CN108079993B - Preparation method of ferrous oxide/cuprous oxide nano composite material - Google Patents
Preparation method of ferrous oxide/cuprous oxide nano composite material Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 37
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 6
- 239000003599 detergent Substances 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- -1 iron ions Chemical class 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000001856 aerosol method Methods 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention relates to a preparation method of a ferrous oxide/cuprous oxide nano composite material, belonging to the technical field of inorganic material preparation, wherein ferric salt is dissolved in water to obtain a ferric salt solution; adding metal copper into the ferric salt solution, and continuously stirring for 5-30 min; putting the solution into a reaction kettle, and reacting at the temperature of 80-150 ℃ for 0.5-8 h; 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 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, the particles and the components are controllable, the cost is low, and the problems of complex preparation process and high cost of the composite material are solved; 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; the obtained product has excellent performance, can be used as a Fenton reaction reagent, can show excellent catalytic performance at neutral pH value, normal temperature and sunlight, and has enhanced catalytic activity and improved structural stability.
Description
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-cupric oxide-ferric oxide cubic lithium ion battery cathode and one-step preparation method thereof |
| CN111135830A (en) * | 2020-01-14 | 2020-05-12 | 江苏海洋大学 | Simple and green preparation method and application of micro-nano powder with copper and cuprous oxide composite structure |
| CN113769742B (en) * | 2021-07-28 | 2023-11-17 | 同济大学 | Copper mesh integrated Cu 2 Preparation method of O@FeO nano array |
| 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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