CN111330600A - Preparation method of cuprous oxide composite material with porous structure - Google Patents

Abstract

The invention discloses a preparation method of a cuprous oxide composite material with a porous structure. The copper sulfate solution and the sodium sulfite solution are respectively prepared with a concentration of 0.15-0.3 mol/L, and the copper sulfate solution is added to the sodium sulfite solution under the condition of heating and stirring. In the process, a mixed solution is obtained; after the mixed solution is aged, solid-liquid separation is performed; the solid after solid-liquid separation is washed and dried to obtain a cuprous oxide composite material with a porous structure; the present invention mixes the copper sulfate solution and the sodium sulfite solution. By controlling the reaction process, a new type of cuprous oxide composite material [Cu ₂ O@Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ] with a porous structure can be generated. The appearance is different from the materials obtained by using 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 of the reaction solution during the preparation process, which reduces the industrial production process conditions of the composite material.

Description

A kind of preparation method of porous structure cuprous oxide composite material

【Technical field】

The invention belongs to the technical field of cuprous oxide composite photocatalytic materials, and in particular relates to a preparation method of a porous structure cuprous oxide composite material.

【Background technique】

The band gap width of cuprous oxide semiconductor is about 2eV, which can effectively absorb visible light in sunlight and can effectively generate photogenerated carriers under the irradiation of visible light. The field has broad application prospects, but its low photoelectric conversion efficiency greatly limits its application prospects.

Cuprous oxide composites can well improve their photocatalytic ability. Some methods for preparing cuprous oxide composite materials are proposed in the existing documents, such as: 1. Guo Ping, Guo Xuan. Preparation of copper sulfate by reduction of sodium sulfite; Jiangxi Chemical Industry, 2008(1), 52-53. 2. Zhang Ping, Liu Heng, Li Dacheng. Preparation of ultrafine cuprous oxide powder by sodium sulfite reduction method, Sichuan Nonferrous Metals, 1998(2), 16-18. 3. Yan Shenghu, Tang Kuanzhen, Zhang Xintao. New technology for preparing cuprous oxide powder by sodium sulfite reduction method, Jinchuan Science and Technology, 2012(3)27-29. ]Wait.

The catalytic performance of heterogeneous solid catalytic materials is mainly related to the surface composition, morphology, number and activity of active sites. Cuprous oxide composites can improve their photocatalytic ability by changing their surface composition, morphology, surface area and number of active sites and improving active centers. Therefore, the cuprous oxide composite material makes up for the defects of cuprous oxide, improves the photocatalytic performance of cuprous oxide, and broadens the application field of cuprous oxide.

However, the pH value of the reaction solution must be strictly controlled in the preparation process of the above-mentioned technology, and the pH value mentioned in the literature does not exceed 5.5 at the highest, that is, the pH value needs to be adjusted in real time during the experimental reaction process. However, this is a very difficult task. Large operation process, because in the process of the experimental reaction, the pH is always changing dynamically, and the pH value of the reaction solution must be tracked and monitored in real time and continuously adjusted during the reaction process, which is difficult to achieve for industrial production.

[Content of the invention]

The purpose of the present invention is to provide a preparation method of a porous structure cuprous oxide composite material, which does not need to continuously adjust the pH value of the solution during the preparation process, reduces the technological conditions of industrial production, and the surface of the prepared composite material particles is composed of [Cu ₂ O] and [Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ] are composed together. During catalysis, due to the synergy between [Cu ₂ O] and [Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ] The photocatalytic performance of cuprous oxide was improved.

The present invention adopts the following technical scheme: a preparation method of a porous structure cuprous oxide composite material, comprising:

Prepare copper sulfate solution and sodium sulfite solution with concentrations of 0.15-0.3mol/L respectively;

Under heating and stirring conditions, the copper sulfate solution is added to the sodium sulfite solution to obtain a mixed solution;

After the mixed solution is aged, solid-liquid separation is carried out;

The solid after solid-liquid separation is washed and dried to obtain a cuprous oxide composite material with a porous structure.

Further, the amount and concentration of substances in the copper sulfate solution and the sodium sulfite solution are the same.

