CN104437650A - Ternary composite biomimetic photocatalyst and preparation method thereof - Google Patents
Ternary composite biomimetic photocatalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a ternary composite biomimetic photocatalyst with the large size and the large pore diameter. The ternary composite biomimetic photocatalyst comprises a binary composite carrier and a photocatalyst deposited on the surface of the binary composite carrier, wherein the photocatalyst is an iron phthalocyanine complex; the content of the iron phthalocyanine complex is 1.5-4 weight percent; the binary composite carrier comprises a ZnO nanocrystalline thin film and a SiO2 macroporous material loading the ZnO nanocrystalline thin film; and the content of the ZnO is 10-20 weight percent. The invention also discloses a preparation method of the ternary composite biomimetic photocatalyst. According to the ternary composite biomimetic photocatalyst disclosed by the invention, the porosity is 80-90 percent, the specific surface area is 86-108m<2>/g, the degradation rate on rhodamine B under visible light radiation within an hour is more than or equal to 95 percent, the catalyst is high in stability and can be repeatedly used, and the ternary composite biomimetic photocatalyst has the advantages of any large-size shape and high strength and can meet the requirement on actual application.
Description
Technical field
The invention belongs to catalysis material technical field, relate to a kind of composite bionic photochemical catalyst, especially a kind of large scale, the agent of wide-aperture tri compound biomimetic photocatalysis, the invention still further relates to the preparation method of this photochemical catalyst.
Background technology
Over nearly 20 years, more and more paid attention to using semi-conducting material as the various water pollutant of photocatalyst for degrading.Light-catalysed general principle is that catalysis material is under the illumination of specific wavelength, absorbed radiation energy produces electron transition, hole-electron pair is formed on surface, electronics is captured from the hydroxide ion of the water being adsorbed on surface in hole, generate the hydroxyl radical free radical that oxidability is very strong, by the organic matter exhaustive oxidation in water.In a semiconductor material, ZnO is a kind of typical n-type photochemical catalyst, it has higher transmission electronic ability, can efficiently stop the compound in light induced electron and hole and there is the photocatalysis performance of making laughs, but the band gap width of ZnO is 3.2eV, it just can only can have photocatalytic activity under UV-irradiation, there is no corresponding to visible ray.Metal phthalocyanine has good chemistry, light and thermally stable, it is a kind of typical p-type semi-conducting material, strong transition is had at visible region, to the visible ray of 600 ~ 800nm, there is strong absorption, wherein FePC is a kind of biomimetic compounds, the similar oxidizing ferment of catalytic action, therefore utilizes FePC to absorb visible-light treatment waste water from dyestuff as biomimetic photocatalysis agent and is of practical significance very much.The present invention adopts tetracarboxylic FePC (III) (Fe (III)-taPc) as photochemical catalyst, it may be dissolved in the organic solvent of strong polarity, but it is water insoluble, by it and ZnO compound use, utilize the electron-transporting of ZnO by photogenerated electrons migrate, stop itself and hole-recombination, thus improve the efficiency of light-catalyzed reaction.Simultaneously in order to also keep molecular diffusivity to the full extent by fixing for catalyst, we use large scale, wide-aperture silica as carrier, catalyst is compounded on three-dimensional continuous print silica hole wall, finally prepare easy to use, stable performance, visible light-responded good, the novel photocatalyst that catalytic efficiency is high.
Summary of the invention
Technical problem to be solved by this invention separately provides a kind of large scale, the agent of wide-aperture tri compound biomimetic photocatalysis, and having can degradation of organic substances and catalytic efficiency high under visible light.
Another technical problem to be solved by this invention is to provide the preparation method of a kind of large scale, the agent of wide-aperture tri compound biomimetic photocatalysis.
The present invention solves the problems of the technologies described above adopted technical scheme: the agent of a kind of tri compound biomimetic photocatalysis, is characterized in that:
Comprise binary complex carrier and be deposited on the photochemical catalyst on this binary complex carrier surface, described photochemical catalyst is iron phthalocyanine complex, and the content of described iron phthalocyanine complex is 1.5 ~ 4wt.%;
Described binary complex carrier comprises the SiO of the brilliant film of ZnO nano and the brilliant film of the above-mentioned ZnO nano of load
2large pore material, in described binary complex carrier, the content of described ZnO is 10 ~ 20wt.%.
