CN101805009B - Simple and controllable method for preparing lobate micron/nano copper oxide two-dimensional assembly - Google Patents
Simple and controllable method for preparing lobate micron/nano copper oxide two-dimensional assembly Download PDFInfo
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- CN101805009B CN101805009B CN2010101278711A CN201010127871A CN101805009B CN 101805009 B CN101805009 B CN 101805009B CN 2010101278711 A CN2010101278711 A CN 2010101278711A CN 201010127871 A CN201010127871 A CN 201010127871A CN 101805009 B CN101805009 B CN 101805009B
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- cupric oxide
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Abstract
The invention belongs to the technical field of synthesizing materials by the micron/nano material preparation technology and a normal-temperature solution method, and in particular relates to a controllable method for preparing a lobate micron/nano copper oxide two-dimensional assembly. The method comprises the following steps: adding a prepared soluble copper salt solution and a solution with hydroxyl ions to a beaker filled with de-ionized water or a mutual solution of a de-ionized water solution and small-molecule organic matters based on the concentration ratio of hydroxyl ion to copper ion of 4-8, magnetic-stirring until the system becomes brownish-black, centrifuge-washing the brownish-black suspension, and reserving the product after the centrifugal separation to obtain the end product. The invention has the advantages of simple process, easy construction of entire preparation system, simple operation, controllable condition, low cost, easily controlled product size, high purity, less byproduct and less environmental pollution, and is applicable to large-scale industrial production.
Description
Technical field
The invention belongs to micro-/ nano material preparation technology and normal temperature solution method synthetic materials technical field, be specifically related to the method for the lobate micro-/ nano cupric oxide two dimension of a kind of simple and easy controlled preparation assembly.
Background technology
As one type of P type transition metal oxide; Cupric oxide (CuO) has very excellent character and purposes widely, such as: cupric oxide can be used as catalyzer, gas sensor, solar cell, electrode materials, ultra water wetted material and high-tc-super conductor body etc.In recent years, has the copper oxide material of nanostructure and the very big interest that assembly causes people thereof.People have prepared the nanostructure of cupric oxide through different methods, like nanometer rod, nano wire, nano belt, nanometer sheet, nano-rings etc.In addition, the complex construction of some cupric oxide also has report like flower shape structure, taraxacum structure, fascircular texture, honey-combed etc.In the method for nano material for preparing more such cupric oxide and nanostructure, include presoma thermal decomposition method, hydrothermal method, solid reaction process, wet chemistry method, hydrolysis method and electrochemical process etc.
In existing lobate micro-/ nano cupric oxide preparation method, the raw material that has is complicated, and what have needs high temperature heat source; What have needs tensio-active agent or the like; Can bring the bad control of some by products and pattern, cost is higher, and technology is complicated; Do not meet the pollution control regulation and the utilization of resources, in industry, be unfavorable for scale operation yet.
Summary of the invention
The object of the invention is to propose that a kind of pattern is controlled, particle size is controlled, high purity, convenient processing, be easy to the method for the lobate micro-/ nano cupric oxide two dimension of industrialized simple and easy controlled preparation assembly.
The present invention adopts normal temperature solution to add the synthetic system of stirring, is that reactant is realized with common, simple pharmaceutical chemicals directly.The presoma of the present invention reaction select cupric nitrate (or other soluble copper salts) be Tong Yuan, with sodium hydroxide (chemical substance of hydroxide ion maybe can be provided) be alkali source, with deionized water and can be that solvent prepares and synthesizes the cupric oxide micro-/ nano crystal with regular morphology and specific crystal formation with the small molecular weight organism that water dissolves each other.The present invention realizes the control to the lobate assembly size of two dimension through the consumption proportion of regulating solvent.