Further, the volume of the sodium sulfite solution is greater than the volume of the copper sulfate solution.

Further, when the copper sulfate solution is added to the sodium sulfite solution, the temperature of the sodium sulfite solution is kept at 80-84°C.

Further, the specific method of solid-liquid separation is suction filtration.

Further, washing and drying the solid after solid-liquid separation includes:

The solid was washed three times with pure water, and the washed solid was dried at 100°C.

Further, the method includes:

Weigh CuSO ₄ ·5H ₂ O and dissolve it in pure water to prepare a copper sulfate solution with a concentration of 0.3mol/L;

Weigh Na ₂ SO ₃ and dissolve it in pure water to prepare a sodium sulfite solution with a concentration of 0.3mol/L;

The sodium sulfite solution was added to the reaction vessel, stirred mechanically, preheated to 81°C and kept the reaction temperature;

The copper sulfate solution was added to the sodium sulfite solution, the addition was completed within 30 minutes, the mixture was aged for 30 minutes, suction filtered, washed three times with pure water, and dried at 100° C. to obtain a cuprous oxide composite material with a porous structure.

Further, the method includes:

Weigh CuSO ₄ ·5H ₂ O and dissolve it in pure water to prepare a copper sulfate solution with a concentration of 0.2mol/L;

Weigh Na ₂ SO ₃ and dissolve it in pure water to prepare a sodium sulfite solution with a concentration of 0.2mol/L;

The sodium sulfite solution was added to the reaction vessel, stirred mechanically, preheated to 82°C and kept the reaction temperature;

The copper sulfate solution was added to the sodium sulfite solution, the addition was completed within 30 minutes, the mixture was aged for 30 minutes, suction filtered, washed three times with pure water, and dried at 100° C. to obtain a cuprous oxide composite material with a porous structure.

Further, the method includes:

Weigh CuSO ₄ ·5H ₂ O and dissolve it in pure water to prepare a copper sulfate solution with a concentration of 0.15mol/L;

Weigh Na ₂ SO ₃ and dissolve it in pure water to prepare a sodium sulfite solution with a concentration of 0.15mol/L;

The sodium sulfite solution was added to the reaction vessel, stirred mechanically, preheated to 83-84°C and kept the reaction temperature;

The copper sulfate solution was added to the sodium sulfite solution, the addition was completed within 30 minutes, the mixture was aged for 30 minutes, suction filtered, washed three times with pure water, and dried at 100° C. to obtain a cuprous oxide composite material with a porous structure.

The beneficial effects of the present invention are as follows: the present invention can generate a new type of cuprous oxide composite material with porous structure [Cu ₂ O@Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ], the chemical composition and morphology of the composite material are different from those obtained by using copper sulfate and sodium sulfite as raw materials in the prior art, and the composite material does not need to continuously adjust the reaction during the preparation process. The pH value in the solution reduces the industrial production process conditions of the composite material.

【Description of drawings】

1 is a flow chart of the preparation process of the cuprous oxide composite material [Cu ₂ O@Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ] with a porous structure in an embodiment of the present invention;

2 is an XRD pattern of a cuprous oxide composite material [Cu ₂ O@Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ] sample with a porous structure in an embodiment of the present invention;

3 is a SEM image of the dispersibility of a cuprous oxide composite material with a porous structure [Cu ₂ O@Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ] in an embodiment of the present invention;

FIG. 4 is a SEM porous structure diagram of a cuprous oxide composite material [Cu ₂ O@Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ] sample with a porous structure in an embodiment of the present invention.

Fig. 5 shows the comparison between the cuprous oxide composite material with porous structure [Cu ₂ O@Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ] and the cuprous oxide material obtained by glucose reduction under visible light in the embodiment of the present invention Catalytic degradation profile of methyl orange.

【Detailed ways】

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 porous structure, as shown in FIG. 1 , comprising the following steps:

Prepare a copper sulfate solution and a sodium sulfite solution with a concentration of 0.15-0.3 mol/L respectively; add the copper sulfate solution to the sodium sulfite solution under heating and stirring conditions to obtain a mixed solution; age the mixed solution and carry out solid-liquid separation; The solid after solid-liquid separation is washed and dried to obtain a cuprous oxide composite material with a porous structure.

