CN107442178B - Visible light catalyst Fe3O4Preparation method of @ PDA @ Ag composite microspheres - Google Patents

Visible light catalyst Fe3O4Preparation method of @ PDA @ Ag composite microspheres Download PDF

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CN107442178B
CN107442178B CN201710651092.3A CN201710651092A CN107442178B CN 107442178 B CN107442178 B CN 107442178B CN 201710651092 A CN201710651092 A CN 201710651092A CN 107442178 B CN107442178 B CN 107442178B
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pda
solution
composite microspheres
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CN107442178A (en
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程琳
郑海旺
李小云
吴小平
金立
汪洋
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Zhejiang University of Technology ZJUT
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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    • B01J35/39—
    • B01J35/393—
    • B01J35/397—
    • B01J35/51—
    • 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
    • C02F2101/40—Organic compounds containing sulfur
    • 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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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention belongs to the technical field of photocatalysts, and particularly relates to a visible-light-driven photocatalyst Fe3O4The preparation method of the @ PDA @ Ag composite microsphere comprises the following steps: step one, respectively dissolving ferric trichloride hexahydrate and sodium acetate into ethylene glycol with the same amount, then mixing and stirring the two solutions uniformly, adding 10-30 wt% of polyacrylic acid solution, continuously stirring for 6-12h, placing the mixture into a reaction kettle, and keeping the mixture to react for 4-12 h at 180-210 ℃ to obtain a black product ferroferric oxide; dispersing ferroferric oxide into an ethanol solution of polyvinylpyrrolidone, adding an aqueous solution of dopamine hydrochloride, carrying out water bath, and carrying out sufficient ultrasonic dispersion to form a mixed solution b; thirdly, dropwise adding ammonia water into the mixed solution b, and continuing the ultrasonic reaction for 2-5 hours to obtain Fe3O4@ PDA composite microspheres; step four, the prepared Fe3O4Adding the @ PDA composite microspheres into ammonia water and silver nitrate to prepare a silver-ammonia solution, placing the silver-ammonia solution into a shaking table to shake for 8-16 hours, carrying out magnetic separation, and carrying out post-treatment to obtain Fe3O4@ PDA @ Ag composite microspheres. The effect of degrading and degrading methyl orange is obvious, and the methyl orange can be repeatedly used.

Description

Visible light catalyst Fe3O4Preparation method of @ PDA @ Ag composite microspheres
Technical Field
The invention belongs to the technical field of photocatalysts, and particularly relates to visible light photocatalysisAgent Fe3O4A preparation method of @ PDA @ Ag composite microspheres.
Background
In recent years, with the rapid development of scientific technology and industrial technology, the living standard of people is greatly improved. However, the rapid development of economy and industry has resulted in serious problems such as environmental pollution and resource shortage. The photocatalysis technology is an effective means for treating environmental pollution which is rapidly developed in recent years. The international union of pure and applied chemistry defines photocatalysis as such: under the irradiation of ultraviolet, visible or infrared light, the photocatalyst absorbs light and participates in chemical changes of reactants to cause the rate of or change of chemical reactions. The essence of the photocatalysis technology is that solar energy is utilized to carry out chemical catalytic reaction, and the photocatalysis technology is a green technology with low cost and high efficiency. At present, due to TiO2It has the advantages of no toxicity, strong oxidizing power, low cost, etc. and is mainly used as the photocatalytic material for environment treatment. However, due to TiO2The band gap of the material is wide (about 3.2eV), and the material can only absorb ultraviolet light with the wavelength of less than 380nm, in sunlight, the ultraviolet light accounts for about 4 percent of the sunlight, the visible light accounts for about 45 percent of the sunlight, and TiO2The nature of the photocatalyst itself limits its practical application as a photocatalyst. In addition, in consideration of the defects that the photocatalytic material is difficult to recycle and causes resource waste, the research on the photocatalyst which has high efficiency, visible light response and can be recycled is the focus of the research in the field of photocatalysis at present.
There are some complex materials in nature, which have both photocatalytic activity and superparamagnetism, such as some perovskites and spinels, but the yield of natural resources is limited and the performance is not stable enough. In order to make the material have magnetism, researchers load the photocatalytic active material on a magnetic carrier, so that the composite material can not only keep the catalytic activity of the photocatalyst, but also enable the material to be quickly magnetically separated under the action of an external magnetic field, effectively improve the reuse rate of the nano photocatalytic material and save the cost. The superparamagnetic ferroferric oxide material well meets the requirement. The noble metal has a strong visible plasma resonance effect, so that the visible absorption of the photocatalyst can be enhanced, wherein Ag + has an electronic structure of d10, and the full or full-empty electronic structure is favorable for improving the photocatalytic activity, so that the noble metal Ag-based micro-nano material becomes an important material for research on photocatalytic degradation of organic pollutants. The magnetic material ferroferric oxide and the photocatalyst are effectively compounded, so that the material not only has photocatalytic performance, but also has the advantages of rapid solid-liquid separation and recycling, and secondary pollution to the environment is avoided.
