CN103223352B - 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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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
Present invention incorporates sol-gel process, the methods such as surface molecule print technology and heating using microwave polymerization, prepare the magnetic surface trace composite photo-catalyst that not only there is good photopermeability but also there is high selectivity, belong to technical field of environmental material preparation.
Background technology
Enrofloxacin HCL (ENRH) is the fluoroquinolone antibiotics medicine of first animal specific of listing, has stronger sterilizing ability and the feature of broad-spectrum antibacterial.But its resistance to the action of a drug and side effect thereof also cause significant damage to ecological environment and health simultaneously, research shows, part Enrofloxacin HCL can enter into soil environment along with excreta, cause the increase of microorganism drug resistance, active in respiration to the Substance Transformation of edaphon, the various enzymatic activitys of soil etc. have an impact; In addition, part Enrofloxacin HCL accumulates in the tissue, organ and products thereof of animal with original shape and metabolite mode, the medicament residue in animal food is caused to accumulate, its toxic and side effect can direct harm humans healthy, more seriously the medicine of residual low concentration easily induces human disease bacterium to produce drug resistance, thus is unfavorable for the treatment of such medicine to human diseases.So the Enrofloxacin HCL pharmaceutical wastewater rationally processed in life, production is an important link.
At present, TiO
2as one of the most promising catalysis material, there is nontoxic cheapness, fabulous electric conductivity, the character such as higher chemistry and heat endurance, be widely used in the process of organic wastewater in water environment, it can absorb sunshine to produce light induced electron and photo-induced hole, thus produces a series of redox reaction and carry out degradable organic pollutant.For cost-saving, improve the object of recovery utilization rate, this invention is with magnetic Fe
3o
4for carrier, introduce SiO
2inert layer, the coated TiO of recycling sol-gel process
2, thus both improved this photochemical catalyst photocatalytic activity under visible light, also improve the recovery utilization rate of this photochemical catalyst, and made it real and reach not only economy but also practical purpose.
In addition, for common photochemical catalyst can not in plurality of target pollutant the shortcoming of degradation selectivity simple target thing, we introduce surface molecule print technology and heating using microwave polymerization, on the one hand, surface molecule print technology is the covalently or non-covalently effect utilized between template molecule and monomer, is prepared the technology having three-dimensional specific structure, template molecule is had to the polymer of specific recognition ability by cross-linked polymeric and wash-out; On the other hand, compared to thermal-initiated polymerization and light initiation polymerization, heating using microwave polymerization has the advantage of its uniqueness, such as: polymerization speed is fast, reaction temperature and, product morphology is all first-class.But photocatalytic activity site can be covered to a certain extent at titanium dioxide optical catalyst Surface coating molecular imprinted polymer on surface, reduce photocatalytic activity, and there is the introducing of the polymethyl methacrylate (PMMA) of good light transmission rate (can reach 92% under visible ray), make surface imprinted layer have good photopermeability, thus solve this problem.
With this, we are not only with magnetic Fe
3o
4for carrier, introduce SiO
2inert layer and TiO
2semiconductor layer, also utilizes the method for surface molecule print technology and heating using microwave polymerization to TiO
2nanosilica has been carried out on surface, and in imprinted layer, introduce polymethyl methacrylate (PMMA), prepared photochemical catalyst not only has highlight catalytic active, high recovery utilization rate, but also can in multiple high density pollution thing the Enrofloxacin HCL of degradation selectivity low-residual.
Summary of the invention
The present invention is with sol-gel process, and the 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 photopermeability.Its advantage is that structure one had not only had highlight catalytic active but also had the photochemical catalyst system of high selectivity.
