CN104128184B - A kind of float type CoFe2O4/TiO2/ float bead composite photochemical catalyst and preparation method thereof - Google Patents

Abstract

The invention discloses a floating CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst and a preparation method thereof, a CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst for treating organic wastewater and a preparation method thereof. Including catalyst active components and catalyst carrier, the catalyst active components and weight percentages are respectively: Co is 0.5-1wt%; Fe is 1-2wt%; Ti is 12-18wt%; the rest is fly ash floating bead catalyst carrier. The obtained CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst is loaded with CoFe ₂ O ₄ on the TiO2 film on the surface of the floating bead, which increases the specific surface area and improves the adsorption performance.

Description

A floating type CoFe2O4/TiO2/floating bead composite photocatalyst and its preparation method

technical field

The invention relates to the technical field of environmental material preparation, in particular to a floating CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst and a preparation method thereof.

Background technique

The use of semiconductors and compound semiconductors to photocatalyze the degradation of organic pollutants has achieved good research results in environmental pollution control in recent years. As a photocatalyst, TiO ₂ has good chemical stability, low cost, non-toxicity, easy access to raw materials, and can directly use visible light in sunlight as an excitation light source for catalytic oxidation, without secondary pollution, and is more environmentally friendly. Therefore, photocatalysis has broad application prospects in energy and environmental governance. However, TiO ₂ photocatalytic oxidation technology also has some shortcomings in the actual application process. For example: TiO ₂ photocatalyst has low quantum efficiency, poor selective adsorption, harsh curing conditions, easy aggregation and deactivation, etc. Moreover, the spectral response range is in the ultraviolet region, and the visible part of the solar spectrum cannot be effectively utilized, which limits its industrial application. In view of the shortcomings of TiO ₂ photocatalytic oxidation technology, the relevant literature at home and abroad mainly conducts research on the modification of TiO ₂ photocatalysts in two aspects: one is modification by doping; the other is the development and research of supported photocatalysts to make them be better utilized in practical applications.

Fly ash floating beads are derived from fly ash produced by thermal power plants. They are cheap and have a wide range of sources. They are porous media materials with a larger specific surface area, which can improve the adsorption effect on organic pollutants. In recent years, this modified fly ash photocatalyst has been widely used in wastewater treatment. The photocatalyst with floating beads as the carrier can float on the water surface, which is conducive to recycling and reuse, and not only solves the shortcomings of traditional photocatalysts such as easy condensation and deactivation. The composite catalyst formed by doping _TiO2 with magnetic materials is beneficial to the recovery and reuse of the catalyst, expands the photoresponse range of the composite catalyst, and can improve the catalytic activity of the modified fly ash bleached pearlescent catalyst in the ultraviolet region , can make its photoresponse wavelength shift from the ultraviolet region to the visible region, and improve the utilization rate of sunlight. The development of low-cost, high-efficiency, and easy-to-recycle photocatalysts will be of great significance.

Contents of the invention

In order to solve the above-mentioned problems in the prior art, an object of the present invention is to provide a floating type CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst, compared with the current photocatalyst, CoFe ₂ O ₄ /TiO ₂ /Floating bead composite photocatalyst can float on the water surface, fully absorb sunlight, and improve the photocatalytic degradation effect. The doped TiO ₂ /floating bead composite photocatalyst shifts the photoresponse wavelength from the ultraviolet region to the visible region, improving the utilization rate of sunlight. The catalyst carrier adopts hollow floating beads, which are cheap and easy to obtain, and the cost is low, which effectively improves the service life of the photocatalyst. CoFe ₂ O ₄ is used as the active component of the catalyst, which is magnetic and easy to recycle and reuse. Another object of the present invention is to provide a method for preparing a floating type CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst, using fly ash hollow floating beads as a carrier, and _TiO2 is loaded on the fly ash floating beads, Then, CoFe ₂ O ₄ particles were supported on the surface of TiO ₂ , so that this modified fly ash bleached pearlescent catalyst could be recycled repeatedly. CoFe ₂ O ₄ /TiO ₂ expands the photoresponse range of the composite catalyst, so the composite catalyst has higher solar photocatalytic activity.

