CN103223352A - Preparation method of magnetic imprinting composite photocatalyst with good light transmission - Google Patents
Preparation method of magnetic imprinting composite photocatalyst with good light transmission Download PDFInfo
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- CN103223352A CN103223352A CN2013101131176A CN201310113117A CN103223352A CN 103223352 A CN103223352 A CN 103223352A CN 2013101131176 A CN2013101131176 A CN 2013101131176A CN 201310113117 A CN201310113117 A CN 201310113117A CN 103223352 A CN103223352 A CN 103223352A
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Abstract
The invention provides a preparation method of a magnetic imprinting composite photocatalyst with good light transmission, belonging to the technical field of preparation of environmental materials. The method comprises using magnetic Fe3O4 nanoparticles as carriers, coating SiO2 insulating layers on surfaces of the nanoparticles, using a sol-gel technology to prepare a TiO2@SiO2@Fe3O4 photocatalyst, using polyethylene glycol to treat surface of the photocatalyst, and using modified TiO2@SiO2@Fe3O4 as a base material, enrofloxacin hydrochloride as a template molecule, methyl methacrylate as an imprinting functional monomer, styrene as a polymerization monomer, trimethylol propane trimethacrylate as a cross-linking agent, azodiisobutyronitrile as an initiator and a mixed solution of dimethyl sulphoxide and water as solvents to prepare the magnetic imprinting composite photocatalyst with the good light transmission. The invention is advantageous in that a magnetic separation characteristic of the photocatalyst enables separation and recovery of samples to be relatively convenient and high-efficiency.
Description
Technical field
The present invention combines sol-gel process, and methods such as surface molecule print technology and heating using microwave polymerization prepare the magnetic surface trace composite photo-catalyst that not only has the good light permeability but also have high selectivity, belong to the environmentally conscious materials preparing technical field.
Background technology
Enrofloxacin HCL (ENRH) is the fluoroquinolone antibiotics medicine of first animal specific of listing, has the characteristics of stronger sterilizing ability and broad-spectrum antibacterial.But its resistance to the action of a drug and side effect thereof have also caused significant damage to ecological environment and health simultaneously, studies show that, part Enrofloxacin HCL can enter into soil environment along with excreta, cause the chemical sproof increase of microorganism, to material activity of conversion such as the respiration of edaphon, the various enzymatic activitys of soil etc. exert an influence; In addition, the part Enrofloxacin HCL accumulates on original shape and metabolite mode in tissue, organ of animal and products thereof, cause the medicament residue accumulation in the animal food, the direct harm humans health of its toxic and side effect meeting, the medicine of even more serious is residual low concentration induces the human disease bacterium to produce drug resistance easily, thereby is unfavorable for the treatment of such medicine to human diseases.So the Enrofloxacin HCL pharmaceutical wastewater of rationally handling in life, the production is an important link.
At present, TiO
2As one of the most promising catalysis material, has nontoxic cheapness, fabulous electric conductivity, character such as higher chemistry and heat endurance, be widely used in the processing of organic wastewater in the water environment, it can absorb sunshine and produce light induced electron and photo-induced hole, comes degradable organic pollutant thereby produce a series of redox reactions.For saving cost, improve the purpose of recovery utilization rate, this is invented with magnetic Fe
3O
4Be carrier, introduce SiO
2Inert layer utilizes sol-gel process to coat TiO again
2Thereby, both improved the photocatalytic activity of this photochemical catalyst under visible light, also improved the recovery utilization rate of this photochemical catalyst, make it the real not only economy but also practical purpose of having reached.
In addition, at the normal optical catalyst can not be in the plurality of target pollutant shortcoming of selectivity degraded simple target thing, we have introduced surface molecule print technology and heating using microwave polymerization, on the one hand, the surface molecule print technology is the covalently or non-covalently effect that utilizes between template molecule and the monomer, prepares the technology that has three-dimensional specific structure, template molecule is had the polymer of specific recognition ability by cross-linked polymeric and wash-out; On the other hand, than thermal-initiated polymerization and light initiation polymerization, the heating using microwave polymerization has its special advantages, and for example: polymerization speed is fast, reaction temperature and, the product pattern is all first-class.But the clad surface molecularly imprinted polymer can cover the photocatalytic activity site to a certain extent on the titanium dioxide optical catalyst surface, reduced photocatalytic activity, and have an introducing of the polymethyl methacrylate (PMMA) of good light transmitance (visible light can reach 92% down), make surface imprinted layer have good photopermeability, thereby solved this problem.
With this, we are not only with magnetic Fe
3O
4Be carrier, introduced SiO
2Inert layer and TiO
2Semiconductor layer, the method for also utilizing surface molecule print technology and heating using microwave polymerization is to TiO
2The trace modification has been carried out on the surface, and in imprinted layer, introduced polymethyl methacrylate (PMMA), prepared photochemical catalyst not only has highlight catalytic active, high recovery utilization rate, but also can be in multiple high density pollution thing the Enrofloxacin HCL of selectivity degraded low-residual.