The technical solution used in the present invention is: a kind of preparation method with the magnetic blotting composite photo-catalyst of good photopermeability, carries out according to following step:
(1) magnetic Fe
3o
4the preparation of nanosphere: first, by Iron(III) chloride hexahydrate, sodium acetate and ethylene glycol proportionally join in beaker, after magnetic agitation to mixture is uniformly dispersed, the solution of yellow is transferred in autoclave, 200 DEG C are reacted 8 hours, are removed by autoclave afterwards, are cooled to room temperature, the black magnetic particle absolute ethyl alcohol drip washing obtained 5 times, utilize magnet to reclaim black magnetic particle, 30 DEG C of vacuum drying, namely obtain magnetic Fe
3o
4nanosphere;
(2) SiO
2fe
3o
4preparation: ethyl orthosilicate and absolute ethyl alcohol are joined in there-necked flask in proportion, close stirring 15 minutes, more dropwise drip the mixed liquor of distilled water, concentrated ammonia liquor and absolute ethyl alcohol composition wherein, dropwise rear rapid stirring 30 minutes, logical nitrogen, then by above-mentioned obtained magnetic Fe
3o
4nanosphere; Continue stirring 6 hours, the black product obtained uses absolute ethyl alcohol and distilled water drip washing 5 times respectively, and utilize magnet to reclaim black product, 30 DEG C of vacuum drying, namely obtain SiO
2fe
3o
4;
(3) TiO
2siO
2fe
3o
4the preparation of photochemical catalyst: butyl titanate is mixed with absolute ethyl alcohol and solution is at the uniform velocity stirred 15 minutes, more dropwise drip and press the mixed liquor of concentrated hydrochloric acid, distilled water and absolute ethyl alcohol, rapid stirring to colloidal sol shape, then by above-mentioned obtained SiO
2fe
3o
4proportionally join this TiO
2in colloidal sol, be at the uniform velocity stirred to evenly to gel, ageing 2 ~ 3 hours under the tungsten lamp of 40W, then 30 DEG C of vacuum drying, namely obtain TiO
2siO
2fe
3o
4photochemical catalyst;
(4) modification TiO
2siO
2fe
3o
4the preparation of photochemical catalyst: by above-mentioned TiO
2siO
2fe
3o
4photochemical catalyst and PEG-4000 and distilled water proportionally join in small beaker, ultrasonic 1 hour, i.e. obtained modification TiO
2siO
2fe
3o
4photochemical catalyst.
(5) preparation of magnetic surface trace composite photo-catalyst: Enrofloxacin HCL (ENRH), methyl methacrylate (MMA), methyl-sulfoxide (DMSO) are added in beaker in proportion, stirring at room temperature is to dissolving and being placed on dark place 12 hours under nitrogen atmosphere, then by ENRH, styrene (St), trimethylol-propane trimethacrylate (TRIM), azodiisobutyronitrile (AIBN), modification TiO
2siO
2fe
3o
4photochemical catalyst is in proportion by TRIM, AIBN and modification TiO
2siO
2fe
3o
4photochemical catalyst joins in above-mentioned solution, is transferred to by this reaction solution in microwave reaction bottle, at N
2500W Microwave Emulsifier-Free Polymerization 1 hour under atmosphere, then reaction bulb is taken out, use absolute ethyl alcohol and each drip washing of distilled water 3 times respectively, add distilled water again, ultraviolet lighting wash-out 5h, after product absolute ethyl alcohol and each drip washing of water 3 times, be placed in 30 DEG C of vacuum drying chambers and dry, namely obtain magnetic surface trace composite photo-catalyst.
Wherein Iron(III) chloride hexahydrate in step (1): sodium acetate: the mass ratio of ethylene glycol is 1:2.7:40.
Wherein in step (2), the volume ratio of ethyl orthosilicate and absolute ethyl alcohol is 1:7.
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.
Wherein magnetic Fe in step (2)
3o
4nanosphere: the mass ratio of ethyl orthosilicate is 1:2.5.
Wherein in step (3), the volume ratio of butyl titanate and absolute ethyl alcohol is 1:4.
Wherein in step (3), in mixed liquor, the volume ratio of concentrated hydrochloric acid, distilled water and absolute ethyl alcohol is 1:15:180.
Wherein SiO in step (3)
2fe
3o
4: the mass ratio of butyl titanate is 1:4.5.
Wherein TiO in step (4)
2siO
2fe
3o
4photochemical catalyst: PEG-4000: the mass ratio of distilled water is 1:5:16.
Wherein Enrofloxacin HCL (ENRH) in step (5): methyl methacrylate (MMA): the mass ratio of methyl-sulfoxide (DMSO) is 1:2:40.
Wherein Enrofloxacin HCL (ENRH) in step (5): styrene (St): trimethylol-propane trimethacrylate (TRIM): azodiisobutyronitrile (AIBN): modification TiO
2siO
2fe
3o
4the mass ratio of photochemical catalyst is 1:25:10:0.25:25.
Wherein ENRH in step (5): 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 except Enrofloxacin HCL, all the other all preparation process are with (5).