The method of the lobate micro-/ nano cupric oxide two dimension of the simple and easy controlled preparation that the present invention proposes assembly, concrete steps are following:
(1) with the deionized water is solvent, preparation Cu
2+Concentration is the cupric nitrate (Cu (NO of 0.05mol/L-0.5mol/L
3)
2) solution;
(2) with the deionized water be solvent, preparation OH-concentration is sodium hydroxide (NaOH) solution of 0.2mol/L-1.0mol/L;
(3) liquid that dissolves each other with deionized water or deionized water and small organic molecule composition is solvent, step (1) and step (2) gained solution is added wherein control OH
-Concentration and Cu
2+The ratio of concentration is 4: 1-8: 1, and the normal temperature lower magnetic force stirs, and gets the brownish black product;
(4) centrifugal, washed product promptly gets desired product.
Among the present invention, said cupric nitrate, sodium hydroxide are not less than CP.
Among the present invention, small organic molecule described in the step (3) be in absolute ethyl alcohol, terepthaloyl moietie or the PEG 400 any, the volume ratio of deionized water and small organic molecule is 1: 1-20: 1.
Among the present invention, the magnetic agitation time described in the step (3) is 8-12 hour.
Among the present invention, washing described in the step (4) adopts deionized water, absolute ethyl alcohol alternately to wash products therefrom, generally alternately washs 3-6 time.
Signs such as the structure of the inventive method products therefrom, pattern, composition are selected X-ray powder diffraction (XRD), sem (SEM), transmission electron microscope (TEM) etc. respectively for use; And its fluorescence, ultraviolet-visible absorbed and electrochemical properties is studied.
The invention has the advantages that:
1. the present invention has realized under the normal temperature obtaining dressing up two-dimentional lobate micro-/ nano cupric oxide product by nano particle or nanometer rod or set of nanowires with the stirred solution mode, is inorganic synthetic a kind of new route of synthesis that provides of nano material.
2. the present invention adopts the presoma of simple common pharmaceutical chemicals for reaction, and the by product that in the preparation process, produces is few, and environmental pollution is little, is a kind of environment-friendly type synthesis technique.
3. the present invention controls lobate product size through the composition of regulating solvent, and the solvent raw material is easy to get, and solvent composition is prone to transfer easily separated, the good dispersivity of products therefrom.
4. the present invention does not use any additives or tensio-active agent, do not need other heating or hydro-thermal, has simplified the operation steps of hydro-thermal reaction etc., makes technology simpler, is convenient to the industriallization operation.
5. technology of the present invention is simple, and whole preparation system makes up easily, and is easy and simple to handle, and condition is prone to control, and is with low cost, and product pattern, size are prone to control, and purity is high, and better crystallinity degree and product convenient processing are succinct, are suitable for large-scale commercial prodn.
6. the product of the present invention's preparation has the physicals of aspects such as good light, electricity; Can be used as catalyzer, gas sensor, solar cell, electrode materials, ultra water wetted material and high-tc-super conductor body etc., comparatively vast potential for future development and application space are arranged.
Description of drawings
Fig. 1 is the XRD figure of embodiment 1 products therefrom, and the XRD figure of other embodiment products therefroms and Fig. 1's is identical basically, does not repeat to list.
Fig. 2 is the TEM figure of embodiment 1-7 products therefrom.Wherein (a) is embodiment 1 products obtained therefrom TEM figure; (b) be embodiment 2 products obtained therefrom TEM figure; (c) being embodiment 3 products obtained therefrom TEM figure, (d) is embodiment 4 products obtained therefrom TEM figure, (e) is embodiment 5 products obtained therefrom TEM figure; (f) being embodiment 6 products obtained therefrom TEM figure, (g) is embodiment 7 products obtained therefrom TEM figure.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1: deionized water is solvent, [OH
-]: [Cu
2+The two dimensional oxidation copper thallus that]=4, churning time preparation in 12 hours nanometer rod/line are assembled into
(1) be deionized water, the sodium hydroxide solution of 2ml 0.2mol/L, the 2ml0.05mol/L copper nitrate solution that adds 36ml in the beaker of 50ml to volume, in the magnetic agitation beaker mixed solution 12 hours brown black suspension liquid;
(2) again suspension-s in the beaker is transferred to spinning in the centrifuge tube, alternately washs respectively 3 times with deionized water and absolute ethyl alcohol, after each washing was accomplished, spinning promptly got the prepared product of inventive method.