Summary of the invention
The present invention is with sol-gel process, and methods such as surface molecule print technology and heating using microwave polymerization are preparation means, prepare a kind of magnetic surface trace composite photo-catalyst with good light permeability.Its advantage is to make up a photochemical catalyst system that had not only had highlight catalytic active but also had high selectivity.
The technical solution used in the present invention is: a kind of preparation method with magnetic blotting composite photo-catalyst of good light permeability, carry out according to following step:
(1) magnetic Fe
3O
4The preparation of nanosphere: at first, with Iron(III) chloride hexahydrate, sodium acetate and ethylene glycol proportionally join in the beaker, after magnetic agitation to mixture is uniformly dispersed, the solution of yellow is transferred in the autoclave, 200 ℃ were reacted 8 hours, afterwards autoclave were removed, and were cooled to room temperature, the black magnetic particle that obtains absolute ethyl alcohol drip washing 5 times, utilize magnet to reclaim the black magnetic particle, 30 ℃ of vacuum drying promptly obtain magnetic Fe
3O
4Nanosphere;
(2) SiO
2@Fe
3O
4Preparation: join ethyl orthosilicate and absolute ethyl alcohol in the there-necked flask in proportion, sealing was stirred 15 minutes, again to wherein dropwise dripping the mixed liquor that distilled water, concentrated ammonia liquor and absolute ethyl alcohol are formed, dropwised the back and stirred 30 minutes fast, logical nitrogen is again with the above-mentioned magnetic Fe that makes
3O
4Nanosphere; Continue to stir 6 hours, the black product that obtains is used absolute ethyl alcohol and distilled water drip washing respectively 5 times, utilizes magnet to reclaim the black product, and 30 ℃ of vacuum drying promptly obtain SiO
2@Fe
3O
4
(3) TiO
2@ SiO
2@Fe
3O
4The preparation of photochemical catalyst: butyl titanate is mixed with absolute ethyl alcohol and solution was at the uniform velocity stirred 15 minutes, dropwise drip the mixed liquor of pressing concentrated hydrochloric acid, distilled water and absolute ethyl alcohol again, be stirred to the colloidal sol shape fast, again with the above-mentioned SiO that makes
2@Fe
3O
4Proportionally join this TiO
2In the colloidal sol, at the uniform velocity be stirred to evenly to gel, ageing is 2～3 hours under the tungsten lamp of 40W, and 30 ℃ of vacuum drying promptly obtain TiO then
2@ SiO
2@Fe
3O
4Photochemical catalyst;
(4) modification TiO
2@ SiO
2@Fe
3O
4The preparation of photochemical catalyst: with above-mentioned TiO
2@ SiO
2@Fe
3O
4Photochemical catalyst and PEG-4000 and distilled water proportionally join in the small beaker, ultrasonic 1 hour, promptly make modification TiO
2@ SiO
2@Fe
3O
4Photochemical catalyst.
(5) preparation of magnetic surface trace composite photo-catalyst: be added to Enrofloxacin HCL (ENRH), methyl methacrylate (MMA), methyl-sulfoxide (DMSO) in the beaker in proportion, stirring at room is to dissolving and being placed on the dark place 12 hours, again with ENRH, styrene (St), trimethylol-propane trimethacrylate (TRIM), azodiisobutyronitrile (AIBN), modification TiO under nitrogen atmosphere
2@ SiO
2@Fe
3O
4Photochemical catalyst is in proportion with TRIM, AIBN and modification TiO
2@ SiO
2@Fe
3O
4Photochemical catalyst joins in the above-mentioned solution, and this reaction solution is transferred in the microwave reaction bottle, at N
2The polymerization of 500W microwave is 1 hour under the atmosphere, then reaction bulb is taken out, use each drip washing of absolute ethyl alcohol and distilled water 3 times respectively, add distilled water again, ultraviolet lighting wash-out 5h, with product with absolute ethyl alcohol and each drip washing of water 3 times after, place 30 ℃ of vacuum drying chambers to dry, promptly obtain magnetic surface trace composite photo-catalyst.
Iron(III) chloride hexahydrate in the step (1) wherein: sodium acetate: the mass ratio of ethylene glycol is 1:2.7:40.
Wherein the volume ratio of ethyl orthosilicate and absolute ethyl alcohol is 1:7 in the step (2).
Distilled water in the mixed liquor in the step (2) wherein: concentrated ammonia liquor: the volume ratio of absolute ethyl alcohol is 1:3:12.
Magnetic Fe in the step (2) wherein
3O
4Nanosphere: the mass ratio of ethyl orthosilicate is 1:2.5.
Wherein the volume ratio of butyl titanate and absolute ethyl alcohol is 1:4 in the step (3).
Wherein the volume ratio of concentrated hydrochloric acid, distilled water and absolute ethyl alcohol is 1:15:180 in the middle mixed liquor of step (3).
