CN104437650B - A kind of tri compound biomimetic photocatalysis agent and preparation method thereof - Google Patents
A kind of tri compound biomimetic photocatalysis agent and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of large scale, wide-aperture tri compound biomimetic photocatalysis agent, including binary complex carrier and the photocatalyst that is deposited on this binary complex carrier surface, described photocatalyst is iron phthalocyanine complex, and the content of described iron phthalocyanine complex is 1.5～4wt.%；Described binary complex carrier includes ZnO nano crystalline substance thin film and loads the SiO of above-mentioned ZnO nano crystalline substance thin film2Large pore material, the content of described ZnO is 10～20wt.%.The invention also discloses the preparation method of this tri compound biomimetic photocatalysis agent.The porosity of the tri compound biomimetic photocatalysis agent of the present invention is 80%～90%, and specific surface area is 86～108m2/ g, under visible light illumination degradation rate >=95% to Luo Dan B in 1 hour, its stability is high, reusable, and large scale arbitrary shape and preferably intensity are the advantages of this material, are adapted to the needs of actual application.
Description
Technical field
The invention belongs to catalysis material technical field, relate to a kind of composite bionic photocatalyst, especially a kind of large scale,
Wide-aperture tri compound biomimetic photocatalysis agent, the invention still further relates to the preparation method of this photocatalyst.
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 ultimate principle be catalysis material under the illumination of specific wavelength, absorb radiation can produce electron transition, at table
Face forms hole-electron pair, and hole captures electronics from absorption at the hydroxide ion of the water on surface, generates oxidability very
Strong hydroxyl radical free radical, by the Organic substance exhaustive oxidation in water.In a semiconductor material, ZnO is a kind of typical n-
Type photocatalyst, it has higher transmission electronic capability, can efficiently stop the compound of light induced electron and hole to have and do
The photocatalysis performance laughed at, but the band gap width of ZnO is 3.2eV, it just can only can have photocatalysis under ultraviolet light irradiates
Activity, there is no visible ray accordingly.Metal phthalocyanine has good chemistry, light and thermally stable, is a kind of typical p-
Type semi-conducting material, has strong transition in visible region, and the visible ray to 600～800nm has strong absorption, its
Middle FePC is a kind of biomimetic compounds, and catalytic action is similar to oxidase, hence with FePC as biomimetic photocatalysis agent
Absorb visible-light treatment waste water from dyestuff to be of practical significance very much.The present invention uses tetracarboxylic FePC (III) (Fe (III)-taPc) conduct
Photocatalyst, it may be dissolved in highly polar organic solvent, but water insoluble, by it and ZnO compound use, profit
With the electron-transporting of ZnO, light induced electron is migrated, stop itself and hole-recombination, thus improve the effect of light-catalyzed reaction
Rate.Simultaneously in order to be fixed by catalyst and keep molecular diffusivity to the full extent, we use large scale, large aperture
Silicon dioxide as carrier, catalyst is compounded on three-dimensional continuous print silicon dioxide hole wall, finally prepares user
Just, stable performance, it is seen that photoresponse is good, the novel photocatalyst that catalytic efficiency is high.
Summary of the invention
The technical problem to be solved is another offer a kind of large scale, wide-aperture tri compound biomimetic photocatalysis
Agent, 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 a kind of large scale, the bionical light of wide-aperture tri compound is urged
The preparation method of agent.
The present invention solves the technical scheme that above-mentioned technical problem used: a kind of tri compound biomimetic photocatalysis agent, and it is special
Levy and be:
Including binary complex carrier and the photocatalyst that is deposited on this binary complex carrier surface, described photocatalyst is ferrum phthalein
Cyanines coordination compound, the content of described iron phthalocyanine complex is 1.5～4wt.%；
Described binary complex carrier includes ZnO nano crystalline substance thin film and loads the SiO of above-mentioned ZnO nano crystalline substance thin film2Macropore material
Material, in described binary complex carrier, the content of described ZnO is 10～20wt.%.