The ferroferric oxide material has high surface energy, and is easy to agglomerate to increase the size of particles and influence the magnetic property of the ferroferric oxide material. Meanwhile, due to the influence of the surface effect, the photocatalyst is easily oxidized in the air, so that the magnetism of the photocatalyst is reduced, and therefore, the research on the photocatalyst which is efficient, has visible light response and can be recycled is the key point of the research in the field of photocatalysis at present.
Disclosure of Invention
The invention aims to provide a visible light photocatalyst Fe3O4A preparation method of @ PDA @ Ag composite microspheres. In the present invention, PDA is polydopamine.
In order to achieve the purpose, the invention adopts the technical scheme that the visible light catalyst Fe3O4The preparation method of the @ PDA @ Ag composite microspheres is characterized by comprising the following steps of:
step one, respectively dissolving ferric trichloride hexahydrate and sodium acetate into ethylene glycol with the same amount, mixing and stirring the two solutions uniformly, adding 10-30 wt% of polyacrylic acid solution, continuously stirring for 6-12 hours to form a mixed solution a, placing the mixed solution a into a reaction kettle, and keeping the temperature of 180-210 ℃ for reaction for 4-12 hours to obtain a black product ferroferric oxide;
dispersing ferroferric oxide into an ethanol solution of polyvinylpyrrolidone, adding an aqueous solution of dopamine hydrochloride, carrying out water bath, and carrying out sufficient ultrasonic dispersion to form a mixed solution b;
thirdly, dropwise adding ammonia water into the mixed solution b, continuing the ultrasonic reaction for 2-5 hours, then carrying out magnetic separation and washing for a plurality of times to obtainTo Fe3O4@ PDA composite microspheres;
step four, the prepared Fe3O4Adding the @ PDA composite microspheres into ammonia water and silver nitrate to prepare a silver-ammonia solution, placing the silver-ammonia solution into a shaking table to shake for 8-16 hours, carrying out magnetic separation, and carrying out post-treatment to obtain Fe3O4@ PDA @ Ag composite microspheres.
Preferably, in the first step, the molar ratio of ferric trichloride hexahydrate to ethylene glycol is 1: 300-500, the molar ratio of sodium acetate to ethylene glycol is 1: 100-300, and the volume ratio of ethylene glycol to 10-30 wt% polyacrylic acid solution in the mixed solution a is 40-80: 1.
Preferably, the mass ratio of the ferroferric oxide to the polyvinylpyrrolidone in the second step is 1: 2-3, and the molar ratio of the polyvinylpyrrolidone to the ethanol is 1: 30-150.
Further, the mass ratio of the dopamine hydrochloride and the water in the second step is 1-3, and the volume ratio of the ethanol to the water is 1: 3-2.
Preferably, the concentration of the ammonia water in the third step is 3-14.5 mol/L.
Specifically, the dropping in the third step is performed by using a peristaltic pump.
Preferably, said step four Fe3O4The mass ratio of the @ PDA composite microspheres to the silver nitrate is 1-6, and the concentration of ammonia water is 0.2-3 mol/L.
Preferably, the temperature of the water bath in the second step is 25 ℃.
Specifically, the post-treatment in the fourth step is to wash the substrate with ethanol for 2-6 times and dry the substrate in an oven at 60-80 ℃.
The invention also comprises Fe3O4The @ PDA @ Ag composite microsphere is characterized by being prepared by any one of the preparation methods.
The invention has the following beneficial effects:
(1) the invention prepares the photocatalyst Fe by loading the photocatalytic active material on a magnetic carrier3O4The @ PDA @ Ag composite microsphere has the photocatalytic effect, and simultaneously, as ferroferric oxide magnetic cores are introduced, the composite microsphere has the advantages of good photocatalytic effect and high photocatalytic efficiencyThe magnetic separation device can perform magnetic separation quickly, effectively improves the reuse rate of the nano photocatalytic material, saves the cost, and avoids secondary pollution to the environment.
(2) The invention utilizes Polydopamine (PDA) as a modifier in Fe3O4The surface of the material is provided with a modification layer, polydopamine has strong adhesion and can be applied to Fe3O4Self-polymerization film formation on the substrate can improve Fe3O4Surface hydrophilicity and biocompatibility; meanwhile, polydopamine has certain reducibility, can realize electroless metallization on the surface of the material, and is convenient for coating Ag particles.