To achieve the above object, the technical solution of the present invention is:

A floating-type CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst, including catalyst active components and catalyst supports, and the contents of each component by weight percentage are: Co is 0.5-1wt%; Fe is 1-2wt% ; Ti is 12-18wt%; the rest is fly ash floating bead catalyst carrier.

Further, in the photocatalyst, the components by weight percentage are: Co is 0.7wt%, Fe is 1.5wt%, Ti is 15wt%, and the rest is fly ash floating bead catalyst carrier.

A kind of preparation method of floating type CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst, described method comprises the following steps:

Step 1. Pretreatment of floating beads

Prepare 10% dilute nitric acid, soak fly ash beads in it for 15-24 hours, filter, rinse with deionized water until neutral, then dry, then put in muffle furnace, calcined at 400-500°C for 2- 4h to carbonize the unremoved organic matter, because the floating beads contain unburned organic carbon, which will affect the surface area and adsorption capacity of the floating beads, and calcine them into CO ₂ , which can increase the specific surface area of the floating beads and increase the pores efficiency, improve the adsorption performance, reduce the quality of the floating beads, and make them float better, which is beneficial to the loading of TiO ₂ and improve the photocatalytic performance. Rinse with distilled water to sort out the floating beads that are completely floating on the water surface, and filter and dry them. After sieving, select floating beads with a particle size of 100-125um as the carrier of the catalyst;

Step 2, _TiO sol preparation

At room temperature, add 30-40mL butyl titanate to 80-100mL absolute ethanol and keep stirring. After fully dissolving, add 10-12mL acetylacetone to obtain A solution, because tetrabutyl titanate reacts with distilled water to form TiO ₂ Sol, the hydrolysis of butyl titanate is very violent, so acetylacetone is added as its inhibitor, acetylacetone and butyl titanate form ligands, so that a large amount of water cannot be removed, and these ligands prevent the hydrolysis reaction from proceeding , and further polymerization with TiO ₂ to form a stable colloidal solution; 1.5-2.0mL distilled water and 50mL absolute ethanol are fully mixed to obtain B solution; absolute ethanol is used as a solvent for butyl titanate, which can reduce the viscosity of the formed sol , the gel becomes thinner and uniform. In addition, the mixed solvent can slow down the hydrolysis reaction rate and make the _TiO2 film formed uniformly dispersed. A single water as a solvent will make the formed _TiO2 polymerized unevenly. Add solution B dropwise to solution A under constant stirring, and adjust its pH to 4-5 with concentrated nitric acid, stir for 1-2 hours to make it fully react, then add 2-3g polyethylene glycol, and the temperature rises to 50 ℃ and continue to stir for 1-1.5h to obtain a yellow and transparent TiO ₂ sol, which is aged at room temperature for 12-15h;

Step 3. Preparation of TiO ₂ /floating bead-supported photocatalyst

Put 30-40g of activated floating beads into the prepared TiO ₂ sol, and keep stirring at room temperature for 1-1.5h to completely mix the floating beads carrier with the sol, then heat in a water bath to 80°C to evaporate the solution to nearly dryness, and put Dry it in a constant temperature drying oven at 80°C, then heat it in a muffle furnace at a constant speed to 500°C for 2 hours, take it out after cooling to room temperature, and repeat the process of mixing the beads with the sol, drying, calcining, and cooling for 3 times , the purpose is to uniformly form a three-layer _TiO2 film on the floating beads to improve adsorption and photocatalytic activity;

Step 4. Preparation of CoFe ₂ O ₄ -TiO ₂ /floating bead-supported photocatalyst

Take 20mL0.02mol/LCo(NO ₃ ) ₂ solution and 80mL0.01mol/LFe(NO ₃ ) ₃ solution respectively (n(Co(NO ₃ ) ₂ ):n(Fe(NO ₃ ) ₃ )=1:2) After fully mixing, add 60ml of 0.02mol/L citric acid (the ratio of the amount of total metal substances to the amount of citric acid is 1:1), stir continuously, adjust the pH to 5-6 with concentrated ammonia water, and place in a water bath at 80°C After stirring at a medium speed for 1-2 hours, add 20-30g of TiO ₂ floating beads, the volume of Co(NO ₃ ) ₂ solution: TiO ₂ floating beads is 1:1-1.5ml/g, continue heating and steaming until nearly dry, and place in an oven at 120°C After drying, move it into a muffle furnace and bake at 500°C for 2h and cool to room temperature for later use. The obtained catalyst sample was rinsed with distilled water, and the floating part was collected and baked in an oven at 105°C for 2-4 hours, and then cooled to obtain the desired CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst.

