CN111330601A - Preparation method of cuprous oxide composite material with core-shell structure - Google Patents
Preparation method of cuprous oxide composite material with core-shell structure Download PDFInfo
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- CN111330601A CN111330601A CN202010178376.7A CN202010178376A CN111330601A CN 111330601 A CN111330601 A CN 111330601A CN 202010178376 A CN202010178376 A CN 202010178376A CN 111330601 A CN111330601 A CN 111330601A
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- 239000002131 composite material Substances 0.000 title claims abstract description 57
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 57
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 54
- 239000011258 core-shell material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 103
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 100
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 64
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 55
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 230000032683 aging Effects 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 29
- 238000005303 weighing Methods 0.000 claims description 19
- 238000000967 suction filtration Methods 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 10
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 5
- 229940012189 methyl orange Drugs 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a cuprous oxide composite material with a core-shell structure, which is characterized by comprising the following steps: respectively preparing a copper sulfate solution with the concentration of 0.05-0.15 mol/L and a sodium sulfite solution with the concentration of 0.1-0.3 mol/L; adding a sodium sulfite solution into a copper sulfate solution under the condition of heating and stirring to obtain a mixed solution; aging the mixed solution, and then carrying out solid-liquid separation; washing and drying the solid after solid-liquid separation to obtain the cuprous oxide composite material with the core-shell structure; the copper sulfate solution and the sodium sulfite solution are mixed and reacted, and the reaction process is controlled, so that the novel cuprous oxide composite material [ Cu ] with the core-shell structure can be generated2O@Cu3(SO3)2·(H2O)2The chemical composition and the appearance of the composite material are different from those of the material obtained by taking copper sulfate and sodium sulfite as raw materials in the prior art, and the composite material does not need to continuously adjust the pH value in a reaction solution in the preparation process, so that the industrial production process of the composite material is reducedAnd (4) conditions.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of cuprous oxide composite photocatalytic materials, and particularly relates to a preparation method of a cuprous oxide composite material with a core-shell structure.
[ background of the invention ]
The cuprous oxide semiconductor has the band gap width of about 2eV, can effectively absorb visible light in sunlight and can effectively generate a photon-generated carrier under the irradiation of the visible light, has no toxicity, and has wide application prospects in the fields of solar cells, photocatalytic environmental pollutant degradation and the like, but the application prospect is greatly limited due to the lower photoelectric conversion efficiency. The catalytic performance of the heterogeneous solid catalytic material is mainly related to the surface composition, morphology, the number and activity of active sites and the like of the material. The cuprous oxide composite material can improve the photocatalytic capacity by changing the surface composition, morphology, surface area and the number of active sites, improving the active center and the like. Therefore, the cuprous oxide composite material makes up the defects of cuprous oxide, improves the photocatalytic performance of the cuprous oxide and widens the application field of the cuprous oxide.
Some methods for producing cuprous oxide related materials are proposed in the prior art, such as: 1. preparing the Guoshu by reducing copper sulfate with sodium sulfite; jiangxi chemical industry, 2008(1), 52-53; 2. preparing superfine cuprous oxide powder, Sichuan nonferrous metal, 1998(2), 16-18 by using Zhang Ping, Liuheng and Li Dacheng sodium sulfite reduction method; 3. new technology for preparing cuprous oxide powder by using sodium sulfite reduction method in Yanshenghu, Tang widing, Zuoxintao, Jinchuan science and technology, 2012(3) 27-29. And the like.
However, the above-mentioned technology requires strict control of the pH of the reaction solution during the preparation process, and the pH mentioned in the literature does not exceed 5.5 at most, i.e. the pH needs to be adjusted in real time during the experimental reaction process, which is a very difficult operation process, because the pH is constantly dynamically changed during the experimental reaction process, and the pH of the reaction solution must be monitored and continuously adjusted during the reaction process in real time, which is difficult to be realized for industrial production.
[ summary of the invention ]
The invention aims to provide a preparation method of a cuprous oxide composite material with a core-shell structure, which does not need to continuously adjust the pH value of a solution in the preparation process, reduces the process conditions of industrial production, and the cuprous oxide composite material with the core-shell structure is formed on the surface of material particles by [ Cu ]3(SO3)2·(H2O)2Mainly comprises [ Cu ] for catalysis3(SO3)2·(H2O)2Is dominating, [ Cu ]2O plays an auxiliary role.