(3) Photocatalyst Fe prepared by the invention3O4The @ PDA @ Ag composite microspheres have a good degradation effect on methyl orange degradation, have a great application value in the aspect of organic sewage treatment, are easy to obtain raw materials, are simple in process and are a nano photocatalytic material with great potential.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to derive other drawings without creative efforts.
FIG. 1 is a scanning electron microscope photograph of superparamagnetic ferroferric oxide nanospheres prepared in example 1;
FIG. 2 is a TEM photograph of superparamagnetic ferroferric oxide microspheres prepared in example 1;
FIG. 3 is Fe prepared in example 13O4Scanning electron microscope photo of @ PDA composite microsphere;
FIG. 4 is Fe prepared in example 13O4A transmission electron microscope photograph of the @ PDA composite microspheres;
FIG. 5 is Fe prepared in example 13O4Scanning electron microscope photo of @ PDA @ Ag composite microsphere;
FIG. 6 is Fe prepared in example 13O4EDS spectrum of @ PDA @ Ag composite microsphere;
FIG. 7 is Fe prepared in example 13O4The MH map of the @ PDA @ Ag composite microsphere;
FIG. 8 is Fe prepared in example 23O4Scanning electron microscope photo of @ PDA @ Ag composite microsphere;
FIG. 9 is Fe prepared in example 33O4Scanning electron microscope photo of @ PDA @ Ag composite microsphere;
FIG. 10 shows the visible-light-induced photocatalyst Fe prepared in examples 1 to 33O4The spectrum of the catalytic performance of the @ PDA @ Ag composite microsphere for photocatalytic degradation of methyl orange.
Detailed Description
The present invention now will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. The embodiments in the present invention, other embodiments obtained by persons skilled in the art without any inventive work, belong to the protection scope of the present invention.
Example 1
Visible light catalyst Fe3O4The preparation method of the @ PDA @ Ag composite microspheres is characterized by comprising the following steps of:
step one, respectively dissolving ferric trichloride hexahydrate and sodium acetate into ethylene glycol with the same amount, mixing and stirring the two solutions uniformly, adding 10-30 wt% of polyacrylic acid solution, continuously stirring for 6-12 hours to form a mixed solution a, placing the mixed solution a into a reaction kettle, and keeping the temperature of 180-210 ℃ for reaction for 4-12 hours to obtain a black product ferroferric oxide;
dispersing ferroferric oxide into an ethanol solution of polyvinylpyrrolidone, adding an aqueous solution of dopamine hydrochloride, carrying out water bath, and carrying out sufficient ultrasonic dispersion to form a mixed solution b;
thirdly, dropwise adding ammonia water into the mixed solution b, continuing to perform ultrasonic reaction for 2-5 hours, then performing magnetic separation and washing for a plurality of times to obtain Fe3O4@ PDA composite microspheres;
step four, the prepared Fe3O4Adding the @ PDA composite microspheres into ammonia water and silver nitrate to prepare a silver-ammonia solution, placing the silver-ammonia solution into a shaking table to shake for 8-16 hours, carrying out magnetic separation, and carrying out post-treatment to obtain Fe3O4@ PDA @ Ag composite microspheres.
The core content of the invention is that the photocatalytic active material Ag is loaded on the magnetic carrier Fe3O4Prepared photocatalyst Fe3O4The @ PDA @ Ag composite microsphere has the photocatalytic effect, and meanwhile, as ferroferric oxide magnetic cores are introduced, the ferroferric oxide magnetic cores can be quickly subjected to magnetic separation, so that the reuse rate of the nano photocatalytic material is effectively improved, the cost is saved, and the secondary pollution to the environment is avoided. In addition, the photocatalyst Fe prepared by the invention3O4The @ PDA @ Ag composite microspheres have a good degradation effect on methyl orange degradation, have a great application value in the aspect of organic sewage treatment, are easy to obtain raw materials, are simple in process and are a nano photocatalytic material with great potential.