SiO in the step (3) wherein
2@Fe
3O
4: the mass ratio of butyl titanate is 1:4.5.
TiO in the step (4) wherein
2@ SiO
2@Fe
3O
4Photochemical catalyst: PEG-4000: the mass ratio of distilled water is 1:5:16.
Enrofloxacin HCL (ENRH) in the step (5) wherein: methyl methacrylate (MMA): the mass ratio of methyl-sulfoxide (DMSO) is 1:2:40.
Enrofloxacin HCL (ENRH) in the step (5) wherein: styrene (St): trimethylol-propane trimethacrylate (TRIM): azodiisobutyronitrile (AIBN): modification TiO
2@ SiO
2@Fe
3O
4The mass ratio of photochemical catalyst is 1:25:10:0.25:25.
ENRH in the step (5) wherein: the mass ratio of distilled water is 1:10000.
Contrast of the present invention: the preparation of the non-trace composite photo-catalyst of magnetic surface: except not adding the Enrofloxacin HCL, all the other all preparation process are with (5).
Technological merit of the present invention: it is more convenient that the magnetic stalling characteristic of photochemical catalyst makes the separation of sample reclaim, efficient; Magnetic surface trace composite photo-catalyst with the method preparation has very high selectivity to photocatalytic degradation ENRH in binary mixing phase antibiotic solution; The imprinted layer of common trace photochemical catalyst has covered TiO
2Avtive spot, make photocatalytic activity reduce greatly, and in this invention, because the introducing of MMA, make and also produced polymethyl methacrylate (PMMA in the forming process of imprinted polymer, a kind of typical lucite, light transmission rate can reach 92% under the visible light), the double action in PMMA in the imprinted layer and trace hole has improved the photocatalytic activity of magnetic surface trace composite photo-catalyst to ENRH greatly, make prepared magnetic surface trace composite photo-catalyst when having high selectivity, also do not influence its photocatalytic activity.
Description of drawings
Fig. 1: be the preparation flow schematic diagram of magnetic surface trace composite photo-catalyst;
Fig. 2: be the photocatalysis design sketch of concentration magnetic surface trace composite photo-catalyst of the different methyl methacrylates (MMA) of preparation, as can be seen from the figure the photocatalysis effect of the magnetic surface trace composite photo-catalyst for preparing with 0.04mL methyl methacrylate (MMA) is best.
Fig. 3: be the fourier infrared spectrogram of sample, a. TiO2@ SiO2@Fe3O4 photochemical catalyst; B. magnetic surface trace composite photo-catalyst, as can be seen from the figure magnetic surface trace composite photo-catalyst has obviously had more a lot of absworption peaks than TiO2@ SiO2@Fe3O4 photochemical catalyst, show that molecular imprinted polymer on surface has coated success, and in imprinted layer, formed polymethyl methacrylate.
Fig. 4: be the X-ray diffraction spectrogram of sample, a.Fe
3O
4B.TiO
2@SiO
2@Fe
3O
4Photochemical catalyst; C. magnetic surface trace composite photo-catalyst, as can be seen from the figure we have successfully prepared Fe
3O
4TiO with Detitanium-ore-type
2, from magnetic surface trace composite photo-catalyst also as can be seen the coating of molecular imprinted polymer on surface do not change TiO
2Crystal formation.
Fig. 5: be the TEM of photochemical catalyst, SEM and EDS spectrogram, a.Fe
3O
4The TEM spectrogram; B.SiO
2@Fe
3O
4The TEM spectrogram; C.TiO
2@SiO
2@Fe
3O
4The TEM spectrogram; D. the TEM spectrogram of magnetic surface trace composite photo-catalyst; E. the SEM spectrogram of magnetic surface trace composite photo-catalyst; F. the EDS spectrogram of magnetic surface trace composite photo-catalyst,
As can be seen from the figure Fe
3O
4The surface is by coated Si O
2, TiO
2, surface molecule print still well kept the spherical structure of sample after modifying; And prepared magnetic surface trace composite photo-catalyst has good hierarchical structure and dispersiveness; Magnetic surface trace composite photo-catalyst prepared as can be seen in the EDS spectrogram has successfully coated Fe
3O
4, SiO
2And TiO
2
Fig. 6: be the thermogravimetric analysis spectrogram of sample, a. TiO
2@SiO
2@Fe
3O
4Photochemical catalyst; B. magnetic surface trace composite photo-catalyst, the surface molecule print layer in the as can be seen from the figure prepared magnetic surface trace composite photo-catalyst has accounted for 1/4th the weight nearly of overall optical catalyst.