The invention adopts the following technical scheme: a preparation method of a cuprous oxide composite material with a core-shell structure is characterized by comprising the following steps:
respectively preparing a copper sulfate solution with the concentration of 0.05-0.15 mol/L and a sodium sulfite solution with the concentration of 0.1-0.3 mol/L;
adding a sodium sulfite solution into a copper sulfate solution under the condition of heating and stirring to obtain a mixed solution;
aging the mixed solution, and then carrying out solid-liquid separation;
and washing and drying the solid after solid-liquid separation to obtain the cuprous oxide composite material with the core-shell structure.
Further, the mass concentration ratio of the copper sulfate solution to the sodium sulfite solution was 1: 2.
Further, the volume of the sodium sulfite solution is greater than the volume of the copper sulfate solution.
Further, when the sodium sulfite solution is added into the copper sulfate solution, the temperature of the copper sulfate solution is kept at 80-84 ℃.
Further, the specific method of solid-liquid separation is suction filtration.
Further, the washing and drying of the solid after the solid-liquid separation comprises:
the solid was washed 3 times with pure water, and the washed solid was dried at 100 ℃.
Further, the method comprises:
weighing CuSO4·5H2Dissolving O in pure water to prepare a copper sulfate solution with the concentration of 0.1 mol/L;
weighing Na2SO3Dissolving in pure water to prepare a sodium sulfite solution with the concentration of 0.2 mol/L;
adding a copper sulfate solution into a reaction container, mechanically stirring, preheating to 81 ℃, and keeping the reaction temperature;
adding a sodium sulfite solution into a copper sulfate solution, finishing adding within 30min, aging for 30min, carrying out suction filtration, washing for 3 times by using pure water, and drying at 100 ℃ to obtain the cuprous oxide composite material with the core-shell structure.
Further, the method comprises:
weighing CuSO4·5H2Dissolving O in pure water to prepare a copper sulfate solution with the concentration of 0.05 mol/L;
weighing Na2SO3Dissolving in pure water to prepare a sodium sulfite solution with the concentration of 0.1 mol/L;
adding a copper sulfate solution into a reaction vessel, mechanically stirring, preheating to 82 ℃ and maintaining the reaction temperature;
and adding a sodium sulfite solution into the copper sulfate solution, finishing adding within 30min, aging for 30min, carrying out suction filtration, washing for 3 times by using pure water, and drying at 100 ℃ to obtain the cuprous oxide composite material with the core-shell structure.
Further, the method comprises:
weighing CuSO4·5H2Dissolving O in pure water to prepare a copper sulfate solution with the concentration of 0.15 mol/L;
weighing Na2SO3Dissolving in pure water to prepare a sodium sulfite solution with the concentration of 0.3 mol/L;
adding a copper sulfate solution into a reaction container, mechanically stirring, preheating to 83-84 ℃, and keeping the reaction temperature;
adding a sodium sulfite solution into a copper sulfate solution, finishing adding within 30min, aging for 30min, carrying out suction filtration, washing for 3 times by using pure water, and drying at 100 ℃ to obtain the cuprous oxide composite material with the core-shell structure.
The invention has the beneficial effects that: the invention is prepared by mixing copper sulfateThe solution and sodium sulfite solution are mixed and reacted, and a novel cuprous oxide composite material [ Cu ] with a core-shell structure can be generated by controlling the reaction process2O@Cu3(SO3)2·(H2O)2The chemical composition and the appearance of the composite material are different from those of the materials obtained by taking copper sulfate and sodium sulfite as raw materials in the prior art, and the pH value of the reaction solution does not need to be continuously adjusted in the preparation process of the composite material, so that the industrial production process condition of the composite material is reduced.
[ description of the drawings ]
FIG. 1 shows a cuprous oxide composite [ Cu ] with a core-shell structure in an embodiment of the present invention2O@Cu3(SO3)2·(H2O)2The preparation process flow chart;
FIG. 2 shows a cuprous oxide composite [ Cu ] with a core-shell structure in an embodiment of the present invention2O@Cu3(SO3)2·(H2O)2XRD pattern of the sample;
FIG. 3 shows a cuprous oxide composite [ Cu ] with a core-shell structure in an embodiment of the present invention2O@Cu3(SO3)2·(H2O)2SEM images of sample dispersion;
FIG. 4 shows a cuprous oxide composite [ Cu ] with a core-shell structure in an embodiment of the present invention2O@Cu3(SO3)2·(H2O)2SEM core shell structure diagram of the sample;
FIG. 5 shows a cuprous oxide composite [ Cu ] with a core-shell structure in an embodiment of the present invention2O@Cu3(SO3)2·(H2O)2EDS energy spectrum of the sample;
FIG. 6 is a cuprous oxide composite [ Cu ] with a core-shell structure in an embodiment of the present invention2O@Cu3(SO3)2·(H2O)2A catalytic degradation spectrum of a cuprous oxide material obtained by reduction with glucose on methyl orange under visible light.
