CN110961108A - Copper ferrite nanocomposite and preparation method and application thereof - Google Patents
Copper ferrite nanocomposite and preparation method and application thereof Download PDFInfo
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- CN110961108A CN110961108A CN201911312053.6A CN201911312053A CN110961108A CN 110961108 A CN110961108 A CN 110961108A CN 201911312053 A CN201911312053 A CN 201911312053A CN 110961108 A CN110961108 A CN 110961108A
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 70
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 63
- 239000010949 copper Substances 0.000 title claims abstract description 63
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 24
- 230000015556 catabolic process Effects 0.000 claims abstract description 17
- 238000006731 degradation reaction Methods 0.000 claims abstract description 17
- 150000001879 copper Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002086 nanomaterial Substances 0.000 claims abstract description 10
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims abstract description 9
- 150000002505 iron Chemical class 0.000 claims abstract description 9
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims abstract description 9
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 210000003278 egg shell Anatomy 0.000 claims description 78
- 102000002322 Egg Proteins Human genes 0.000 claims description 71
- 108010000912 Egg Proteins Proteins 0.000 claims description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
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- 241000272525 Anas platyrhynchos Species 0.000 claims description 3
- 241000272814 Anser sp. Species 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
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- 239000003054 catalyst Substances 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 20
- 239000004098 Tetracycline Substances 0.000 description 17
- 229960002180 tetracycline Drugs 0.000 description 17
- 229930101283 tetracycline Natural products 0.000 description 17
- 235000019364 tetracycline Nutrition 0.000 description 17
- 150000003522 tetracyclines Chemical class 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 244000144977 poultry Species 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 241000186361 Actinobacteria <class> Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000010796 biological waste Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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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
- 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
- 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Magnetic Ceramics (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention belongs to the field of nano materials, and particularly discloses a copper ferrite nano composite material as well as a preparation method and application thereof. The copper ferrite nano composite material takes waste shell substances as a template; then the iron salt and the copper salt are calcined at high temperature by a coprecipitation method, thereby obtaining the catalyst. The nano composite material has good effect on the adsorption and degradation of tetracycline hydrochloride. The prepared material has the advantages of wide source, large quantity, simple preparation process and equipment requirements, no environmental pollution, low cost and contribution to the utilization of wastes.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of a copper ferrite composite material and application of the copper ferrite composite material in adsorption and degradation of tetracycline hydrochloride.
Background
Tetracycline hydrochloride is widely used as a broad-spectrum antibiotic produced by actinomycetes for treating diseases of human beings and animals due to low price, wide antimicrobial spectrum and small toxic and side effects. However, tetracycline hydrochloride cannot be completely degraded due to the benzene-containing skeleton, and the wide application in animal husbandry and aquaculture production results in a series of residues which are harmful to ecological environment and human health, and therefore, the removal of tetracycline hydrochloride from the environment is very important.
Ferrite is a composite iron oxide functional material consisting of iron and one or more other transition metals (cobalt, nickel, zinc, manganese, copper, magnesium, barium, rare earth metals and the like). The ferrite material has excellent electrical, magnetic, thermal and optical properties, and has great application value in the aspects of medicine, communication and broadcasting, automatic control, computing technology, aerospace, satellite communication, information display, environmental management and the like. Ferrite materials can be classified into spinel-type ferrites, garnet-type ferrites, and magnetoplumbite-type ferrites according to their crystal structures. Among them, spinel ferrite has soft magnetism and perfect symmetry, so that it is easy to exert its own value, and its application is also wider. The spinel ferrite has a structure with a plurality of cation vacancies and has large edge defects, so the material has good catalytic performance.
The egg shell mainly contains CaCO3The iron-based composite material occupies about 94 percent of the total weight, and also contains magnesium carbonate, magnesium phosphate, calcium phosphate, some organic matters (3.5 to 4.0 percent) and more iron elements. The eggshell, as a solid waste material, is a porous substance with high calcium content, has a large specific surface area and good gas phase and liquid phase adsorption functions, and the adsorption function is mainly determined by the high calcium carbonate component and the multilayer microporous structure.