Described binary complex carrier is by the silicon dioxide large pore material of three-dimensional superthin structure, and it is big to be deposited on this silicon dioxide
ZnO nano crystalline substance thin film in the three-dimensional through duct of Porous materials is constituted, and described iron phthalocyanine complex is deposited on binary and is combined
Carrier surface, the aperture of described silicon dioxide 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 surface area is 86～108m2/ g,
Radiation of visible light degradation rate >=95% to Luo Dan B in 1 hour.
The preparation method of a kind of tri compound biomimetic photocatalysis agent, it is characterised in that comprise the steps:
1. the preparation of three-dimensional framework polymer, mixes epoxy resin and the Polyethylene Glycol that mass ratio is 1: 2～1: 2.5 also
And it is heated to 60～80 DEG C, and stir 5～15 minutes after becoming clear solution, adding with epoxy resin mass ratio is 1: 4～1: 4.5
Triethylene tetramine liquid, pour into after stirring in mould and shape, keep setting temperature in 70～80 DEG C 1～10h
The rear solid fraction blend polymer forming white, soaks 12～20 hours with pure water, leaves the epoxy of three dimensional skeletal structure
Resin, at room temperature vacuum drying 1～2 day；
2. the preparation of silicon dioxide large pore material, by the epoxy resin of step three dimensional skeletal structure 1. at positive silicic acid tetrem
Ester soaks 4～5 hours, after exposing 10～12 hours at 25～30 DEG C in ammonia atmosphere, forms SiO2/ asphalt mixtures modified by epoxy resin
Fat complexes, is dried 1～5 hour, rises to 800～900 DEG C with the heating rate of 5～10 DEG C/min in Muffle furnace,
Keep the silicon dioxide large pore material i.e. obtaining three-dimensional superthin structure for 10～60 minutes；
3. ZnO nano crystalline substance thin film fabricated in situ in silicon dioxide large pore material, is 1: 1～1: 1.2 by mol ratio
Zn(NO3)2·6H2O and tetrahydroxypropyl ethylenediamine are made into aqueous solution, obtain required precursor liquid, in described precursor liquid,
Zn(NO3)2Concentration be 0.2～1.0mol/L, silicon dioxide large pore material is placed in precursor liquid and fully soaks, take out
After at 70～80 DEG C dry 2～3 hours, then in Muffle furnace with the speed of 10～15 DEG C/min be warming up to 600～
650 DEG C, then insulation calcining 1～2 hour after be cooled to room temperature, obtain binary complex carrier；
4. the deposition of iron phthalocyanine complex, presses the ratio of 3～6mg/ml by iron phthalocyanine complex and N,N-dimethylacetamide
Example is made into dipping solution, by step 3. in binary complex carrier soak in above-mentioned dipping solution and take out, directly after fully
Put in clear water, obtain tri compound biomimetic photocatalysis agent 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%, specific surface area be 86～
108m2/ g, under visible light illumination degradation rate >=95% to Luo Dan B in 1 hour.
Compared with prior art, it is an advantage of the current invention that:
1) this composite bionic photocatalyst stability is high, and the ZnO nano crystalline substance thin film of load is uniformly dispersed, will not be with dioxy
SiClx large pore material departs from, and the structure of itself will not change, and catalyst can repeatedly use；
2) silicon dioxide large pore material has the duct of continuous through IPN, aperture big (0.5～1.5 μm) and the tool that is evenly distributed
The circulation having strong permeability, beneficially material is spread；
3) use tetrahydroxypropyl ethylenediamine simple as chelating agent carrying method, it is not necessary to special instruments and equipment；
4) the ZnO quasiconductor of n-type makes photocatalysis efficiency improve with Fe (the III)-taPc recombination energy of p-type；
5) large scale arbitrary shape and preferably intensity are the advantages of this material, are adapted to the needs of actual application.
