltosic oxide are regulated and controlled by regulating the concentration of raw materials, the hydrothermal reaction time and temperature, the regulation and control means is easy to implement, and the industrial synthesis is easy to realize.
Drawings
FIG. 1 is an XRD spectrum of the products M-1, M-2, M-3, M-4 and M-5 obtained in examples 1-5, in which curves a, b, c, d and e correspond to XRD spectra of M-1, M-2, M-3, M-4 and M-5, respectively;
FIG. 2 is an SEM photograph of a sea urchin-like cobaltosic oxide material M-1 obtained in example 1;
FIG. 3 is an SEM photograph of a sea urchin-like cobaltosic oxide material M-2 obtained in example 2;
FIG. 4 is an SEM photograph of a sea urchin-like cobaltosic oxide material M-3 obtained in example 3;
FIG. 5 is an SEM photograph of a sea urchin-like cobaltosic oxide material M-4 obtained in example 4;
FIG. 6 is an SEM photograph of a sea urchin-like cobaltosic oxide material M-5 obtained in example 5.
Detailed Description
In order to facilitate the understanding of the invention, the invention is further illustrated below with reference to several examples, without thereby restricting the invention.
Example 1
50g of cobalt nitrate hexahydrate and 20g of PEG-600 were weighed out and dissolved in 70ml of deionized water, 15g of ethylenediamine was added with vigorous stirring to form a mixture, and the mixture was stirred for 5 minutes and then placed in a reaction vessel with a 100ml polytetrafluoroethylene liner and subjected to hydrothermal reaction at 150 ℃ for 20 hours. And after the reaction is finished, filtering the product, washing the product with water and ethanol for three times respectively, drying the product in a vacuum drying oven at 60 ℃ for 10 hours, roasting the dried product at 400 ℃ for 3 hours, and finally obtaining the sea urchin-shaped cobaltosic oxide material, wherein the number of the product is M-1.
Example 2
0.5g of cobalt chloride hexahydrate and 1g of PEG-200 were weighed out and dissolved in 65ml of deionized water, 1g of propylenediamine was added with vigorous stirring to form a mixture, and the mixture was stirred for 20min and then placed in a reaction vessel with a 100ml polytetrafluoroethylene liner and subjected to hydrothermal reaction at 200 ℃ for 16 hours. And after the reaction is finished, filtering the product, washing the product with water and isopropanol for three times respectively, drying the product in a vacuum drying oven at 80 ℃ for 8h, roasting the dried product at 350 ℃ for 4h, and finally obtaining the sea urchin-shaped cobaltosic oxide material, wherein the number of the cobaltosic oxide material is M-2.
Example 3
7.5g of cobalt acetate tetrahydrate and 5g of PEG-8000 were weighed out and dissolved in 60ml of deionized water, 7.5g of cyclohexylamine was added with vigorous stirring to form a mixture, and the mixture was stirred for 40min and then placed in a reaction vessel with a 100ml polytetrafluoroethylene lining and subjected to hydrothermal reaction at 120 ℃ for 24 h. And after the reaction is finished, filtering the product, washing the product with water and ethanol for three times respectively, drying the product in a vacuum drying oven at 70 ℃ for 12 hours, roasting the dried product at 500 ℃ for 2 hours, and finally obtaining the sea urchin-shaped cobaltosic oxide material, wherein the number of the cobaltosic oxide material is M-3.
Example 4
60g of cobalt nitrate hexahydrate and 1g of PEG20000 are weighed out and dissolved in 50ml of deionized water, 15g of triethanolamine are added under vigorous stirring to form a mixture, and the mixture is placed in a reaction kettle with a 100ml polytetrafluoroethylene lining after being stirred for 120min and undergoes hydrothermal reaction for 48h at 100 ℃. And after the reaction is finished, filtering the product, washing the product with water and ethanol for three times respectively, drying the product in a vacuum drying oven at 60 ℃ for 12 hours, roasting the dried product at 300 ℃ for 6 hours, and finally obtaining the sea urchin-shaped cobaltosic oxide material, wherein the number of the cobaltosic oxide material is M-4.
Example 5
15g of cobalt sulfate heptahydrate and 8g of PEG-2000 were weighed out and dissolved in 62.5ml of deionized water, 15g of tert-butylamine were added with vigorous stirring to form a mixture, and the mixture was stirred for 90 minutes and then placed in a reaction vessel with a 100ml polytetrafluoroethylene lining and subjected to hydrothermal reaction at 220 ℃ for 6 hours. And after the reaction is finished, filtering the product, washing the product with water and isopropanol for three times respectively, drying the product in a vacuum drying oven at 70 ℃ for 10 hours, roasting the dried product at 600 ℃ for 1.5 hours, and finally obtaining the sea urchin-shaped cobaltosic oxide material, wherein the number of the cobaltosic oxide material is M-5.
The XRD patterns of M-1, M-2, M-3, M-4 and M-5 obtained in examples 1-5 correspond to curves a, b, c, d and e in FIG. 1, respectively, and the crystal structures of the analyzed products are cubic cobaltosic oxide.
The morphologies of M-1, M-2, M-3, M-4 and M-5 obtained in examples 1 to 5, as shown in FIGS. 2, 3, 4, 5 and 6, respectively, all showed that the resulting cobaltosic oxide was sea urchin-like.
Claims (5)
1. A preparation method of sea urchin-shaped cobaltosic oxide material is characterized by comprising the following steps:
(1) adding metal salt and polyethylene glycol into deionized water to form a uniform solution A; the polyethylene glycol is polyethylene glycol with different molecular weights, and specifically comprises polyethylene glycol of PEG-200, PEG-600, PEG-2000, PEG-8000 or PEG-20000;
(2) adding water-soluble organic amine into the solution A obtained in the step (1) under stirring to obtain a mixture B;
(3) continuously stirring the mixture B obtained in the step (2) for 5-120min, and transferring the mixture B to a reaction kettle for hydrothermal reaction; the water-soluble organic amine is one or a mixture of more than two of cyclohexylamine, tert-butylamine, ethylenediamine, propylenediamine and triethanolamine; the hydrothermal reaction temperature is 80-220 ℃, and the hydrothermal reaction time is 5-48 h;
(4) washing, separating, drying and roasting the product obtained in the step (3) to obtain a sea urchin-shaped cobaltosic oxide nano material;
in the step (1), the concentration of the metal salt is 0.01-5mol/L, and the mass concentration range of the polyethylene glycol is 0.1-40% by taking the mass of the deionized water as a reference;
the concentration of the water-soluble organic amine in the step (2) is 5-300 g/L.
2. The method for preparing sea urchin-shaped cobaltosic oxide material according to claim 1, wherein: in the step (1), the metal salt is nitrate, sulfate, acetate or chloride of cobalt.
3. The method for preparing sea urchin-shaped cobaltosic oxide material according to claim 1, wherein the method comprises the following steps: and (4) the washing liquid used in the washing process in the step (4) is one or more than two of deionized water, ethanol and isopropanol.
4. The method for preparing sea urchin-shaped cobaltosic oxide material according to claim 1, wherein the method comprises the following steps: the roasting temperature in the step (4) is 300-.
5. The preparation method of the sea urchin-shaped cobaltosic oxide material according to claim 1, characterized in that the prepared sea urchin-shaped cobaltosic oxide nano material has high product purity, the yield is up to more than 95%, and the diameter of the sea urchin-shaped cobaltosic oxide is 8-10 μm.
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