CN104128184A - Floating type CoFe2O4/TiO2/floating bead composite photocatalyst and preparation method thereof - Google Patents
Floating type CoFe2O4/TiO2/floating bead composite photocatalyst and preparation method thereof Download PDFInfo
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- CN104128184A CN104128184A CN201410286125.5A CN201410286125A CN104128184A CN 104128184 A CN104128184 A CN 104128184A CN 201410286125 A CN201410286125 A CN 201410286125A CN 104128184 A CN104128184 A CN 104128184A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a floating type CoFe2O4/TiO2/floating bead composite photocatalyst and a preparation method thereof, and specifically relates to a CoFe2O4/TiO2/floating bead composite photocatalyst for treating organic wastewater, and a preparation method thereof. The CoFe2O4/TiO2/floating bead composite photocatalyst comprises catalyst active components and a catalyst carrier. The catalyst active components comprise, by weight, 0.5-1 wt% of Co, 1-2 wt% of Fe, 12-18 wt% of Ti, and the balance being a fly ash floating bead catalyst carrier. In the obtained CoFe2O4/TiO2/floating bead composite photocatalyst, CoFe2O4 is loaded on TiO2 film on the surface of the floating bead, thereby increasing specific surface area and increasing absorption performance.
Description
Technical field
The present invention relates to environmentally conscious materials preparing technical field, particularly a kind of float type CoFe
2o
4/ TiO
2/ float bead composite photochemical catalyst and preparation method thereof.
Background technology
Utilize semiconductor and composite semiconductor photocatalysis degradable organic pollutant, in environmental pollution improvement, obtain in recent years good research effect.TiO
2as photochemical catalyst, have that good chemical stability, cost are low, nontoxic, raw material easily obtains, and can directly utilize the visible ray in sunshine as excitation source, to carry out catalytic oxidation, non-secondary pollution, more environmental protection.Therefore, photocatalysis is being with a wide range of applications aspect the energy and environmental improvement.But TiO
2the photocatalysis oxidation technique part that also comes with some shortcomings in actual application.For example: TiO
2photochemical catalyst quantum efficiency is low, and Selective adsorption is poor, and condition of cure is harsh, easily cohesion, easy inactivation etc.And spectral response range is at ultraviolet region, and in solar spectrum, visible light part can not effectively utilize, and has limited its commercial Application.For TiO
2the deficiency that photocatalysis oxidation technique exists, at present domestic and international pertinent literature is mainly to TiO
2photochemical catalyst carries out the study on the modification of two aspects: the one, pass through doping vario-property; The 2nd, developmental research loaded photocatalyst, is utilized it in actual applications better.
Fly ash float derives from the flyash that thermal power plant produces, low price, and wide material sources, are a kind of more porous media materials of bigger serface that has, and can improve the adsorption effect to organic pollution.This modified coal ash photochemical catalyst is widely used aspect wastewater treatment in recent years.Take float photochemical catalyst that pearl is carrier can the floating and water surface, be conducive to reclaim and reuse, not only solve that traditional photochemical catalyst easily condenses, the easy shortcoming such as inactivation.Utilize magnetic material to TiO
2the composite catalyst that adulterates and form, be conducive to the recovery and reuse of catalyst, expanded the photoresponse scope of composite catalyst, and can improve modified coal ash and float pearly-lustre catalyst in the catalytic activity of ultraviolet region, can make its photoresponse wavelength move to visible region from ultraviolet region, improve the utilization rate of sunshine.The development of photochemical catalyst low-cost, efficient, that easily reclaim is by significant.
Summary of the invention
The problem existing for solving above-mentioned prior art, one object of the present invention is to provide a kind of float type CoFe
2o
4/ TiO
2/ float bead composite photochemical catalyst, compare CoFe with current photochemical catalyst
2o
4/ TiO
2/ float bead composite photochemical catalyst can float on the water surface, fully absorb sunshine, improve photocatalytic degradation effect.TiO through doping
2/ float bead composite photochemical catalyst to make its photoresponse wavelength move to visible region from ultraviolet region, improve the utilization rate of sunshine.Catalyst carrier adopts hollow float bead, and cheap and easy to get, cost is low, has effectively improved photochemical catalyst service life.Adopt CoFe
2o
4as catalyst activity composition, there is magnetic, be easy to reclaim and recycling.Another object of the present invention is to provide a kind of float type CoFe
2o
4/ TiO
2/ floating bead composite photochemical catalyst preparation method, the fly ash hollow of usining floats pearl as carrier, by TiO
2load on fly ash float, then at TiO
2area load CoFe
2o
4particle, makes this modified coal ash float pearly-lustre catalyst and can repeat to recycle.CoFe
2o
4/ TiO
2expanded the photoresponse scope of composite catalyst, thereby composite catalyst has higher sunlight catalytic activity.