Accompanying drawing explanation
Fig. 1 is SEM (scanning electron microscope) picture of embodiment 1, and wherein a is silicon dioxide large pore material
SEM picture；B is Fe (III)-taPc/ZnO/SiO2The SEM picture of tri compound biomimetic photocatalysis agent；
Fig. 2 is ZnO (the 20wt%)/SiO of embodiment 32The XRD figure spectrum of sample；
Fig. 3 is Fe (the III)-taPc/ZnO/SiO of different loads amount2The ultraviolet-visible of tri compound biomimetic photocatalysis agent is unrestrained anti-
Penetrate spectrum；
Fig. 4 is different loads amount Fe (III)-taPc/ZnO/SiO2The tri compound biomimetic photocatalysis agent degraded to rhodamine B
Curve.
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 epoxy resin (trade mark E-44) that mass ratio is 1: 2.5 and poly-
Ethylene glycol 1000 mixes and is heated to 60 DEG C, stirs 5 minutes after becoming clear solution, adds and epoxy resin mass ratio
It is the triethylene tetramine liquid of 1: 4, pours into after stirring in mould and shape, keep setting temperature in 70 DEG C 1 hour
The rear solid fraction blend polymer forming white, removes Polyethylene Glycol phase with pure water after soaking 12 hours, leave three-dimensional bone
The epoxy resin of shelf structure, at room temperature vacuum drying 1 day；
Step 2:SiO2The preparation of large pore material, will in step 1 epoxy resin of three dimensional skeletal structure at positive silicic acid four
Ethyl ester soaks 5 hours, after exposing 10 hours in 30 DEG C in ammonia atmosphere, forms SiO2/ epoxy resin composite,
It is dried the ethanol and the ammonia of absorption generated with removing 1 hour, in Muffle furnace, rises to 800 with the heating rate of 5 DEG C/min
DEG C, keep the SiO of 10 minutes i.e. available three-dimensional superthin structures2Large pore material, aperture is about 0.5～1.5 micron, thick
Degree is about 20～50nm, shown in its SEM picture such as Fig. 1 (a)；
Step 3:ZnO nano-crystal film is at SiO2Fabricated in situ in large pore material, by Zn (NO3)2·6H2O with etc. rub
You are made into aqueous solution by the tetrahydroxypropyl ethylenediamine of number, obtain required precursor liquid, in precursor liquid, and Zn (NO3)2Mole
Concentration is 0.2mol/L.By SiO2Large pore material is placed in precursor liquid and fully soaks, and dries 2 hours after taking-up at 80 DEG C,
Remove major part water, then in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min, then insulation is calcined 1 hour
After be cooled to room temperature, obtain binary complex carrier；
The deposition of step 4:Fe (III)-taPc, is dissolved in Fe (III)-taPc in N,N-dimethylacetamide and is made into dipping
Solution (Fe (III)-taPc concentration is 3mg/mL), takes out after being soaked by above-mentioned binary complex carrier fully in dipping solution,
Being directly placed in clear water, solvent exchanges with water, Fe (III)-taPc autodeposition at carrier surface, sample through washing,
Obtain cyan tri compound biomimetic photocatalysis agent after drying, shown in its SEM picture such as Fig. 1 (b).
Repeat step 3 once, can make the content of ZnO be 10wt.%, Fe (III)-taPc content be 2.3wt.%, ternary
The porosity of composite bionic photocatalyst is 89%, and specific surface area is 108m2/ g, to sieve in radiation of visible light 1 hour
The photocatalytic activity of red bright B is >=95%.