Dissolving ferric trichloride hexahydrate and sodium acetate into equivalent ethylene glycol according to the molar ratio of 1: 350, wherein the molar ratio of the sodium acetate to the ethylene glycol is 1: 200, then mixing and stirring the two solutions uniformly, adding 10-30 wt% of polyacrylic acid solution, continuously stirring for 8 hours to form a mixed solution a, wherein the volume ratio of the total amount of the ethylene glycol in the mixed solution a to the 10-30 wt% of polyacrylic acid solution is 40: 1, injecting the mixed solution into a reaction kettle at 203 ℃, and keeping the reaction for 8 hours to obtain a black product ferroferric oxide;
dispersing ferroferric oxide into an ethanol solution of polyvinylpyrrolidone, wherein the mass ratio of the ferroferric oxide to the polyvinylpyrrolidone is 1: 1, the molar ratio of the polyvinylpyrrolidone to the ethanol is 1: 80, adding a dopamine hydrochloride aqueous solution, the mass ratio of the dopamine hydrochloride to the water is 2: 1, the volume ratio of the ethanol to the water in the system is 1: 2, and performing full ultrasonic dispersion at 25 ℃ in a water bath to form a mixed solution b;
step three, taking 5ml of ammonia water with the concentration of 5mol/L for vermicular cast ironDripping the mixture into the mixed solution by a pump, continuing the ultrasonic reaction for 3 hours, then carrying out magnetic separation and washing for a plurality of times to obtain Fe3O4@ PDA composite microspheres;
step four, the prepared Fe3O4Adding the @ PDA composite microspheres into ammonia water and silver nitrate to prepare a silver-ammonia solution, and placing the silver-ammonia solution into a shaking table to shake for 12 hours; wherein Fe3O4The mass ratio of the @ PDA composite microspheres to the silver nitrate is 2: 1, and the concentration of ammonia water is 2 mol/L.
Performing magnetic separation on the mixture obtained in the step, washing the mixture for 2-6 times by using ethanol, and drying the mixture in a 70 ℃ drying oven to obtain Fe3O4@ PDA @ Ag composite microspheres.
The scanning electron microscope and transmission electron microscope photographs of the superparamagnetic ferroferric oxide microspheres prepared in the embodiment are shown in fig. 1 and 2, and it can be seen from fig. 2 that the synthesized product is very uniform, the dispersibility is good, and the average particle size is 200 nm. Fe prepared in this example3O4Scanning electron microscope and transmission electron microscope photographs of the @ PDA composite microsphere are shown in figures 3 and 4, and it can be seen from the scanning image of figure 3 that good dispersibility is still maintained after the composite microsphere is coated with a layer of polydopamine, and an obvious polydopamine shell layer with the thickness of about 20nm can be seen from the transmission image of figure 4. The final product Fe prepared in this example3O4The scanning electron micrograph of the @ PDA @ Ag composite microsphere is shown in FIG. 5, in which it can be seen that a layer of Ag nanosheet is coated on Fe3O4The surface of the @ PDA composite microsphere keeps good dispersibility. For Fe prepared in this example3O4EDS spectrum characterization of the @ PDA @ Ag composite microspheres is shown in figure 6, and obvious peaks of Fe, Ag and O elements appear in the spectrum, and no other miscellaneous peaks appear. For the superparamagnetic Fe prepared in this example3O4And Fe3O4The magnetic characterization of the @ PDA @ Ag composite microspheres is shown in FIG. 7, the saturation magnetization ratio is 53 and 33emu/g, and the final product is Fe3O4The @ PDA @ Ag composite microsphere is Fe3O4The saturation magnetization of the microspheres is reduced, but the requirement of rapid magnetic separation can still be met.
Example 2
Visible light catalyst Fe3O4The preparation method of the @ PDA @ Ag composite microspheres is characterized by comprising the following steps of:
step one, respectively dissolving ferric trichloride hexahydrate and sodium acetate into equivalent ethylene glycol according to the molar ratio of 1: 500, wherein the molar ratio of the sodium acetate to the ethylene glycol is 1: 200, then uniformly mixing and stirring the two solutions, adding 10-30 wt% of polyacrylic acid solution, continuously stirring for 8 hours, wherein the volume ratio of the total amount of the ethylene glycol to the 10-30 wt% of polyacrylic acid solution is 40: 1, injecting the mixed solution into a reaction kettle at 203 ℃, and keeping the reaction for 12 hours to obtain a black product ferroferric oxide;
step two, dispersing ferroferric oxide into an ethanol solution of polyvinylpyrrolidone, wherein the mass ratio of the ferroferric oxide to the polyvinylpyrrolidone is 1: 1, the molar ratio of the polyvinylpyrrolidone to the ethanol is 1: 100, then adding an aqueous solution of dopamine hydrochloride, the mass ratio of the dopamine hydrochloride to the water is 3: 1, the volume ratio of the ethanol to the water in the system is 1: 2, and fully performing ultrasonic dispersion at 25 ℃ in a water bath;
step three, dropwise adding 5ml of 6mol/L ammonia water into the mixed solution obtained in the step two by using a peristaltic pump, continuing the ultrasonic reaction for 3 hours, then carrying out magnetic separation and washing for a plurality of times to obtain Fe3O4@ PDA composite microspheres;
step four, the prepared Fe3O4Adding the @ PDA composite microspheres into ammonia water and silver nitrate to prepare a silver-ammonia solution, and placing the silver-ammonia solution into a shaking table to vibrate for 8 hours, wherein Fe3O4The mass ratio of the @ PDA composite microspheres to the silver nitrate is 4: 1, and the concentration of ammonia water is 2 mol/L;
performing magnetic separation on the mixture obtained by the reaction in the step, washing the mixture for 2-6 times by using ethanol, and drying the mixture in a 70 ℃ drying oven to obtain Fe3O4@ PDA @ Ag composite microspheres.