In conclusion, the test utilizes the porous structure of the egg shell, and takes the egg shell as the substrate to load the copper ferrite on the egg shell to synthesize the composite material of the copper ferrite egg shell. The eggshell makes the copper ferrites disperse more uniformly so that they do not deactivate due to aggregation. These excellent properties make it a highly efficient and durable degradable tetracyclic material. Based on this, we developed a material that effectively degrades and adsorbs tetracycline.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a copper ferrite composite material and application thereof in adsorption and degradation of tetracycline hydrochloride.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a copper ferrite composite material is prepared by taking a waste shell substance as a carrier and then carrying out high-temperature calcination on an iron salt and a copper salt by a coprecipitation method.
Furthermore, the waste shell substances are eggshells of other poultry such as eggshells, duck eggshells, goose eggshells and the like.
The preparation method of the copper ferrite composite material comprises the following specific steps:
(1) egg shell pretreatment: removing egg membrane on the surface of the eggshell, repeatedly washing the eggshell with clear water, respectively washing with clear water and ultrapure water for three times, taking out, drying, grinding with a grinder, and sieving with a 200-mesh sieve to obtain an eggshell carrier;
(2) preparing an eggshell carrier: taking the eggshell powder pretreated in the step (1), and soaking the eggshell powder in NaOH at room temperature for 12 hours; then washing with deionized water for 3-5 times, and drying for later use;
(3) loading of copper ferrite: soaking the eggshell carrier obtained in the step (2) into 50mL of copper salt and iron salt solution, soaking and stirring at room temperature for 12-24 h, and adsorbing two ions onto the eggshell carrier;
(4) preparing a copper ferrite nano composite material: standing the solution obtained in the step (3) for 1h, taking out supernatant, and evaporating the remaining suspension to dryness by using an oil bath pan;
(5) preparing a copper ferrite nano composite material: calcining the dried eggshell loaded with the ferric salt and the copper salt in a muffle furnace to obtain the copper ferrite nanocomposite;
the eggshell in the step (1) is an eggshell of other poultry such as a chicken eggshell, a duck eggshell, a goose eggshell and the like.
In the step (2), the using amount of the eggshell powder is 10-20g, the volume percentage concentration of the NaOH solution is 10%, the volume is 20 ml, and the drying temperature is 60 ℃.
The eggshell powder taken in the step (3) is 2-5g, the concentration of the copper salt solution and the iron salt solution is 10mM-30mM, and the volume is 50 mL.
The temperature at which the oil bath is evaporated to dryness in the above step (4) is 70 ℃.
The calcination temperature in the step (5) is 300-500 ℃, the calcination time is 2-5h, and the amount of the copper ferrite in the generated copper ferrite nano composite material is 0.17-0.51 percent of the total mass of the composite material.
The copper ferrite nanocomposite material is applied to photocatalytic degradation of tetracycline hydrochloride.
Compared with the prior art, the invention has the following beneficial effects:
1. the carrier used by the nano material is the waste egg shells, so that the nano material has wide raw material source and low cost, does not generate any pollution, and can realize the recycling of biological wastes;
2. according to the nano material prepared by the invention, the copper ferrite accounts for 0.17-0.51% of the total mass of the composite material, the content of the copper ferrite required to be loaded is low, and the photocatalysis effect is good.
3. The invention has the advantages of easily obtained preparation materials, simple preparation process and equipment requirements and mild reaction conditions.
Drawings
FIG. 1 is a diagram of a copper ferrite nanocomposite prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a copper ferrite nanocomposite prepared according to example 1 of the present invention;
FIG. 3 is a graph showing the degradation rate of tetracycline by the copper ferrite nanocomposite obtained in examples 1 to 3 at different calcination temperatures.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
A copper ferrite composite material is prepared by taking eggshells as carriers; and then loading the copper ferrite to obtain the copper ferrite nano composite material.