Described binary complex carrier is by the silica large pore material of three-dimensional superthin structure, and the brilliant film of ZnO nano be deposited in the three-dimensional through duct of this silica large pore material is formed, described iron phthalocyanine complex is deposited on binary complex carrier surface, the aperture of described silica large pore material is 0.5 ~ 1.5 μm, and thickness is 20 ~ 50nm.
Described iron phthalocyanine complex is tetracarboxylic FePC (III).
The porosity of described tri compound biomimetic photocatalysis agent is 80% ~ 90%, and specific area is 86 ~ 108m
2/ g, degradation rate>=95% to Luo Dan B in radiation of visible light 1 hour.
A preparation method for tri compound biomimetic photocatalysis agent, is characterized in that comprising the steps:
1. the preparation of three-dimensional framework polymer, by mass ratio be 1: 2 ~ 1: 2.5 epoxy resin and polyethylene glycol mixing and be heated to 60 ~ 80 DEG C, stir after within 5 ~ 15 minutes, becoming clear solution, add with epoxy resin mass ratio be 1: 4 ~ 1: 4.5 triethylene tetramine liquid, pour in mould after stirring and shape, keep setting temperature in 70 ~ 80 DEG C, after 1 ~ 10h, form the solid fraction blend polymer of white, soak 12 ~ 20 hours with pure water, leave the epoxy resin of three dimensional skeletal structure, at room temperature vacuum drying 1 ~ 2 day;
2. the preparation of silica large pore material, soaks 4 ~ 5 hours by the epoxy resin of step three dimensional skeletal structure 1. in tetraethyl orthosilicate, forms SiO after exposing 10 ~ 12 hours in ammoniacal liquor atmosphere at 25 ~ 30 DEG C
2/ epoxy resin composite, dry 1 ~ 5 hour, rises to 800 ~ 900 DEG C with the heating rate of 5 ~ 10 DEG C/min in Muffle furnace, keeps the silica large pore material namely obtaining three-dimensional superthin structure for 10 ~ 60 minutes;
3. the fabricated in situ of the brilliant film of ZnO nano in silica large pore material, is the Zn (NO of 1: 1 ~ 1: 1.2 by mol ratio
3)
26H
2o and tetrahydroxypropyl ethylenediamine are made into the aqueous solution, obtain required precursor liquid, in described precursor liquid, and Zn (NO
3)
2concentration be 0.2 ~ 1.0mol/L, silica large pore material is placed in precursor liquid fully soak, dry 2 ~ 3 hours at 70 ~ 80 DEG C after taking-up, then in Muffle furnace, 600 ~ 650 DEG C are warming up to the speed of 10 ~ 15 DEG C/min, be incubated calcining again and be cooled to room temperature after 1 ~ 2 hour, obtain binary complex carrier;
4. the deposition of iron phthalocyanine complex, by iron phthalocyanine complex and N, N-dimethylacetylamide is made into dipping solution in the ratio of 3 ~ 6mg/ml, by step 3. in binary complex carrier soak in above-mentioned dipping solution fully and take out, directly put into clear water, obtain the agent of tri compound biomimetic photocatalysis after drying.
Described iron phthalocyanine complex is tetracarboxylic FePC (III).
The trade mark of described epoxy resin is E-44.
The molecular weight of described ethylene glycol is 1000 or/and 2000.
Repeating said steps is 3. to regulate the deposition of ZnO.
The porosity of the tri compound biomimetic photocatalysis agent that 4. described step is prepared is 80% ~ 90%, and specific area is 86 ~ 108m
2/ g, degradation rate>=95% under visible light illumination to Luo Dan B in 1 hour.