Further, the amount of the cobalt salt is 0.5-1wt% of the photocatalyst CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst based on the weight of cobalt in the catalyst; Fe is 1-2wt%; Ti is 12-18wt% ; The rest is divided into fly ash floating bead catalyst carrier. The amount of the iron salt is 1-2wt% of the photocatalyst CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst by the weight of iron in the catalyst, and the amount of titanium is the photocatalyst CoFe ₂ O by the weight of titanium in the catalyst. 12-18wt% of ₄ /TiO ₂ /floating bead composite photocatalyst.

Further, the cobalt and iron soluble salts are respectively selected from the following compounds: any one of cobalt nitrate, iron molybdate, copper nitrate, nickel nitrate, zinc nitrate, bismuth nitrate, and the titanium comes from butyl titanate.

Compared with the prior art, the beneficial effects of the present invention are: the present invention provides a floating type CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst, compared with the current photocatalyst, CoFe ₂ O ₄ /TiO ₂ / The floating bead composite photocatalyst can float on the water surface, fully absorb sunlight, and improve the photocatalytic degradation effect. The doped TiO ₂ /floating bead composite photocatalyst shifts the photoresponse wavelength from the ultraviolet region to the visible region, improving the utilization rate of sunlight. The catalyst carrier adopts hollow floating beads, which are cheap and easy to obtain, and the cost is low, which effectively improves the service life of the photocatalyst. CoFe ₂ O ₄ is used as the active component of the catalyst, which is magnetic and easy to recycle and reuse. The advantage of the present invention is that the fly ash hollow floating beads with large specific surface area, strong adsorption and photocatalysis functions, cheap and easy to obtain are used as the catalyst carrier and floated in water. The catalytically active components with magnetic properties are cobalt and iron. , Titanium composite components, cobalt, iron, titanium composite components are distributed on the surface of floating beads in the form of particles, which increases the surface area and adsorption performance, makes organic wastewater better photocatalytic performance, and improves the degradation rate of organic matter. The photoresponse wavelength can be shifted from the ultraviolet region to the visible region, and the utilization rate of sunlight can be improved. The catalyst is simple to prepare, has strong catalytic activity, is magnetic, can be recycled and reused, and has the advantages of potential and better treatment of floating organic pollutants.

Description of drawings

Fig. 1 is a scanning electron micrograph of CoFe ₂ O ₄ -TiO ₂ /floating bead supported photocatalyst.

Fig. 2 is a solid ultraviolet-visible spectrum diagram of TiO ₂ /floating bead-supported photocatalyst and CoFe ₂ O ₄ -TiO ₂ /floating bead-supported photocatalyst.

Figure 3 is the FT-IR spectrum of CoFe ₂ O ₄ /TiO ₂ /floating beads.

Fig. 4 is a diagram of the time degradation rate of the photocatalytic degradation of methylene blue solution by the CoFe ₂ O ₄ -TiO ₂ /floating bead supported photocatalyst.

Fig. 5 is a graph of time degradation rate of photocatalytic degradation of phenol solution by CoFe ₂ O ₄ -TiO ₂ /floating bead supported photocatalyst.

Figure 6 shows the CoFe _{2 O 4 -TiO 2 photocatalyst loaded with uncalcined floating beads as a carrier and the CoFe 2 O 4 -TiO 2 photocatalyst loaded with} calcined floating beads as a carrier for photocatalytic degradation of methylene blue solution The time degradation rate graph of the experiment.

detailed description

The scheme of the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments,

Example 1

A floating type CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst, the components by weight percentage are: Co is 0.7wt%; Fe is 1.5wt%; Ti is 15wt%, and the rest is pulverized coal Gray floating bead catalyst carrier.