A preparation method of a copper ferrite composite material comprises the following steps:
(1) egg shell pretreatment: removing egg membrane on the surface of the eggshell, repeatedly washing the eggshell with clear water, respectively washing with clear water and ultrapure water for three times, taking out, drying, grinding with a grinder, and sieving with a 200-mesh sieve to obtain an eggshell carrier;
(2) preparing an eggshell carrier: taking 20g of the eggshell powder pretreated in the step (1), and soaking the eggshell powder with 10% of NaOH at room temperature for 12 hours; then washing with deionized water for 3-5 times, and drying for later use;
(3) loading of copper ferrite: soaking 2g of the eggshell carrier obtained in the step (2) into 50mL of copper salt and iron salt solution with the concentration of 20mM, soaking and stirring at room temperature for 12h, and adsorbing two ions onto the eggshell carrier;
(4) the preparation method of the copper ferrite composite material comprises the following steps: standing the solution obtained in the step (3) for 1h, taking out supernatant, evaporating the rest solid to dryness in an oil bath kettle at 70 ℃,
(5) and placing the dried eggshell loaded with the copper ferrite particles in a muffle furnace to calcine for 2h at 300 ℃ to obtain the copper ferrite nanocomposite.
Example 2
A preparation method of a copper ferrite composite material comprises the following steps:
(1) egg shell pretreatment: removing egg membrane on the surface of the eggshell, repeatedly washing the eggshell with clear water, respectively washing with clear water and ultrapure water for three times, taking out, drying, grinding with a grinder, and sieving with a 200-mesh sieve to obtain an eggshell carrier;
(2) preparing an eggshell carrier: taking 20g of the eggshell powder pretreated in the step (1), and soaking the eggshell powder with 10% of NaOH at room temperature for 12 hours; then washing with deionized water for 3-5 times, and drying for later use;
(3) loading of copper ferrite: soaking 2g of the eggshell carrier obtained in the step (2) into 50mL of copper salt and iron salt solution with the concentration of 20mM, soaking and stirring at room temperature for 12h, and adsorbing two ions onto the eggshell carrier;
(4) the preparation method of the copper ferrite composite material comprises the following steps: standing the solution obtained in the step (3) for 1h, taking out supernatant, evaporating the rest solid to dryness in an oil bath kettle at 70 ℃,
(5) and (3) calcining the dried eggshell loaded with the copper ferrite particles in a muffle furnace at 400 ℃ for 2h to obtain the copper ferrite nanocomposite.
Example 3
A preparation method of a copper ferrite composite material comprises the following steps:
(1) egg shell pretreatment: removing egg membrane on the surface of the eggshell, repeatedly washing the eggshell with clear water, respectively washing with clear water and ultrapure water for three times, taking out, drying, grinding with a grinder, and sieving with a 200-mesh sieve to obtain an eggshell carrier;
(2) preparing an eggshell carrier: taking 20g of the eggshell powder pretreated in the step (1), and soaking the eggshell powder with 10% of NaOH at room temperature for 12 hours; then washing with deionized water for 3-5 times, and drying for later use;
(3) loading of copper ferrite: soaking 2g of the eggshell carrier obtained in the step (2) into 50mL of copper salt and iron salt solution with the concentration of 20mM, soaking and stirring at room temperature for 12h, and adsorbing two ions onto the eggshell carrier;
(4) the preparation method of the copper ferrite composite material comprises the following steps: standing the solution obtained in the step (3) for 1h, taking out supernatant, evaporating the rest solid to dryness in an oil bath kettle at 70 ℃,
(5) and placing the dried eggshell loaded with the copper ferrite particles in a muffle furnace to calcine for 2h at 500 ℃ to obtain the copper ferrite nanocomposite.
Application example 1
Prepare 50mg/L tetracycline solution, stir until homogeneous. 50ml of the prepared tetracycline solution is taken, 30mg of the copper ferrite composite material in the embodiment 1 is weighed and added into the prepared tetracycline solution, and a magnetic stirrer is used for stirring continuously under the condition of visible light irradiation. The degradation condition of the tetracycline is tested once every ten minutes to obtain a UV (ultraviolet) graph of the degradation of the tetracycline, so that the degradation rate is 78% in 80min of illumination.