Fig. 7: be the solid uv atlas of sample, the commercially available P25 photochemical catalyst of a.; B.TiO
2@SiO
2@Fe
3O
4Photochemical catalyst; C. magnetic surface trace composite photo-catalyst; D. the non-trace composite photo-catalyst of magnetic surface, as can be seen from the figure than commercially available P25 photochemical catalyst, no matter at ultraviolet region still at visible region, magnetic surface trace composite photo-catalyst all has good absorption, and the absorption of magnetic surface trace composite photo-catalyst is not than TiO
2@SiO
2@Fe
3O
4Photochemical catalyst is much lower, illustrates in the surface imprinted layer of magnetic surface trace composite photo-catalyst to contain polymethyl methacrylate (PMMA, the light transmittance under visible light can reach 92%).
Fig. 8: be the magnetic stalling characteristic spectrogram of sample, a.Fe
3O
4B.TiO
2@SiO
2@Fe
3O
4Photochemical catalyst; C. magnetic surface trace composite photo-catalyst, illustration is the design sketch of the magnetic stalling characteristic directly perceived of sample, as can be seen from the figure prepared magnetic surface trace composite photo-catalyst has good magnetic stalling characteristic.
Fig. 9: be the photocatalysis design sketch of different photochemical catalysts, a.TiO
2@SiO
2@Fe
3O
4Photochemical catalyst; B. magnetic surface trace composite photo-catalyst; C. with the acrylamide conventional surface trace composite photo-catalyst of function monomer; D. with the o-phenylenediamine conventional surface trace composite photo-catalyst of function monomer; E. with the methacrylic acid conventional surface trace composite photo-catalyst of function monomer; F. be the conventional surface trace composite photo-catalyst of function monomer with the 4-vinylpridine, as can be seen from the figure, the photocatalysis effect of prepared magnetic surface trace composite photo-catalyst compares TiO
2@SiO
2@Fe
3O
4Photochemical catalyst is lower slightly, but all higher than conventional surface trace composite photo-catalyst, and this shows in surface imprinted layer and has formed polymethyl methacrylate (PMMA).
Figure 10: under 90 minutes radiation of visible light, different photochemical catalysts mix efficient liquid phase spectrogram in the antibiotic waste water mutually, a. binary mixed solution stoste in the binary that contains Enrofloxacin HCL (ENRH) and tetracycline (TC); B. the solution of the non-trace composite photo-catalyst of magnetic surface light degradation after 90 minutes; C. the solution of magnetic surface trace composite photo-catalyst light degradation after 90 minutes; D.TiO
2@SiO
2@Fe
3O
4The solution of photochemical catalyst light degradation after 90 minutes; As can be seen from the figure magnetic surface trace composite photo-catalyst has very high selectivity to the photocatalytic degradation Enrofloxacin HCL in binary mixing phase antibiotic waste water.
Figure 11: be the photocatalysis design sketch of different photochemical catalysts in binary mixing phase antibiotic waste water, a.TiO
2@SiO
2@Fe
3O
4Photochemical catalyst; B. magnetic surface trace composite photo-catalyst; C. the non-trace composite photo-catalyst of magnetic surface mixes in binary as can be seen from the figure that magnetic surface trace composite photo-catalyst has very high selectivity to the photocatalytic degradation Enrofloxacin HCL in the phase antibiotic waste water.
Figure 12: be 5 circulation light catalytic effect figure of magnetic surface trace composite photo-catalyst photocatalytic degradation Enrofloxacin HCL solution, as can be seen from the figure prepared magnetic surface trace composite photo-catalyst has good photochemical stability.
The specific embodiment
The present invention will be further described below in conjunction with concrete embodiment.
Photocatalytic activity is estimated: carry out in DW-01 type photochemical reaction instrument (available from Educational Instrument Factory of Yangzhou University), the visible lamp irradiation, add 60mL 20mg/L Enrofloxacin HCL simulated wastewater in the reactor and measure its initial value, the photochemical catalyst that adds 0.1g then, magnetic agitation is also opened the aerator bubbling air, interval 15min sample analysis in the illumination process is with getting supernatant liquor at ultraviolet specrophotometer λ after the magnet separation
MaxMeasure its concentration in=276nm place or the high-efficient liquid phase chromatogram discuss, and pass through formula: ln (C/C
0The kt of)=-calculates its reaction rate constant k, wherein C
0Be the Enrofloxacin HCL initial concentration of solution, C is the concentration of the Enrofloxacin HCL solution of t chronometry, and t is the reaction time.
Selective evaluation: in DW-01 type photochemical reaction instrument (available from Educational Instrument Factory of Yangzhou University), carry out, the visible lamp irradiation, the mixed liquor (containing 20mg/L Enrofloxacin HCL and 20mg/L tetracycline) of 60mL is added in the reactor, the photochemical catalyst that adds 0.2g then, magnetic agitation is also opened the aerator bubbling air, interval 15min sample analysis in the illumination process is measured its concentration with getting supernatant liquor after the magnet separation, and is passed through formula: ln (C/C in high-efficient liquid phase chromatogram discuss
0The kt of)=-calculates its reaction rate constant k.
