CN109225236B - Fe3O4ZnO nano composite and its synthesis method - Google Patents

Fe3O4ZnO nano composite and its synthesis method Download PDF

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CN109225236B
CN109225236B CN201811280378.6A CN201811280378A CN109225236B CN 109225236 B CN109225236 B CN 109225236B CN 201811280378 A CN201811280378 A CN 201811280378A CN 109225236 B CN109225236 B CN 109225236B
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杨永梅
李瑞峰
郑春梅
张顺虎
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Huangshan University
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Abstract

Fe3O4The synthesis method of the/ZnO nano composite comprises the following steps: (1) preparation of Fe3O4Magnetic nanoparticles: heating soluble salt of iron in glycol to react with NaAc and polyethylene glycol to prepare Fe3O4Magnetic nanoparticles; (2) fe3O4Modification of (2): preparing Fe from the step (1)3O4Reacting the magnetic nano-particles in an ethanol solution of a modifier to prepare a modified product; (3) preparation of Fe3O4ZnO: ultrasonically reacting the product obtained in the step (2), soluble salt of zinc and a proper amount of ammonia water in water to prepare Fe3O4a/ZnO nanocomposite. The invention synthesizes the required product by using a mild method, has low cost and is easy to form large-scale production.

Description

Fe3O4ZnO nano composite and its synthesis method
Technical Field
The invention belongs to the technical field of nano composite material synthesis, and particularly relates to Fe3O4A ZnO nano-composite and its synthesis method are provided.
Background
With the rapid development of industrialization, the problem of soil and water pollution caused by organic dyes in industrial wastewater becomes more serious, and most of the organic dyes are difficult to degrade. The semiconductor material can effectively decompose organic dye into H by photocatalysis2O and CO2And the inorganic substances are used as a green catalytic degradation method and are widely applied to degrading organic pollutants in water and the atmosphere. The semiconductor material currently used as a photocatalyst is mainly TiO2CdS and WO3And the like n-type semiconductor compounds. TiO compared with other common semiconductor materials2The catalyst has strong oxidation-reduction capability, but the photoproduction electrons and holes are easy to recombine, and the quantum efficiency is low.
ZnO, an inorganic material, attracts much attention as an excellent semiconductor-type material, shows good photocatalytic activity under ultraviolet irradiation, and has quantum efficiency and sunlight utilization efficiency higher than those of TiO2Etc. photocatalytic materials. In addition, ZnO is a common chemical additive, and is widely applied to the manufacture of products such as plastics, silicate products, synthetic rubber, lubricating oil, paint coatings, ointments, adhesives, foods, batteries, flame retardants and the like. The ZnO has larger energy band gap and exciton constraint energy, high transparency and excellent normal-temperature luminous performance, and is applied to products such as liquid crystal displays, thin film transistors, light emitting diodes and the like. However, ZnO is suspended in the system during the reaction, and is difficult to recover, thereby causing great waste. Based on the consideration of material recycling, magnetic particles can be doped into the magnetic material to be separated from the system under an applied magnetic field. Among the many superparamagnetic materials, iron oxides are of great interest due to their ferromagnetic properties. Core-shell nanowire Fe prepared from Li and the like2O3the/ZnO can be used as a gas sensor (Si SF, Li C H, Wang X, et al, Fe)3O4/ZnO Core-Shell Nanorods for Gas Sensors[J]Sens initiators B,2006,119: 52-56); gedanke et al filled Fe in hollow hexagonal ZnO by ultrasonic method3O4Magnetic particles (Gedanke et al, Crystallization of ZnO on Crystallization of magnetic Nanoparticles in the Presence of ultrasonic irradiation [ J)]Crystal Growth Design,2006,6(10): 2260-2265); chu et al deposited Fe on ZnO nanorods by hydrothermal method2O3And Fe3O4Magnetic particles (Chu X Y et al, ZnO micro Coated with Iron Oxide nanoparticles [ J)].J Phys Chem C,2008,112:15980-15984)。
At present, Fe3O4The preparation method of the/ZnO compound mainly comprises the following steps:
(1) a hydrothermal-high temperature calcination method: the preparation method comprises the steps of taking zinc acetate and ferric nitrate as raw materials, preparing a precursor by a hydrothermal synthesis method, and calcining the precursor in a 600 ℃ muffle furnace for 2.5 hours to obtain Fe3O4ZnO powder (Guo Yu Liang, etc., Fe3O4Microstructure characterization and photocatalytic performance analysis of/ZnOAnalysis, guangdong chemical, 2017, 44 (14): 20-21);
(2) a two-step method of coprecipitation and annealing treatment: guanwei et al synthesized magnetic Fe with core-shell structure by a method combining coprecipitation and annealing treatment3O4The ZnO nano material researches the catalytic degradation effect of the product on 3 tetracycline antibiotics of tetracycline, doxycycline and oxytetracycline hydrochloride (Guanwei province, etc., magnetic Fe3O4Preparation of ZnO core-shell material and degradation of tetracycline antibiotics, applied chemistry, 2013.9, 1023-1029).