Embodiment 2
Step 1: the preparation of three-dimensional framework polymer, by epoxy resin (trade mark E-44) that mass ratio is 1: 2 and poly-second
Glycol (PEG1000 with PEG2000 is by 7: 1 combinations) mixes and is heated to 65 DEG C, stirs 10 minutes and becomes clear solution
After, add and the triethylene tetramine liquid that epoxy resin mass ratio is 1: 4, pour into after stirring in mould and shape, protect
Hold setting temperature in 75 DEG C, after 5 hours, form the solid fraction blend polymer of white, remove after soaking 18 hours with pure water
Go Polyethylene Glycol phase, leave the epoxy resin of three dimensional skeletal structure, at room temperature vacuum drying 1 day；
Step 2:SiO2The preparation of large pore material, will in step 1 epoxy resin of three dimensional skeletal structure at positive silicic acid four
Ethyl ester soaks 5 hours, after exposing 10 hours in 30 DEG C in ammonia atmosphere, forms SiO2/ epoxy resin composite,
It is dried the ethanol and the ammonia of absorption generated with removing 2 hours, in Muffle furnace, rises to 850 with the heating rate of 8 DEG C/min
DEG C, keep the SiO of 30 minutes i.e. available three-dimensional superthin structures2Large pore material, aperture is about 0.5～1.5 micron, thick
Degree is about 20～50nm；
Step 3:ZnO nano-crystal film is at SiO2Fabricated in situ in large pore material, by Zn (NO3)2·6H2O with etc. rub
You are made into aqueous solution by the tetrahydroxypropyl ethylenediamine of number, obtain required precursor liquid, in precursor liquid, and Zn (NO3)2Mole
Concentration is 0.5mol/L.By SiO2Large pore material is placed in precursor liquid and fully soaks, and dries 2 hours after taking-up at 80 DEG C,
Remove major part water, then in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min, then insulation is calcined 1 hour
After be cooled to room temperature, obtain binary complex carrier；
The deposition of step 4:Fe (III)-taPc, is dissolved in Fe (III)-taPc in N,N-dimethylacetamide and is made into dipping
Solution (Fe (III)-taPc concentration is 4mg/mL), takes out after being soaked by above-mentioned binary complex carrier fully in dipping solution,
Being directly placed in clear water, solvent exchanges with water, Fe (III)-taPc autodeposition at carrier surface, sample through washing,
Become blackish green after drying, i.e. obtain tri compound biomimetic photocatalysis agent.
Repeat step 3 two times so that the content of ZnO be 16wt.%, Fe (III)-taPc content be 2.9wt.%, ternary
The porosity of composite bionic photocatalyst is 82%, and specific surface area is 95m2/ g, to Luo Dan in radiation of visible light 1 hour
The photocatalytic activity of bright B is >=95%.
Embodiment 3
Step 1: the preparation of three-dimensional framework polymer, by epoxy resin (trade mark E-44) that mass ratio is 1: 2 and poly-second
Glycol (PEG1000 with PEG2000 is by 7: 1 combinations) mixes and is heated to 60～80 DEG C, stirs 15 minutes and becomes transparent molten
After liquid, add and the triethylene tetramine liquid that epoxy resin mass ratio is 1: 4, pour into after stirring in mould and shape,
Setting temperature is kept after 10 hours, to form the solid fraction blend polymer of white in 80 DEG C, after soaking 20 hours with pure water
Remove Polyethylene Glycol phase, leave the epoxy resin of three dimensional skeletal structure, at room temperature vacuum drying 2 days；
Step 2:SiO2The preparation of large pore material, will in step 1 epoxy resin of three dimensional skeletal structure at positive silicic acid four
Ethyl ester soaks 5 hours, after exposing 10 hours in 30 DEG C in ammonia atmosphere, forms SiO2/ epoxy resin composite,
It is dried the ethanol and the ammonia of absorption generated with removing 5 hours, rises to the heating rate of 10 DEG C/min in Muffle furnace
900 DEG C, keep the SiO of 60 minutes i.e. available three-dimensional superthin structures2Large pore material, aperture is about 0.5～1.5 micron,
Thickness is about 20～50nm；
Step 3:ZnO nano-crystal film is at SiO2Fabricated in situ in large pore material, by Zn (NO3)2·6H2O with etc.
