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CN108079993B - Preparation method of ferrous oxide/cuprous oxide nano composite material - Google Patents

Preparation method of ferrous oxide/cuprous oxide nano composite material Download PDF

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CN108079993B
CN108079993B CN201711444507.6A CN201711444507A CN108079993B CN 108079993 B CN108079993 B CN 108079993B CN 201711444507 A CN201711444507 A CN 201711444507A CN 108079993 B CN108079993 B CN 108079993B
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copper
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cuprous oxide
oxide
composite material
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CN108079993A (en
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张建
刘国栋
吴思奇
毕旺杰
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Shandong Copolymer Silicone Technology Research Institute Co ltd
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Jining University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
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    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • C02F2305/026Fenton's reagent

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Abstract

本发明氧化亚铁/氧化亚铜纳米复合材料的制备方法,属于无机材料制备技术领域,将铁盐溶解于水中,得到铁盐溶液;将金属铜加入到上述铁盐溶液中,持续搅拌5‑30min;将上述溶液置于反应釜内,80‑150℃的温度下反应0.5‑8h;将步骤3)所得产物洗涤剂洗涤1‑3次,再在0‑120℃温度下干燥2‑12h。本发明利用简单的一步低温水热方法,不添加有机溶剂,一步即可制备氧化亚铁/氧化亚铜复合纳米材料,颗粒及组成均可控,成本低廉,解决了复合材料制备工艺复杂和成本高的问题;制备方法简便,对环境无害,适于大规模工业化生产,应用前景广泛;所得产品性能优异,作为Fenton反应试剂,可在中性pH值、常温和太阳光下展现出优异的催化性能,催化活性增强,结构稳定性提高。

Figure 201711444507

The preparation method of the ferrous oxide/cuprous oxide nanocomposite material of the present invention belongs to the technical field of inorganic material preparation. The iron salt is dissolved in water to obtain an iron salt solution; the metallic copper is added to the iron salt solution, and the stirring is continued for 5-5 30min; place the above solution in a reactor, react at a temperature of 80-150°C for 0.5-8h; wash the product obtained in step 3) with a detergent for 1-3 times, and then dry it at a temperature of 0-120°C for 2-12h. The invention utilizes a simple one-step low-temperature hydrothermal method without adding organic solvent, and can prepare ferrous oxide/cuprous oxide composite nanomaterials in one step, the particles and the composition are controllable, and the cost is low, and the complex preparation process and cost of the composite material are solved. high problem; the preparation method is simple, harmless to the environment, suitable for large-scale industrial production, and has wide application prospects; the obtained product has excellent performance, and as a Fenton reaction reagent, it can show excellent performance at neutral pH value, room temperature and sunlight. Catalytic performance, enhanced catalytic activity, and improved structural stability.