In addition, Chinese patent CN106495232A discloses a hollow sea urchin type magneto-optical nano composite drug-carrying system and a preparation method thereof, in the scheme, by adding sodium dodecyl sulfate in a solvothermal method, Fe with good water solubility can be prepared in a short time3O4The hollow sphere is organically combined with the ZnO nano-rod in a self-assembly mode to prepare the hollow sphere with Fe3O4The hollow sea urchin type nano composite drug-carrying system with the hollow sphere @ ZnO nanorod structure. However, this method produces nanocomposites in which Fe is present3O4The occupied mass proportion is not good, the magnetism is not ideal, and the recovery and the recycling of the nano compound are influenced.
At present, factors such as production cost, output ratio and the like are comprehensively considered, a production method beneficial to realizing scale is developed, and the problem to be solved in the further development process of the composite material is urgent.
Disclosure of Invention
In order to solve the above problems, it is an object of the present invention to provide a mild synthesis method of Fe3O4The method of the ZnO nano compound can synthesize the required product without high-temperature calcination, and has the advantages of low production cost, short reaction time, simple operation and easy formation of large-scale production;
the second technical problem to be solved by the invention is to provide Fe prepared by the method3O4ZnO nano composite with uniform spherical Fe appearance3O4Is wrapped in the sheetThe ZnO has the advantages of uniform size and good photocatalysis and magnetic recovery effects.
In order to achieve the purpose, the invention adopts the technical scheme that:
fe3O4The synthesis method of the/ZnO nano composite comprises the following steps:
(1) preparation of Fe3O4Magnetic nanoparticles: using soluble salt of iron as raw material, in glycol solvent, under the existance of NaAc and polyglycol, heating to react and obtain Fe3O4Magnetic nanoparticles;
(2)Fe3O4modification of (2): preparing Fe from the step (2)3O4Reacting the magnetic nano-particles in an ethanol solution containing a modifier to prepare a modified product;
(3) preparation of Fe3O4ZnO: ultrasonically reacting the product obtained in the step (2), soluble salt of zinc and a proper amount of ammonia water in water to prepare Fe3O4a/ZnO nanocomposite.
Through a large amount of researches, the invention discovers that Fe can be synthesized by adopting a layer-by-layer self-assembly method3O4a/ZnO nanocomposite. The method has mild reaction conditions, can reduce the cost of preparing the product, can be applied in large scale and creates economic value.
Preferably, in step (1), the soluble salt of iron comprises ferric chloride, ferric nitrate or ferric sulfate.
Preferably, the concentration of the soluble salt of iron in the ethylene glycol is 15-80g/L, and the mass concentration can prepare Fe by using the iron source as less as possible3O4The method has the advantages of reducing cost, promoting the iron salt to be fully dissolved, and forming a uniform and stable light yellow clear solution, preferably 30-40g/L, and more preferably 34 g/L.
The order of addition of the raw materials may be: the soluble salt of iron was dispersed in ethylene glycol, stirred until completely dissolved to become a homogeneous clear solution, and then NaAc and polyethylene glycol were added.
Preferably, the mass ratio of NaAc, polyethylene glycol and iron soluble salt is 0.4-1.8:0.2-0.8:1, which is beneficial to regulating and stabilizing the pH value of the solution and better dispersing, and is preferably 0.8-1.5:0.25-0.5: 1. The polyethylene glycol is preferably polyethylene glycol 2000.