[ detailed description ] embodiments
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention discloses a preparation method of a cuprous oxide composite material with a core-shell structure, which comprises the following steps as shown in figure 1:
respectively preparing a copper sulfate solution with the concentration of 0.05-0.15 mol/L and a sodium sulfite solution with the concentration of 0.1-0.3 mol/L; adding a sodium sulfite solution into a copper sulfate solution under the condition of heating and stirring to obtain a mixed solution; aging the mixed solution, and then carrying out solid-liquid separation; and washing and drying the solid after solid-liquid separation to obtain the cuprous oxide composite material with the core-shell structure.
The copper sulfate solution and the sodium sulfite solution are mixed and reacted, and the reaction process is controlled, so that the novel cuprous oxide composite material [ Cu ] with the core-shell structure can be generated2O@Cu3(SO3)2·(H2O)2The chemical composition and the appearance of the composite material are different from those of the materials obtained by taking copper sulfate and sodium sulfite as raw materials in the prior art, and the pH value of the reaction solution does not need to be continuously adjusted in the preparation process of the composite material, so that the industrial production process condition of the composite material is reduced.
In the invention, the concentration of the copper sulfate solution and the sodium sulfite solution is not easy to be too large, and the particles are easy to agglomerate when the concentration is too large, so that the cuprous oxide composite material [ Cu ] with a porous structure is formed2O@Cu3(SO3)2·(H2O)2Cuprous oxide composite [ Cu ] with difficulty in forming core-shell structure2O@Cu3(SO3)2·(H2O)2】。
In the present invention, the mass concentration of the copper sulfate solution and the sodium sulfite solution was the same at 1: 2. The volume of the sodium sulfite solution is greater than the volume of the copper sulfate solution (the preferred ratio of the volume of sodium sulfite solution consumed to the volume of copper sulfate solution is 3:2) and the rate of sodium sulfite addition is slower in the present invention, so that there is an excess of copper sulfate in solution, the solution is in an acidic environment and the pH is less than 4.During the reaction, cuprous oxide particles are firstly generated, the pH value is gradually increased along with the addition of sodium sulfite solution, and Cu is generated after the pH value is more than 53(SO3)2·(H2O)2Newly formed Cu3(SO3)2·(H2O)2Adsorption to Cu due to small particles with large surface energy2The surface of the O particles is reduced to form the composite material [ Cu ] with a core-shell structure2O@Cu3(SO3)2·(H2O)2】。
Specifically, when the sodium sulfite solution is added into the copper sulfate solution, the temperature of the copper sulfate solution is kept at 80-84 ℃. The specific method of solid-liquid separation is selected as suction filtration, and the suction filtration mode is more suitable for large-scale industrial application and can improve the yield.
As a specific embodiment, the following method is adopted for washing and drying the solid after solid-liquid separation:
the solid was washed 3 times with pure water, and the washed solid was dried at 100 ℃.
Composite material [ Cu ] with core-shell structure obtained by using method2O@Cu3(SO3)2·(H2O)2The particle size is large, the washing is easy, the loss of the washing is avoided, and the industrialization is facilitated. The whole process is simple to operate, the product is easy to wash, raw materials can be utilized to the maximum degree, the raw materials are saved, the reaction end point is easy to control, meanwhile, the pH value of the solution does not need to be considered and controlled in the whole process, the process difficulty is greatly reduced, other raw materials are not introduced, the environmental pollution is reduced, and the productivity is effectively improved.
Example 1:
weighing 12.5g of CuSO4·5H2Dissolving O in pure water to obtain 500mL solution (copper sulfate concentration is 0.1mol/L), weighing 18.9g Na2SO3Dissolving in pure water to obtain 750mL solution (sodium sulfite concentration is 0.2mol/L), adding copper sulfate solution into 2L beaker, mechanically stirring, preheating to 81 deg.C, maintaining the reaction temperature, adding sodium sulfite solution within 30min, aging for 30min, vacuum filtering, and adding pure waterWashing for 3 times, and drying at 100 ℃ to obtain the product.