Figure 201711444507

Description

Preparation method of ferrous oxide/cuprous oxide nano composite material
Technical Field
The invention belongs to the technical field of inorganic material preparation, and particularly relates to a preparation method of a ferrous oxide/cuprous oxide nano composite material.
Background
With the rapid development of human society, the shortage of energy and environmental pollution threaten the survival of human beings more and more. At present, organic wastewater has the defects of difficult biodegradation, high toxicity and difficult degradation by a traditional method. After long-term efforts, many methods for purifying sewage have been established, such as physical adsorption, chemical reaction and biodegradation, but the treatment of organic pollutants in sewage still has the disadvantages of incomplete degradation, high catalyst cost, large dosage, high cost and the like. With the enhancement of environmental protection in the world and countries, there is a need to explore efficient, harmless and novel catalyst materials.
Among a plurality of catalyst materials, a photocatalyst for degrading organic pollution in water by utilizing sunlight becomes an effective method and is more and more paid attention to by people. The light Fenton reaction is one of advanced oxidation technologies, light energy is used as drive, active groups with strong oxidizing property generated by catalyzing hydrogen peroxide by iron ions can completely degrade organic pollutants in water to form carbon dioxide, water, inorganic salt and the like which are harmless to the environment, and the method has the advantages of low price, convenience, harmlessness to the environment, easiness in industrialization and the like, and is concerned. Cuprous oxide is a typical p-type semiconductor, has unique optical properties, can initiate a photocatalytic reaction under sunlight, and has attracted the attention of numerous researchers. At present, some methods for preparing cuprous oxide materials have been tried, for example, the patent of the invention (CN107162038A) reports a method for preparing cuprous oxide by using an aerosol method; the invention patent (CN106423166A) reports a method for preparing cuprous oxide using organic reducing agent; the invention patent (CN105836787A) reports a method for preparing cuprous oxide by using organic alkylamine. But also has the defects of complex preparation process and high organic matter content and is difficult to remove, thereby greatly increasing the cost of the product. At the same time, ferrous oxide also exhibits very excellent effects as a fenton reagent. The single metal oxide still can not meet the requirements of practical application, and the composite catalyst can solve the defects of a single-component catalyst, so that the ferrous oxide/cuprous oxide-based composite material has more excellent performance than single cuprous oxide or ferrous oxide. The preparation of the ferrous oxide/cuprous oxide composite nano material by using simple and cheap raw materials and a simple one-step method becomes a difficult point in scientific research and production application at present.
Disclosure of Invention
The invention aims to provide a preparation method of a ferrous oxide/cuprous oxide nanocomposite, the ferrous oxide/cuprous oxide nanocomposite is prepared by a simple one-step low-temperature hydrothermal method, the particle size and composition of particles of a composite structure are controllable, the catalytic performance and the structural stability are improved, and the preparation method is simple in process flow, low in cost and suitable for large-scale production.
In order to achieve the purpose, the invention adopts the technical scheme that:
the preparation method of the ferrous oxide/cuprous oxide nano composite material takes ferric salt and metallic copper as raw materials, and prepares the composite material with controllable composition and particle size by using redox reaction between the ferric salt and the metallic copper and a one-step low-temperature hydrothermal method.
The preparation method of the ferrous oxide/cuprous oxide nanocomposite material comprises the following steps:
1) dissolving iron salt in water to obtain iron salt solution, and controlling concentration to be 2.5 x 10-3-7.5*10-2mol/L;
2) Adding metal copper into the ferric salt solution, and continuously stirring for 5-30 min;
3) putting the solution into a reaction kettle, and reacting at the temperature of 80-150 ℃ for 0.5-8 h;
4) washing the product obtained in the step 3) with a detergent for 1-3 times, and drying at the temperature of 0-120 ℃ for 2-12 h.
The iron salt is one or more of ferric chloride, ferric nitrate or ferric sulfate.
The metal copper is one or more of copper powder, copper sheet or foam copper.
Controlling the amount of iron ions on the copper metal to be 1 x 10-5mol/cm2-3*10-4mol/cm2
The detergent in the step 4) is water, ethanol or acetone.
The invention has the beneficial effects that:
(1) the invention can prepare the ferrous oxide/cuprous oxide composite nano material by one step by using a simple one-step low-temperature hydrothermal method without adding an organic solvent, has controllable particles and components and low cost, and solves the problems of complex preparation process and high cost of the composite material.
(2) The preparation method is simple and convenient, has no harm to the environment, is suitable for large-scale industrial production, and has wide application prospect.
(3) The prepared ferrous oxide/cuprous oxide composite nano material has excellent performance, can show excellent catalytic performance at neutral pH value, normal temperature and sunlight as a Fenton reaction reagent, and has enhanced catalytic activity and improved structural stability.
Drawings
FIG. 1 is the XRD pattern of ferrous/cuprous oxide in example 1;
FIG. 2 is an SEM image of ferrous/cuprous oxide in example 1;
FIG. 3 is a graph showing the degradation of the dye molecules in example 1.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
The degradation product is 5mg/L of methylene blue and rhodamine B dye mixed solution (each accounts for 50 wt%).
Example 1
The preparation method of the ferrous oxide/cuprous oxide nanocomposite comprises the steps of dissolving ferric trichloride in water, wherein the concentration of the ferric trichloride is 0.01 mol/L; adding a metal copper sheet into the ferric trichloride solution, and continuously stirring for 15 minutes, wherein the amount of iron ions on the copper sheet is 1 x 10-4mol/cm2Then the mixture is put into a reaction kettle to react for 5 hours at the temperature of 100 ℃; the resulting product was washed 3 times with ethanol and dried at 90 ℃ for 8 hours.
The diffraction pattern of the crystal structure of fig. 1 shows that the product is a ferrous oxide/cuprous oxide composite material. As can be seen from fig. 2, the composite nanostructure of ferrous oxide/cuprous oxide is spherical particles with an average particle size of about 80 nm. 0.05g of ferrous oxide/cuprous oxide composite material is added into 100mL of mixed solution of methylene blue and rhodamine B dye (the concentration is 5mg/L), stirred for 40min in the dark, and then added with 0.5mL of hydrogen peroxide (the concentration is 30 wt%) for degradation experiment. As shown in the degradation of rhodamine B in FIG. 3, the ferrous oxide/cuprous oxide composite material can completely degrade organic pollutants within 30 min.
Example 2
As described in example 1, except that iron nitrate was added. The average grain diameter of the obtained ferrous oxide/cuprous oxide composite material is 90 nanometers, and the degradation of organic matters reaches 100 percent within 30 minutes.
Example 3
As described in example 1, except that iron sulfate was added. The average grain diameter of the obtained ferrous oxide/cuprous oxide composite material is 100 nanometers, and the degradation of organic matters reaches 100 percent in 30 min.
Example 4
As described in example 1, except that the concentration of the iron trichloride solution was 0.005 mol/L. The average grain diameter of the obtained ferrous oxide/cuprous oxide composite material is 75 nanometers, and the degradation of organic matters reaches 100 percent in 30 min.
Example 5
As described in example 1, except that the concentration of the iron trichloride solution was 0.05 mol/L. The average grain diameter of the obtained ferrous oxide/cuprous oxide composite material is 110 nanometers, and the degradation of organic matters reaches 95 percent in 30 min.
Example 6
Except that copper foam was added as described in example 1. The average grain diameter of the obtained ferrous oxide/cuprous oxide composite material is 60 nanometers, and the degradation of organic matters reaches 100 percent in 30 min.
Example 7
Except that copper foam was added as described in example 1. The average grain diameter of the obtained ferrous oxide/cuprous oxide composite material is 65 nanometers, and the degradation of organic matters reaches 100 percent in 30 min.
Example 8
As described in example 1, except that the amount of iron ions on the copper sheet was 2 x 10-5mol/cm2. The average grain diameter of the obtained ferrous oxide/cuprous oxide composite material is 70 nanometers, and the degradation of organic matters reaches 100 percent in 30 min.
Example 9
The reaction was carried out in a reaction vessel at 80 ℃ for 7 hours, as described in example 1. The average grain diameter of the obtained ferrous oxide/cuprous oxide composite material is 65 nanometers, and the degradation of organic matters reaches 100 percent in 30 min.
Example 10
The reaction was carried out in a reaction vessel at 140 ℃ for 3 hours, as described in example 1. The average grain diameter of the obtained ferrous oxide/cuprous oxide composite material is 95 nanometers, and the degradation of organic matters reaches 100 percent in 30 min.