Compared with prior art, the invention has the advantages that:
1) this composite bionic photochemical catalyst stability is high, and the brilliant film of ZnO nano of load is uniformly dispersed, and can not depart from silica large pore material, the structure of itself can not change, and catalyst can repeatedly use;
2) silica large pore material has the duct of continuous through IPN, aperture large (0.5 ~ 1.5 μm) and be evenly distributed and have strong permeability, is conducive to the circulation diffusion of material;
3) use tetrahydroxypropyl ethylenediamine simple as complexing agent carrying method, do not need special instruments and equipment;
4) the ZnO semiconductor of n-type and Fe (the III)-taPc recombination energy of p-type make photocatalysis efficiency improve;
5) large scale arbitrary shape and good intensity are the advantages of this material, can adapt to the needs of practical application.
Accompanying drawing explanation
Fig. 1 is SEM (SEM) picture of embodiment 1, and wherein a is the SEM picture of silica large pore material; B is Fe (III)-taPc/ZnO/SiO
2the SEM picture of tri compound biomimetic photocatalysis agent;
Fig. 2 is ZnO (the 20wt%)/SiO of embodiment 3
2the XRD collection of illustrative plates of sample;
Fig. 3 is Fe (the III)-taPc/ZnO/SiO of different loads amount
2the UV-Vis diffuse reflection spectroscopy of tri compound biomimetic photocatalysis agent;
Fig. 4 is different loads amount Fe (III)-taPc/ZnO/SiO
2the agent of tri compound biomimetic photocatalysis is to the degradation curve of rhodamine B.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment 1
Step 1: the preparation of three-dimensional framework polymer, by mass ratio be 1: 2.5 epoxy resin (trade mark E-44) and cetomacrogol 1000 mixing and be heated to 60 DEG C, stir after within 5 minutes, becoming clear solution, add with epoxy resin mass ratio be 1: 4 triethylene tetramine liquid, pour in mould after stirring and shape, keep setting temperature in 70 DEG C, after 1 hour, form the solid fraction blend polymer of white, polyethylene glycol phase is removed after soaking 12 hours with pure water, leave the epoxy resin of three dimensional skeletal structure, at room temperature vacuum drying 1 day;
Step 2:SiO
2the preparation of large pore material, the epoxy resin by three dimensional skeletal structure in step 1 soaks 5 hours in tetraethyl orthosilicate, forms SiO after exposing 10 hours in ammoniacal liquor atmosphere in 30 DEG C
2/ epoxy resin composite, to remove the ammoniacal liquor of ethanol and the absorption generated, rises to 800 DEG C with the heating rate of 5 DEG C/min in dry 1 hour, keeps the SiO that can obtain three-dimensional superthin structure for 10 minutes in Muffle furnace
2large pore material, aperture is about 0.5 ~ 1.5 micron, and thickness is about 20 ~ 50nm, and its SEM picture is as shown in Fig. 1 (a);
Step 3:ZnO nano-crystal film is at SiO
2fabricated in situ in large pore material, by Zn (NO
3)
26H
2o is made into the aqueous solution with the tetrahydroxypropyl ethylenediamine of molal quantity such as grade, obtains required precursor liquid, in precursor liquid, and Zn (NO
3)
2molar concentration be 0.2mol/L.By SiO
2large pore material is placed in precursor liquid and fully soaks, and dries 2 hours, removes most of water, then in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min, then be incubated calcining and be cooled to room temperature after 1 hour, obtain binary complex carrier after taking-up at 80 DEG C;
The deposition of step 4:Fe (III)-taPc, Fe (III)-taPc is dissolved in N, dipping solution (Fe (III)-taPc concentration is 3mg/mL) is made in N-dimethylacetylamide, above-mentioned binary complex carrier is soaked in dipping solution fully and take out, directly put into clear water, solvent and water exchange, Fe (III)-taPc autodeposition is at carrier surface, sample obtains the agent of cyan tri compound biomimetic photocatalysis after washing, drying, and its SEM picture is as shown in Fig. 1 (b).
Repeat step 3 once, it is 2.3wt.% that the content of ZnO can be made to be 10wt.%, Fe (III)-taPc content, and the porosity of tri compound biomimetic photocatalysis agent is 89%, and specific area is 108m
2/ g is>=95% to the photocatalytic activity of rhodamine B in radiation of visible light 1 hour.