For achieving the above object, technical scheme of the present invention is:
A kind of float type CoFe
2o
4/ TiO
2/ float bead composite photochemical catalyst, comprise catalyst activity composition and catalyst carrier, each component by weight percentage composition is respectively: Co is 0.5-1wt%; Fe is 1-2wt%; Ti is 12-18wt%; All the other are fly ash float catalyst carrier.
Further, in described photochemical catalyst, each component by weight percentage composition is respectively: Co is 0.7wt%; Fe is 1.5wt%; Ti is 15wt%, and all the other are fly ash float catalyst carrier.
A kind of float type CoFe
2o
4/ TiO
2/ float the preparation method of bead composite photochemical catalyst, described method comprises the steps:
Step 1, float the pretreatment of pearl
Rare nitric acid of preparation 10%, by fly ash float soak wherein 15-24h, filtration, by rinsed with deionized water to neutral post-drying, then be put in Muffle furnace, at 400-500 ℃, calcine 2-4h by the organic carbon of wherein not removing, because float and contain unburnt organic carbon in pearl, can affect surface area and the adsorption capacity of floating pearl, calcining makes it to become CO
2, can increase and float pearl specific area, increase porosity, improve absorption property, alleviate and float pearl quality, make it floating better, be conducive to TiO
2load, improve photocatalysis performance, with distilled water rinsing, sub-elect the pearl that floats swimming in completely on the water surface, after filtration drying sieves, that chooses particle diameter and be 100-125um floats pearl as the carrier of catalyst;
Step 2, TiO
2the 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, adding 10-12mL acetylacetone,2,4-pentanedione, obtaining A solution, because butyl titanate and distilled water generation hydrolysis generate TiO
2colloidal sol, the hydrolysis of butyl titanate is very violent, so add acetylacetone,2,4-pentanedione as its inhibitor, acetylacetone,2,4-pentanedione and butyl titanate form ligand, and a large amount of water can not be removed, these ligands have stoped hydrolysis to carry out, and TiO
2further polymerization, forms stable colloidal solution; After fully mixing, 1.5-2.0mL distilled water and 50mL absolute ethyl alcohol obtain B solution; Absolute ethyl alcohol, as the solvent of butyl titanate, can make the colloidal sol viscosity forming diminish, gel attenuation and even, and in addition, mixed solvent can slow down hydrolysis reaction, makes it the TiO forming
2film is uniformly dispersed, and single water can make the TiO forming as solvent
2polymerization and inhomogeneous.Under the condition constantly stirring, B solution is dropwise added in A solution, and with red fuming nitric acid (RFNA), to regulate its pH be 4-5, stir l-2h it is fully reacted, then add 2-3g polyethylene glycol, temperature rises to 50 ℃ and continue to stir l-1.5h, obtains the TiO of yellow transparent
2colloidal sol, is placed in ageing 12-15h under room temperature;
Step 3, TiO
2/ float the preparation of pearl loaded photocatalyst
The pearl that floats that 30-40g was activated is put in into the TiO preparing
2in colloidal sol, under room temperature, continue stirring 1-1.5h makes to float bead carrier and mixes completely with colloidal sol, then heating water bath to 80 ℃ steams near dry solution, put into 80 ℃ of oven dry of thermostatic drying chamber, then constant-speed heating to 500 ℃ calcining 2h in Muffle furnace, is cooled to and takes out after room temperature standbyly, will float that pearl repeats to mix with colloidal sol, oven dry, calcining, cooling, repeat this process 3 times, object is to make to float even three layers of TiO of formation on pearl
2film, improves adsorptivity and photocatalytic activity;
Step 4, CoFe
2o
4-TiO
2/ float the preparation of pearl loaded photocatalyst
Get respectively 20mL0.02mol/LCo (NO
3)
2solution and 80mL0.01mol/L Fe (NO
3)
3solution (n (Co (NO
3)
2): n (Fe (NO
3)
3)=1:2) fully after mixing, add 60ml0.02mol/L citric acid (the total amount of substance of metal is 1:1 with the ratio of the amount of substance of citric acid), constantly stir, with concentrated ammonia liquor, adjust pH to 5～6, in 80 ℃ of water-baths, at the uniform velocity stir after 1-2h, add 20-30gTiO
2float pearl, Co (NO
3)
2liquor capacity: TiO
2floating pearl is 1:1-1.5ml/g, continues heating and steams near dry, and after drying in 120 ℃ of baking ovens, moving in Muffle furnace at 500 ℃ roasting 2h, to be cooled to room temperature standby.By the catalyst sample obtaining, through distilled water rinsing, floating part collects at 105 ℃ of baking ovens dries 2-4h, cooling, makes required CoFe
2o
4/ TiO
2/ float bead composite photochemical catalyst.