Technological merit of the present invention: the Magneto separate characteristic of photochemical catalyst makes the separation and recovery of sample more convenient, efficiently; The magnetic surface trace composite photo-catalyst prepared in this approach has very high selective in two end number mixing phase antibiotic solution to photocatalytic degradation ENRH; The imprinted layer of common trace photochemical catalyst covers TiO
2avtive spot, photocatalytic activity is reduced greatly, and in the invention, due to the introducing of MMA, make also to create polymethyl methacrylate (PMMA in the forming process of imprinted polymer, a kind of typical lucite, under visible ray, light transmission rate can reach 92%), the double action in the PMMA in imprinted layer and trace hole substantially increases magnetic surface trace composite photo-catalyst to the photocatalytic activity of ENRH, make prepared magnetic surface trace composite photo-catalyst while having high selectivity, also do not affect its photocatalytic activity.
Accompanying drawing explanation
Fig. 1: be the preparation flow schematic diagram of magnetic surface trace composite photo-catalyst;
Fig. 2: the photocatalysis effect figure of concentration magnetic surface trace composite photo-catalyst being the different methyl methacrylates (MMA) of preparation, the photocatalysis effect of the magnetic surface trace composite photo-catalyst as can be seen from the figure prepared with 0.04mL methyl methacrylate (MMA) is best.
Fig. 3: be the fourier infrared spectrogram of sample, a. TiO2 SiO2Fe3O4 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 peak than TiO2 SiO2Fe3O4 photochemical catalyst, show molecular imprinted polymer on surface coated success, and define polymethyl methacrylate in imprinted layer.
Fig. 4: be the X-ray diffraction spectrogram of sample, a.Fe
3o
4; B.TiO
2siO
2fe
3o
4photochemical catalyst; C. magnetic surface trace composite photo-catalyst, as can be seen from the figure we have successfully prepared Fe
3o
4with the TiO of Detitanium-ore-type
2, also can find out that the coated of molecular imprinted polymer on surface does not change TiO from magnetic surface trace composite photo-catalyst
2crystal formation.
Fig. 5: be the TEM of photochemical catalyst, SEM and EDS spectrogram, a.Fe
3o
4tEM spectrogram; B.SiO
2fe
3o
4tEM spectrogram; C.TiO
2siO
2fe
3o
4tEM 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
4surface is by coated Si O
2, TiO
2, surface molecule print still well maintains the spherical structure of sample after modifying; And prepared magnetic surface trace composite photo-catalyst has good hierarchical structure and dispersiveness; The coated Fe of prepared magnetic surface trace composite photo-catalyst success can be found out in EDS spectrogram
3o
4, SiO
2and TiO
2.
Fig. 6: be the thermogravimetric analysis spectrogram of sample, a. TiO
2siO
2fe
3o
4photochemical catalyst; B. magnetic surface trace composite photo-catalyst, the surface molecule print layer in as can be seen from the figure prepared magnetic surface trace composite photo-catalyst account for whole photochemical catalyst nearly 1/4th weight.
Fig. 7: be the solid uv atlas of sample, the commercially available P25 photochemical catalyst of a.; B.TiO
2siO
2fe
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 compared to commercially available P25 photochemical catalyst, no matter at ultraviolet region or 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
2siO
2fe
3o
4photochemical catalyst is much lower, illustrates in the surface imprinted layer of magnetic surface trace composite photo-catalyst containing polymethyl methacrylate (PMMA, light transmittance under visible light can reach 92%).
Fig. 8: be the Magneto separate characteristic spectrogram of sample, a.Fe
3o
4; B.TiO
2siO
2fe
3o
4photochemical catalyst; C. magnetic surface trace composite photo-catalyst, illustration is the design sketch of the Magneto separate characteristic directly perceived of sample, and as can be seen from the figure prepared magnetic surface trace composite photo-catalyst has good Magneto separate characteristic.
Fig. 9: be the photocatalysis effect figure of different photochemical catalyst, a.TiO
2siO
2fe
3o
4photochemical catalyst; B. magnetic surface trace composite photo-catalyst; C. be the conventional surface trace composite photo-catalyst of function monomer with acrylamide; D. be the conventional surface trace composite photo-catalyst of function monomer with o-phenylenediamine; E. be the conventional surface trace composite photo-catalyst of function monomer with methacrylic acid; F. be the conventional surface trace composite photo-catalyst of function monomer with 4-vinylpridine, as can be seen from the figure, the photocatalysis effect of prepared magnetic surface trace composite photo-catalyst compares TiO
2siO
2fe
3o
4photochemical catalyst is lower slightly, but all higher than conventional surface trace composite photo-catalyst, and this shows in surface imprinted layer, define polymethyl methacrylate (PMMA).
