CN109796039B - Method for synthesizing silver copper sulfide - Google Patents
Method for synthesizing silver copper sulfide Download PDFInfo
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- CN109796039B CN109796039B CN201910269411.3A CN201910269411A CN109796039B CN 109796039 B CN109796039 B CN 109796039B CN 201910269411 A CN201910269411 A CN 201910269411A CN 109796039 B CN109796039 B CN 109796039B
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Abstract
The invention discloses a method for synthesizing silver copper sulfide, which belongs to the field of chemical engineering, and comprises the steps of firstly reacting soluble inorganic copper salt with thiosulfate solution to generate copper thiosulfate, activating silver sulfide by nitric acid, adding the activated silver sulfide into the copper thiosulfate solution to obtain a mixed solution, vacuumizing the mixed solution to remove dissolved oxygen in the mixed solution, and then carrying out ultrasonic strengthening reaction to obtain the silver copper sulfide.
Description
Technical Field
The invention relates to a method for synthesizing silver copper sulfide, belonging to the technical field of chemical engineering.
Background
The silver copper sulfide (CuAgS) has good absorption to ultraviolet rays and near infrared light, has low absorption to visible light, and can be used as an excellent optical material with selective light transmission; when the temperature is higher than 366K, the silver ions and the copper ions in the silver-copper sulfide can conduct electricity, and the silver-copper sulfide is a good semiconductor material and has wide application.
Currently, the trend in semiconductor synthesis is to obtain high quality materials under mild conditions. The synthesis of silver-copper sulfide compounds usually adopts high-temperature silicon oxide tube technology, hydrothermal method and solvothermal method, but the methods have harsh production conditions, large energy consumption and difficult product separation.
Disclosure of Invention
The invention aims to provide a method for synthesizing silver copper sulfide, which is simple to operate and saves energy and takes the most common silver (Ag) sulfide2S) and copper thiosulfate to obtain a silver copper sulfide (CuAgS) product.
The technical scheme of the invention is as follows: firstly, soluble inorganic copper salt reacts with thiosulfate solution to generate copper thiosulfate, silver sulfide is activated by nitric acid and then added into the copper thiosulfate solution to obtain mixed solution, then the mixed solution is vacuumized to remove dissolved oxygen in the mixed solution, and then ultrasonic strengthening reaction is carried out to obtain the silver sulfide copper.
The method comprises the following specific steps:
(1) adding a thiosulfate solution into a soluble inorganic copper salt solution, and then stirring and reacting for 3-20 min at the temperature of 1-60 ℃ and under the condition that the pH value is 2-9 to prepare a copper thiosulfate solution;
(2) weighing silver sulfide, soaking the silver sulfide in a dilute nitric acid solution for 0.5-3 min to activate the silver sulfide, and then carrying out solid-liquid separation to obtain activated silver sulfide;
(3) adding activated silver sulfide into the copper thiosulfate solution prepared in the step (1) to obtain a mixed solution, vacuumizing the mixed solution, reacting for 10-60 min at the temperature of 1-60 ℃ and under the condition that the pH value is 2-11, filtering after the reaction is finished to obtain a blue-gray silver-copper sulfide compound solid, washing the solid with pure water, and drying at the temperature of 40-70 ℃ to obtain the silver-copper sulfide with a porous structure.
The soluble inorganic copper salt is a copper sulfate solution, a copper chloride solution or a copper nitrate solution, and the molar concentration ratio of the soluble inorganic copper salt to the thiosulfate solution is 0.2-0.8.
The molar ratio of the silver sulfide and the copper thiosulfate solution weighed in the step (2) is 0.1-0.6.
The thiosulfate solution is sodium thiosulfate.
The invention has the characteristics that:
the principle of the invention is as follows: the solubility product constant of silver copper sulfide is less than that of silver sulfide, and Ag (S)2O3)n -2n+1Has a relatively high stability constant as compared with Cu (S)2O3)n -2n+1Has a larger stability constant, and adopts simple copper sulfate (CuSO)4) Or copper chloride (CuCl)2) Or copper nitrate (CuNO)3) Soluble copper salt such as solution, and thiosulfate solution to produce copper (S) thiosulfate2O3)n -2n+1(n is 1 to 3), silver sulfide (Ag)2S) in copper Thiosulfate Cu (S)2O3)n -2n+1The solution will produce a less soluble silver copper sulfide (CuAgS) compound and a more stable Ag (S)2O3)n -2n+1(n＝1～3)。
The invention uses nitric acid to activate silver sulfide to dissolve trace oxide on the surface.
The invention vacuumizes the mixed solution of silver sulfide and copper thiosulfate solution to remove dissolved oxygen in the solution, prevent the degradation of the copper thiosulfate and the silver thiosulfate and improve the purity of the silver sulfide copper.
The ultrasonic strengthening reaction is carried out because the ultrasonic wave is beneficial to the external diffusion and the internal diffusion of ions, and the yield of the silver-copper sulfide is improved.