Embodiment 1:(1) magnetic Fe
3O
4The preparation of nanosphere: with the 1.35g Iron(III) chloride hexahydrate, 3.6g sodium acetate join in the beaker that contains 50mL ethylene glycol, after magnetic agitation to mixture is uniformly dispersed, the solution of yellow is transferred in the autoclave, 200 ℃ were reacted 8 hours, afterwards autoclave is removed, be cooled to room temperature, the black magnetic particle that obtains utilizes magnet to reclaim the black magnetic particle with absolute ethyl alcohol drip washing 5 times, 30 ℃ of vacuum drying promptly obtain magnetic Fe
3O
4Nanosphere.
(2) SiO
2@Fe
3O
4Preparation: the ethyl orthosilicate of 5mL and the absolute ethyl alcohol of 35mL are joined in the there-necked flask, sealing was stirred 15 minutes, contain 3mL distilled water to wherein dropwise dripping again, the mixed liquor of 9mL concentrated ammonia liquor and 36mL absolute ethyl alcohol, dropwising the back stirred 30 minutes fast, logical nitrogen is again with the above-mentioned Fe that makes of 2g
3O
4Join in the there-necked flask, continue to stir 6 hours, the black product that obtains is used absolute ethyl alcohol and distilled water drip washing respectively 5 times, utilizes magnet to reclaim the black product, and 30 ℃ of vacuum drying promptly obtain SiO
2@Fe
3O
4
(3) TiO
2@SiO
2@Fe
3O
4The preparation of photochemical catalyst: the butyl titanate of 9mL and the absolute ethyl alcohol of 36mL are joined in the there-necked flask, at the uniform velocity stirred 15 minutes, and dropwise dripped again and contain 0.2mL concentrated hydrochloric acid, the mixed liquor of 3mL distilled water and 36mL absolute ethyl alcohol, be stirred to the colloidal sol shape fast, again with the above-mentioned SiO that makes of 2g
2@Fe
3O
4Join in this colloidal sol, at the uniform velocity be stirred to evenly to gel, ageing is 2～3 hours under the tungsten lamp of 40W, and 30 ℃ of vacuum drying promptly obtain TiO then
2@SiO
2@Fe
3O
4Photochemical catalyst.
(4) modification TiO
2@SiO
2@Fe
3O
4The preparation of photochemical catalyst: with the above-mentioned TiO of 0.5g
2@SiO
2@Fe
3O
4Photochemical catalyst and 2.5gPEG-4000 join in the small beaker that contains 8mL distilled water, ultrasonic 1 hour, promptly make modification TiO
2@SiO
2@Fe
3O
4Photochemical catalyst.
(5) preparation of magnetic surface trace composite photo-catalyst: with 0.02g Enrofloxacin HCL (ENRH), 0.04mL methyl methacrylate (MMA) is added in the small beaker that contains 1mL methyl-sulfoxide (DMSO), stirring at room is to dissolving and being placed on the dark place 12 hours under nitrogen atmosphere, again with the styrene (St) of 0.5mL, 0.25mL trimethylol-propane trimethacrylate (TRIM), the above-mentioned modification TiO of the azodiisobutyronitrile of 0.005g (AIBN) and 0.5g
2@SiO
2@Fe
3O
4Photochemical catalyst joins in the above-mentioned solution, and this reaction solution is transferred in the microwave reaction bottle, at N
2The polymerization of 500W microwave is 1 hour under the atmosphere, then reaction bulb is taken out, use each drip washing of absolute ethyl alcohol and distilled water 3 times respectively, add 200mL distilled water again, ultraviolet lighting wash-out 5h, with product with absolute ethyl alcohol and each drip washing of water 3 times after, place 30 ℃ of vacuum drying chambers to dry, promptly obtain magnetic surface trace composite photo-catalyst.
(6) preparation of the non-trace composite photo-catalyst of magnetic surface: except not adding the Enrofloxacin HCL, all the other all preparation process are with (5).
(7) get 0.1g(5) in sample in the photochemical reaction instrument, carry out photocatalytic degradation test, experimental result ultraviolet specrophotometer analysis records this magnetic surface trace composite photo-catalyst and can reach 1.08min to the reaction rate constant of Enrofloxacin HCL in the 90min radiation of visible light
-1, show that this magnetic surface trace composite photo-catalyst has stronger photocatalytic activity.
(8) get 0.2g(5) in sample in the photochemical reaction instrument, carry out photocatalytic degradation test, experimental result is analyzed with high-efficient liquid phase chromatogram discuss, and calculate under the 90min radiation of visible light, this magnetic surface trace composite photo-catalyst is to the reaction rate constant of Enrofloxacin HCL in the mixed solution (EH) and tetracycline (TC).