Figure 10: under the radiation of visible light of 90 minutes, the high-efficient liquid phase spectrogram of different photochemical catalyst in the two end number mixing phase antibiotic waste water containing Enrofloxacin HCL (ENRH) and tetracycline (TC), a. Binary Mixtures stoste; B. the solution of magnetic surface non-trace composite photo-catalyst light degradation after 90 minutes; C. the solution of magnetic surface trace composite photo-catalyst light degradation after 90 minutes; D.TiO
2siO
2fe
3o
4the solution of photochemical catalyst light degradation after 90 minutes; As can be seen from the figure in two end number mixing phase antibiotic waste water, magnetic surface trace composite photo-catalyst has very high selective to photocatalytic degradation Enrofloxacin HCL.
Figure 11: be the photocatalysis effect figure of different photochemical catalyst in two end number mixing phase antibiotic waste water, a.TiO
2siO
2fe
3o
4photochemical catalyst; B. magnetic surface trace composite photo-catalyst; C. the non-trace composite photo-catalyst of magnetic surface, as can be seen from the figure in two end number mixing phase antibiotic waste water, magnetic surface trace composite photo-catalyst has very high selective to photocatalytic degradation Enrofloxacin HCL.
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.
Detailed description of the invention
Below in conjunction with concrete embodiment, the present invention will be further described.
Photocatalytic activity evaluation: carry out in DW-01 type photochemical reaction instrument (purchased from Educational Instrument Factory of Yangzhou University), visible lamp irradiates, 60mL 20mg/L Enrofloxacin HCL simulated wastewater to be added in reactor and to measure its initial value, then the photochemical catalyst of 0.1g is added, magnetic agitation is also opened aerator and is passed into air, 15min sample analysis in interval in During Illumination, gets supernatant liquor at ultraviolet specrophotometer λ after being separated with magnet
maxmeasure its concentration in=276nm place or high-efficient liquid phase chromatogram discuss, and pass through formula: ln (C/C
0)=-kt calculates its reaction rate constant k, wherein C
0for the initial concentration of Enrofloxacin HCL solution, C is the concentration of the Enrofloxacin HCL solution that t measures, and t is the reaction time.
Selective evaluation: carry out in DW-01 type photochemical reaction instrument (purchased from Educational Instrument Factory of Yangzhou University), visible lamp irradiates, the mixed liquor (containing 20mg/L Enrofloxacin HCL and 20mg/L tetracycline) of 60mL is added in reactor, then the photochemical catalyst of 0.2g is added, magnetic agitation is also opened aerator and is passed into air, 15min sample analysis in interval in During Illumination, get supernatant liquor after being separated with magnet in high-efficient liquid phase chromatogram discuss, measure its concentration, and pass through formula: ln (C/C
0)=-kt calculates its reaction rate constant k.
Embodiment 1:(1) magnetic Fe
3o
4the preparation of nanosphere: by 1.35g Iron(III) chloride hexahydrate, the sodium acetate of 3.6g joins in the beaker containing 50mL ethylene glycol, after magnetic agitation to mixture is uniformly dispersed, transfer in autoclave by the solution of yellow, 200 DEG C are reacted 8 hours, afterwards autoclave is removed, be cooled to room temperature, the black magnetic particle absolute ethyl alcohol drip washing obtained 5 times, utilize magnet to reclaim black magnetic particle, 30 DEG C of vacuum drying, namely obtain magnetic Fe
3o
4nanosphere.
(2) SiO
2fe
3o
4preparation: the ethyl orthosilicate of 5mL and the absolute ethyl alcohol of 35mL are joined in there-necked flask, close stirring 15 minutes, dropwise drip containing 3mL distilled water wherein again, the mixed liquor of 9mL concentrated ammonia liquor and 36mL absolute ethyl alcohol, dropwise rear rapid stirring 30 minutes, logical nitrogen, then by above-mentioned for 2g obtained Fe
3o
4join in there-necked flask, continue stirring 6 hours, the black product obtained uses absolute ethyl alcohol and distilled water drip washing 5 times respectively, and utilize magnet to reclaim black product, 30 DEG C of vacuum drying, namely obtain SiO
2fe
3o
4.