Preferably, the mixed solution of the soluble salt of iron and ethylene glycol, NaAc, polyethylene glycol is vigorously stirred for 5-25min, preferably 15 min.
Preferably, the reaction temperature is 80-180 ℃ and the reaction time is 2.5-4.5 h. The energy consumption can be reduced by adopting the hydrothermal reaction at low temperature for a short time, the obtained product has uniform appearance and small size, the reaction temperature is preferably 150 ℃, and the reaction time is preferably 3 hours.
The reaction can be carried out in a reaction kettle with a polytetrafluoroethylene substrate. The mixed solution should be stirred uniformly after being placed in the reaction kettle to prevent coagulation.
Preferably, the method further comprises the steps of washing and drying after the product obtained by the reaction is recovered and separated by a magnet.
Preferably, the washing is performed with double distilled water and absolute ethanol, and may be sequentially performed a plurality of times.
Preferably, the drying is carried out at 40-70 deg.C under vacuum for 6-18h, so that the product can be completely dried at relatively low temperature in the absence of oxygen, and the product is ensured not to be changed at this stage, preferably at 60 deg.C under vacuum for 12 h.
In one embodiment, the process of step (1) is: taking FeCl3·6H2O was dispersed in ethylene glycol and stirred until complete dissolution became a homogeneous clear solution, followed by addition of NaAc and polyethylene glycol. Stirring the mixed solution vigorously, transferring into a reaction kettle with polytetrafluoroethylene as a substrate, heating for a certain time, taking out, naturally cooling to room temperature, and recovering and separating black Fe with a magnet3O4The product is washed with redistilled water and absolute ethyl alcohol for a plurality of times and dried in vacuum.
Preferably, in the step (2), the modifying agent includes at least one of thioglycolic acid (MAA), polyvinylpyrrolidone (PVP), and tween.
Preferably, Fe3O4The concentration of the magnetic nanoparticles in the ethanol solution of the modifier is 3-9g/L, and the ethanol solution of the modifierThe concentration of the modifier in the solution is 0.1-0.3 mmol/L. Fe as described above3O4The concentration of the magnetic nano-particles and the concentration range of the ethanol solution of the modifier can prevent Fe3O4The magnetic particles are agglomerated, and the use amount of reagents and the cost are reduced.
Preferably, Fe3O4The concentration of the magnetic nano-particles in the ethanol solution of the modifier is 4-7 g/L.
Preferably, the concentration of the modifying agent in the ethanol solution of the modifying agent is 0.15-0.2mmol/L, preferably 0.18 mmol/L.
Preferably, the reaction is carried out for 12 to 28 hours under shaking to ensure that Fe3O4Fully surface-modified to increase Fe3O4Dispersion of (2).
After the reaction is finished, the black product can be recovered by using a magnet and then washed, for example, by sequentially washing with absolute ethyl alcohol and distilled water for several times.
In one embodiment, the process of step (2) is: mixing Fe3O4Magnetic nanoparticles are added into an ethanol solution of thioglycolic acid, and after shaking the reaction, the black product is recovered with a magnet and washed several times, for example three times, with absolute ethanol and distilled water, respectively.
Preferably, in the step (3), the soluble salt of zinc comprises ZnAc 2H2O、ZnCl2、 Zn(NO3)2。
Preferably, the product obtained in step (2) is reacted with ZnAc.2H2The mass ratio of O is 1: 1, the wrapped ZnO is more uniform and sufficient.
Preferably, the concentration of the ammonia water is 0.5-1.2M, the volume is 0.2-1.5mL, the pH of the solution is favorably controlled to be 9.0, and the yield of ZnO is improved. Preferably, the concentration of ammonia is 1M.
Preferably, the power of the ultrasonic wave is 80-110W, the time is 5-25min, the energy is saved on the basis of ensuring the sufficient reaction, and the ultrasonic reaction is carried out for 20min under 100W.
Preferably, after the reaction is finished, the off-white product is recovered and separated by a magnet, washed and dried to obtain Fe3O4a/ZnO nanocomposite.
Preferably, the washing step may be performed with double distilled water for several times.
Preferably, the drying temperature is 40-70 ℃ and vacuum drying is carried out for 8-14h, so that the product is prevented from being changed in the drying process.
The water used in step (3) may be distilled water.