The preparation method of the floating type CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst comprises the following steps:

1) Pretreatment of floating beads

Prepare 10% dilute nitric acid, soak the fly ash floating beads in it for 15 hours, filter, rinse with deionized water until neutral, then dry it, then put it in a muffle furnace, and calcinate it at 400°C for 2 hours to remove the unremoved Carbonization of organic matter. Rinse with distilled water to sort out the floating beads that are completely floating on the water surface. After filtering, drying and sieving, select the floating beads with a particle size of 100-125um as the carrier of the catalyst;

2) Preparation of TiO ₂ sol

Add 40mL of butyl titanate to 100mL of absolute ethanol at room temperature and keep stirring. After fully dissolving, add 10mL of acetylacetone to obtain A solution; 2.0mL of distilled water and 50mL of absolute ethanol are fully mixed to obtain B solution. Add solution B dropwise to solution A under constant stirring, adjust its pH to 4-5 with concentrated nitric acid, stir for 1-2 hours to fully react, then add 3g of polyethylene glycol, the temperature rises to 50°C and Stirring was continued for 1h, and a yellow transparent TiO ₂ sol was obtained, which was aged at room temperature for 12h.

3) Preparation of TiO ₂ /floating bead-supported photocatalyst

Put 30g of activated floating beads into the prepared TiO ₂ sol, and keep stirring at room temperature for 1.5h to completely mix the floating beads carrier with the sol, then heat in a water bath to 80°C to evaporate the solution to nearly dry, and put it in a constant temperature drying oven (80°C) drying, then heating to 500°C at a constant speed in a muffle furnace for calcination for 2 hours, cooling to room temperature, taking out for later use, repeated mixing of floating beads with sol, drying, calcination, and cooling, repeating this process 3 times.

4) Preparation of CoFe ₂ O ₄ -TiO ₂ /floating bead-supported photocatalyst

Take 20mL0.02mol/LCo(NO ₃ ) ₂ solution and 80mL0.01mol/LFe(NO ₃ ) ₃ solution respectively (n(Co(NO ₃ ) ₂ ):n(Fe(NO ₃ ) ₃ )=1:2) After fully mixing, add 60ml of 0.02mol/L citric acid (the ratio of the amount of total metal substances to the amount of citric acid is 1:1), stir continuously, adjust the pH to 5-6 with concentrated ammonia water, and place in a water bath at 80°C After stirring at a medium and constant speed for 2 hours, add 30g TiO ₂ /floating beads, continue heating and steaming until nearly dry, dry in an oven at 120°C, and then transfer to a muffle furnace for roasting at 500°C for 2 hours and cool to room temperature for later use. The obtained catalyst sample was rinsed with distilled water, and the floating part was collected and baked in an oven at 105° C. for 4 hours, and then cooled to obtain the desired CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst. Its topography is shown in Figure 1.

It can be seen from the figure that the floating beads are spherical, and CoFe ₂ O ₄ -TiO ₂ forms a film on the surface of the floating beads. The surface of the film is rough, which is conducive to increasing the specific surface area, increasing the adsorption performance and photocatalytic activity.

Figure 2 is the solid ultraviolet-visible spectrogram of TiO ₂ /floating bead-supported photocatalyst and CoFe ₂ O ₄ -TiO ₂ /floating bead-supported photocatalyst. TiO ₂ has a wide band gap (3.2eV). As can be seen from Figure 2, the band gap of the TiO ₂ /floating bead-supported photocatalyst is reduced to 2.85eV, and the CoFe ₂ O ₄ -TiO ₂ /floating bead-loaded The bandgap of the photocatalyst is further reduced to 2.5eV, which shows that it has better catalytic activity for visible light, thereby improving the utilization efficiency of visible light. It can be seen from Figure 2 that the photoresponse range of CoFe ₂ O ₄ -TiO ₂ /pearl photocatalyst has been extended to the visible light region.