(3) TiO
2siO
2fe
3o
4the preparation of photochemical catalyst: the butyl titanate of 9mL and the absolute ethyl alcohol of 36mL are joined in there-necked flask, at the uniform velocity stir 15 minutes, more dropwise drip containing 0.2mL concentrated hydrochloric acid, the mixed liquor of 3mL distilled water and 36mL absolute ethyl alcohol, rapid stirring to colloidal sol shape, then by above-mentioned for 2g obtained SiO
2fe
3o
4join in this colloidal sol, be at the uniform velocity stirred to evenly to gel, ageing 2 ~ 3 hours under the tungsten lamp of 40W, then 30 DEG C of vacuum drying, namely obtain TiO
2siO
2fe
3o
4photochemical catalyst.
(4) modification TiO
2siO
2fe
3o
4the preparation of photochemical catalyst: by above-mentioned for 0.5g TiO
2siO
2fe
3o
4photochemical catalyst and 2.5gPEG-4000 join in the small beaker containing 8mL distilled water, ultrasonic 1 hour, i.e. obtained modification TiO
2siO
2fe
3o
4photochemical catalyst.
(5) preparation of magnetic surface trace composite photo-catalyst: by 0.02g Enrofloxacin HCL (ENRH), 0.04mL methyl methacrylate (MMA) is added in the small beaker containing 1mL methyl-sulfoxide (DMSO), stirring at room temperature is to dissolving and being placed on dark place 12 hours under nitrogen atmosphere, again by the styrene (St) of 0.5mL, the trimethylol-propane trimethacrylate (TRIM) of 0.25mL, the azodiisobutyronitrile (AIBN) of 0.005g and the above-mentioned modification TiO of 0.5g
2siO
2fe
3o
4photochemical catalyst joins in above-mentioned solution, is transferred to by this reaction solution in microwave reaction bottle, at N
2500W Microwave Emulsifier-Free Polymerization 1 hour under atmosphere, then reaction bulb is taken out, use absolute ethyl alcohol and each drip washing of distilled water 3 times respectively, add 200mL distilled water again, ultraviolet lighting wash-out 5h, after product absolute ethyl alcohol and each drip washing of water 3 times, be placed in 30 DEG C of vacuum drying chambers and dry, namely obtain magnetic surface trace composite photo-catalyst.
(6) preparation of the non-trace composite photo-catalyst of magnetic surface: except not adding except Enrofloxacin HCL, all the other all preparation process are with (5).
(7) get 0.1g(5) in sample in 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 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 photochemical reaction instrument, carry out photocatalytic degradation test, experimental result high-efficient liquid phase chromatogram discuss is analyzed, and calculate under 90min radiation of visible light, this magnetic surface trace composite photo-catalyst is to the reaction rate constant of Enrofloxacin HCL in mixed solution (EH) and tetracycline (TC).
Embodiment 2: undertaken by the same step of embodiment 1 preparation technology, different magnetic surface trace composite photo-catalysts is prepared unlike the methyl methacrylate (MMA) getting five groups of (0.01mL, 0.02mL, 0.04mL, 0.06mL, 0.08mL) variable concentrations in step (5), the methyl methacrylate (MMA) investigating variable concentrations, on the impact of magnetic surface trace composite photo-catalyst photocatalytic activity, investigates the activity of light degradation Enrofloxacin HCL antibiotic waste water by (7) step in embodiment 1.Photocatalysis effect as shown in Figure 2, can find out with concentration to be that the effect of magnetic surface trace composite photo-catalyst light degradation Enrofloxacin HCL antibiotic waste water prepared by 0.04mL methyl methacrylate (MMA) is best.
Embodiment 3:TiO
2siO
2fe
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
-1place is the characteristic absorption peak of hydroxyl and water, 1106cm
-1place 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 had more in Fig. 3 b is respectively: 1600cm
-1to 1450cm
-1between absworption peak be because the phenyl ring in styrene causes, 1718cm
-1, 1443cm
-1and 1298cm
-1the absworption peak at place is by-C=O respectively, O-CH
3cause with C-O, the above results illustrates that surface imprinted polymer has successfully been coated on TiO
2siO
2fe
3o
4surface, and in surface imprinted layer, also form polymethyl methacrylate (PMMA).