The final product Fe prepared in this example3O4The scanning electron micrograph of the @ PDA @ Ag composite microsphere is shown in FIG. 8, in which it can be seen that a layer of denser Ag nanoparticles is coated on Fe3O4The Ag nano-particle size on the surface of the @ PDA composite microsphere is about 8nm。
Example 3
Visible light catalyst Fe3O4The preparation method of the @ PDA @ Ag composite microspheres is characterized by comprising the following steps of:
step one, respectively dissolving ferric trichloride hexahydrate and sodium acetate into equivalent ethylene glycol according to the molar ratio of 1: 350, wherein the molar ratio of the sodium acetate to the ethylene glycol is 1: 200, then uniformly mixing and stirring the two solutions, adding 10-30 wt% of polyacrylic acid solution, continuously stirring for 8 hours, wherein the volume ratio of the total ethylene glycol to the 10-30 wt% of polyacrylic acid solution is 40: 1, injecting the mixed solution into a reaction kettle at 203 ℃, and keeping the reaction for 8 hours to obtain a black product ferroferric oxide;
dispersing ferroferric oxide into an ethanol solution of polyvinylpyrrolidone, wherein the mass ratio of the ferroferric oxide to the polyvinylpyrrolidone is 1: 1, the molar ratio of the polyvinylpyrrolidone to the ethanol is 1: 80, adding an aqueous solution of dopamine hydrochloride, the mass ratio of the dopamine hydrochloride to the water is 2: 1, the volume ratio of the ethanol to the water in the system is 1: 2, and fully performing ultrasonic dispersion at 25 ℃ in a water bath;
step three, dropwise adding 5ml of ammonia water with the concentration of 5mol/L into the mixed solution by using a peristaltic pump, continuing the ultrasonic reaction for 3 hours, then carrying out magnetic separation and washing for a plurality of times to obtain Fe3O4@ PDA composite microspheres;
step four, the prepared Fe3O4Adding the @ PDA composite microspheres into ammonia water and silver nitrate to prepare a silver-ammonia solution, and placing the silver-ammonia solution into a shaking table to shake for 12 hours; wherein Fe3O4The mass ratio of the @ PDA composite microspheres to the silver nitrate is 1: 1, and the concentration of ammonia water is 1 mol/L.
Performing magnetic separation on the mixture obtained by the reaction, washing the mixture for 2-6 times by using ethanol, and drying the mixture in a 70 ℃ drying oven to obtain Fe3O4@ PDA @ Ag composite microspheres.
The final product Fe prepared in this example3O4The scanning electron micrograph of the @ PDA @ Ag composite microsphere is shown in FIG. 9, in which it can be seen that a layer of sparser Ag nanoparticles is coated on Fe3O4@ PDA composite microsphere surface。
Example 4
Degradation test
Separately, 180mL of 10mg/mL methyl orange aqueous solution was added to the visible light catalyst Fe prepared in examples 1, 2 and 33O4@ PDA @ Ag composite microsphere 30mg, then irradiating three groups of methyl orange aqueous solutions for 80min under the light source of a 400nm optical filter xenon lamp (500W), and obtaining the degradation result shown in figure 10. As shown in FIG. 6, the degradation results in examples 1, 2 and 3 are represented by a, ● and ■, respectively. As can be seen from the figure, the photocatalysts prepared in examples 1 to 3 have good degradation effect on methyl orange. The flaky Ag has a better degradation effect, and compared with the granular Ag, the dense Ag particles have better degradation effect than the sparse Ag particles.