As shown in Figure 3, the FT-IR spectrum of CoFe ₂ O ₄ /TiO ₂ /floating beads, in which 450-700 is the characteristic peak of CoFe ₂ O ₄ and TiO ₂ , and 1081 is the O-Si-O stretching vibration The peak at 3411 is the OH stretching vibration peak of surface adsorbed water molecules.

Embodiment 2,

A floating type CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst, the components by weight percentage are: Co is 0.5wt%; Fe is 2wt%; Ti is 18wt%, and the rest is fly ash Floating bead catalyst carrier.

Its preparation method is with embodiment 1.

Example 3

A floating-type CoFe ₂ O ₄ /TiO ₂ /floating bead composite photocatalyst, the components by weight percentage are: Co is 1wt%, Fe is 1wt%, Ti is 12wt%, and the rest is fly ash float Bead Catalyst Support.

Its preparation method is with embodiment 1.

Test example 1

With the obtained CoFe ₂ O ₄ -TiO ₂ / floating bead loaded photocatalyst photocatalytic degradation methylene blue solution, reaction initial conditions: methylene blue initial concentration 100mg/L, catalyst consumption 0.4g, pH=5, will The degradation experiment was carried out in a visible light catalytic reactor, and the degradation time was 120 minutes. Samples were taken every 20 minutes to measure the absorbance with a visible light spectrophotometer, and the degradation efficiency of methylene blue was measured. As shown in Figure 4, the degradation efficiency reached 85% at 80 min. Test example 2

Carry out photocatalytic degradation methylene blue solution comparison with Example 1 TiO ₂ /floating beads and CoFe ₂ O ₄ -TiO ₂ /floating bead supported photocatalysts, experimental conditions: catalyst dosage 0.4g, methylene blue initial concentration 50mg/L, pH =5. The degradation experiment was carried out in a visible light catalytic reactor. The degradation time was 60 minutes. Samples were taken every 10 minutes to measure the absorbance, and the degradation efficiency of methylene blue was calculated, as shown in Table 1.

Test example 3

With the obtained CoFe ₂ O ₄ -TiO ₂ / floating bead loaded photocatalyst photocatalytic degradation phenol solution, experimental conditions: catalyst consumption 1.0g, phenol solution initial concentration 25, 50, 75, 100mg/L, pH = 5. The degradation experiment was carried out in a visible light catalytic reactor. The degradation time was 7 hours. Samples were taken every 1 hour to measure the absorbance, and the degradation efficiency of methylene blue was calculated, as shown in Figure 5.

Test example 4

The CoFe _{2 O 4 -TiO 2 photocatalyst loaded with uncalcined floating beads as a carrier and the CoFe 2 O 4 -TiO 2 photocatalyst loaded with} calcined floating beads as a carrier were used for the photocatalytic degradation experiment of methylene blue solution. Reaction initial conditions: the initial concentration of methylene blue is 75mg/L, the amount of catalyst is 0.3g, and pH=5. It is subjected to a degradation experiment in a visible light catalytic reactor. Absorbance, a measure of methylene blue degradation efficiency. As shown in Figure 6, within 120 min, the degradation efficiency of the calcined floating bead-supported CoFe ₂ O ₄ -TiO ₂ photocatalyst was significantly better than that of the calcined floating bead-supported CoFe ₂ O ₄ -TiO ₂ photocatalyst.

In summary, the present invention is a floating _- type CoFe ₂ O ₄ / _{TiO 2} /floating bead composite photocatalyst _. Absorb sunlight and improve photocatalytic degradation effect. The doped TiO ₂ /floating bead composite photocatalyst shifts the photoresponse wavelength from the ultraviolet region to the visible region, improving the utilization rate of sunlight. The catalyst carrier adopts hollow floating beads, which are cheap and easy to obtain, and the cost is low, which effectively improves the service life of the photocatalyst. CoFe ₂ O ₄ is used as the active component of the catalyst, which is magnetic and easy to recycle and reuse. The advantage of the present invention is that the fly ash hollow floating beads with large specific surface area, strong adsorption and photocatalysis functions, cheap and easy to obtain are used as the catalyst carrier and floated in water. The catalytically active components with magnetic properties are cobalt and iron. , Titanium composite components, cobalt, iron, titanium composite components are distributed on the surface of floating beads in the form of particles, which increases the surface area and adsorption performance, makes organic wastewater better photocatalytic performance, and improves the degradation rate of organic matter. The photoresponse wavelength can be shifted from the ultraviolet region to the visible region, and the utilization rate of sunlight can be improved. The catalyst is simple to prepare, has strong catalytic activity, is magnetic, can be recycled and reused, and has the advantages of potential and better treatment of floating organic pollutants.