Example 2:
6.25g of CuSO are weighed out4·5H2Dissolving O in pure water to obtain 500mL solution (copper sulfate concentration is 0.05mol/L), weighing 9.5g Na2SO3Dissolving in pure water to prepare 750mL solution (the concentration of sodium sulfite is 0.1mol/L), adding copper sulfate solution into a beaker of 2L, mechanically stirring, preheating to 82 ℃ and keeping the reaction temperature, adding sodium sulfite solution, finishing adding within 30min, aging for 30min, performing suction filtration, washing with pure water for 3 times, and drying at 100 ℃ to obtain the product.
Example 3:
weighing 18.8g of CuSO4·5H2Dissolving O in pure water to obtain 500mL solution (copper sulfate concentration is 0.15mol/L), weighing 28.5g Na2SO3Dissolving in pure water to prepare 750mL solution (the concentration of sodium sulfite is 0.3mol/L), adding copper sulfate solution into a 2L beaker, mechanically stirring, preheating to 83 ℃, keeping the reaction temperature, adding the sodium sulfite solution, finishing adding within 30min, aging for 30min, performing suction filtration, washing with pure water for 3 times, and drying at 100 ℃ to obtain the product.
Example 4:
weighing 18.8g of CuSO4·5H2Dissolving O in pure water to obtain 500mL solution (copper sulfate concentration is 0.15mol/L), weighing 28.5g Na2SO3Dissolving in pure water to prepare 750mL solution (the concentration of sodium sulfite is 0.3mol/L), adding copper sulfate solution into a 2L beaker, mechanically stirring, preheating to 84 ℃, keeping the reaction temperature, adding the sodium sulfite solution, finishing adding within 25min, aging for 30min, performing suction filtration, washing for 4 times by pure water, and drying at 105 ℃ to obtain the product.
Referring to FIG. 2, which is an XRD pattern of the best mode 1 of the present invention, the data of the peaks on the left side, which is found from the peak positions showing diffraction peaks in the pattern, are identical to those of PDF card No. 11-0240, which is classified as Cu, in comparison with PDF card3(SO3)2·(H2O)2Has diffraction peaks having crystal plane indices of (-101), (002) and (112), respectively.
Compare PDF card, peak data on right side with number of PDF card numbers 99-0041Consistently, can be attributed to cubic phase Cu2The diffraction peaks and the plane indices of O are (111), (200) and (220), respectively. Thus, it was confirmed that the composition of the sample obtained in this example was Cu2O@Cu3(SO3)2·(H2O)2The composite material of (1).
Referring to fig. 3, which is an SEM image of the dispersibility of the sample in example 1 of the present invention, it can be seen that the sample is 2 μm spherical particles and their agglomerates are less than 10 μm.
Referring to fig. 4, which is a structure diagram of an SEM core-shell structure of a sample in example 1 of the present invention, it can be seen that the sample is a core-shell structure material.
As shown in FIG. 5, the core in FIG. 5a is composed of two elements, copper and oxygen; in FIG. 5b, the shell is composed of Cu, S and O, further demonstrating that the composition of the sample obtained by the present invention is Cu2O@Cu3(SO3)2·(H2O)2The composite material having a core-shell structure of (1).
The invention not only solves the technical problem that the process conditions are difficult to control in the implementation process of the technology, but also prepares the novel cuprous oxide composite material with the core-shell structure, which is easy to industrialize and has excellent photocatalytic performance. The cuprous oxide composite material with the core-shell structure is composed of [ Cu ] on the surface of material particles3(SO3)2·(H2O)2[ Cu ] mainly (as can be confirmed from FIG. 2), and is catalyzed by3(SO3)2·(H2O)2Is dominating, [ Cu ]2O plays an auxiliary role. The method has the advantages of simple process, convenient operation, easily obtained raw materials, simple process flow and easy washing of the obtained product.
Through a methyl orange visible light photocatalytic degradation experiment under the same conditions, as shown in fig. 6, the cuprous oxide composite material [ Cu ] with the core-shell structure obtained in the embodiment of the invention2O@Cu3(SO3)2·(H2O)2The photocatalytic degradation rate of methyl orange reaches 91.2 percent when the material is illuminated for 180min, and the photocatalysis of methyl orange is realized when cuprous oxide material obtained by reducing fresh copper hydroxide by glucose is illuminated for 180minThe degradation rate is only 67.7%.
Therefore, the cuprous oxide composite material [ Cu ] with the core-shell structure obtained in the embodiment of the invention2O@Cu3(SO3)2·(H2O)2The capacity of degrading methyl orange by photocatalysis is obviously superior to that of a common cuprous oxide material.