Further, described cobalt salt consumption is counted photochemical catalyst CoFe with the weight of cobalt in catalyst
2o
4/ TiO
2/ float the 0.5-1wt% of bead composite photochemical catalyst; Fe is 1-2wt%; Ti is 12-18wt%; More than be divided into fly ash float catalyst carrier.Described molysite consumption is counted photochemical catalyst CoFe with the weight of iron in catalyst
2o
4/ TiO
2/ floating the 1-2wt% of bead composite photochemical catalyst, described titanium consumption is counted photochemical catalyst CoFe with the weight of titanium in catalyst
2o
4/ TiO
2/ float the 12-18wt% of bead composite photochemical catalyst.
Further, described cobalt, iron soluble-salt are selected from respectively following compound: any in cobalt nitrate, iron molybdate, copper nitrate, nickel nitrate, zinc nitrate, bismuth nitrate, described titanium is from butyl titanate.
With respect to prior art, beneficial effect of the present invention is: the invention provides a kind of float type CoFe
2o
4/ TiO
2/ float bead composite photochemical catalyst, compare CoFe with current photochemical catalyst
2o
4/ TiO
2/ float bead composite photochemical catalyst can float on the water surface, fully absorb sunshine, improve photocatalytic degradation effect.TiO through doping
2/ float bead composite photochemical catalyst to make its photoresponse wavelength move to visible region from ultraviolet region, improve the utilization rate of sunshine.Catalyst carrier adopts hollow float bead, and cheap and easy to get, cost is low, has effectively improved photochemical catalyst service life.Adopt CoFe
2o
4as catalyst activity composition, there is magnetic, be easy to reclaim and recycling.The invention has the advantages that employing specific area is larger, there is stronger absorption, photo-catalysis function, fly ash hollow cheap and easy to get and float pearl as catalyst carrier, float in water, catalytic active component tool is magnetic is cobalt, iron, titanium compounding ingredients, cobalt, iron, titanium compounding ingredients are distributed in and float bead surface with particle form, increase surface area and absorption property, made the better photocatalysis performance of organic wastewater, improved degradation effect of organic compound.Can make its photoresponse wavelength move to visible region from ultraviolet region, improve the utilization rate of sunshine.The preparation of this catalyst is simple, catalytic activity is strong, have magnetic, recyclable recycling, have advantages of potential, process floating organic pollution preferably.
Accompanying drawing explanation
Fig. 1 is CoFe
2o
4-TiO
2/ float the scanning electron microscope (SEM) photograph of pearl loaded photocatalyst.
Fig. 2 is TiO
2/ float pearl loaded photocatalyst and CoFe
2o
4-TiO
2/ float the solid ultraviolet-visible light spectrogram of pearl loaded photocatalyst.
Fig. 3 is CoFe
2o
4/ TiO
2/ float the FT-IR spectrogram of pearl.
Fig. 4 is CoFe
2o
4-TiO
2/ float the time degradation rate figure of pearl loaded photocatalyst photocatalytic degradation methylene blue solution.
Fig. 5 is CoFe
2o
4-TiO
2/ float the time degradation rate figure of pearl loaded photocatalyst Photocatalytic Degradation of Phenol solution.
Fig. 6 floats pearl as carrier loaded CoFe for what do not calcine
2o
4-TiO
2photochemical catalyst and the pearl that floats of having calcined carry out the CoFe of load as carrier
2o
4-TiO
2photochemical catalyst, the time degradation rate figure that carries out the experiment of methylene blue solution photocatalytic degradation.
The specific embodiment
Below in conjunction with the drawings and the specific embodiments, the present invention program is described in further detail,
Embodiment 1
A kind of float type CoFe
2o
4/ TiO
2/ float bead composite photochemical catalyst, each component by weight percentage composition is respectively: Co is 0.7wt%; Fe is 1.5wt%; Ti is 15wt%, and all the other are fly ash float catalyst carrier.