The tetrahydroxypropyl ethylenediamine of molal quantity is made into aqueous solution, obtains required precursor liquid, in precursor liquid, and Zn (NO3)2Rub
Your concentration is 1.0mol/L, by SiO2Large pore material is placed in precursor liquid and fully soaks, and dries 2 little after taking-up at 80 DEG C
Time, remove major part water, then in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min, then be incubated calcining 1
It is cooled to room temperature after hour, obtains binary complex carrier；
The deposition of step 4:Fe (III)-taPc, is dissolved in Fe (III)-taPc in N,N-dimethylacetamide and is made into leaching
Stain solution (Fe (III)-taPc concentration is 5mg/mL), after soaking above-mentioned binary complex carrier in dipping solution fully
Taking out, be directly placed in clear water, solvent exchanges with water, and Fe (III)-taPc autodeposition is at carrier surface, sample
Through washing, become blackish green after drying, i.e. obtain tri compound biomimetic photocatalysis agent.
Repeat step 3 three times so that the content of ZnO be 20wt.%, Fe (III)-taPc content be 3.2wt.%, ternary
The porosity of composite bionic photocatalyst is 82%, and specific surface area is 89m2/ g, to sieve in radiation of visible light 1 hour
The photocatalytic activity of red bright B is >=99%, and Fig. 2 is ZnO (the 20wt%)/SiO of embodiment 32The XRD figure of sample
Spectrum, owing to its XRD spectra of sample of different embodiments is similar, simply intensity is different, so only with a spectrogram
Supported.
Embodiment 4
Step 1: the preparation of three-dimensional framework polymer, by epoxy resin (trade mark E-44) that mass ratio is 1: 2.5 and poly-
Ethylene glycol (PEG1000 with PEG2000 is by 7: 1 combinations) mixes and is heated to 80 DEG C, stirs 15 minutes and becomes transparent molten
After liquid, add and the triethylene tetramine liquid that epoxy resin mass ratio is 1: 4, pour into after stirring in mould and shape,
Setting temperature is kept after 10 hours, to form the solid fraction blend polymer of white in 80 DEG C, after soaking 20 hours with pure water
Remove Polyethylene Glycol phase, leave the epoxy resin of three dimensional skeletal structure, at room temperature vacuum drying 2 days；
Step 2:SiO2The preparation of large pore material, will in step 1 epoxy resin of three dimensional skeletal structure at positive silicic acid four
Ethyl ester soaks 5 hours, after exposing 10 hours in 30 DEG C in ammonia atmosphere, forms SiO2/ epoxy resin composite,
It is dried the ethanol and the ammonia of absorption generated with removing 5 hours, rises to the heating rate of 10 DEG C/min in Muffle furnace
900 DEG C, keep the SiO of 160 minutes i.e. available three-dimensional superthin structures2Large pore material, aperture is about 0.5～1.5 micron,
Thickness is about 20～50nm；
Step 3:ZnO nano-crystal film is at SiO2Fabricated in situ in large pore material, by Zn (NO3)2·6H2O with etc.
The tetrahydroxypropyl ethylenediamine of molal quantity is made into aqueous solution, obtains required precursor liquid, in precursor liquid, and Zn (NO3)2's
Molar concentration is 1.0mol/L.By SiO2Large pore material is placed in precursor liquid and fully soaks, and dries 2 after taking-up at 80 DEG C
Hour, remove major part water, then in Muffle furnace, be warming up to 600 DEG C with the speed of 10 DEG C/min, then be incubated calcining
It is cooled to room temperature after 1 hour, obtains binary complex carrier；
The deposition of step 4:Fe (III)-taPc, is dissolved in Fe (III)-taPc in N,N-dimethylacetamide and is made into leaching
Stain solution (Fe (III)-taPc concentration is 6mg/mL), takes after being soaked by above-mentioned binary complex carrier fully in dipping solution
Going out, be directly placed in clear water, solvent exchanges with water, and Fe (III)-taPc autodeposition passes through at carrier surface, sample
Wash, become blackish green after drying, i.e. obtain tri compound biomimetic photocatalysis agent.