Embodiment 2
Step 1: the preparation of three-dimensional framework polymer, be epoxy resin (trade mark E-44) and polyethylene glycol (PEG1000 and PEG2000 by 7: the 1 combination) mixing and be heated to 65 DEG C of 1: 2 by mass ratio, stir after within 10 minutes, becoming clear solution, add with epoxy resin mass ratio be 1: 4 triethylene tetramine liquid, pour in mould after stirring and shape, keep setting temperature in 75 DEG C, after 5 hours, form the solid fraction blend polymer of white, polyethylene glycol phase is removed after soaking 18 hours with pure water, leave the epoxy resin of three dimensional skeletal structure, at room temperature vacuum drying 1 day,
Step 2:SiO
2the preparation of large pore material, the epoxy resin by three dimensional skeletal structure in step 1 soaks 5 hours in tetraethyl orthosilicate, forms SiO after exposing 10 hours in ammoniacal liquor atmosphere in 30 DEG C
2/ epoxy resin composite, to remove the ammoniacal liquor of ethanol and the absorption generated, rises to 850 DEG C with the heating rate of 8 DEG C/min in dry 2 hours, keeps the SiO that can obtain three-dimensional superthin structure for 30 minutes in Muffle furnace
2large pore material, aperture is about 0.5 ~ 1.5 micron, and thickness is about 20 ~ 50nm;
Step 3:ZnO nano-crystal film is at SiO
2fabricated in situ in large pore material, by Zn (NO
3)
26H
2o is made into the aqueous solution with the tetrahydroxypropyl ethylenediamine of molal quantity such as grade, obtains required precursor liquid, in precursor liquid, and Zn (NO
3)
2molar concentration be 0.5mol/L.By SiO
2large pore material is placed in precursor liquid and fully soaks, and dries 2 hours, removes most of water, then in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min, then be incubated calcining and be cooled to room temperature after 1 hour, obtain binary complex carrier after taking-up at 80 DEG C;
The deposition of step 4:Fe (III)-taPc, Fe (III)-taPc is dissolved in N, dipping solution (Fe (III)-taPc concentration is 4mg/mL) is made in N-dimethylacetylamide, above-mentioned binary complex carrier is soaked in dipping solution fully and take out, directly put into clear water, solvent and water exchange, Fe (III)-taPc autodeposition is at carrier surface, sample becomes blackish green after washing, drying, namely obtains the agent of tri compound biomimetic photocatalysis.
Repeat step 3 two times, making the content of ZnO be 16wt.%, Fe (III)-taPc content is 2.9wt.%, and the porosity of tri compound biomimetic photocatalysis agent is 82%, and specific area is 95m
2/ g is>=95% to the photocatalytic activity of rhodamine B in radiation of visible light 1 hour.
Embodiment 3
Step 1: the preparation of three-dimensional framework polymer, be epoxy resin (trade mark E-44) and polyethylene glycol (PEG1000 and PEG2000 by 7: the 1 combination) mixing and be heated to 60 ~ 80 DEG C of 1: 2 by mass ratio, stir after within 15 minutes, becoming clear solution, add with epoxy resin mass ratio be 1: 4 triethylene tetramine liquid, pour in mould after stirring and shape, keep setting temperature in 80 DEG C, after 10 hours, form the solid fraction blend polymer of white, polyethylene glycol phase is removed after soaking 20 hours with pure water, leave the epoxy resin of three dimensional skeletal structure, at room temperature vacuum drying 2 days,
Step 2:SiO
2the preparation of large pore material, the epoxy resin by three dimensional skeletal structure in step 1 soaks 5 hours in tetraethyl orthosilicate, forms SiO after exposing 10 hours in ammoniacal liquor atmosphere in 30 DEG C
2/ epoxy resin composite, to remove the ammoniacal liquor of ethanol and the absorption generated, rises to 900 DEG C with the heating rate of 10 DEG C/min in dry 5 hours, keeps the SiO that can obtain three-dimensional superthin structure for 60 minutes in Muffle furnace
2large pore material, aperture is about 0.5 ~ 1.5 micron, and thickness is about 20 ~ 50nm;
Step 3:ZnO nano-crystal film is at SiO
2fabricated in situ in large pore material, by Zn (NO
3)
26H
2o is made into the aqueous solution with the tetrahydroxypropyl ethylenediamine of molal quantity such as grade, obtains required precursor liquid, in precursor liquid, and Zn (NO
3)
2molar concentration be 1.0mol/L, by SiO
2large pore material is placed in precursor liquid and fully soaks, and dries 2 hours, removes most of water, then in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min, then be incubated calcining and be cooled to room temperature after 1 hour, obtain binary complex carrier after taking-up at 80 DEG C;
The deposition of step 4:Fe (III)-taPc, Fe (III)-taPc is dissolved in N, dipping solution (Fe (III)-taPc concentration is 5mg/mL) is made in N-dimethylacetylamide, above-mentioned binary complex carrier is soaked in dipping solution fully and take out, directly put into clear water, solvent and water exchange, Fe (III)-taPc autodeposition is at carrier surface, sample becomes blackish green after washing, drying, namely obtains the agent of tri compound biomimetic photocatalysis.
