CN114408943A - Method for preparing cuprous thiocyanate nanoparticles through solid-phase synthesis - Google Patents
Method for preparing cuprous thiocyanate nanoparticles through solid-phase synthesis Download PDFInfo
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- C01C3/20—Thiocyanic acid; Salts thereof
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Abstract
The invention discloses a method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis, which comprises the following steps: taking thiocyanate, cupric salt and a reducing agent as raw materials, and carrying out solid-phase reaction under the action of ball milling to obtain the product. The method is simple, avoids the use of organic or inorganic solvents and dispersants, is environment-friendly, meets the green synthesis requirement of materials, and is suitable for industrial mass production.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a method for preparing cuprous thiocyanate nanoparticles through solid phase synthesis.
Background
The fouling effect of marine organisms, which grow on and attach to the surface of all facilities below the waterline of ships and in the sea, causes the facilities to be corroded and damaged due to pollution, and the damage to the sea and the transportation industry is very serious. Cuprous oxide has proven to be a very effective anti-fouling component and is widely used due to its biocidal properties against most polluting organisms. The red color of the cuprous oxide limits further coloration of the paint, however, the hull immersed in water can only have one color. In order to solve the problem, other organic compounds of tributyltin oxide and tributyltin fluoride have been used, but are finally eliminated due to too strong toxicity, and the application of organic lead and mercury compounds is limited due to the requirement of environmental protection. Other white cuprous compounds such as cuprous bromide, cuprous iodide, or cuprous cyanide, which are soluble in water and expensive, have caused problems in application, and cuprous cyanide, which is insoluble in water but has too strong anion toxicity.
Cuprous thiocyanate avoids the above-mentioned disadvantages. Experiments prove that cuprous thiocyanate (CuSCN) is an inorganic pigment with excellent performance, is nontoxic and harmless to human bodies and environments, and can be used as ship bottom antifouling paint. Therefore, the demand of the fertilizer is more and more increased abroad in recent years. With the development of fishing in the ocean shipping fishery in China, the use amount of the antifouling paint at the bottom of the ship is rapidly increased. The existing methods for preparing cuprous thiocyanate mainly comprise the following steps:
1, a liquid phase precipitation method, such as a method of using water as a solvent and using polyethylene glycol 400 as a surfactant to prepare cuprous thiocyanate nanoparticles with the particle size of 70-90 nm (proceedings of university of Dalian industries, 2009,28(3), 188-; 2, a precursor method, wherein the precursor method needs to prepare a complex precursor containing product elements, and then the complex precursor is treated by corresponding chemical and physical methods to obtain the product. The size and morphology of the product can be controlled by the size and morphology of the precursor. Yang et al obtained spherical cuprous thiocyanate nanocrystals using copper oxide (CuO) powder as a precursor (J Disper Sci Technol,2009,30(3), 361-364). Liu and the like form a dithizone copper precursor compound by utilizing dithizone and copper ions, and then the compound is decomposed into cuprous cyanate spherical nano particles (J Exp Nanosci,2013,8(6), 625-632); 3, other, continuous ion layer adsorption and reaction methods (aerospace materials technology, 2010, 30(4), 5-9) and electrodeposition methods (inorganic materials science, 2009, 24(1),8-12), etc.
In the above preparation methods, chemical substances irrelevant to the reaction, such as a dispersant or a surfactant, are required to be added, and some waste is inevitably generated in the purification process. The equipment used in the continuous ionic layer adsorption and reaction process and electrodeposition process also limits the large-scale industrial application of these processes. Therefore, it is urgently needed to provide a simple, green and environment-friendly preparation method of nano cuprous thiocyanate.
Disclosure of Invention
Based on the technical problem, the invention provides a method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis. The method does not need any organic or inorganic solvent and dispersant, is green and efficient, and is suitable for industrial mass production.
The technical scheme of the invention is as follows:
the invention provides a method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis, which comprises the following steps: taking thiocyanate, cupric salt and a reducing agent as raw materials, and carrying out solid-phase reaction under the action of ball milling to obtain the product.
Preferably, the thiocyanate is sodium thiocyanate or potassium thiocyanate.