Fig. 1 provides the X-ray powder diffraction collection of illustrative plates of products obtained therefrom, and the gained peak is cupric oxide (CuO) crystalline diffraction peak.What a provided among Fig. 2 is transmission electron microscope (TEM) photo of embodiment 1 product, and visible product is the two-dimentional thallus that tiny nanometer rod/line is assembled into from figure, and its length is about 500nm; Width is about 200nm; Length-to-diameter ratio is about 2.5, and the thallus two ends are not very fine and close, and are a bit loose.
Embodiment 2: deionized water: the mixed solution of absolute ethyl alcohol=1: 1 is solvent, [OH
-]: [Cu
2+The two dimensional oxidation copper thallus that]=4, churning time preparation in 12 hours nano particle/line are assembled into
(1) be deionized water, the absolute ethyl alcohol of 10ml, the sodium hydroxide solution of 2ml 0.2mol/L, the 2ml 0.05mol/L copper nitrate solution that adds 6ml in the beaker of 50ml to volume, in the magnetic agitation beaker mixed solution 12 hours brown black suspension liquid;
(2) again suspension-s in the beaker is transferred to spinning in the centrifuge tube, alternately washs respectively 3 times with deionized water and absolute ethyl alcohol, after each washing was accomplished, spinning promptly got the prepared product of inventive method.
The X-ray powder diffraction collection of illustrative plates of products therefrom and Fig. 1's is identical basically, and the gained peak is cupric oxide (CuO) crystalline diffraction peak.What b provided among Fig. 2 is transmission electron microscope (TEM) photo of embodiment 2 products; Visible product is the two-dimentional thallus that tiny nano particle/line is assembled into from figure, and its length is about 200nm, and width is about 100nm; Length-to-diameter ratio is about 2, and disperse a little a little at the thallus two ends that have.
Embodiment 3: deionized water: the mixed solution of absolute ethyl alcohol=1: 1 is solvent, [OH
-]: [Cu
2+The two dimensional oxidation copper thallus that]=8, churning time preparation in 12 hours set of nanowires are dressed up
(1) be deionized water, 10ml absolute ethyl alcohol, the sodium hydroxide solution of 2ml 0.2mol/L, the 1ml 0.05mol/L copper nitrate solution that adds 7ml in the beaker of 50ml to volume, in the magnetic agitation beaker mixed solution 12 hours brown black suspension liquid;
(2) again suspension-s in the beaker is transferred to spinning in the centrifuge tube, alternately washs respectively 3 times with deionized water and absolute ethyl alcohol, after each washing was accomplished, spinning promptly got the prepared product of inventive method.
The X-ray powder diffraction collection of illustrative plates of products therefrom and Fig. 1's is identical basically, and the gained peak is cupric oxide (CuO) crystalline diffraction peak.What c provided among Fig. 2 is transmission electron microscope (TEM) photo of embodiment 3 products, and visible product is the two-dimentional thallus that tiny set of nanowires is dressed up from figure, and its length is about 200nm; Width is about 100nm; Length-to-diameter ratio is about 2, and the thallus two ends are not very fine and close, and are a bit loose.
Embodiment 4: deionized water is solvent, [OH
-]: [Cu
2+The two dimensional oxidation copper thallus that]=4, churning time preparation in 8 hours nanometer rod/line are assembled into
(1) be deionized water, the sodium hydroxide solution of 1ml 0.2mol/L, the 1ml0.05mol/L copper nitrate solution that adds 18ml in the beaker of 50ml to volume, in the magnetic agitation beaker mixed solution 8 hours brown black suspension liquid;
(2) again suspension-s in the beaker is transferred to spinning in the centrifuge tube, alternately washs respectively 3 times with deionized water and absolute ethyl alcohol, after each washing was accomplished, spinning promptly got the prepared product of inventive method.