In the present invention, a new type of cuprous oxide composite material [Cu ₂ O@Cu ₃ (SO ₃ ) ₂ ·(H ₂ O ) can be generated by controlling the reaction process by mixing the copper sulfate solution and the sodium sulfite solution ) ₂ ], the chemical composition and morphology of the composite material are different from those obtained by using 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 the reaction solution during the preparation process, reducing The industrial production process conditions of the composite material are described.

In the present invention, the copper sulfate solution and the sodium sulfite solution have the same substance concentration. The volume of the sodium sulfite solution is greater than the volume of the copper sulfate solution (the volume ratio of the sodium sulfite solution and the copper sulfate solution is preferably 1.5:1), and in the present invention, the adding speed of the copper sulfate is slower, so, the sodium sulfite in the solution is greatly excessive, and a part of It is directly reduced to cuprous oxide, and the other part is reduced to a complex structure. The particles are relatively small and agglomerate with each other.

In addition, due to the excess of sodium sulfite, the speed of adding the copper sulfate solution is slow, so that when the copper sulfate solution is added to the sodium sulfite solution, it is ensured that the solution is weakly alkaline. The reaction is carried out in a weak alkaline environment, part of the Cu ²⁺ ions is reduced to directly form cuprous oxide, and the other part is partially reduced to Cu ^{2+ ions and [SO 3 ] 2- to form Cu with unreduced Cu 2+ ions} and [SO ₃ ] ^2- ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ , Cu ₂ O and Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ formed at the same time in the solution have larger surface, and can adsorb and agglomerate with each other. In order to reduce its surface energy, a composite material with porous structure [Cu ₂ O@Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ] is finally formed.

Specifically, when the copper sulfate solution is added to the sodium sulfite solution, the temperature of the sodium sulfite solution is kept at 80-84°C. The specific method of solid-liquid separation is suction filtration, which is more suitable for large-scale industrial applications and can increase production.

As a specific embodiment, the solid after solid-liquid separation is washed and dried in the following manner:

The solid was washed three times with pure water, and the washed solid was dried at 100°C.

The composite material with porous structure [Cu ₂ O@Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ] obtained by the present invention has larger particle size, is easy to wash and has no loss in washing, and is beneficial to industrialization. The whole process is simple to operate, can maximize the use of raw materials, save raw materials, and the reaction end point is easy to control. At the same time, the entire process does not need to consider the pH value of the solution, which greatly reduces the difficulty of the process, and no other raw materials are introduced, reducing environmental pollution. , effectively increase production capacity.

Example 1:

37.6 g of CuSO ₄ ·5H ₂ O was weighed and dissolved in pure water to prepare a 500 mL solution (the concentration of copper sulfate was 0.3 mol/L).

Weigh 28.7g Na ₂ SO ₃ and dissolve it in pure water to make 750mL solution (sodium sulfite concentration is 0.3mol/L).

Add the sodium sulfite solution into a 2L beaker, stir mechanically, preheat to 80°C and keep the reaction temperature, add copper sulfate solution, add it within 30min, age for 30min, suction filter, wash with pure water 3 times, 100 drying at ℃ to obtain a cuprous oxide composite material with a porous structure.

Example 2:

Weigh 37.6g CuSO ₄ ·5H ₂ O and dissolve it in pure water to prepare 500mL copper sulfate solution with a concentration of 0.3mol/L;

Weigh 28.7g Na ₂ SO ₃ and dissolve it in pure water to prepare 750 mL of sodium sulfite solution with a concentration of 0.3 mol/L;

Add sodium sulfite solution to a 2L beaker, stir mechanically, preheat to 81°C and keep the reaction temperature;

The copper sulfate solution was added to the sodium sulfite solution, the addition was completed within 40 minutes, the mixture was aged for 25 minutes, suction filtered, washed with pure water 4 times, and dried at 95° C. to obtain a cuprous oxide composite material with a porous structure.

Example 3:

Weigh 25.1g CuSO4·5H2O and dissolve it in pure water to make 500mL solution (the concentration of copper sulfate is 0.2mol/L).