Repeat step 3 three times so that the content of ZnO be 19wt.%, Fe (III)-taPc content be 3.6wt.%, ternary
The porosity of composite bionic photocatalyst is 80%, and specific surface area is 86m2/ g, photocatalysis to rhodamine B in 1 hour
Degradation rate is >=99%.
Fe (III)-taPc/ZnO/SiO2 tri compound biomimetic photocatalysis agent by different loads amount prepared in four embodiments
Carry out the photocatalytic degradation test of XRD, UV-Vis diffuse-reflectance and RhB, obtain Fig. 2 to Fig. 4.
Method of testing in embodiment is specific as follows:
Use the pattern of scanning electron microscope (JSM-5600LV type) observation sample, 5kV's after i.e. sample sprays platinum
Surface topography sign is carried out under accelerating potential；X-ray diffractometer (Rigaku D/max-1200) is used to analyze sample brilliant
Body structure and composition, running voltage 30mV, operating current 30mV, Cu K α radiation (λ=0.154nm), scan model
Enclose 2 θ=10 °～70 °；Test specific surface area with specific surface area and pore-size distribution tester (JW-K type), use BET formula
Calculate its specific surface area；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 not
With load capacity Fe (III)-taPc/SiO2Photocatalytic activity and recycling.With the halogen lamp (λ >=400nm) of 150W it is
Visible light source, light source distance reactor 10cm.Weigh Fe (the III)-taPc/SiO of 50mg different loads amount respectively2
Catalyst, makes graininess sample (size is about 1mm), is scattered in the rhodamine B aqueous solution of 50ml10 μm ol/L,
It is placed in homemade airtight Photoreactor, is passed through oxygen.Under magnetic stirring, reaction system is placed in dark place 1h,
Open light source after guaranteeing adsorption equilibrium and carry out light-catalyzed reaction.Course of reaction samples every 10min, its supernatant of centrifuging and taking
Liquid, measures rhodamine B absorbance at 552nm with ultraviolet-visible spectrophotometer, and calculates its concentration.According to
Formula Ct/C0Calculate photocatalytic activity, C in formula0And CtIt is respectively original solution and in the taken sample solution of 10min
The concentration of rhodamine B.
The present invention utilize a kind of large scale, high intensity, high porosity, high connectivity silicon dioxide large pore material as load
Body, is loaded with ZnO nano crystalline substance thin film in its three through ducts, is then adsorbed by Fe (III)-taPc by infusion process
To ZnO nano crystalline substance surface, constitute the photocatalysis system that n-type quasiconductor is collaborative with p-type quasiconductor.This tri compound is imitated
Third contact of a total solar or lunar eclipse catalyst use tetracarboxylic FePC (III) (Fe (III)-taPc) as photocatalyst, and with ZnO compound use, profit
With the electron-transporting of ZnO, light induced electron is migrated, stop itself and hole-recombination, thus improve the effect of light-catalyzed reaction
Rate；Simultaneously in order to by fixing for catalyst and keep molecular diffusivity to the full extent, use large scale, wide-aperture two
Catalyst, as carrier, is compounded on three-dimensional continuous print silicon dioxide hole wall, the photocatalyst finally prepared by silicon oxide
Easy to use, stable performance, it is seen that photoresponse is good, catalytic efficiency is high.