Embodiment 4:Fe
3o
4, TiO
2siO
2fe
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 (2 θ=30.1 °, 35.5 °, 43.1 ° in Fig. 4 a, 53.4 °, 57 ° of and 62.5 °) illustrate that we have successfully prepared magnetic Fe
3o
4; And the diffraction maximum had more as can be seen from Fig. 4 b, the TiO prepared by us
2for Detitanium-ore-type; Diffraction maximum in diffraction maximum in Fig. 4 c and Fig. 4 b is about the same, illustrates that the coated of molecular imprinted polymer on surface does not change TiO
2crystal formation.
Embodiment 5:Fe
3o
4, SiO
2fe
3o
4, TiO
2siO
2fe
3o
4the TEM figure of photochemical catalyst and magnetic surface trace composite photo-catalyst is as Fig. 5 a, and shown in 5b, 5c and 5d, Fig. 5 e is the SEM figure of magnetic surface trace composite photo-catalyst, from above-mentioned figure, and magnetic Fe
3o
4surface is through coated Si O
2, TiO
2, surface molecule print modify after, still well maintain extraordinary spherical structure, and there is good dispersiveness and hierarchical structure; In addition as can be seen from the ratio in figure also, magnetic surface trace composite photo-catalyst surface ratio TiO
2siO
2fe
3o
4photochemical catalyst is coarse, and this is because the trace hole on magnetic surface trace composite photo-catalyst surface causes, and imprinted polymer coated success is described.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, Si and Ti element, has reconfirmed the conclusion in embodiment 3 and embodiment 4.
Embodiment 6: be TiO
2siO
2fe
3o
4the thermogravimetric analysis spectrogram of photochemical catalyst and magnetic surface trace composite photo-catalyst, as can be seen from the figure, being warmed up to when 350 degree, the loss in weight of prepared magnetic surface trace composite photo-catalyst is 3.52%, and this causes due to hydrone evaporation; And temperature is when rising to 800 degree from 350 degree, the loss in weight of magnetic surface trace composite photo-catalyst is 21.47%, this caused because molecular engram layer decomposes, the surface molecule print layer illustrating in magnetic surface trace composite photo-catalyst account for whole photochemical catalyst nearly 1/4th weight.
Embodiment 7: commercially available P25 photochemical catalyst, TiO
2siO
2fe
3o
4photochemical catalyst, the solid uv atlas of magnetic surface trace composite photo-catalyst and the non-trace composite photo-catalyst of magnetic surface as shown in Figure 7, as can be seen from the figure compared to commercially available P25 photochemical catalyst, no matter at ultraviolet region or 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
2siO
2fe
3o
4photochemical catalyst is much lower, illustrates in the surface imprinted layer of magnetic surface trace composite photo-catalyst containing polymethyl methacrylate (PMMA, light transmittance under visible light can reach 92%).
Embodiment 8:Fe
3o
4, TiO
2siO
2fe
3o
4the Magneto separate characteristic spectrogram of photochemical catalyst and magnetic surface trace composite photo-catalyst as shown in Figure 8, illustration is the Magneto separate 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 Magneto separate characteristic, and magnetic saturation intensity can reach 11.59emu/g.
Embodiment 9: undertaken by the same step of embodiment 1 preparation technology, unlike in step (5) respectively with acrylamide (AM), o-phenylenediamine (OPD), methacrylic acid (MAA) and 4-vinylpridine (4-Vpy) prepare different conventional surface trace composite photo-catalysts for function monomer, investigate the photocatalytic activity of different photochemical catalyst, investigate the activity of light degradation Enrofloxacin HCL antibiotic waste water by (7) step in embodiment 1.Fig. 9 is with the photocatalysis effect figure of different photocatalyst for degrading Enrofloxacin HCL waste water, other conventional surface trace composite photo-catalyst of specific activity of the magnetic surface trace composite photo-catalyst light degradation Enrofloxacin HCL antibiotic waste water that result display is prepared for function monomer with methyl methacrylate (MMA) all good, just a little less than TiO
2siO
2fe
3o
4photochemical catalyst, this is owing to defining polymethyl methacrylate (PMMA in surface imprinted layer, light transmittance under visible light can reach 92%) cause, magnetic surface trace composite photo-catalyst prepared by explanation the method has extraordinary photocatalytic activity.
Embodiment 10: undertaken by (8) step in embodiment 1, unlike in this link, investigates the activity that different photochemical catalyst light degradation contains the two end number mixing phase antibiotic waste water of Enrofloxacin HCL (EH) and tetracycline (TC).Figure 10 is the high-efficient liquid phase spectrogram of different photocatalyst for degrading mixed phase antibiotic waste water, can find out when photocatalytic degradation two end number mixing phase antibiotic waste water from figure intuitively, magnetic surface trace composite photo-catalyst is very high to the degradation effect of Enrofloxacin HCL, and the degradation effect of magnetic surface trace composite photo-catalyst to tetracycline is minimum.It is very high selective that the above results shows that in two end number mixing phase antibiotic waste water magnetic surface trace composite photo-catalyst has Enrofloxacin HCL.