Weigh 19.1g Na2SO3 and dissolve it in pure water to make 750mL solution (sodium sulfite concentration is 0.2mol/L).

Add the sodium sulfite solution into a 2L beaker, stir mechanically, preheat to 82°C and keep the reaction temperature, add copper sulfate solution, add it within 30min, age for 30min, suction filter, wash with pure water 3 times, 100 drying at ℃ to obtain a cuprous oxide composite material with a porous structure.

Example 4:

Weigh 18.8g CuSO ₄ ·5H ₂ O and dissolve it in pure water to make 500mL solution (the concentration of copper sulfate is 0.15mol/L);

Weigh 14.3g Na ₂ SO ₃ and dissolve it in pure water to make 750mL solution (sodium sulfite concentration is 0.15mol/L);

Add the sodium sulfite solution to a 2L beaker, stir mechanically, preheat to 83°C and keep the reaction temperature, add copper sulfate solution, add it within 30min, age for 30min, suction filter, wash with pure water 3 times, 100 drying at ℃ to obtain a cuprous oxide composite material with a porous structure.

Example 5:

Weigh 18.8g CuSO ₄ ·5H ₂ O and dissolve it in pure water to prepare 500mL copper sulfate solution with a concentration of 0.15mol/L;

Weigh 14.3g Na ₂ SO ₃ and dissolve it in pure water to prepare 750mL of sodium sulfite solution with a concentration of 0.15mol/L;

Add sodium sulfite solution to a 2L beaker, stir mechanically, preheat to 84°C and keep the reaction temperature;

The copper sulfate solution was added to the sodium sulfite solution, the addition was completed within 30 minutes, the mixture was aged for 30 minutes, suction filtered, washed three times with pure water, and dried at 100° C. to obtain a cuprous oxide composite material with a porous structure.

Referring to Figure 2, this is the XRD pattern of the preferred embodiment 4 of the present invention. According to the peak positions of the diffraction peaks displayed in the pattern, it can be seen from the comparison with the PDF card that the peak data on the left is consistent with the data of the PDF card number 11-0240, which can be attributed Based on the diffraction peaks of Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ , the crystal plane indices are (-101), (002) and (112), respectively.

Compared with the PDF card, the peak data on the right is consistent with the data of the PDF card number 99-0041, which can be attributed to the diffraction peaks of cubic Cu ₂ O, and the crystal plane indices are (111), (200) and (220), respectively. Thus, it was confirmed that the composition of the sample obtained in this example was a composite material of Cu ₂ O@Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ .

Referring to FIG. 3 , it is an SEM image of the dispersibility of the sample in Example 4 of the present invention, and it can be seen from the figure that the sample is agglomerated into agglomerates smaller than 25 μm. Referring to FIG. 4 , which is a SEM porous structure diagram of the sample in Example 4 of the present invention, it can be seen from the figure that the sample is a porous structure material.

The invention not only reduces the technical problem that the process conditions are difficult to control during the implementation of the above technology, but also prepares a novel porous structure cuprous oxide composite material with excellent photocatalytic performance that is easy to industrialize, improves the photocatalytic performance of cuprous oxide, and simultaneously , Due to the participation of sulfite, the photocatalytic performance of the cuprous oxide material is enhanced, and the content of copper in the catalytic material is greatly reduced, saving costs. The surface of the porous structure cuprous oxide composite material particles involved in the present invention is composed of [Cu ₂ O] and [Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ] together. During catalysis, [Cu 2 O] and [Cu ₂ O] and The synergistic effect of [Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ] (as can be seen in Figure 2 ) improves the photocatalytic performance of cuprous oxide. The invention has simple process, convenient operation, easy-to-obtain raw material sources, simple technological process, and easy washing of the obtained product.

Through the visible light photocatalytic degradation experiment of methyl orange under the same conditions, as shown in FIG. 5 , the cuprous oxide composite material with porous structure [Cu ₂ O@Cu ₃ (SO ₃ ) ₂ ·( H ₂ O) ₂ ] photocatalytic degradation rate of methyl orange reached 82.6% under 180min illumination, while the photocatalytic degradation rate of methyl orange was only 67.7% for cuprous oxide material obtained by reducing fresh copper hydroxide with glucose under 180min illumination. Therefore, the ability of photocatalytic degradation of methyl orange of the cuprous oxide composite material with porous structure [Cu ₂ O@Cu ₃ (SO ₃ ) ₂ ·(H ₂ O) ₂ ] obtained in the examples of the present invention is obviously better than that of Common cuprous oxide material.