The reaction route of the invention is as follows:
(1)2Cu2++(2n+2)S2O3 2-＝2Cu(S2O3)n -2n+1+S4O6 2-
(2)Ag2S+Cu(S2O3)n -2n+1＝CuAgS+Ag(S2O3)n -2n+1
the invention has the beneficial effects that:
(1) the invention overcomes the problems of high energy consumption and difficult product separation of the conventional method, saves energy, and the prepared silver copper sulfide (CuAgS) has higher purity and higher yield, and the product has a three-dimensional porous pore structure and excellent selective light transmission.
(2) The method has the advantages of simple operation, quick reaction, convenient preparation process and wide application prospect.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1: 50mL of sodium thiosulfate solution (0.lmol/L) was prepared, and then the sodium thiosulfate solution was slowly added to 50mL of copper chloride solution (0.02mol/L), and stirred and reacted at 1 ℃ and pH 2 for 3min to obtain copper thiosulfate [ Cu (S) solution2O3)n -2n+1]Solution 0.1g silver sulfide (Ag) was weighed2S) solid, i.e. 0.0004mol silver sulfide (Ag)2S), copper thiosulfate [ Cu (S)2O3)n -2n+1]Activating the solution with 0.001mol and 0.4 mol/mol ratio with dilute nitric acid for 0.5min, performing solid-liquid separation to obtain activated silver sulfide, and adding the activated silver sulfide to copper thiosulfate [ Cu (S)2O3)n -2n+1]Obtaining a mixed solution from the solution, then placing the mixed solution into an ultrasonic generator after vacuumizing, carrying out ultrasonic enhanced reaction for 20min under the conditions of 1 ℃ and pH 2, filtering after the reaction is finished to obtain a blue gray silver copper sulfide compound solid, washing the solid with pure water, and then carrying out vacuum drying at 40 ℃ for 3 hours to obtain 0.08 g of silver copper sulfide (CuAgS) compound with a pore structure, wherein the purity of the obtained silver copper sulfide (CuAgS) is 99.2%, and the yield is 99.2%.
Example 2: 50mL of a sodium thiosulfate solution (0.2mol/L) was prepared, and then the sodium thiosulfate solution was slowly added to 50mL of a copper sulfate solution (0.1mol/L), and stirred and reacted at 20 ℃ and pH 4.5 for 10min to obtain copper thiosulfate [ Cu (S) in which S is a metal salt of copper (S) and copper (Cu) is dissolved in water2O3)n -2n+1]Solution 0.124g silver sulfide (Ag) was weighed out2S) solid, i.e. 0.0005mol of silver sulfide (Ag)2S), copper thiosulfate [ Cu (S)2O3)n -2n+1]Activating the solution with nitric acid at a molar ratio of 0.005mol to 0.1 min, and performing solid-liquid separation to obtain activated silver sulfide (Ag)2S) solid, then adding the activated silver sulfide to copper thiosulfate [ Cu (S) ]2O3)n -2n+1]Obtaining a mixed solution from the solution, then placing the mixed solution into an ultrasonic generator after vacuumizing, carrying out an intensive reaction for 30min under the conditions of 20 ℃ and pH 5, filtering after the reaction is finished to obtain a blue gray silver copper sulfide compound solid, washing the solid with pure water, and then carrying out vacuum drying at 50 ℃ for 3 hours to obtain 0.607 g of a silver copper sulfide (CuAgS) compound with a pore structure, wherein the purity of the silver copper sulfide is 99.2%, and the yield is 99.0%.
Example 3: 50mL of a sodium thiosulfate solution (2mol/L) was prepared, and then the sodium thiosulfate solution was slowly added to 50mL of a copper nitrate solution (1mol/L), and stirred and reacted at 30 ℃ and pH 9 for 15min to obtain copper thiosulfate [ Cu (S) in which Cu is present in a small amount2O3)n -2n+1]Solution 2.5g silver sulfide (Ag) was weighed2S) solid, i.e. 0.01mol silver sulfide (Ag)2S), copper thiosulfate [ Cu (S)2O3)n -2n+1]The solution is 0.05mol, twoThe molar ratio of the silver sulfide to the copper sulfide is 0.2, activation is carried out for 2min by dilute nitric acid, then solid-liquid separation is carried out to obtain activated silver sulfide, and then the activated silver sulfide is added into copper thiosulfate [ Cu (S)2O3)n -2n+1]Obtaining a mixed solution from the solution, then placing the mixed solution into an ultrasonic generator after vacuumizing, carrying out ultrasonic strengthening reaction for 40min under the conditions of 30 ℃ and pH 10, filtering after the reaction is finished to obtain a blue gray silver copper sulfide compound solid, washing the solid with pure water, and then carrying out vacuum drying for 3 hours at 60 ℃ to obtain 1.998 g of silver copper sulfide (CuAgS) compound with a pore structure, wherein the purity of the obtained silver copper sulfide (CuAgS) is 99.1%, and the yield is 99.2%.