Embodiment 2: undertaken by the same step of embodiment 1 preparation technology, different is that the methyl methacrylate (MMA) of getting five groups of (0.01mL, 0.02mL, 0.04mL, 0.06mL, 0.08mL) variable concentrations in the step (5) prepares different magnetic surface trace composite photo-catalysts, investigate of the influence of the methyl methacrylate (MMA) of variable concentrations, press the activity of (7) step investigation light degradation Enrofloxacin HCL antibiotic waste water among the embodiment 1 magnetic surface trace composite photo-catalyst photocatalytic activity.The photocatalysis effect is that the effect of magnetic surface trace composite photo-catalyst light degradation Enrofloxacin HCL antibiotic waste water of 0.04mL methyl methacrylate (MMA) preparation is best with concentration as shown in Figure 2 as can be seen.
Embodiment 3:TiO
2@SiO
2@Fe
3O
4The fourier infrared spectrogram of photochemical catalyst and magnetic surface trace composite photo-catalyst as shown in Figure 3, as can be seen from the figure 3442cm
-1Place and 2924cm
-1The place is the characteristic absorption peak of hydroxyl and water, 1106cm
-1The place is the characteristic absorption peak of Si-O-Si, 600cm
-1To 400cm
-1Between be the absworption peak of inorganic matter Ti-O and Fe-O.In addition, compare with Fig. 3 a, the absworption peak that has more among Fig. 3 b is respectively: 1600cm
-1To 1450cm
-1Between absworption peak be since styrene in phenyl ring cause 1718cm
-1, 1443cm
-1And 1298cm
-1The absworption peak at place is respectively by-C=O, O-CH
3Cause with C-O, The above results explanation surface imprinted polymer successfully has been coated on TiO
2@ SiO
2@Fe
3O
4The surface, and in surface imprinted layer, also formed polymethyl methacrylate (PMMA).
Embodiment 4:Fe
3O
4, TiO
2@SiO
2@Fe
3O
4The X-ray diffraction spectrogram of photochemical catalyst and magnetic surface trace composite photo-catalyst as shown in Figure 4, six place's diffraction maximums among Fig. 4 a (2 θ=30.1 °, 35.5 °, 43.1 °, 53.4 °, 62.5 ° of 57 ° of and) illustrate that we have successfully prepared magnetic Fe
3O
4And the diffraction maximum that has more from Fig. 4 b as can be seen, the TiO that we are prepared
2For Detitanium-ore-type; Diffraction maximum among diffraction maximum among Fig. 4 c and Fig. 4 b is about the same, illustrates that the coating of molecular imprinted polymer on surface does not change TiO
2Crystal formation.
Embodiment 5:Fe
3O
4, SiO
2@Fe
3O
4, TiO
2@SiO
2@Fe
3O
4The TEM of photochemical catalyst and magnetic surface trace composite photo-catalyst schemes as Fig. 5 a, 5b, and shown in 5c and the 5d, Fig. 5 e is the SEM figure of magnetic surface trace composite photo-catalyst, by above-mentioned figure as can be known, magnetic Fe
3O
4The surface is through coated Si O
2, TiO
2, after surface molecule print modifies, still well kept extraordinary spherical structure, and had good dispersiveness and hierarchical structure; In addition also as can be seen, magnetic surface trace composite photo-catalyst surface ratio TiO by the ratio among the figure
2@SiO
2@Fe
3O
4Photochemical catalyst is coarse, and this is because the trace hole on magnetic surface trace composite photo-catalyst surface causes, and illustrates that imprinted polymer has coated success.In addition, Fig. 5 f is the EDS spectrogram of magnetic surface trace composite photo-catalyst, and as seen from the figure, magnetic surface trace composite photo-catalyst contains a large amount of Fe, and Si and Ti element have been reconfirmed the conclusion among embodiment 3 and the embodiment 4.
Embodiment 6: be TiO
2@SiO
2@Fe
3O
4The thermogravimetric analysis spectrogram of photochemical catalyst and magnetic surface trace composite photo-catalyst, as can be seen from the figure, when being warmed up to 350 degree, the loss in weight of prepared magnetic surface trace composite photo-catalyst is 3.52%, and this is owing to the hydrone evaporation causes; And temperature rose to for 800 degree time from 350 degree, the loss in weight of magnetic surface trace composite photo-catalyst is 21.47%, this is because the decomposition of molecular engram layer causes, and illustrates that the surface molecule print layer in the magnetic surface trace composite photo-catalyst has accounted for 1/4th the weight nearly of overall optical catalyst.
Embodiment 7: commercially available P25 photochemical catalyst, TiO
2@SiO
2@Fe
3O
4Photochemical catalyst, the solid uv atlas of the non-trace composite photo-catalyst of magnetic surface trace composite photo-catalyst and magnetic surface as shown in Figure 7, as can be seen from the figure than commercially available P25 photochemical catalyst, no matter at ultraviolet region still at visible region, magnetic surface trace composite photo-catalyst all has good absorption, and the absorption of magnetic surface trace composite photo-catalyst is not than TiO
2@SiO
2@Fe
3O
4Photochemical catalyst is much lower, illustrates in the surface imprinted layer of magnetic surface trace composite photo-catalyst to contain polymethyl methacrylate (PMMA, the light transmittance under visible light can reach 92%).