Repeat step 3 three times, making the content of ZnO be 20wt.%, Fe (III)-taPc content is 3.2wt.%, and the porosity of tri compound biomimetic photocatalysis agent is 82%, and specific area is 89m
2/ g, to ZnO (the 20wt%)/SiO of the photocatalytic activity of rhodamine B to be>=99%, Fig. 2 be embodiment 3 in radiation of visible light 1 hour
2the XRD collection of illustrative plates of sample, because its XRD spectra of sample of different embodiment is similar, just intensity is different, so only supported with a spectrogram.
Embodiment 4
Step 1: the preparation of three-dimensional framework polymer, be epoxy resin (trade mark E-44) and polyethylene glycol (PEG1000 and PEG2000 by 7: the 1 combination) mixing and be heated to 80 DEG C of 1: 2.5 by mass ratio, stir after within 15 minutes, becoming clear solution, add with epoxy resin mass ratio be 1: 4 triethylene tetramine liquid, pour in mould after stirring and shape, keep setting temperature in 80 DEG C, after 10 hours, form the solid fraction blend polymer of white, polyethylene glycol phase is removed after soaking 20 hours with pure water, leave the epoxy resin of three dimensional skeletal structure, at room temperature vacuum drying 2 days,
Step 2:SiO
2the preparation of large pore material, the epoxy resin by three dimensional skeletal structure in step 1 soaks 5 hours in tetraethyl orthosilicate, forms SiO after exposing 10 hours in ammoniacal liquor atmosphere in 30 DEG C
2/ epoxy resin composite, to remove the ammoniacal liquor of ethanol and the absorption generated, rises to 900 DEG C with the heating rate of 10 DEG C/min in dry 5 hours, keeps the SiO that can obtain three-dimensional superthin structure for 160 minutes in Muffle furnace
2large pore material, aperture is about 0.5 ~ 1.5 micron, and thickness is about 20 ~ 50nm;
Step 3:ZnO nano-crystal film is at SiO
2fabricated in situ in large pore material, by Zn (NO
3)
26H
2o is made into the aqueous solution with the tetrahydroxypropyl ethylenediamine of molal quantity such as grade, obtains required precursor liquid, in precursor liquid, and Zn (NO
3)
2molar concentration be 1.0mol/L.By SiO
2large pore material is placed in precursor liquid and fully soaks, and dries 2 hours, removes most of water, then in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min, then be incubated calcining and be cooled to room temperature after 1 hour, obtain binary complex carrier after taking-up at 80 DEG C;
The deposition of step 4:Fe (III)-taPc, Fe (III)-taPc is dissolved in N, dipping solution (Fe (III)-taPc concentration is 6mg/mL) is made in N-dimethylacetylamide, above-mentioned binary complex carrier is soaked in dipping solution fully and take out, directly put into clear water, solvent and water exchange, Fe (III)-taPc autodeposition is at carrier surface, sample becomes blackish green after washing, drying, namely obtains the agent of tri compound biomimetic photocatalysis.