Preferably, the reducing agent is a sulfite; more preferably, the reducing agent is selected from any one of sodium sulfite, sodium bisulfite, potassium sulfite, potassium bisulfite, amine sulfite, and amine bisulfite.
Preferably, the cupric salt is cupric salt or hydrate of cupric salt; more preferably, the cupric salt is copper sulfate or copper sulfate pentahydrate.
Preferably, the molar ratio of the thiocyanate to the divalent copper salt to the reducing agent is 1:1: 0.5-2.
Preferably, the ball milling conditions are as follows: the ball milling speed is 300 and 500rpm, and the ball milling time is 2-10 h.
Preferably, the grinding balls used for ball milling are selected from zirconia balls, hard alloy balls or iron alloy balls; preferably, the diameter of the grinding ball is less than or equal to 15 mm.
Preferably, the temperature of the solid phase reaction is 20-25 ℃.
Preferably, the method further comprises washing, centrifuging and drying the reactant obtained by the solid-phase reaction with distilled water; the drying temperature is 80-110 ℃, and the drying time is 1-3 h.
Preferably, the diameter of the prepared cuprous thiocyanate nanoparticles is 20-100 nm.
The invention has the beneficial effects that:
the method takes thiocyanate, cupric salt and a reducing agent as raw materials, and performs solid-phase reaction under the action of ball milling to obtain cuprous thiocyanate nanoparticles with the diameter of 20-100 nm. Compared with the traditional synthesis method, the method has the following characteristics:
(1) the solid-phase reaction is a solid-phase oxidation-reduction reaction at room temperature, and is carried out at normal temperature by selecting reaction raw materials and a solid-phase reaction mode without heating, cooling or sealing and pressurizing conditions; (2) no organic or inorganic solvent, dispersant, template agent and surfactant are needed to be used, and the purification operation is also not needed, so that the whole process is green and environment-friendly; (3) only the raw materials are subjected to ball milling to promote reaction, and the particles are subjected to continuous collision and friction, so that cuprous thiocyanate particles generated by the reaction in the process become smaller and smaller, the agglomeration of the nano particles can be well controlled, and the diameter of the obtained cuprous thiocyanate nano particles is 20-100 nm; (4) the purity of the prepared product is as high as 99.9%, the yield is as high as 100%, and the method is suitable for industrial mass production.
Drawings
FIG. 1 is an XRD pattern of cuprous thiocyanate nanoparticles as prepared in example 1;
FIG. 2 is a TEM image of the product nano-cuprous thiocyanate prepared in example 1.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis is obtained by taking copper sulfate, sodium thiocyanate and a reducing agent as raw materials and performing solid phase reaction under the action of ball milling, and specifically comprises the following steps:
(1) 0.01mol of copper sulfate pentahydrate (CuSO) is weighed respectively4·5H2O), sodium thiocyanate (NaSCN) and the reducing agent sodium bisulfite (NaHSO)3)；
(2) Rapidly adding the weighed raw materials into a 50mL zirconia ball milling tank with a stainless steel vacuum sleeve and provided with 50 zirconia grinding balls with the diameter of 6mm and 8 zirconia grinding balls with the diameter of 10mm at room temperature (25 ℃), and continuously ball-milling for 2 hours in a QM-3SP04 planetary high-energy ball mill at 480rpm to obtain a product;
(3) washing the product of the solid phase reaction with distilled water, centrifuging, and then drying by blowing air at 100 ℃ for 1h to obtain the nano cuprous thiocyanate with the content of 99.9 percent and the yield of 100 percent.
The product cuprous thiocyanate obtained in this example was analyzed by X-ray diffraction (XRD), and the results are shown in fig. 1: as can be seen, the XRD spectrum only has the characteristic diffraction peak of cuprous thiocyanate, and no diffraction peak of copper sulfate exists, which indicates that the copper sulfate is completely converted into cuprous thiocyanate.
The product obtained in this example was observed by field emission electron microscopy (TEM image), and the results are shown in FIG. 2: it can be seen that the size of the obtained nano cuprous thiocyanate particles is about 20-100 nm.