Application example 2
Prepare 50mg/L tetracycline solution, stir until homogeneous. 50ml of the prepared tetracycline solution is taken, 30mg of the copper ferrite composite material in the embodiment 2 is weighed and added into the prepared tetracycline solution, and a magnetic stirrer is used for stirring continuously under the condition of visible light irradiation. The degradation condition of the tetracycline is tested once every ten minutes, a UV (ultraviolet) graph of the degradation of the tetracycline is obtained, and the degradation rate is calculated to be 73% in 80min of illumination.
Application example 3
Prepare 50mg/L tetracycline solution, stir until homogeneous. 50ml of the prepared tetracycline solution is taken, 30mg of the copper ferrite composite material in the embodiment 3 is weighed and added into the prepared tetracycline solution, and a magnetic stirrer is used for stirring continuously under the condition of visible light irradiation. The degradation condition of the tetracycline is tested once every ten minutes to obtain a UV (ultraviolet) graph of the degradation of the tetracycline, so that the degradation rate is 81 percent in 80min of illumination.
Example 1 a sample of copper ferrite nanocomposite is shown in figure 1, the sample being a grey powder.
Fig. 2 is a scanning electron microscope image of the sample of fig. 1, from fig. 2, it can be seen that copper ferrite nanoparticles are loaded on the surface of an eggshell, the particle size of the copper ferrite nanoparticles is about 400nm, and fig. 3 is a comparative graph of the degradation rate of the three copper ferrite nanocomposite materials obtained in example 1, example 2, and example 3, from which it can be seen that the copper ferrite nanocomposite materials obtained at three different calcination temperatures have good effects on the degradation of tetracycline hydrochloride, but in comparison, the sample of 500 ℃ has a better effect, and the degradation rate is 81%.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. A copper ferrite nanocomposite is characterized in that: the material is prepared by using eggshells as carriers and then calcining ferric salt and copper salt at high temperature by a coprecipitation method.
2. A method for preparing the copper ferrite nanocomposite material of claim 1, wherein the method comprises the steps of: the method comprises the following steps: (1) egg shell pretreatment: removing egg membrane on the surface of the eggshell, repeatedly washing the eggshell with clear water, respectively washing with clear water and ultrapure water for three times, taking out, drying, grinding with a grinder, and sieving with a 200-mesh sieve to obtain an eggshell carrier;
(2) preparing an eggshell carrier: taking the eggshell powder pretreated in the step (1), and soaking the eggshell powder in NaOH at room temperature for 12 hours; then washing with deionized water for 3-5 times, and drying for later use;
(3) loading of copper ferrite: soaking the eggshell carrier obtained in the step (2) into 50mL of copper salt and iron salt solution, soaking and stirring at room temperature for 12-24 h, and adsorbing two ions onto the eggshell carrier;
(4) preparing a copper ferrite nano composite material: standing the solution obtained in the step (3) for 1h, taking out supernatant, and evaporating the remaining suspension to dryness by using an oil bath pan;
(5) preparing a copper ferrite nano composite material: and (3) calcining the dried eggshell loaded with the ferric salt and the copper salt in a muffle furnace to obtain the copper ferrite nano composite material.
3. The method for preparing copper ferrite nano-material according to claim 2, characterized in that: the eggshell in the step (1) is an eggshell, a duck eggshell or a goose eggshell.
4. The method for preparing copper ferrite nano-material according to claim 2, characterized in that: in the step (2), the using amount of the eggshell powder is 10-20g, the volume percentage concentration of the NaOH solution is 10%, the volume is 20 ml, and the drying temperature is 60 ℃.
5. The method for preparing copper ferrite nano-material according to claim 2, characterized in that: 2-5g of eggshell carrier is taken in the step (3), the concentration of the copper salt solution and the iron salt solution is 10mM-30mM, and the volume is 50 mL.
6. The method for preparing copper ferrite nano-material according to claim 2, characterized in that: the temperature at which the oil bath is evaporated to dryness in step (4) is 70 ℃.
7. The method for preparing copper ferrite nano-material according to claim 2, characterized in that: the calcining temperature in the step (5) is 300-.
8. Use of the copper ferrite nanocomposite of claim 1 in adsorptive degradation of tetracycline hydrochloride.
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