The X-ray powder diffraction collection of illustrative plates of products therefrom and Fig. 1's is identical basically, and the gained peak is cupric oxide (CuO) crystalline diffraction peak.What d provided among Fig. 2 is transmission electron microscope (TEM) photo of embodiment 4 products, and visible product is the two-dimentional thallus that tiny nanometer rod/line is assembled into from figure, and its length is about 500nm; Width is about 200nm; Length-to-diameter ratio is about 2.5, compares with embodiment 1 products therefrom, and the thallus two ends are not to shrink closely; Relatively more sharp-pointed, smoother around the thallus.
Embodiment 5: deionized water: the mixed solution of terepthaloyl moietie=9: 1 is solvent, [OH
-]: [Cu
2+The two dimensional oxidation copper thallus that]=4, churning time preparation in 16 hours set of nanowires are dressed up
(1) be deionized water, 2ml terepthaloyl moietie, the sodium hydroxide solution of 1ml 0.2mol/L, the 1ml 0.05mol/L copper nitrate solution that adds 16ml in the beaker of 50ml to volume, in the magnetic agitation beaker mixed solution 16 hours brown black suspension liquid;
(2) again suspension-s in the beaker is transferred to spinning in the centrifuge tube, alternately washs respectively 3 times with deionized water and absolute ethyl alcohol, after each washing was accomplished, spinning promptly got the prepared product of inventive method.
The X-ray powder diffraction collection of illustrative plates of products therefrom and Fig. 1's is identical basically, and the gained peak is cupric oxide (CuO) crystalline diffraction peak.What e provided among Fig. 2 is transmission electron microscope (TEM) photo of embodiment 5 products, and visible product is the two-dimentional thallus that tiny set of nanowires is dressed up from figure, and its length is about 500nm, and width is about 80nm, and length-to-diameter ratio is about 6, and it is elongated that thallus becomes.
Embodiment 6: deionized water: PEG 400=19: 1 is solvent, [OH
-]: [Cu
2+The two dimensional oxidation copper thallus that]=4, churning time preparation in 24 hours nanometer rod are assembled into
(1) be deionized water, 1ml PEG 400, the sodium hydroxide solution of 1ml 0.2mol/L, the 1ml 0.05mol/L copper nitrate solution that adds 17ml in the beaker of 50ml to volume, in the magnetic agitation beaker mixed solution 24 hours brown black suspension liquid;
(2) again suspension-s in the beaker is transferred to spinning in the centrifuge tube, alternately washs respectively 3 times with deionized water and absolute ethyl alcohol, after each washing was accomplished, spinning promptly got the prepared product of inventive method.
The X-ray powder diffraction collection of illustrative plates of products therefrom and Fig. 1's is identical basically, and the gained peak is cupric oxide (CuO) crystalline diffraction peak.What f provided among Fig. 2 is transmission electron microscope (TEM) photo of embodiment 6 products, and visible product is tiny nanometer rod and the two-dimentional thallus that is assembled into by nanometer rod from figure, and its length is about 400nm, and width is about 200nm, and length-to-diameter ratio is about 2.
Embodiment 7: deionized water: absolute ethyl alcohol=4: 1 is solvent, [OH
-]: [Cu
2+The two dimensional oxidation copper thallus that]=4, churning time preparation in 4 hours set of nanowires are dressed up
(1) be to add 16ml absolute ethyl alcohol, the sodium hydroxide solution of 2ml 0.2mol/L, 2ml0.05mol/L copper nitrate solution in the beaker of 50ml to volume, in the magnetic agitation beaker mixed solution 4 hours brown black suspension liquid;
(2) again suspension-s in the beaker is transferred to spinning in the centrifuge tube, alternately washs respectively 3 times with deionized water and absolute ethyl alcohol, after each washing was accomplished, spinning promptly got the prepared product of inventive method.