Repeat step 3 three times, making the content of ZnO be 19wt.%, Fe (III)-taPc content is 3.6wt.%, and the porosity of tri compound biomimetic photocatalysis agent is 80%, and specific area is 86m
2/ g was>=99% to the photocatalytic activity of rhodamine B in 1 hour.
Fe (the III)-taPc/ZnO/SiO2 tri compound biomimetic photocatalysis agent of different loads amount obtained in four embodiments is carried out the photocatalytic degradation test of XRD, UV-Vis diffuse reflection and RhB, obtain Fig. 2 to Fig. 4.
Method of testing in embodiment is specific as follows:
Adopt SEM (JSM-5600LV type) to observe the pattern of sample, namely under the accelerating potential of 5kV, carry out surface topography sign after sample spray platinum; X-ray diffractometer (Rigaku D/max-1200) is adopted to analyze Sample crystals structure and composition, operating voltage 30mV, operating current 30mV, Cu K α radiation (λ=0.154nm), sweep limits 2 θ=10 ° ~ 70 °; Test specific area with specific area and pore-size distribution tester (JW-K type), calculate its specific area with BET formula; The content gravimetric detemination of ZnO and Fe (III)-taPc in composite sample;
Photocatalysis performance method of testing:
With organic dyestuff rhodamine B for target degradation product, oxygen is oxidant, carries out light-catalyzed reaction, has investigated different loads amount Fe (III)-taPc/SiO
2photocatalytic activity and recycling.With the halogen lamp of 150W (λ >=400nm) for visible light source, light source distance reactor 10cm.Take Fe (the III)-taPc/SiO of 50mg different loads amount respectively
2catalyst, makes graininess sample (size is about 1mm), is scattered in the rhodamine B aqueous solution of 50ml10 μm of ol/L, is placed in homemade airtight Photoreactor, passes into oxygen.Under magnetic stirring, reaction system is placed in dark place 1h, opens light source after guaranteeing adsorption equilibrium and carry out light-catalyzed reaction.Every 10min sampling in course of reaction, its supernatant of centrifuging and taking, measures the absorbance of rhodamine B at 552nm place with ultraviolet-visible spectrophotometer, and calculates its concentration.According to formula C
t/ C
0calculate photocatalytic activity, C in formula
0and C
tbe respectively original solution and the concentration of rhodamine B in 10min institute extracting sample solution.
The present invention utilize a kind of large scale, high strength, high porosity, high connectivity silica large pore material as carrier, the brilliant film of ZnO nano is had at its three through duct internal burdens, then Fe (III)-taPc is adsorbed onto the brilliant surface of ZnO nano, the photocatalysis system that formation n-type semiconductor and p-type semiconductor are worked in coordination with by infusion process.This tri compound biomimetic photocatalysis agent adopts tetracarboxylic FePC (III) (Fe (III)-taPc) as photochemical catalyst, and with ZnO compound use, utilize the electron-transporting of ZnO by photogenerated electrons migrate, stop itself and hole-recombination, thus improve the efficiency of light-catalyzed reaction; Simultaneously in order to also keep molecular diffusivity to the full extent by fixing for catalyst, use large scale, wide-aperture silica as carrier, catalyst is compounded on three-dimensional continuous print silica hole wall, the photochemical catalyst finally prepared is easy to use, stable performance, visible light-responded good, catalytic efficiency is high.
Claims (10)
1. a tri compound biomimetic photocatalysis agent, is characterized in that:
Comprise binary complex carrier and be deposited on the photochemical catalyst on this binary complex carrier surface, described photochemical catalyst is iron phthalocyanine complex, and the content of described iron phthalocyanine complex is 1.5 ~ 4wt.%;
Described binary complex carrier comprises the SiO of the brilliant film of ZnO nano and the brilliant film of the above-mentioned ZnO nano of load
2large pore material, in described binary complex carrier, the content of described ZnO is 10 ~ 20wt.%.