Claims (6)
1. a tri compound biomimetic photocatalysis agent, it is characterised in that:
Including binary complex carrier and the active substance that is deposited on this binary complex carrier surface, described active substance is ferrum phthalein
Cyanines coordination compound, in described tri compound biomimetic photocatalysis agent, the content of iron phthalocyanine complex is 1.5～4wt.%, this iron-phthalocyanine
Coordination compound is tetracarboxylic FePC (III)；
Described binary complex carrier is by the silicon dioxide large pore material of three-dimensional superthin structure, and it is big to be deposited on this silicon dioxide
ZnO nano crystalline substance thin film in the three-dimensional through duct of Porous materials is constituted, and described iron phthalocyanine complex is deposited on binary and is combined
Carrier surface, in described binary complex carrier, the content of described ZnO is 10～20wt.%；
Described tri compound biomimetic photocatalysis agent is prepared by following steps: the 1. preparation of three-dimensional framework polymer, by matter
Amount mixes than epoxy resin and the Polyethylene Glycol for 1:2～1:2.5 and is heated to 60～80 DEG C, stirs 5～15 minutes one-tenth
After clear solution, add and the triethylene tetramine liquid that epoxy resin mass ratio is 1:4～1:4.5, pour into after stirring
Mould is shaped, keeps setting temperature to form the solid fraction blend polymer of white in 70～80 DEG C after 1～10h, use
Pure water soaks 12～20 hours, leaves the epoxy resin of three dimensional skeletal structure, at room temperature vacuum drying 1～2 day；
2. the preparation of silicon dioxide large pore material, by the epoxy resin of step three dimensional skeletal structure 1. at positive silicic acid tetrem
Ester soaks 4～5 hours, after exposing 10～12 hours at 25～30 DEG C in ammonia atmosphere, forms SiO2/ asphalt mixtures modified by epoxy resin
Fat complexes, is dried 1～5 hour, rises to 800～900 DEG C with the heating rate of 5～10 DEG C/min in Muffle furnace,
Keep the silicon dioxide large pore material i.e. obtaining three-dimensional superthin structure for 10～60 minutes；
3. ZnO nano crystalline substance thin film fabricated in situ in silicon dioxide large pore material, is 1:1's～1:1.2 by mol ratio
Zn(NO3)2·6H2O and tetrahydroxypropyl ethylenediamine are made into aqueous solution, obtain required precursor liquid, in described precursor liquid,
Zn(NO3)2Concentration be 0.2～1.0mol/L, silicon dioxide large pore material is placed in precursor liquid and fully soaks, take out
After at 70～80 DEG C dry 2～3 hours, then in Muffle furnace with the speed of 10～15 DEG C/min be warming up to 600～
650 DEG C, then insulation calcining 1～2 hour after be cooled to room temperature, obtain binary complex carrier；
4. the deposition of iron phthalocyanine complex, presses the ratio of 3～6mg/ml by iron phthalocyanine complex and N,N-dimethylacetamide
Example is made into dipping solution, by step 3. in binary complex carrier soak in above-mentioned dipping solution and take out, directly after fully
Put in clear water, obtain tri compound biomimetic photocatalysis agent after drying.
Tri compound biomimetic photocatalysis agent the most according to claim 1, it is characterised in that: described silicon dioxide is big
The aperture of Porous materials is 0.5～1.5 μm, and thickness is 20～50nm.
Tri compound biomimetic photocatalysis agent the most according to claim 1 and 2, it is characterised in that: described ternary is multiple
The porosity closing biomimetic photocatalysis agent is 80%～90%, and specific surface area is 86～108m2/ g is little at radiation of visible light 1
Time interior degradation rate >=95% to Luo Dan B.
Tri compound biomimetic photocatalysis agent the most according to claim 1, it is characterised in that: described epoxy resin
The trade mark is E-44.
Tri compound biomimetic photocatalysis agent the most according to claim 1, it is characterised in that: described ethylene glycol is for dividing
Son amount is 1000 or/and the ethylene glycol of 2000.
Tri compound biomimetic photocatalysis agent the most according to claim 1, it is characterised in that: repeating said steps is 3.
To regulate the deposition of ZnO.
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