Embodiment 11: the reaction rate constant value mapping calculated by the high-efficient liquid phase data in embodiment 10, result as shown in figure 11, can draw when photocatalytic degradation two end number mixing phase antibiotic waste water from data, magnetic surface trace composite photo-catalyst is very high to the degradation effect of Enrofloxacin HCL, and the degradation effect of magnetic surface trace composite photo-catalyst to tetracycline is minimum.It is very high selective that the above results shows that in two end number mixing phase antibiotic waste water magnetic surface trace composite photo-catalyst has Enrofloxacin HCL.
Embodiment 12: the photochemical stability investigating magnetic surface trace composite photo-catalyst 5 circulation photocatalytic degradation Enrofloxacin HCL antibiotic waste waters by (7) step in embodiment 1, result as shown in figure 12, as can be seen from the figure after 5 circulations, the change of reaction rate constant k is very little, and the magnetic surface trace composite photo-catalyst prepared by explanation has good photochemical stability.
Claims (8)
1. there is a preparation method for the magnetic blotting composite photo-catalyst of good photopermeability, it is characterized in that carrying out according to following step:
(1) magnetic Fe
3o
4the preparation of nanosphere: first, by Iron(III) chloride hexahydrate, sodium acetate and ethylene glycol proportionally join in beaker, after magnetic agitation to mixture is uniformly dispersed, transfer in autoclave by the solution of yellow, autoclave is removed by 200 DEG C of reactions for 8 hours afterwards, be cooled to room temperature, the black magnetic particle absolute ethyl alcohol drip washing obtained 5 times, utilize magnet to reclaim black magnetic particle, 30 DEG C of vacuum drying, namely obtain magnetic Fe
3o
4nanosphere;
(2) SiO
2fe
3o
4preparation: ethyl orthosilicate and absolute ethyl alcohol are joined in there-necked flask in proportion, close stirring 15 minutes, dropwise drip the mixed liquor of distilled water, concentrated ammonia liquor and absolute ethyl alcohol composition more wherein, dropwise rear rapid stirring 30 minutes, logical nitrogen, then by magnetic Fe obtained in step (1)
3o
4nanosphere joins in there-necked flask; Continue stirring 6 hours, the black product obtained uses absolute ethyl alcohol and distilled water drip washing 5 times respectively, and utilize magnet to reclaim black product, 30 DEG C of vacuum drying, namely obtain SiO
2fe
3o
4;
(3) TiO
2siO
2fe
3o
4the preparation of photochemical catalyst: butyl titanate mixed with absolute ethyl alcohol and solution is at the uniform velocity stirred 15 minutes, more dropwise dripping the mixed liquor of concentrated hydrochloric acid, distilled water and absolute ethyl alcohol, rapid stirring to colloidal sol shape, then by above-mentioned obtained SiO
2fe
3o
4proportionally join this TiO
2in colloidal sol, be at the uniform velocity stirred to evenly to gel, ageing 2 ~ 3 hours under the tungsten lamp of 40W, then 30 DEG C of vacuum drying, namely obtain TiO
2siO
2fe
3o
4photochemical catalyst;
(4) modification TiO
2siO
2fe
3o
4the preparation of photochemical catalyst: by above-mentioned TiO
2siO
2fe
3o
4photochemical catalyst and PEG-4000 and distilled water proportionally join in small beaker, ultrasonic 1 hour, i.e. obtained modification TiO
2siO
2fe
3o
4photochemical catalyst;
(5) preparation of magnetic surface trace composite photo-catalyst: Enrofloxacin HCL (ENRH), methyl methacrylate (MMA), methyl-sulfoxide (DMSO) are added in beaker in proportion, stirring at room temperature is to dissolving and being placed on dark place 12 hours under nitrogen atmosphere, then by styrene (St), trimethylol-propane trimethacrylate (TRIM), azodiisobutyronitrile (AIBN), modification TiO
2siO
2fe
3o
4photochemical catalyst joins in above-mentioned solution in proportion, is transferred to by this reaction solution in microwave reaction bottle, at N
2500W Microwave Emulsifier-Free Polymerization 1 hour under atmosphere, then reaction bulb is taken out, use absolute ethyl alcohol and each drip washing of distilled water 3 times respectively, add distilled water again, ultraviolet lighting wash-out 5h, after product absolute ethyl alcohol and each drip washing of water 3 times, be placed in 30 DEG C of vacuum drying chambers and dry, namely obtain magnetic surface trace composite photo-catalyst.