2. tri compound biomimetic photocatalysis according to claim 1 agent, it is characterized in that: described binary complex carrier is by the silica large pore material of three-dimensional superthin structure, and the brilliant film of ZnO nano be deposited in the three-dimensional through duct of this silica large pore material is formed, described iron phthalocyanine complex is deposited on binary complex carrier surface, the aperture of described silica large pore material is 0.5 ~ 1.5 μm, and thickness is 20 ~ 50nm.
3. tri compound biomimetic photocatalysis according to claim 1 and 2 agent, is characterized in that: described iron phthalocyanine complex is tetracarboxylic FePC (III).
4. tri compound biomimetic photocatalysis according to claim 1 and 2 agent, is characterized in that: the porosity of described tri compound biomimetic photocatalysis agent is 80% ~ 90%, and specific area is 86 ~ 108m
2/ g, degradation rate>=95% to Luo Dan B in radiation of visible light 1 hour.
5. a preparation method for the tri compound biomimetic photocatalysis agent in Claims 1-4 described in any one, is characterized in that comprising the steps:
1. the preparation of three-dimensional framework polymer, by mass ratio be 1: 2 ~ 1: 2.5 epoxy resin and polyethylene glycol mixing and be heated to 60 ~ 80 DEG C, stir after within 5 ~ 15 minutes, becoming clear solution, add with epoxy resin mass ratio be 1: 4 ~ 1: 4.5 triethylene tetramine liquid, pour in mould after stirring and shape, keep setting temperature in 70 ~ 80 DEG C, after 1 ~ 10h, form the solid fraction blend polymer of white, soak 12 ~ 20 hours with pure water, leave the epoxy resin of three dimensional skeletal structure, at room temperature vacuum drying 1 ~ 2 day;
2. the preparation of silica large pore material, soaks 4 ~ 5 hours by the epoxy resin of step three dimensional skeletal structure 1. in tetraethyl orthosilicate, forms SiO after exposing 10 ~ 12 hours in ammoniacal liquor atmosphere at 25 ~ 30 DEG C
2/ epoxy resin composite, dry 1 ~ 5 hour, rises to 800 ~ 900 DEG C with the heating rate of 5 ~ 10 DEG C/min in Muffle furnace, keeps the silica large pore material namely obtaining three-dimensional superthin structure for 10 ~ 60 minutes;
3. the fabricated in situ of the brilliant film of ZnO nano in silica large pore material, is the Zn (NO of 1: 1 ~ 1: 1.2 by mol ratio
3)
26H
2o and tetrahydroxypropyl ethylenediamine are made into the aqueous solution, obtain required precursor liquid, in described precursor liquid, and Zn (NO
3)
2concentration be 0.2 ~ 1.0mol/L, silica large pore material is placed in precursor liquid fully soak, dry 2 ~ 3 hours at 70 ~ 80 DEG C after taking-up, then in Muffle furnace, 600 ~ 650 DEG C are warming up to the speed of 10 ~ 15 DEG C/min, be incubated calcining again and be cooled to room temperature after 1 ~ 2 hour, obtain binary complex carrier;
4. the deposition of iron phthalocyanine complex, by iron phthalocyanine complex and N, N-dimethylacetylamide is made into dipping solution in the ratio of 3 ~ 6mg/ml, by step 3. in binary complex carrier soak in above-mentioned dipping solution fully and take out, directly put into clear water, obtain the agent of tri compound biomimetic photocatalysis after drying.
6. preparation method according to claim 5, is characterized in that: described iron phthalocyanine complex is tetracarboxylic FePC (III).
7. preparation method according to claim 5, is characterized in that: the trade mark of described epoxy resin is E-44.
8. preparation method according to claim 5, is characterized in that: the molecular weight of described ethylene glycol is 1000 or/and 2000.
9. preparation method according to claim 5, is characterized in that: repeating said steps is 3. to regulate the deposition of ZnO.
10. preparation method according to claim 5, is characterized in that: the porosity of the tri compound biomimetic photocatalysis agent that 4. described step is prepared is 80% ~ 90%, and specific area is 86 ~ 108m
2/ g, degradation rate>=95% under visible light illumination to Luo Dan B in 1 hour.
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