The above is only a specific implementation of the present invention, but the scope of protection of the present invention is not limited thereto, and any changes or replacements that do not come to mind through creative work shall be covered within the scope of protection of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope defined in the claims.

Claims (1)

1. a float type CoFe₂O₄/TiO₂/ float the preparation method of bead composite photochemical catalyst, it is characterized in that described method bagDraw together following steps:

Step 1, float the pretreatment of pearl

Preparation rare nitric acid of 10%, soaks fly ash float wherein 15-24h, filtration, after neutral, dries by rinsed with deionized waterDry, be then put in Muffle furnace, at 400-500 DEG C, calcine 2-4h by the organic carbon of wherein not removing, float with distilled waterWash and sub-elect the pearl that floats swimming in completely on the water surface, after filtration drying sieves, the pearl that floats of choosing particle diameter and be 100-125 μ m doesFor the carrier of catalyst;

Step 2, TiO₂The preparation of colloidal sol

Under room temperature, in every 80-100mL absolute ethyl alcohol, add 30-40mL butyl titanate and constantly stir, after fully dissolving, adding10-12mL acetylacetone,2,4-pentanedione, obtains A solution; After fully mixing, 1.5-2.0mL distilled water and 50mL absolute ethyl alcohol obtain B solution; ?Under the condition constantly stirring, B solution is dropwise added in A solution, and to regulate its pH with red fuming nitric acid (RFNA) be 4-5, stir l-2h it is filledPoint reaction, then adds 2-3g polyethylene glycol, temperature rise to 50 DEG C also continues to stir l-1.5h, obtains yellow transparentTiO₂Colloidal sol, is placed in ageing 12-15h under room temperature;

Step 3, TiO₂/ float the preparation of pearl loaded photocatalyst

The pearl that floats of 30-40g activation is added to the TiO preparing₂In colloidal sol, under room temperature continue stir 1-1.5h, make to float bead carrier withColloidal sol mixes completely, and then heating water bath to 80 DEG C steams near dry solution, puts into 80 DEG C of oven dry of thermostatic drying chamber, then horseNot constant-speed heating to 500 DEG C calcining 2h in stove, is cooled to and takes out after room temperature for subsequent usely, will float pearl and repeat to mix, dry, forge with colloidal solBurning, cooling, repeats this process 3 times, and object is to make to float even three layers of TiO of formation on pearl₂Film, improves adsorptivity and photocatalysis and livesProperty;

Step 4, CoFe₂O₄-TiO₂/ float the preparation of pearl loaded photocatalyst

Described step 4 CoFe₂O₄-TiO₂/ the preparation process of floating pearl loaded photocatalyst is to get respectively 20mL0.02mol/LCo²⁺Solution and 80mL0.01mol/LFe³⁺Solution makes n (Co²⁺):n(Fe³⁺)=1:2, adds 0.02mol/ after fully mixingL citric acid, making the total amount of substance of metal and the ratio of the amount of substance of citric acid is 1:1, constantly stir, with concentrated ammonia liquor adjust pH extremely5～6, in 80 DEG C of water-baths, at the uniform velocity stir after 1-2h, add TiO₂/ float pearl, Co²⁺Liquor capacity: TiO₂/ to float pearl be 1:1-1.5mL/g, extremely near doing steamed in continuation heating, and after drying in 120 DEG C of baking ovens, in immigration Muffle furnace, at 500 DEG C, roasting 2h is cooled toRoom temperature is for subsequent use, and by the catalyst sample obtaining, through distilled water rinsing, floating part collects at 105 DEG C of baking ovens dries 2-4h, coldBut, make required CoFe₂O₄/TiO₂/ float bead composite photochemical catalyst.