2. a kind of preparation method with the magnetic blotting composite photo-catalyst of good photopermeability according to claim 1, 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.
3. a kind of preparation method with the magnetic blotting composite photo-catalyst of good photopermeability according to claim 1, is characterized in that the volume ratio of the wherein middle ethyl orthosilicate of step (2) and absolute ethyl alcohol is 1:7.
4. a kind of preparation method with the magnetic blotting composite photo-catalyst of good photopermeability 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;
Wherein magnetic Fe in step (2)
3o
4nanosphere: the mass ratio of ethyl orthosilicate is 1:2.5.
5. a kind of preparation method with the magnetic blotting composite photo-catalyst of good photopermeability according to claim 1, is characterized in that the volume ratio of the wherein middle butyl titanate of step (3) and absolute ethyl alcohol is 1:4;
Wherein in step (3), in mixed liquor, the volume ratio of concentrated hydrochloric acid, distilled water and absolute ethyl alcohol is 1:15:180;
Wherein SiO in step (3)
2fe
3o
4: the mass ratio of butyl titanate is 1:4.5.
6. a kind of preparation method with the magnetic blotting composite photo-catalyst of good photopermeability according to claim 1, is characterized in that the wherein middle TiO of step (4)
2siO
2fe
3o
4photochemical catalyst: PEG-4000: the mass ratio of distilled water is 1:5:16.
7. a kind of preparation method with the magnetic blotting composite photo-catalyst of good photopermeability according to claim 1, 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.
8. a kind of preparation method with the magnetic blotting composite photo-catalyst of good photopermeability according to claim 1, wherein Enrofloxacin HCL (ENRH) in step (5): styrene (St): trimethylol-propane trimethacrylate (TRIM): azodiisobutyronitrile (AIBN): modification TiO
2siO
2fe
3o
4the mass ratio of photochemical catalyst is 1:25:10:0.25:25;
Wherein ENRH in step (5): the mass ratio of distilled water is 1:10000.
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| CN103721752B (en) * | 2013-12-20 | 2016-04-06 | 江苏大学 | The preparation method of a kind of pair of electroconductive magnetic trace photochemical catalyst |
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| CN104788612A (en) * | 2014-01-16 | 2015-07-22 | 中国药科大学 | Preparation method of magnetic microspheres-based levofloxacin surface imprinted material |
| CN104926990A (en) * | 2015-06-04 | 2015-09-23 | 福州大学 | Methylmercury ion imprinted magnetic microsphere, and preparation method and application thereof |
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| CN106362802A (en) * | 2016-08-26 | 2017-02-01 | 江苏大学 | PEDOT/CdS/Fe3O4/HNT imprinted photocatalyst with high photocatalytic activity and selectivity and preparation method of PEDOT/CdS/Fe3O4/HNT imprinted photocatalyst |
| CN106311109A (en) * | 2016-08-26 | 2017-01-11 | 江苏大学 | Embedded hollow magnetic imprinted photocatalytic nanoreactor and preparation method thereof |
| CN107880980A (en) * | 2017-12-04 | 2018-04-06 | 苏州市宽道模具机械有限公司 | A kind of preparation method of antidetonation anti-attrition nano lubricating oil additive |
| CN109187481B (en) * | 2018-07-20 | 2020-08-28 | 江苏大学 | Based on Fe3O4@ Au NPs and molecularly imprinted pesticide detection method |
| CN110652868B (en) * | 2019-10-22 | 2022-04-05 | 上海创健环保科技有限公司 | Environment-friendly formaldehyde purification spray capable of releasing negative oxygen ions and preparation method thereof |
| CN113336959B (en) * | 2021-06-11 | 2022-08-02 | 中国科学院青岛生物能源与过程研究所 | Preparation method of magnetic graft polymer carrier, prepared carrier and application thereof |
| CN113600214B (en) * | 2021-09-02 | 2023-10-24 | 广州大学 | Core-shell type Fe 2 O 3 @Ti x O y -P z Preparation method and application of photocatalyst |
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