The X-ray powder diffraction collection of illustrative plates of products therefrom and Fig. 1's is identical basically, and the gained peak is cupric oxide (CuO) crystalline diffraction peak.What g provided among Fig. 2 is transmission electron microscope (TEM) photo of embodiment 7 products, and visible product is the two-dimentional thallus that tiny nanometer rod/line is assembled into from figure, and its length is about 100nm, and width is about 20nm, and length-to-diameter ratio is about 5, and thallus is very tiny.
Claims (4)
1. the method for the lobate micro-/ nano cupric oxide two dimension of simple and easy controlled preparation assembly is characterized in that concrete steps are following:
(1) with the deionized water is solvent, preparation Cu
2+Concentration is the cupric nitrate (Cu (NO of 0.05mol/L-0.5mol/L
3)
2) solution;
(2) with the deionized water be solvent, preparation OH
-Concentration is sodium hydroxide (NaOH) solution of 0.2mol/L-1.0mol/L;
(3) liquid that dissolves each other with deionized water or deionized water and small organic molecule composition is solvent, step (1) and step (2) gained solution is added wherein control OH
-Concentration and Cu
2+The ratio of concentration is 4: 1-8: 1, and the normal temperature lower magnetic force stirs, and gets the brownish black product;
(4) centrifugal, washed product promptly gets desired product;
Wherein: small organic molecule described in the step (3) be in absolute ethyl alcohol, terepthaloyl moietie or the PEG 400 any, the volume ratio of deionized water and small organic molecule is 1: 1-20: 1.
2. the method for the lobate micro-/ nano cupric oxide two dimension of controlled preparation according to claim 1 assembly is characterized in that said cupric nitrate, sodium hydroxide are not less than CP.
3. the method for the lobate micro-/ nano cupric oxide two dimension of controlled preparation according to claim 1 assembly is characterized in that the magnetic agitation time is 8-12 hour described in the step (3).
4. the method for the lobate micro-/ nano cupric oxide two dimension of controlled preparation according to claim 1 assembly is characterized in that the employing of washing described in the step (4) deionized water, absolute ethyl alcohol alternately wash synthetic product, alternately wash 3-6 time.
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| CN102328949A (en) * | 2011-06-22 | 2012-01-25 | 哈尔滨工程大学 | Preparation method for copper oxide nanoribbon with high hydrogen storage capacity |
| CN102951671B (en) * | 2012-10-22 | 2014-10-08 | 洛阳师范学院 | Preparation method of copper oxide nano particle |
| CN103771490B (en) * | 2014-01-04 | 2015-08-19 | 东华理工大学 | A kind of simple and easy stirring at room temperature prepares the method for micro-/ nano zinc oxide |
| CN108128795A (en) * | 2018-01-17 | 2018-06-08 | 上海电力学院 | A kind of method nanocrystalline room temperature synthesis CuO |
| CN109110795B (en) * | 2018-08-10 | 2021-03-19 | 暨南大学 | Copper-based nano/micron composite particles and preparation method and application thereof |
| CN109665555A (en) * | 2019-03-01 | 2019-04-23 | 西北工业大学 | One seed shrimp shape copper oxide and its preparation method and application |
Citations (1)
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| CN1778682A (en) * | 2005-09-30 | 2006-05-31 | 南京理工大学 | Production of nanometer copper oxide with controllable microstructure |
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| CN1778682A (en) * | 2005-09-30 | 2006-05-31 | 南京理工大学 | Production of nanometer copper oxide with controllable microstructure |
Non-Patent Citations (4)
| Title |
|---|
| Li-Xia Yang et al..Multistep synthesis of CuO nanorod bundles and interconnected nanosheets using Cu2(OH)3Cl plates as precursor.《Material Chemistry and Physics》.2008,第112卷442-447. * |
| 朱俊武等.纳米CuO的形貌控制合成及其性能研究.《无机化学学报》.2004,(第7期),863-867. * |
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