Example 5
Visible light catalyst Fe3O4The preparation method of the @ PDA @ Ag composite microsphere comprises the following steps:
firstly, respectively dissolving ferric trichloride hexahydrate and sodium acetate into equivalent ethylene glycol according to the molar ratio of 1: 300, wherein the molar ratio of the sodium acetate to the ethylene glycol is 1: 100, then uniformly mixing and stirring the two solutions, adding 10-30 wt% of polyacrylic acid solution, continuously stirring for 6 hours to form a mixed solution a, wherein the volume ratio of the total amount of the ethylene glycol in the mixed solution a to the 10-30 wt% of the polyacrylic acid solution is 40: 1, injecting the mixed solution into a reaction kettle at 180 ℃, and keeping the reaction for 4 hours to obtain a black product ferroferric oxide;
dispersing ferroferric oxide into an ethanol solution of polyvinylpyrrolidone, wherein the mass ratio of the ferroferric oxide to the polyvinylpyrrolidone is 1: 1, the molar ratio of the polyvinylpyrrolidone to the ethanol is 1: 30, adding an aqueous solution of dopamine hydrochloride, the mass ratio of the dopamine hydrochloride to the water is 1: 1, the volume ratio of the ethanol to the water in the system is 1: 2, and performing full ultrasonic dispersion at 25 ℃ in a water bath to form a mixed solution b;
step three, dropwise adding 5ml of ammonia water with the concentration of 3mol/L into the mixed solution by using a peristaltic pump, continuing the ultrasonic reaction for 2 hours, then carrying out magnetic separation andwashing several times to obtain Fe3O4@ PDA composite microspheres;
step four, the prepared Fe3O4Adding the @ PDA composite microspheres into ammonia water and silver nitrate to prepare a silver-ammonia solution, and placing the silver-ammonia solution into a shaking table to shake for 8 hours; wherein Fe3O4The mass ratio of the @ PDA composite microspheres to the silver nitrate is 1: 1, and the concentration of ammonia water is 0.2 mol/L.
Performing magnetic separation on the mixture obtained in the step, washing the mixture for 2-6 times by using ethanol, and drying the mixture in a 60 ℃ drying oven to obtain Fe3O4@ PDA @ Ag composite microspheres.
Example 6
Visible light catalyst Fe3O4The preparation method of the @ PDA @ Ag composite microsphere comprises the following steps:
firstly, respectively dissolving ferric trichloride hexahydrate and sodium acetate into equivalent ethylene glycol according to the molar ratio of 1: 500, wherein the molar ratio of the sodium acetate to the ethylene glycol is 1: 300, then uniformly mixing and stirring the two solutions, adding 10-30 wt% of polyacrylic acid solution, continuously stirring for 12 hours to form a mixed solution a, wherein the volume ratio of the total amount of the ethylene glycol in the mixed solution a to the 10-30 wt% of the polyacrylic acid solution is 80: 1, injecting the mixed solution into a reaction kettle at 210 ℃, and keeping the reaction for 12 hours to obtain a black product ferroferric oxide;
dispersing ferroferric oxide into an ethanol solution of polyvinylpyrrolidone, wherein the mass ratio of the ferroferric oxide to the polyvinylpyrrolidone is 1: 3, the molar ratio of the polyvinylpyrrolidone to the ethanol is 1: 150, adding a dopamine hydrochloride aqueous solution, the mass ratio of the dopamine hydrochloride to the water is 3: 1, the volume ratio of the ethanol to the water in the system is 1: 3, and performing full ultrasonic dispersion at 25 ℃ in a water bath to form a mixed solution b;
step three, dropwise adding 5ml of ammonia water with the concentration of 14.5mol/L into the mixed solution by using a peristaltic pump, continuing the ultrasonic reaction for 5 hours, then carrying out magnetic separation and washing for a plurality of times to obtain Fe3O4@ PDA composite microspheres;
step four, the prepared Fe3O4The @ PDA composite microspheres are added into ammonia water and silver nitrate to preparePlacing the silver ammonia solution into a shaking table to shake for 16 hours; wherein Fe3O4The mass ratio of the @ PDA composite microspheres to the silver nitrate is 6: 1, and the concentration of ammonia water is 3 mol/L.
Performing magnetic separation on the mixture obtained in the step, washing the mixture for 2-6 times by using ethanol, and drying the mixture in an oven at the temperature of 80 ℃ to obtain Fe3O4@ PDA @ Ag composite microspheres.