Claims (9)
1. A preparation method of a cuprous oxide composite material with a core-shell structure is characterized by comprising the following steps:
respectively preparing a copper sulfate solution with the concentration of 0.05-0.15 mol/L and a sodium sulfite solution with the concentration of 0.1-0.3 mol/L;
adding the sodium sulfite solution into the copper sulfate solution under the condition of heating and stirring to obtain a mixed solution;
aging the mixed solution and then carrying out solid-liquid separation;
and washing and drying the solid after solid-liquid separation to obtain the cuprous oxide composite material with the core-shell structure.
2. The method for preparing cuprous oxide composite material with core-shell structure according to claim 1, wherein the mass concentration ratio of copper sulfate solution to sodium sulfite solution is 1: 2.
3. The method of claim 3, wherein a volume of the sodium sulfite solution is greater than a volume of the copper sulfate solution.
4. The method for preparing cuprous oxide composite material with core-shell structure according to claim 2 or 3, wherein when said sodium sulfite solution is added to said copper sulfate solution, the temperature of said copper sulfate solution is maintained at 80-84 ℃.
5. The preparation method of cuprous oxide composite material with core-shell structure according to claim 4, wherein the specific method of solid-liquid separation is suction filtration.
6. The preparation method of the cuprous oxide composite material with the core-shell structure, according to claim 2 or 3, wherein the step of washing and drying the solid after the solid-liquid separation comprises the steps of:
the solid was washed 3 times with pure water, and the washed solid was dried at 100 ℃.
7. The method for preparing the cuprous oxide composite material with the core-shell structure according to claim 1, wherein the method comprises:
weighing CuSO4·5H2Dissolving O in pure water to prepare a copper sulfate solution with the concentration of 0.1 mol/L;
weighing Na2SO3Dissolving in pure water to prepare a sodium sulfite solution with the concentration of 0.2 mol/L;
adding the copper sulfate solution into a reaction vessel, mechanically stirring, preheating to 81 ℃ and maintaining the reaction temperature;
and adding the sodium sulfite solution into the copper sulfate solution, finishing adding within 30min, aging for 30min, performing suction filtration, washing for 3 times by using pure water, and drying at 100 ℃ to obtain the cuprous oxide composite material with the core-shell structure.
8. The method for preparing the cuprous oxide composite material with the core-shell structure according to claim 1, wherein the method comprises:
weighing CuSO4·5H2Dissolving O in pure water to prepare a copper sulfate solution with the concentration of 0.05 mol/L;
weighing Na2SO3Dissolving in pure water to prepare a sodium sulfite solution with the concentration of 0.1 mol/L;
adding the copper sulfate solution into a reaction vessel, mechanically stirring, preheating to 82 ℃ and maintaining the reaction temperature;
and adding the sodium sulfite solution into the copper sulfate solution, finishing adding within 30min, aging for 30min, performing suction filtration, washing for 3 times by using pure water, and drying at 100 ℃ to obtain the cuprous oxide composite material with the core-shell structure.
9. The preparation method of the cuprous oxide composite material with the core-shell structure, according to claim 1, wherein the method comprises:
weighing CuSO4·5H2Dissolving O in pure water to prepare a copper sulfate solution with the concentration of 0.15 mol/L;
weighing Na2SO3Dissolving in pure water to prepare a sodium sulfite solution with the concentration of 0.3 mol/L;
adding the copper sulfate solution into a reaction container, mechanically stirring, preheating to 83-84 ℃, and keeping the reaction temperature;
and adding the sodium sulfite solution into the copper sulfate solution, finishing adding within 30min, aging for 30min, performing suction filtration, washing for 3 times by using pure water, and drying at 100 ℃ to obtain the cuprous oxide composite material with the core-shell structure.
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| CN110227457A (en) * | 2019-06-26 | 2019-09-13 | 成都理工大学 | A kind of preparation method of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst |
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| CN106673049A (en) * | 2017-01-18 | 2017-05-17 | 西安工业大学 | Preparation method of porous-graded sphere activated copper oxide powder |
| CN108609645A (en) * | 2018-08-06 | 2018-10-02 | 金川集团股份有限公司 | A method of producing cuprous oxide with copper-bath |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116924488A (en) * | 2023-09-18 | 2023-10-24 | 浙江帕瓦新能源股份有限公司 | Precursor of sodium ion battery anode material, preparation method and application thereof |
| CN116924488B (en) * | 2023-09-18 | 2023-12-22 | 浙江帕瓦新能源股份有限公司 | Precursor of sodium ion battery anode material, preparation method and application thereof |
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