Example 2
A method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis is obtained by taking copper sulfate, sodium thiocyanate and a reducing agent as raw materials and performing solid phase reaction under the action of ball milling, and specifically comprises the following steps:
(1) 0.015mol of copper sulfate pentahydrate (CuSO) is weighed respectively4·5H2O), sodium thiocyanate (NaSCN) and the reducing agent sodium bisulfite (NaHSO)3)；
(2) Rapidly adding the weighed raw materials into a 50mL zirconia ball milling tank with a stainless steel vacuum sleeve and provided with 50 zirconia grinding balls with the diameter of 6mm and 8 zirconia grinding balls with the diameter of 10mm at room temperature (25 ℃), and continuously ball-milling for 2 hours in a QM-3SP04 planetary high-energy ball mill at 480rpm to obtain a product;
(3) washing the product of the solid phase reaction with distilled water, centrifuging, and then drying by blowing air at 100 ℃ for 1h to obtain the nano cuprous thiocyanate with the content of 99.8% and the yield of 99.9%.
Example 3
A method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis is obtained by taking copper sulfate, sodium thiocyanate and a reducing agent as raw materials and performing solid phase reaction under the action of ball milling, and specifically comprises the following steps:
(1) 0.01mol of copper sulfate pentahydrate (CuSO) is weighed respectively4·5H2O), sodium thiocyanate (NaSCN) and reducing agent potassium hydrogen sulfite (KHSO)3)；
(2) Rapidly adding the weighed raw materials into a 50mL zirconia ball milling tank with a stainless steel vacuum sleeve and provided with 50 zirconia grinding balls with the diameter of 6mm and 8 zirconia grinding balls with the diameter of 10mm at room temperature (25 ℃), and continuously ball-milling for 2 hours in a QM-3SP04 planetary high-energy ball mill at 480rpm to obtain a product;
(3) washing the product of the solid phase reaction with distilled water, centrifuging, and then drying by blowing air at 100 ℃ for 1h to obtain the nano cuprous thiocyanate with the content of 99.7 percent and the yield of 100 percent.
Example 4
A method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis is obtained by taking copper sulfate, potassium thiocyanate and a reducing agent as raw materials and performing solid phase reaction under the action of ball milling, and specifically comprises the following steps:
(1) 0.01mol of copper sulfate pentahydrate (CuSO) is weighed4·5H2O), 0.01mol of potassium thiocyanate (KSCN) and 0.02mol of reducing agent potassium sulfite (K)2SO3)；
(2) Rapidly adding the weighed raw materials into a 50mL zirconia ball milling tank with a stainless steel vacuum sleeve and provided with 50 zirconia grinding balls with the diameter of 6mm and 8 zirconia grinding balls with the diameter of 10mm at room temperature (25 ℃), and continuously ball-milling 5 in a QM-3SP04 planetary high-energy ball mill at 300rpm to obtain a product;
(3) washing the product of the solid phase reaction with distilled water, centrifuging, and then drying by blowing air at 90 ℃ for 3h to obtain the nano cuprous thiocyanate with the content of 99.8% and the yield of 99.7%.
Comparative example 1
A method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis is obtained by taking copper sulfate, sodium thiocyanate and a reducing agent as raw materials and performing solid phase reaction under the action of ball milling, and specifically comprises the following steps:
(1) 0.01mol of copper sulfate pentahydrate (CuSO) is weighed respectively4·5H2O), sodium thiocyanate (NaSCN) and the reducing agent sodium bisulfite (NaHSO)3)；
(2) Rapidly adding the weighed raw materials into a 50mL zirconia ball milling tank with a stainless steel vacuum sleeve and provided with 50 zirconia grinding balls with the diameter of 6mm and 8 zirconia grinding balls with the diameter of 10mm at room temperature (25 ℃), and continuously ball-milling for 1 hour in a QM-3SP04 planetary high-energy ball mill at 480rpm to obtain a product;
(3) washing the product of the solid phase reaction with distilled water, centrifuging, and then drying by blowing air at 100 ℃ for 1h to obtain the nano cuprous thiocyanate with the content of 99.8% and the yield of 48.9%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis is characterized by comprising the following steps: taking thiocyanate, cupric salt and a reducing agent as raw materials, and carrying out solid-phase reaction under the action of ball milling to obtain the product.
2. The method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis according to claim 1, wherein the thiocyanate is sodium thiocyanate or potassium thiocyanate.