Above-mentioned float type CoFe
2o
4/ TiO
2/ float the preparation method of bead composite photochemical catalyst, comprise the steps:
1) float the pretreatment of pearl
Preparation rare nitric acid of 10%, by fly ash float soak wherein 15h, filtration, by rinsed with deionized water to neutral post-drying, be then put in Muffle furnace, at 400 ℃, calcine 2h by the organic carbon of wherein not removing.With distilled water rinsing, sub-elect the pearl that floats swimming in completely on the water surface, after filtration drying sieves, that chooses particle diameter and be 100-125um floats pearl as the carrier of catalyst;
2) TiO
2the preparation of colloidal sol
Under room temperature, in 100mL absolute ethyl alcohol, add 40mL butyl titanate and constantly stir, after fully dissolving, adding 10mL acetylacetone,2,4-pentanedione, obtaining A solution; After fully mixing, 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 with red fuming nitric acid (RFNA), to regulate its pH be 4-5, stir l-2h it is fully reacted, then add 3g polyethylene glycol, temperature rises to 50 ℃ and continue to stir lh, obtains the TiO of yellow transparent
2colloidal sol, is placed in ageing 12h under room temperature.
3) TiO
2/ float the preparation of pearl loaded photocatalyst
The pearl that floats that 30g was activated is put in into the TiO preparing
2in colloidal sol, under room temperature, continue stirring 1.5h makes to float bead carrier and mixes completely with colloidal sol, then heating water bath to 80 ℃ steams near dry solution, putting into thermostatic drying chamber (80 ℃) dries, then in Muffle furnace, constant-speed heating to 500 ℃ is calcined 2h, be cooled to and take out after room temperature standbyly, will float that pearl repeats to mix with colloidal sol, oven dry, calcining, cooling, repeat this process 3 times.
4) CoFe
2o
4-TiO
2/ float the preparation of pearl loaded photocatalyst
Get respectively 20mL0.02mol/LCo (NO
3)
2solution and 80mL0.01mol/L Fe (NO
3)
3solution (n (Co (NO
3)
2): n (Fe (NO
3)
3)=1:2) fully after mixing, add 60ml0.02mol/L citric acid (the total amount of substance of metal is 1:1 with the ratio of the amount of substance of citric acid), constantly stir, with concentrated ammonia liquor, adjust pH to 5～6, in 80 ℃ of water-baths, at the uniform velocity stir after 2h, add 30gTiO
2/ float pearl, continue heating and steam near dry, after drying in 120 ℃ of baking ovens, moving in Muffle furnace at 500 ℃ roasting 2h, to be cooled to room temperature standby.By the catalyst sample obtaining, through distilled water rinsing, floating part collects at 105 ℃ of baking ovens dries 4h, cooling, makes required CoFe
2o
4/ TiO
2/ float bead composite photochemical catalyst.Its shape appearance figure as shown in Figure 1.
As can be seen from Figure: float pearl glomeration, CoFe
2o
4-TiO
2formed film floating bead surface, film rough surface, is conducive to increase specific area, increases absorption property and photocatalytic activity.
If Fig. 2 is TiO
2/ float pearl loaded photocatalyst and CoFe
2o
4-TiO
2/ float the solid ultraviolet-visible light spectrogram of pearl loaded photocatalyst.TiO
2there is wider energy gap (3.2eV), as can be seen from Figure 2, TiO
2/ float pearl loaded photocatalyst energy gap to be reduced to 2.85eV, CoFe
2o
4-TiO
2/ float pearl loaded photocatalyst energy gap to be further reduced to 2.5eV, show that visible ray is had to better catalytic activity, thereby improve the utilization ratio to visible ray.CoFe as can be seen from Figure 2
2o
4-TiO
2/ float pearly-lustre catalyst photoresponse scope to have extended to visible region.
Be illustrated in figure 3 CoFe
2o
4/ TiO
2/ float the FT-IR spectrogram of pearl, wherein 450-700 place is CoFe
2o
4and TiO
2characteristic peak, 1081 places are O-Si-O stretching vibration peak, 3411 places are the O-H stretching vibration peak of adsorption hydrone.
Embodiment 2,
A kind of float type CoFe
2o
4/ TiO
2/ float bead composite photochemical catalyst, each component by weight percentage composition is respectively: Co is 0.5wt%; Fe is 2wt%; Ti is 18wt%, and all the other are fly ash float catalyst carrier.