Claims (9)

1. a preparation method of the cuprous oxide composite material of porous structure, is characterized in that, comprises: Prepare copper sulfate solution and sodium sulfite solution with concentrations of 0.15-0.3mol/L respectively; Under heating and stirring conditions, the copper sulfate solution is added to the sodium sulfite solution to obtain a mixed solution; Carry out solid-liquid separation after ageing the mixed solution; The solid after solid-liquid separation is washed and dried to obtain a cuprous oxide composite material with a porous structure. 2 . The method for preparing a cuprous oxide composite material with a porous structure as claimed in claim 1 , wherein the copper sulfate solution and the sodium sulfite solution have the same substance concentration. 3 . 3 . The method for preparing a porous-structured cuprous oxide composite material according to claim 3 , wherein the volume of the sodium sulfite solution is greater than the volume of the copper sulfate solution. 4 . 4. the preparation method of the cuprous oxide composite material of a kind of porous structure as claimed in claim 2 or 3, is characterized in that, when described cupric sulfate solution joins in described sodium sulfite solution, keeps described sodium sulfite solution The temperature is 80-84 ℃. 5 . The method for preparing a porous-structured cuprous oxide composite material according to claim 4 , wherein the specific method for the solid-liquid separation is suction filtration. 6 . 6. The preparation method of a porous-structured cuprous oxide composite material according to claim 2 or 3, wherein washing and drying the solid after the solid-liquid separation comprises: The solid was washed three times with pure water, and the washed solid was dried at 100°C. 7. The preparation method of a porous-structured cuprous oxide composite material according to claim 1, wherein the method comprises: Weigh CuSO ₄ ·5H ₂ O and dissolve it in pure water to prepare a copper sulfate solution with a concentration of 0.3mol/L; Weigh Na ₂ SO ₃ and dissolve it in pure water to prepare a sodium sulfite solution with a concentration of 0.3mol/L; The sodium sulfite solution was added to the reaction vessel, stirred mechanically, preheated to 81°C and maintained at the reaction temperature; The copper sulfate solution was added to the sodium sulfite solution, and the addition was completed within 30 minutes, followed by aging for 30 minutes, suction filtration, washing with pure water three times, and drying at 100° C. to obtain a cuprous oxide composite material with a porous structure. 8. The method for preparing a porous-structured cuprous oxide composite material according to claim 1, wherein the method comprises: Weigh CuSO4·5H2O and dissolve it in pure water to prepare a copper sulfate solution with a concentration of 0.2mol/L; Weigh Na ₂ SO ₃ and dissolve it in pure water to prepare a sodium sulfite solution with a concentration of 0.2mol/L; The sodium sulfite solution was added to the reaction vessel, stirred mechanically, preheated to 82°C and maintained at the reaction temperature; The copper sulfate solution was added to the sodium sulfite solution, and the addition was completed within 30 minutes, followed by aging for 30 minutes, suction filtration, washing with pure water three times, and drying at 100° C. to obtain a cuprous oxide composite material with a porous structure. 9. The preparation method of a porous-structured cuprous oxide composite material according to claim 1, wherein the method comprises: Weigh CuSO ₄ ·5H ₂ O and dissolve it in pure water to prepare a copper sulfate solution with a concentration of 0.15mol/L; Weigh Na ₂ SO ₃ and dissolve it in pure water to prepare a sodium sulfite solution with a concentration of 0.15mol/L; adding the sodium sulfite solution into the reaction vessel, stirring mechanically, preheating to 83-84°C and maintaining the reaction temperature; The copper sulfate solution was added to the sodium sulfite solution, added within 30 minutes, aged for 30 minutes, suction filtered, washed three times with pure water, and dried at 100° C. to obtain a cuprous oxide composite material with a porous structure.

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