In one embodiment, the process of step (3) is: mixing Fe3O4And ZnAc 2H2O is simultaneously dissolved in distilled water, and NH is then added3·H2O, continuously performing ultrasonic treatment for 20min (100W), recovering and separating off-white products by using a magnet, washing the off-white products by using secondary distilled water for multiple times, and drying the off-white products in vacuum to finally obtain Fe3O4The ZnO product.
Preferably, the method comprises the steps of:
(1) preparation of Fe3O4: taking FeCl3·6H2Dispersing O in ethylene glycol, stirring until the O is completely dissolved to form a uniform and clear solution, then adding NaAc and polyethylene glycol, stirring the mixed solution vigorously, transferring the mixed solution into a reaction kettle with 100mL of polytetrafluoroethylene as a substrate, heating for a certain time, taking out, and naturally cooling to room temperature. Separation of black Fe by magnet recovery3O4Washing the product with redistilled water and absolute ethyl alcohol for multiple times, and drying in vacuum;
(2)Fe3O4modification of (2): weighing the prepared Fe3O4Adding magnetic nanoparticles into 20mL of mercaptoacetic acid (MAA) ethanol solution, after oscillation reaction, recovering a black product by using a magnet, and washing the black product by using absolute ethyl alcohol and distilled water for three times respectively;
(3) preparation of Fe3O4ZnO: respectively taking Fe3O4And ZnAc 2H2O was simultaneously dissolved in 10mL of distilled water, and NH was then added3·H2O, continuously performing ultrasonic treatment for 20min (100W), recovering and separating off-white products by using a magnet, washing the off-white products by using secondary distilled water for multiple times, and drying the off-white products in vacuum to finally obtain Fe3O4The ZnO product.
It is also an object of the present invention to provide a method of the present inventionPrepared Fe3O4ZnO nanocomposite, Fe in said nanocomposite3O4The nanospheres are uniformly distributed on the ZnO thin sheet.
Fe according to the invention3O4Synthesis method of/ZnO composite material, and controllable synthesis method for preparing Fe by utilizing self-assembly3O4the/ZnO nano-composite, especially polyethylene glycol is used as a dispersant to effectively prevent Fe3O4Compared with the prior art that sodium dodecyl sulfate and the like are used as dispersing agents, the agglomeration is more beneficial to mutual solubility with ethylene glycol, and impurities are not easy to introduce.
Fe prepared by the method of the invention3O4In the/ZnO composite, Fe3O4The upper layer and the lower layer are covered by the flaky ZnO to form a compound similar to a sandwich structure, so that the compound has the advantages of magnetic property, recyclability and the like, and can realize applications such as photocatalysis, removal of water pollutants and the like, and meanwhile, the compound under the structure and the compound with the same quality contain Fe3O4The nano composite material has larger occupied mass ratio and stronger magnetism, is more favorable for recovery and recycling, is suitable for large-scale popularization, thereby promoting the development of the technical field of nano materials, breaking through the bottleneck of the development of the prior art, and being a method for preparing the nano composite material with economic value and social value.
Drawings
FIG. 1 is Fe3O4A scanning electron microscope image of the/ZnO nano composite material;
FIG. 2 is Fe3O4Transmission electron microscope picture of/ZnO nano composite material;
FIG. 3 is Fe3O4Energy spectrum of/ZnO nano composite material;
FIG. 4 is Fe3O4XRD pattern of/ZnO nanocomposite;
FIG. 5 is Fe3O4Hysteresis regression curve of/ZnO nano composite material;
FIG. 6 is a graph of UV-VIS absorption spectra of various samples, wherein (a) Fe3O4[ ZnO (1mg/mL), ] methyl orange (2mg/mL), (b), (c), (d) and (I) are Fe respectively3O4Adding a methyl orange solution into ZnO, and respectively irradiating absorption spectra of different times under 532nm ultraviolet light; wherein, (b)0min, (c)2min, (d)5min, (f)15min, (g)25min, (h)35min, and (I)1h of ultraviolet-visible absorption spectrogram.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Example 1
Fe3O4The synthesis method of the/ZnO nano composite comprises the following steps:
(1) preparation of Fe3O4: 1.05g of FeCl was taken3·6H2O was dispersed in 40mL of ethylene glycol and stirred until completely dissolved to become a homogeneous clear solution, followed by the addition of 1.7g NaAc and 0.6g polyethylene glycol. The mixed solution is stirred vigorously for 15min and then transferred into a reaction kettle with a substrate of 100mL polytetrafluoroethylene, and is taken out after being heated for 4h at 160 ℃, and is naturally cooled to room temperature. Separation of black Fe by magnet recovery3O4Washing the product with redistilled water and absolute ethyl alcohol for multiple times, and vacuum-drying at 50 ℃ for 10 hours;
(2)Fe3O4modification of (2): 0.15g of prepared Fe was weighed3O4Adding magnetic nanoparticles into 40mL of 0.15mM MAA ethanol solution, oscillating for 16h, recovering black product with magnet, washing with anhydrous ethanol and distilled water for three times, and marking the final product as Fe3O4-MAA；
(3) Preparation of Fe3O4ZnO: according to the following steps of 1: 1, 0.1g of MAA-modified Fe3O4And 0.1g ZnAc 2H2O was simultaneously dissolved in 10mL of distilled water, and NH was then added3·H2O, continuously performing ultrasonic treatment for 8min (90W), recovering and separating off-white products by using a magnet, washing the off-white products by using secondary distilled water for multiple times, and drying the off-white products under vacuum to finally obtain Fe3O4The ZnO product.