Example 4: 50mL of sodium thiosulfate solution (2mol/L) was prepared, and then the sodium thiosulfate solution was slowly added to 50mL of copper chloride solution (0.8mol/L), and stirred and reacted at 50 ℃ and pH 6 for 18min to obtain copper thiosulfate [ Cu (S) in which Cu (S) is dissolved in water2O3)n -2n+1]Solution 3g of silver sulfide (Ag) was weighed2S) solid, i.e. 0.012mol silver sulfide (Ag)2S), copper thiosulfate [ Cu (S)2O3)n -2n+1]Activating the solution with 0.04mol and the molar ratio of the two to 0.3 with dilute nitric acid for 2.5min, performing solid-liquid separation to obtain activated silver sulfide, and adding the activated silver sulfide to copper thiosulfate [ Cu (S)2O3)n -2n+1]Obtaining a mixed solution from the solution, then placing the mixed solution into an ultrasonic generator after vacuumizing, carrying out ultrasonic strengthening reaction for 50min under the conditions of 50 ℃ and pH 8, filtering after the reaction is finished to obtain a blue gray silver copper sulfide compound solid, washing the solid with pure water, and then carrying out vacuum drying at 70 ℃ for 3 hours to obtain 2.43 g of silver copper sulfide (CuAgS) compound with a pore structure, wherein the purity of the obtained silver copper sulfide (CuAgS) is 99.0%, and the yield is 99.1%.
Example 5: 50mL of a sodium thiosulfate solution (4mol/L) was prepared, and then the sodium thiosulfate solution was slowly added to 50mL of a copper chloride solution (3.2mol/L), and the mixture was stirred and reacted at 60 ℃ and pH 9 for 20min to obtain copper thiosulfate [ Cu (S-S) ]2O3)n -2n+1]Solution 23.8g silver sulfide (Ag) was weighed2S) solid, i.e. 0.096mol silver sulfide (Ag)2S), copper thiosulfate [ Cu (S)2O3)n -2n+1]Activating the solution with 0.16mol and 0.6 mol ratio with dilute nitric acid for 3min, performing solid-liquid separation to obtain activated silver sulfide, and adding the activated silver sulfide to copper thiosulfate [ Cu (S)2O3)n -2n+1]Obtaining a mixed solution from the solution, then placing the mixed solution into an ultrasonic generator after vacuumizing, carrying out ultrasonic strengthening reaction for 60min under the conditions of 60 ℃ and pH value of 11, filtering after the reaction is finished to obtain a blue gray silver copper sulfide compound solid, washing the solid with pure water, and then carrying out vacuum drying for 3 hours at 70 ℃ to obtain 3.28 g of silver copper sulfide (CuAgS) compound with a pore structure, wherein the purity of the obtained silver copper sulfide (CuAgS) is 99.0%, and the yield is 99.0%.
While the present invention has been described in detail with reference to the specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (2)
1. A method for synthesizing silver copper sulfide is characterized in that soluble inorganic copper salt reacts with thiosulfate solution to generate copper thiosulfate, silver sulfide is activated by nitric acid and then added into the copper thiosulfate solution to obtain mixed solution, then the mixed solution is vacuumized to remove dissolved oxygen, and ultrasonic strengthening reaction is carried out to obtain the silver copper sulfide, wherein the method comprises the following specific steps:
(1) adding a thiosulfate solution into a soluble inorganic copper salt solution, and then stirring and reacting for 3-20 min at the temperature of 1-60 ℃ and under the condition that the pH is = 2-9 to prepare a copper thiosulfate solution, wherein the soluble inorganic copper salt is a copper sulfate, copper chloride or copper nitrate solution, and the molar concentration ratio of the soluble inorganic copper salt to the thiosulfate solution is 0.2-0.8;
(2) weighing silver sulfide, soaking the silver sulfide in a dilute nitric acid solution for 0.5-3 min to activate the silver sulfide, and then carrying out solid-liquid separation to obtain activated silver sulfide, wherein the molar ratio of the silver sulfide weighed in the step (2) to the copper thiosulfate solution is 0.1-0.6;
(3) adding activated silver sulfide into the copper thiosulfate solution prepared in the step (1) to obtain a mixed solution, vacuumizing the mixed solution, performing ultrasonic strengthening reaction for 10-60 min at the temperature of 1-60 ℃ and under the condition that the pH value is = 2-11, filtering after the reaction is finished to obtain a blue-gray silver-copper sulfide compound solid, washing the solid with pure water, and drying at the temperature of 40-70 ℃ to obtain the silver-copper sulfide with a porous structure.
2. The method of synthesizing silver copper sulfide of claim 1, wherein: the thiosulfate solution is sodium thiosulfate.
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| 无氨硫代硫酸盐法浸出硫化银矿的工艺和机理研究;崔毅琦;《中国博士学位论文全文数据库 工程科技I辑》;20120115;第38-85页 * |
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