3. The method for preparing cuprous thiocyanate nanoparticles using solid phase synthesis according to claim 1 or 2, wherein the reducing agent is sulfite; more preferably, the reducing agent is selected from any one of sodium sulfite, sodium bisulfite, potassium sulfite, potassium bisulfite, amine sulfite, and amine bisulfite.
4. The method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis according to any of claims 1-3, wherein the cupric salt is cupric salt or hydrate of cupric salt; preferably, the cupric salt is copper sulfate or copper sulfate pentahydrate.
5. The method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis according to any of claims 1-4, wherein the molar ratio of thiocyanate, cupric salt, reducing agent is 1:1: 0.5-2.
6. The method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis according to any of claims 1-5, wherein the ball milling conditions are as follows: the ball milling speed is 300 and 500rpm, and the ball milling time is 2-10 h.
7. The method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis according to any of claims 1-6, wherein grinding balls used for ball milling are selected from zirconia balls, cemented carbide balls or iron alloy balls; preferably, the diameter of the grinding ball is less than or equal to 15 mm.
8. The method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis according to any of claims 1-7, wherein the temperature of the solid phase reaction is 20-25 ℃.
9. The method for preparing cuprous thiocyanate nanoparticles by solid phase synthesis as claimed in claims 1-8, further comprising washing, centrifuging and drying the reactant obtained by solid phase reaction with distilled water; the drying temperature is 80-110 ℃, and the drying time is 1-3 h.
10. The method for preparing cuprous thiocyanate nanoparticles using solid phase synthesis according to any of claims 1-9, wherein cuprous thiocyanate nanoparticles have a diameter of 20-100 nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114806547A (en) * | 2022-06-02 | 2022-07-29 | 中国计量大学 | Method for preparing CuIP2S type complex fluorescent sensing material by ball milling |
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| JPS5836921A (en) * | 1981-08-31 | 1983-03-04 | Hokko Chem Ind Co Ltd | Improved manufacture of cuprous thiocyanate |
| JPS634845A (en) * | 1986-06-24 | 1988-01-09 | Mitsubishi Heavy Ind Ltd | Adsorbent for carbon monoxide |
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| CN101428822A (en) * | 2008-11-27 | 2009-05-13 | 宜兴市燎原化工有限公司 | Cuprous thiocyanate and production method |
| US20120301528A1 (en) * | 2011-05-24 | 2012-11-29 | Uhlmann Donald R | Compositions and methods for antimicrobial metal nanoparticles |
| CN106745064A (en) * | 2016-11-23 | 2017-05-31 | 安徽工业大学 | A kind of method that ammonium thiocyanate is removed in the crude salt from ammonium sulfate |
| CN109943839A (en) * | 2019-03-06 | 2019-06-28 | 上海理工大学 | A kind of preparation method based on copper-based growth cuprous sulfocyanide |
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- 2021-11-26 CN CN202111422178.1A patent/CN114408943B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3857762A (en) * | 1968-12-09 | 1974-12-31 | Fischer & Porter Co | Continuous analysis for copper concentration |
| JPS5836921A (en) * | 1981-08-31 | 1983-03-04 | Hokko Chem Ind Co Ltd | Improved manufacture of cuprous thiocyanate |
| JPS634845A (en) * | 1986-06-24 | 1988-01-09 | Mitsubishi Heavy Ind Ltd | Adsorbent for carbon monoxide |
| CN101109101A (en) * | 2007-07-27 | 2008-01-23 | 中国科学院上海硅酸盐研究所 | Method for manufacturing cuprous thiocyanate membrane in liquid phase condition |
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| US20120301528A1 (en) * | 2011-05-24 | 2012-11-29 | Uhlmann Donald R | Compositions and methods for antimicrobial metal nanoparticles |
| CN106745064A (en) * | 2016-11-23 | 2017-05-31 | 安徽工业大学 | A kind of method that ammonium thiocyanate is removed in the crude salt from ammonium sulfate |
| CN109943839A (en) * | 2019-03-06 | 2019-06-28 | 上海理工大学 | A kind of preparation method based on copper-based growth cuprous sulfocyanide |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114806547A (en) * | 2022-06-02 | 2022-07-29 | 中国计量大学 | Method for preparing CuIP2S type complex fluorescent sensing material by ball milling |
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