FIG. 1 shows Fe obtained in this example3O4A scanning electron microscope image of the/ZnO nano composite material; FIG. 2 shows Fe obtained in this example3O4Transmission electron microscope picture of/ZnO nano composite material; FIG. 3 shows Fe obtained in this example3O4Energy spectrum of/ZnO nano composite material; FIG. 4 shows Fe obtained in this example3O4XRD pattern of/ZnO nano composite material; FIG. 5 shows the production of Fe3O4Hysteresis regression curve of/ZnO nano composite material.
Thus, the Fe prepared by the method of the invention3O4In the/ZnO nanocomposite, Fe3O4The upper and lower layers are covered by flaky ZnO to form a sandwich-like compound, and Fe in the compound with the same mass under the structure3O4The occupied mass ratio is larger, the magnetism is stronger, and the recovery and the recycling are more facilitated.
Example 2
Fe3O4The synthesis method of the/ZnO nano composite comprises the following steps:
(1) preparation of Fe3O4: 1.65g of FeCl was taken3·6H2O was dispersed in 30mL of ethylene glycol and stirred until completely dissolved to become a homogeneous clear solution, followed by the addition of 2.8g NaAc and 0.7g polyethylene glycol. The mixed solution is stirred vigorously for 20min and then transferred into a reaction kettle with a substrate of 50mL polytetrafluoroethylene, and is taken out after being heated for 3h at 150 ℃, and is naturally cooled to room temperature. Separation of black Fe by magnet recovery3O4Washing the product with redistilled water and absolute ethyl alcohol for multiple times, and vacuum-drying at 70 ℃ for 6 hours;
(2)Fe3O4modification of (2): 0.2g of prepared Fe was weighed3O4The magnetic nanoparticles were added to 30mL of a 0.18mM polyvinyl pyrrolidone (PVP) ethanol solution, and after shaking reaction for 15 hours, the black product was recovered with a magnet and washed three times with absolute ethanol and distilled water, respectively. Final labelling of the product as Fe3O4-PVP。
(3) Preparation of Fe3O4ZnO: 0.1g of PVP modified Fe was taken separately3O4And 0.1g ZnAc 2H2O was simultaneously dissolved in 10mL of distilled water, and NH was then added3·H2O, continuous ultrasound for 5min (80W), separation of off-white product with magnet recovery, multiple washing with redistilled water, and drying under vacuum to obtain Fe3O4The ZnO product.