Embodiment 8:Fe
3O
4, TiO
2@SiO
2@Fe
3O
4The magnetic stalling characteristic spectrogram of photochemical catalyst and magnetic surface trace composite photo-catalyst as shown in Figure 8, illustration is the magnetic stalling characteristic photo directly perceived of magnetic surface trace composite photo-catalyst, as can be seen from the figure prepared magnetic surface trace composite photo-catalyst has good magnetic stalling characteristic, and magnetic saturation intensity can reach 11.59emu/g.
Embodiment 9: undertaken by the same step of embodiment 1 preparation technology, different is respectively with acrylamide (AM) in the step (5), o-phenylenediamine (OPD), the conventional surface trace composite photo-catalyst that methacrylic acid (MAA) is different for function monomer prepares with 4-vinylpridine (4-Vpy), investigate the photocatalytic activity of different photochemical catalysts, press the activity of (7) step investigation light degradation Enrofloxacin HCL antibiotic waste water among the embodiment 1.Fig. 9 is the photocatalysis design sketch with different photocatalyst for degrading Enrofloxacin HCL waste water, it be other conventional surface trace composite photo-catalyst of specific activity all good of the magnetic surface trace composite photo-catalyst light degradation Enrofloxacin HCL antibiotic waste water for preparing of function monomer that the result shows with methyl methacrylate (MMA), is a little less than TiO
2@SiO
2@Fe
3O
4Photochemical catalyst, this is owing to formed polymethyl methacrylate (PMMA in surface imprinted layer, light transmittance under visible light can reach 92%) caused, illustrate that the magnetic surface trace composite photo-catalyst with this method preparation has extraordinary photocatalytic activity.
Embodiment 10: undertaken by (8) step among the embodiment 1, different is in this link, investigates the binary that different photochemical catalyst light degradation contain Enrofloxacin HCL (EH) and tetracycline (TC) and mixes the activity of antibiotic waste water mutually.Figure 10 is the efficient liquid phase spectrogram that different photocatalyst for degrading mix the phase antibiotic waste water, from figure, can find out intuitively when the photocatalytic degradation binary is mixed the phase antibiotic waste water, magnetic surface trace composite photo-catalyst is very high to the degradation effect of Enrofloxacin HCL, and magnetic surface trace composite photo-catalyst is minimum to the degradation effect of tetracycline.The above results shows that magnetic surface trace composite photo-catalyst has very high selectivity to Enrofloxacin HCL in binary mixing phase antibiotic waste water.
Embodiment 11: map by the reaction rate constant value that the efficient liquid phase data computation among the embodiment 10 draws, the result as shown in figure 11, can draw when the photocatalytic degradation binary is mixed the phase antibiotic waste water from data, magnetic surface trace composite photo-catalyst is very high to the degradation effect of Enrofloxacin HCL, and magnetic surface trace composite photo-catalyst is minimum to the degradation effect of tetracycline.The above results shows that magnetic surface trace composite photo-catalyst has very high selectivity to Enrofloxacin HCL in binary mixing phase antibiotic waste water.
Embodiment 12: the photochemical stability of pressing 5 circulation light catalytic degradations of (7) step investigation magnetic surface trace composite photo-catalyst Enrofloxacin HCL antibiotic waste water among the embodiment 1, the result as shown in figure 12, as can be seen from the figure after 5 circulations, the variation of reaction rate constant k is very little, illustrates that prepared magnetic surface trace composite photo-catalyst has good photochemical stability.