Claims (4)

1. A preparation method of a ferrous oxide/cuprous oxide nano composite material is characterized in that ferric salt and metallic copper are used as raw materials, and a composite material with controllable composition and particle size is prepared by using an oxidation-reduction reaction between the ferric salt and the metallic copper and a one-step low-temperature hydrothermal method; the method specifically comprises the following steps:
1) dissolving iron salt in water to obtain iron salt solution with concentration of 2.5 × 10-3-7.5×10-2mol/L;
2) Adding metal copper into the ferric salt solution, and continuously stirring for 5-30 min;
3) putting the solution into a reaction kettle, and reacting at the temperature of 80-150 ℃ for 0.5-8 h;
4) washing the product obtained in the step 3) with a detergent for 1-3 times, and drying at the temperature of 0-120 ℃ for 2-12 h;
in the step 2), the amount of iron ions on the metal copper is controlled to be 1 multiplied by 10-5mol/cm2-3×10-4mol/cm2
2. The method of claim 1, wherein the ferric salt is one or more of ferric chloride, ferric nitrate, or ferric sulfate.
3. The method of claim 1, wherein the copper metal is one or a combination of copper powder, copper flakes, or copper foam.
4. The method for preparing ferrous oxide/cuprous oxide nanocomposite as claimed in claim 1, wherein said detergent in step 4) is water, ethanol or acetone.
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CN111193012B (en) * 2020-01-08 2021-02-19 四川大学 Hollow porous cuprous oxide-copper oxide-iron trioxide cube negative electrode for lithium ion battery and one-step preparation method thereof
CN111135830A (en) * 2020-01-14 2020-05-12 江苏海洋大学 A simple green preparation method and application of micro-nano powder of copper and cuprous oxide composite structure
CN113769742B (en) * 2021-07-28 2023-11-17 同济大学 A preparation method of copper mesh integrated Cu2O@FeO nanoarray
CN115072856A (en) * 2022-04-27 2022-09-20 赣南医学院 Application of copper-iron-oxygen nanoenzyme in removing colored printing and dyeing dye and kit for removing printing and dyeing dye

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