Example 3
Fe3O4The synthesis method of the/ZnO nano composite comprises the following steps:
(1) preparation of Fe3O4: 1.95g of FeCl was taken3·6H2O was dispersed in 40mL of ethylene glycol and stirred until completely dissolved to become a homogeneous clear solution, followed by the addition of 1.8g NaAc and 1.7g polyethylene glycol. The mixed solution is stirred vigorously for 25min and then transferred into a reaction kettle with a substrate of 100mL polytetrafluoroethylene, and is taken out after being heated for 4h at 160 ℃, and is naturally cooled to room temperature. Separation of black Fe by magnet recovery3O4Washing the product with redistilled water and absolute ethyl alcohol for multiple times, and vacuum-drying at 80 ℃ for 5 hours;
(2)Fe3O4modification of (2): 0.3g of prepared Fe was weighed3O4The magnetic nanoparticles were added to 60mL of an ethanol solution of Tween 80 with a concentration of 0.18mM, and after shaking for 18 hours, the black product was recovered with a magnet and washed three times with absolute ethanol and distilled water, respectively. Final labelling of the product as Fe3O4-Tween；
(3) Preparation of Fe3O4ZnO: 0.15g of Tween-modified Fe was added3O4And 0.15g ZnAc 2H2O was simultaneously dissolved in 10mL of distilled water, and NH was then added3·H2O, continuously performing ultrasonic treatment for 8min (100W), recovering and separating off-white products by using a magnet, washing the off-white products by using secondary distilled water for multiple times, and drying the off-white products in vacuum to finally obtain Fe3O4The ZnO product.
Example 4
Fe3O4The synthesis method of the/ZnO nano composite comprises the following steps:
(1) preparation of Fe3O4: 1.05g of FeCl was taken3·6H2O was dispersed in 40mL of ethylene glycol and stirred until completely dissolved to become a homogeneous clear solution, followed by the addition of 1.7g NaAc and 0.6g polyethylene glycol. The mixed solution is stirred vigorously for 5min and then transferred into a reaction kettle with a substrate of 100mL polytetrafluoroethylene, and is taken out after being heated for 2.5h at 180 ℃, and is naturally cooled to room temperature. Separation of black Fe by magnet recovery3O4The product was washed with redistilled water and absolute ethanol several times and dried under vacuum at 40 ℃ for 18 h.
(2)Fe3O4Modification of (2): 0.15g of prepared Fe was weighed3O4The magnetic nanoparticles were added to 40mL of 0.1mM MAA in ethanol, and after 28 hours of shaking reaction, the black product was recovered with a magnet and washed three times with absolute ethanol and distilled water, respectively. Final labelling of the product as Fe3O4-MAA。
(3) Preparation of Fe3O4ZnO: according to the following steps of 1: 1, respectively taking MAA modified Fe3O4And ZnAc 2H2O was simultaneously dissolved in 10mL of distilled water, and NH was then added3·H2O, continuous ultrasonic treatment for 25min (80W), separation of off-white product by magnet recovery, multiple washing with redistilled water, and drying under vacuum to obtain Fe3O4The ZnO product.
Example 5
Fe3O4The synthesis method of the/ZnO nano composite comprises the following steps:
(1) preparation of Fe3O4: 1.05g of FeCl was taken3·6H2O was dispersed in 40mL of ethylene glycol and stirred until completely dissolved to become a homogeneous clear solution, followed by the addition of 1.7g NaAc and 0.6g polyethylene glycol. The mixed solution is stirred vigorously for 25min, then transferred into a reaction kettle with a substrate of 100mL polytetrafluoroethylene, heated at 80 ℃ for 4.5h, taken out and naturally cooled to room temperature. Separation of black Fe by magnet recovery3O4Washing the product with redistilled water and absolute ethyl alcohol for multiple times, and vacuum-drying at 70 ℃ for 6 hours;
(2)Fe3O4modification of (2): 0.15g of prepared Fe was weighed3O4The magnetic nanoparticles were added to 40mL of 0.3mM MAA in ethanol, and after 12 hours of shaking reaction, the black product was recovered with a magnet and washed three times with absolute ethanol and distilled water, respectively. Final labelling of the product as Fe3O4-MAA；
(3) Preparation of Fe3O4ZnO: according to the following steps of 1: 1, respectively taking MAA modified Fe3O4And ZnAc2·2H2O was simultaneously dissolved in 10mL of distilled water, and NH was then added3·H2O, continuous sonication for 5min (110W), separation of the off-white product with magnet recovery, multiple washings with double distilled water, and drying under vacuum to give Fe3O4The ZnO product.
Comparative example 1
Fe in this comparative example3O4The synthesis of the/ZnO nanocomposite differed from example 1 only in that sodium lauryl sulfate was used instead of polyethylene glycol.