Example 7
Visible light catalyst Fe3O4The preparation method of the @ PDA @ Ag composite microsphere comprises the following steps:
firstly, respectively dissolving ferric trichloride hexahydrate and sodium acetate into equivalent ethylene glycol according to the molar ratio of 1: 400, wherein the molar ratio of the sodium acetate to the ethylene glycol is 1: 200, then uniformly mixing and stirring the two solutions, adding 10-30 wt% of polyacrylic acid solution, continuously stirring for 8 hours to form a mixed solution a, wherein the volume ratio of the total amount of the ethylene glycol in the mixed solution a to the 10-30 wt% of polyacrylic acid solution is 60: 1, injecting the mixed solution into a reaction kettle at 190 ℃ and keeping the reaction for 6 hours to obtain a black product ferroferric oxide;
dispersing ferroferric oxide into an ethanol solution of polyvinylpyrrolidone, wherein the mass ratio of the ferroferric oxide to the polyvinylpyrrolidone is 1: 3, the molar ratio of the polyvinylpyrrolidone to the ethanol is 1: 120, adding a dopamine hydrochloride aqueous solution, the mass ratio of the dopamine hydrochloride to the water is 3: 1, the volume ratio of the ethanol to the water in the system is 1: 2, and performing full ultrasonic dispersion at 25 ℃ in a water bath to form a mixed solution b;
step three, dropwise adding 5ml of 10mol/L ammonia water into the mixed solution by using a peristaltic pump, continuing the ultrasonic reaction for 3 hours, then carrying out magnetic separation and washing for a plurality of times to obtain Fe3O4@ PDA composite microspheres;
step four, the prepared Fe3O4Adding the @ PDA composite microspheres into ammonia water and silver nitrate to prepare a silver-ammonia solution, and placing the silver-ammonia solution into a shaking table to shake for 10 hours; wherein Fe3O4The mass ratio of the @ PDA composite microspheres to the silver nitrate is 3: 1, and the concentration of ammonia water is 2 mol/L.
Obtained by the reaction of step (a)After magnetic separation, the mixture is washed for 2-6 times by ethanol and then dried in an oven at 80 ℃ to obtain Fe3O4@ PDA @ Ag composite microspheres.
Example 8
Visible light catalyst Fe3O4The preparation method of the @ PDA @ Ag composite microsphere comprises the following steps:
step one, dissolving 2.16g of ferric trichloride hexahydrate in 40mL of ethylene glycol, dissolving 18g of sodium acetate in 40mL of ethylene glycol, mixing and stirring the two solutions uniformly, adding 2mL of 10-wt% polyacrylic acid solution, continuously stirring for 6 hours to form a mixed solution a, placing the mixed solution a in a reaction kettle, and keeping the temperature of 180 ℃ for reaction for 4 hours to obtain a black product ferroferric oxide;
step two, dispersing 0.02g of ferroferric oxide into 0.1-0.5g of ethanol solution of polyvinylpyrrolidone, dissolving 0.1g of dopamine hydrochloride into 25mL of water, adding the formed dopamine hydrochloride aqueous solution into the ethanol solution, and carrying out water bath at 25 ℃ on the aqueous solution to fully carry out ultrasonic dispersion to form a mixed solution b;
step three, dropwise adding 0.5mL of ammonia water into the mixed solution b by using a peristaltic pump, continuing the ultrasonic reaction for 2 hours, then carrying out magnetic separation and washing for a plurality of times to obtain Fe3O4@ PDA composite microspheres;
step four, 0.05g of Fe prepared above is added3O4Adding the @ PDA composite microspheres into ammonia water and silver nitrate to prepare a silver-ammonia solution, placing the silver-ammonia solution into a shaking table to shake for 8-16 hours, carrying out magnetic separation, washing the silver-ammonia solution with ethanol for 2-6 times, and drying the washed silver-ammonia solution in a drying oven at the temperature of 60-80 ℃ to obtain Fe3O4@ PDA @ Ag composite microspheres; the ammonia water and the silver nitrate are prepared into silver ammonia solution, wherein the ammonia water is 2mL, the silver nitrate is 0.4g, and the water is 40 mL.