Claims (8)
1. preparation method with magnetic blotting composite photo-catalyst of good light permeability is characterized in that carrying out according to following step:
(1) magnetic Fe
3O
4The preparation of nanosphere: at first, with Iron(III) chloride hexahydrate, sodium acetate and ethylene glycol proportionally join in the beaker, after magnetic agitation to mixture is uniformly dispersed, the solution of yellow is transferred in the autoclave, 200 ℃ were reacted 8 hours, afterwards autoclave were removed, and were cooled to room temperature, the black magnetic particle that obtains absolute ethyl alcohol drip washing 5 times, utilize magnet to reclaim the black magnetic particle, 30 ℃ of vacuum drying promptly obtain magnetic Fe
3O
4Nanosphere;
(2) SiO
2@Fe
3O
4Preparation: join ethyl orthosilicate and absolute ethyl alcohol in the there-necked flask in proportion, sealing was stirred 15 minutes, again to wherein dropwise dripping the mixed liquor that distilled water, concentrated ammonia liquor and absolute ethyl alcohol are formed, dropwised the back and stirred 30 minutes fast, logical nitrogen is again with the above-mentioned magnetic Fe that makes
3O
4Nanosphere; Continue to stir 6 hours, the black product that obtains is used absolute ethyl alcohol and distilled water drip washing respectively 5 times, utilizes magnet to reclaim the black product, and 30 ℃ of vacuum drying promptly obtain SiO
2@Fe
3O
4
(3) TiO
2@ SiO
2@Fe
3O
4The preparation of photochemical catalyst: butyl titanate is mixed with absolute ethyl alcohol and solution was at the uniform velocity stirred 15 minutes, dropwise drip the mixed liquor of concentrated hydrochloric acid, distilled water and absolute ethyl alcohol again, be stirred to the colloidal sol shape fast, again with the above-mentioned SiO that makes
2@Fe
3O
4Proportionally join this TiO
2In the colloidal sol, at the uniform velocity be stirred to evenly to gel, ageing is 2～3 hours under the tungsten lamp of 40W, and 30 ℃ of vacuum drying promptly obtain TiO then
2@ SiO
2@Fe
3O
4Photochemical catalyst;
(4) modification TiO
2@ SiO
2@Fe
3O
4The preparation of photochemical catalyst: with above-mentioned TiO
2@ SiO
2@Fe
3O
4Photochemical catalyst and PEG-4000 and distilled water proportionally join in the small beaker, ultrasonic 1 hour, promptly make modification TiO
2@ SiO
2@Fe
3O
4Photochemical catalyst.
2.(5) preparation of magnetic surface trace composite photo-catalyst: be added to Enrofloxacin HCL (ENRH), methyl methacrylate (MMA), methyl-sulfoxide (DMSO) in the beaker in proportion, stirring at room is to dissolving and being placed on the dark place 12 hours, again with ENRH, styrene (St), trimethylol-propane trimethacrylate (TRIM), azodiisobutyronitrile (AIBN), modification TiO under nitrogen atmosphere
2@ SiO
2@Fe
3O
4Photochemical catalyst is in proportion with TRIM, AIBN and modification TiO
2@ SiO
2@Fe
3O
4Photochemical catalyst joins in the above-mentioned solution, and this reaction solution is transferred in the microwave reaction bottle, at N
2The polymerization of 500W microwave is 1 hour under the atmosphere, then reaction bulb is taken out, use each drip washing of absolute ethyl alcohol and distilled water 3 times respectively, add distilled water again, ultraviolet lighting wash-out 5h, with product with absolute ethyl alcohol and each drip washing of water 3 times after, place 30 ℃ of vacuum drying chambers to dry, promptly obtain magnetic surface trace composite photo-catalyst.
3. a kind of preparation method with magnetic blotting composite photo-catalyst of good light permeability according to claim 1, it is characterized in that the wherein middle Iron(III) chloride hexahydrate of step (1): sodium acetate: the mass ratio of ethylene glycol is 1:2.7:40.
4. a kind of preparation method with magnetic blotting composite photo-catalyst of good light permeability according to claim 1 is characterized in that the volume ratio of ethyl orthosilicate and absolute ethyl alcohol is 1:7 in the step (2) wherein.
5. a kind of preparation method with magnetic blotting composite photo-catalyst of good light permeability according to claim 1, wherein distilled water in the middle mixed liquor of step (2): concentrated ammonia liquor: the volume ratio of absolute ethyl alcohol is 1:3:12;
Magnetic Fe in the step (2) wherein
3O
4Nanosphere: the mass ratio of ethyl orthosilicate is 1:2.5.
6. a kind of preparation method with magnetic blotting composite photo-catalyst of good light permeability according to claim 1 is characterized in that the volume ratio of butyl titanate and absolute ethyl alcohol is 1:4 in the step (3) wherein;
Wherein the volume ratio of concentrated hydrochloric acid, distilled water and absolute ethyl alcohol is 1:15:180 in the middle mixed liquor of step (3);
SiO in the step (3) wherein
2@Fe
3O
4: the mass ratio of butyl titanate is 1:4.5.
7. a kind of preparation method with magnetic blotting composite photo-catalyst of good light permeability according to claim 1 is characterized in that the wherein middle TiO of step (4)
2@ SiO
2@Fe
3O
4Photochemical catalyst: PEG-4000: the mass ratio of distilled water is 1:5:16.
8. a kind of preparation method according to claim 1 with magnetic blotting composite photo-catalyst of good light permeability, it is characterized in that the wherein middle Enrofloxacin HCL (ENRH) of step (5): methyl methacrylate (MMA): the mass ratio of methyl-sulfoxide (DMSO) is 1:2:40;
A kind of preparation method according to claim 1, wherein Enrofloxacin HCL (ENRH) in the step (5): styrene (St): trimethylol-propane trimethacrylate (TRIM): azodiisobutyronitrile (AIBN): modification TiO with magnetic blotting composite photo-catalyst of good light permeability
2@ SiO
2@Fe
3O
4The mass ratio of photochemical catalyst is 1:25:10:0.25:25;
ENRH in the step (5) wherein: the mass ratio of distilled water is 1:10000.
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