The Fe prepared in example 1 of the present invention was determined to be3O4In a/ZnO nanocomposite, Fe3O4The mass ratio of the Fe is higher than that of the Fe prepared by the conventional method in the comparative example 13O4Fe in/ZnO nano composite material3O4The mass ratio of the components. Thus, the Fe of the present invention3O4the/ZnO compound has stronger magnetism, and the magnetism can be recycled, so that the applications of photocatalysis, water pollutant removal and the like can be realized.
Examples of the experiments
Fe was obtained as in example 13O4the/ZnO composite material is subjected to ultraviolet-visible test, and ultraviolet-visible absorption spectrograms of different samples are shown in figure 6, wherein, (a) Fe3O4[ ZnO (1mg/mL), ] methyl orange (2mg/mL), (b), (c), (d) and (I) are Fe respectively3O4Adding methyl orange solution into ZnO, and respectively irradiating absorption spectra of 532nm ultraviolet light for different time periods, wherein (b)0min, (c)2min, (d)5min, (f)15min, and (g)25min(h)35min, and (I) an ultraviolet-visible absorption spectrogram of 1 h.
Thus, the Fe prepared by the method of the invention3O4the/ZnO composite material has better photocatalytic performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (9)

1. Fe3O4The synthesis method of the/ZnO nano composite comprises the following steps:
(1) preparation of Fe3O4Magnetic nanoparticles: using soluble salt of iron as raw material, in glycol solvent, under the existance of NaAc and polyglycol, heating to react and obtain Fe3O4Magnetic nanoparticles;
（2）Fe3O4modification of (2): preparing Fe from the step (1)3O4Reacting the magnetic nano-particles in an ethanol solution containing a modifier to prepare a modified product; the modifier comprises at least one of thioglycollic acid, polyvinylpyrrolidone and Tween;
(3) preparation of Fe3O4ZnO: ultrasonically reacting the product obtained in the step (2), soluble salt of zinc and a proper amount of ammonia water in water to prepare Fe3O4a/ZnO nanocomposite;
the soluble salt of zinc comprises ZnAc ∙ 2H2O；
The product obtained in the step (2) is mixed with ZnAc ∙ 2H2The mass ratio of O is 1: 1;
the concentration of the ammonia water is 0.5-1.2M, and the pH value of the solution is adjusted to 9.0;
the power of the ultrasonic reaction is 80-110W, and the time is 5-25 min.
2. The synthesis method according to claim 1, wherein in the step (1), the soluble salt of iron comprises ferric chloride, ferric nitrate or ferric sulfate;
the concentration of the soluble salt of iron in ethylene glycol is 15-80 g/L;
the mass ratio of NaAc, polyethylene glycol and soluble salt of iron is 0.4-1.8:0.2-0.8: 1.
3. The synthesis method according to claim 2, wherein the mixed solution of soluble salts of iron and ethylene glycol, NaAc, polyethylene glycol in step (1) is vigorously stirred for 5-25 min; the reaction temperature is 80-180 ℃.
4. The synthesis method according to claim 3, wherein the step (1) further comprises the steps of washing and drying the product obtained by the reaction after recovery and separation by a magnet;
washing with redistilled water and absolute ethyl alcohol;
drying at 40-70 deg.C under vacuum for 6-18 h.
5. The synthesis method according to any one of claims 1 to 4, wherein in the step (2), the Fe is3O4The concentration of the magnetic nanoparticles in the ethanol solution of the modifier is 3-9g/L, and the concentration of the modifier in the ethanol solution of the modifier is 0.1-0.3 mmol/L;
the reaction is carried out for 12-28h under shaking.
6. The synthesis method according to any one of claims 1 to 4, wherein in the step (3), the concentration of ammonia water is 1M.
7. The synthesis method according to claim 6, wherein in the step (3), the ultrasonic reaction is 100W ultrasonic reaction for 20 min.
8. The synthesis of claim 7The method is characterized in that in the step (3), after the reaction is finished, a magnet is used for recovering and separating off-white products, and the off-white products are washed and dried to obtain Fe3O4a/ZnO nanocomposite;
drying at 40-70 deg.C for 8-14 h.
9. Fe prepared by the method of any one of claims 1 to 83O4ZnO nanocomposite, Fe in said nanocomposite3O4The nanospheres are uniformly distributed on the ZnO thin sheet.
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