Its preparation method is with embodiment 1.
Embodiment 3
A kind of float type CoFe
2o
4/ TiO
2/ float bead composite photochemical catalyst, each component by weight percentage composition is respectively: Co is 1wt%; Fe is 1wt%; Ti is 12wt%, and all the other are fly ash float catalyst carrier.
Its preparation method is with embodiment 1.
Test example 1
With embodiment 1 gained CoFe
2o
4-TiO
2/ float pearl loaded photocatalyst photocatalytic degradation methylene blue solution, reaction initial conditions: methylene blue initial concentration 100mg/L, catalyst amount 0.4g, pH=5, it is carried out under visible light catalytic reactor to degradation experiment, degradation time is 120min, carries out visible spectrophotometer measure its absorbance every 20min sampling, measures methylenum careuleum degradation efficiency.As shown in Figure 4, when 80min, degradation efficiency reaches 85%.Test example 2
With embodiment 1TiO
2/ float pearl and CoFe
2o
4-TiO
2/ floating pearl loaded photocatalyst carries out the comparison of photocatalytic degradation methylene blue solution, experiment condition: catalyst amount 0.4g, methylene blue initial concentration 50mg/L, pH=5.It is carried out under visible light catalytic reactor to degradation experiment, degradation time is 60min, every 10min sampling, measures its absorbance, calculates methylenum careuleum degradation efficiency, as shown in table 1.
Test example 3
With embodiment 1 gained CoFe
2o
4-TiO
2/ float pearl loaded photocatalyst Photocatalytic Degradation of Phenol solution, experiment condition: catalyst amount 1.0g, phenol solution initial concentration 25,50,75,100mg/L, pH=5.It is carried out under visible light catalytic reactor to degradation experiment, degradation time is 7h, every 1h sampling, measures its absorbance, calculates methylenum careuleum degradation efficiency, as shown in Figure 5.
Test example 4
Using do not calcine float pearl as carrier loaded CoFe
2o
4-TiO
2photochemical catalyst and the pearl that floats of calcining of usining carry out the CoFe of load as carrier
2o
4-TiO
2photochemical catalyst, carry out the experiment of methylene blue solution photocatalytic degradation, reaction initial conditions: methylene blue initial concentration 75mg/L, catalyst amount 0.3g, pH=5 carries out it degradation experiment under visible light catalytic reactor, and degradation time is 120min, every 20min sampling, carry out visible spectrophotometer and measure its absorbance, measure methylenum careuleum degradation efficiency.As shown in Figure 6, in 120min, the CoFe that floats pearl load of calcining
2o
4-TiO
2photocatalyst for degrading efficiency is obviously better than the CoFe that floats pearl load of calcining
2o
4-TiO
2photochemical catalyst.
To sum up, a kind of float type CoFe of the present invention
2o
4/ TiO
2/ float bead composite photochemical catalyst, compare CoFe with current photochemical catalyst
2o
4/ TiO
2/ float bead composite photochemical catalyst can float on the water surface, fully absorb sunshine, improve photocatalytic degradation effect.TiO through doping
2/ float bead composite photochemical catalyst to make its photoresponse wavelength move to visible region from ultraviolet region, improve the utilization rate of sunshine.Catalyst carrier adopts hollow float bead, and cheap and easy to get, cost is low, has effectively improved photochemical catalyst service life.Adopt CoFe
2o
4as catalyst activity composition, there is magnetic, be easy to reclaim and recycling.The invention has the advantages that employing specific area is larger, there is stronger absorption, photo-catalysis function, fly ash hollow cheap and easy to get and float pearl as catalyst carrier, float in water, catalytic active component tool is magnetic is cobalt, iron, titanium compounding ingredients, cobalt, iron, titanium compounding ingredients are distributed in and float bead surface with particle form, increase surface area and absorption property, made the better photocatalysis performance of organic wastewater, improved degradation effect of organic compound.Can make its photoresponse wavelength move to visible region from ultraviolet region, improve the utilization rate of sunshine.The preparation of this catalyst is simple, catalytic activity is strong, have magnetic, recyclable recycling, have advantages of potential, process floating organic pollution preferably.
The above, be only the specific embodiment of the present invention, but protection scope of the present invention is not limited to this, and any variation of expecting without creative work or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims were limited.
Claims (5)
1. a float type CoFe
2o
4/ TiO
2/ float bead composite photochemical catalyst, it is characterized in that, comprise catalyst activity composition and catalyst carrier, each component by weight percentage composition is respectively: Co is 0.5-1wt%; Fe is 1-2wt%; Ti is 12-18wt%; All the other are fly ash float catalyst carrier.