Example 9
Visible light catalyst Fe3O4The preparation method of the @ PDA @ Ag composite microsphere comprises the following steps:
step one, dissolving 2.16g of ferric trichloride hexahydrate in 40mL of ethylene glycol, dissolving 18g of sodium acetate in 40mL of ethylene glycol, mixing and stirring the two solutions uniformly, adding 2mL of 30 wt% polyacrylic acid solution, continuously stirring for 12 hours to form a mixed solution a, placing the mixed solution a in a reaction kettle, and keeping the temperature at 210 ℃ for reaction for 12 hours to obtain a black product ferroferric oxide;
step two, dispersing 0.02g of ferroferric oxide into 0.1-0.5g of ethanol solution of polyvinylpyrrolidone, dissolving 0.1g of dopamine hydrochloride into 25mL of water, adding the formed dopamine hydrochloride aqueous solution into the ethanol solution, and carrying out water bath at 25 ℃ on the aqueous solution to fully carry out ultrasonic dispersion to form a mixed solution b;
step three, dropwise adding 0.5mL of ammonia water into the mixed solution b by using a peristaltic pump, continuing the ultrasonic reaction for 5 hours, then carrying out magnetic separation and washing for a plurality of times to obtain Fe3O4@ PDA composite microspheres;
step four, 0.05g of Fe prepared above is added3O4Adding the @ PDA composite microspheres into ammonia water and silver nitrate to prepare a silver-ammonia solution, placing the silver-ammonia solution into a shaking table to vibrate for 16 hours, carrying out magnetic separation, washing the silver-ammonia solution with ethanol for 2-6 times, and drying the silver-ammonia solution in a drying oven at the temperature of 60-80 ℃ to obtain Fe3O4@ PDA @ Ag composite microspheres; the ammonia water and the silver nitrate are prepared into silver ammonia solution, wherein the ammonia water is 2mL, the silver nitrate is 0.4g, and the water is 40 mL.
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 (8)

1. Visible light catalyst Fe3O4The preparation method of the @ PDA @ Ag composite microspheres is characterized by comprising the following steps of:
step one, respectively dissolving ferric trichloride hexahydrate and sodium acetate into ethylene glycol with the same amount, mixing and stirring the two solutions uniformly, adding 10-30 wt% of polyacrylic acid solution, continuously stirring for 6-12 hours to form a mixed solution a, placing the mixed solution a into a reaction kettle, and keeping the temperature of 180-210 ℃ for reaction for 4-12 hours to obtain a black product ferroferric oxide;
dispersing ferroferric oxide into an ethanol solution of polyvinylpyrrolidone, adding an aqueous solution of dopamine hydrochloride, carrying out water bath, and carrying out sufficient ultrasonic dispersion to form a mixed solution b;
thirdly, dropwise adding ammonia water into the mixed solution b, continuing to perform ultrasonic reaction for 2-5 hours, then performing magnetic separation and washing for a plurality of times to obtain Fe3O4@ PDA composite microspheres;
step four, the prepared Fe3O4Adding the @ PDA composite microspheres into a silver-ammonia solution synthesized by ammonia water and silver nitrate, placing the silver-ammonia solution into a shaking table to vibrate for 8-16 hours, carrying out magnetic separation and post-treatment, and coating a layer of Ag nano-sheets on Fe3O4The surface of the @ PDA composite microsphere is prepared to obtain Fe3O4@ PDA @ Ag composite microsphere, Fe3O4Fe in @ PDA @ Ag composite microsphere3O4The average particle size of the core is 200nm, and the average thickness of the PDA is 20 nm; the concentration of the ammonia water in the third step is 3-14.5 mol/L; fe of said step four3O4The mass ratio of the @ PDA composite microspheres to the silver nitrate is 1-6: 1, and the concentration of ammonia water is 0.2-3 mol/L.
2. Fe as claimed in claim 13O4The preparation method of the @ PDA @ Ag composite microspheres is characterized in that in the first step, the molar ratio of ferric trichloride hexahydrate to ethylene glycol is 1: 300-500, the molar ratio of sodium acetate to ethylene glycol is 1: 100-300, and the volume ratio of ethylene glycol to 10-30 wt% polyacrylic acid solution in the mixed solution a is 40-80: 1.
3. Fe as claimed in claim 13O4The preparation method of the @ PDA @ Ag composite microspheres is characterized in that in the second step, the mass ratio of ferroferric oxide to polyvinylpyrrolidone is 1: 1-3, and the molar ratio of polyvinylpyrrolidone to ethanol is 1: 30-150.
4. Fe according to claim 1 or 33O4The preparation method of the @ PDA @ Ag composite microspheres is characterized in that hydrochloric acid in the second stepThe mass ratio of the dopamine to the water is 1-3: 1, and the volume ratio of the ethanol to the water is 1: 3-2.
5. Fe as claimed in claim 13O4The preparation method of the @ PDA @ Ag composite microspheres is characterized in that a peristaltic pump is adopted for dropwise adding in the third step.
6. Fe as claimed in claim 13O4The preparation method of the @ PDA @ Ag composite microspheres is characterized in that the water bath temperature in the second step is 25 ℃.
7. Fe as claimed in claim 13O4The preparation method of the @ PDA @ Ag composite microspheres is characterized in that the post-treatment in the fourth step is that the microspheres are washed for 2-6 times by using ethanol and dried in an oven at the temperature of 60-80 ℃.
8. Fe3O4The @ PDA @ Ag composite microsphere is characterized by being prepared by the preparation method of any one of claims 1-7.
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