2. photochemical catalyst according to claim 1, is characterized in that, in described photochemical catalyst, each component by weight percentage composition is respectively: Co is 0.7wt%; Fe is 1.5wt%; Ti is 15wt%, and all the other are fly ash float catalyst carrier.
3. a float type CoFe
2o
4/ TiO
2/ float the preparation method of bead composite photochemical catalyst, it is characterized in that, described method comprises the steps:
Step 1, float the pretreatment of pearl
Rare nitric acid of preparation 10%, by fly ash float soak wherein 15-24h, filtration, by rinsed with deionized water to neutral post-drying, then be put in Muffle furnace, at 400-500 ℃, calcine 2-4h by the organic carbon of wherein not removing, with distilled water rinsing, sub-elect the pearl that floats swimming in completely on the water surface, after filtration drying sieves, that chooses particle diameter and be 100-125um floats pearl as the carrier of catalyst;
Step 2, TiO
2the 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, adding 10-12mL acetylacetone,2,4-pentanedione, obtaining 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 with red fuming nitric acid (RFNA), to regulate its pH be 4-5, stir l-2h it is fully reacted, then add 2-3g polyethylene glycol, temperature rises to 50 ℃ and continue to stir l-1.5h, obtains the TiO of yellow transparent
2colloidal sol, is placed in ageing 12-15h under room temperature;
Step 3, TiO
2/ float the preparation of pearl loaded photocatalyst
The pearl that floats that every 30-40g was activated is put in into the TiO preparing
2in colloidal sol, under room temperature, continue stirring 1-1.5h makes to float bead carrier and mixes completely with colloidal sol, then heating water bath to 80 ℃ steams near dry solution, put into 80 ℃ of oven dry of thermostatic drying chamber, then constant-speed heating to 500 ℃ calcining 2h in Muffle furnace, is cooled to and takes out after room temperature standbyly, will float that pearl repeats to mix with colloidal sol, oven dry, calcining, cooling, repeat this process 3 times, object is to make to float even three layers of TiO of formation on pearl
2film, improves adsorptivity and photocatalytic activity;
Step 4, CoFe
2o
4-TiO
2/ float the preparation of pearl loaded photocatalyst
Described step 4 CoFe
2o
4-TiO
2/ the preparation process of floating pearl loaded photocatalyst is to get respectively 0.02mol/LCo (NO
3)
2solution and 0.01mol/LFe (NO
3)
3solution makes n (Co (NO
3)
2): n (Fe (NO
3)
3)=1:2, adds 0.02mol/L citric acid after fully mixing, and making the total amount of substance of metal and the ratio of the amount of substance of citric acid is 1:1, constantly stirs, and with concentrated ammonia liquor, adjusts pH to 5～6, in 80 ℃ of water-baths, at the uniform velocity stirs after 1-2h, adds TiO
2float pearl, Co (NO
3)
2liquor capacity: TiO
2floating pearl is 1:1-1.5ml/g, continuing heating steams near dry, after drying in 120 ℃ of baking ovens, moving in Muffle furnace at 500 ℃ roasting 2h, to be cooled to room temperature standby, by the catalyst sample obtaining through distilled water rinsing, floating part collects at 105 ℃ of baking ovens dries 2-4h, cooling, make required CoFe
2o
4/ TiO
2/ float bead composite photochemical catalyst.
4. method according to claim 3, is characterized in that, described cobalt salt consumption is counted photochemical catalyst CoFe with the weight of cobalt in catalyst
2o
4/ TiO
2/ float the 0.5-1wt% of bead composite photochemical catalyst; Fe is 1-2wt%; Ti is 12-18wt%; More than be divided into fly ash float catalyst carrier, described molysite consumption is counted photochemical catalyst CoFe with the weight of iron in catalyst
2o
4/ TiO
2/ floating the 1-2wt% of bead composite photochemical catalyst, described titanium consumption is counted photochemical catalyst CoFe with the weight of titanium in catalyst
2o
4/ TiO
2/ float the 12-18wt% of bead composite photochemical catalyst.
5. according to the method described in claim 3 or 4, it is characterized in that, described cobalt, iron soluble-salt are selected from respectively following compound: any in cobalt nitrate, iron molybdate, copper nitrate, nickel nitrate, zinc nitrate, bismuth nitrate, described titanium is from butyl titanate.
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