CN103785476A - Preparation method of surface imprinting CdS compound photocatalyst based on magnetic carbon material - Google Patents
Preparation method of surface imprinting CdS compound photocatalyst based on magnetic carbon material Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of environmental materials, and particularly relates to a preparation method of a surface imprinting CdS compound photocatalyst based on a magnetic carbon material. The preparation method comprises the following steps: coating the surface of Fe3O4 with a C layer on as adopting the Fe3O4 as a carrier, loading CdS to prepare a CdS@C@Fe3O4 compound photocatalyst, and modifying the surface of CdS@C@Fe3O4 by utilizing polyethylene glycol-4000; preparing the magnetic surface imprinting CdS compound photocatalyst by taking the CdS@C@Fe3O4 as a base body, ciprofloxacin as a template molecule, methacrylic acid as a functional monomer, trimethylol-propane trimethacrylate as a cross-linking agent and azobisisobutyronitrile as an initiator by adopting a surface imprinting technology and an ultraviolet light-induced polymerization method. The surface imprinting CdS compound photocatalyst is relatively conveniently, fast and efficiently separated and recovered and has the very high selectivity on photodegradable ciprofloxacin in a binary mixed-phase antibiotic solution. According to the method, photo-induced electrons and a photo-induced cavity of a common CdS photocatalyst are separated to the greatest degree due to the introduction of the C layer, so that the photocatalysis activity of the photocatalyst is enhanced.
Description
Technical field
The invention belongs to environmentally conscious materials preparing technical field, be specifically related to a kind of preparation method of the surface imprinted CdS composite photo-catalyst based on magnetic carbon material.
Background technology
Ciprofloxacin is the carbostyril antibiotic medicine that a kind of use is one of the most extensive, there is antibacterial spectrum, act on the features such as strong, be used for treating intestines and stomach and infection in respiratory system, but Ciprofloxacin residual in environment easily causes toxic and side effect, can produce strong drug resistance by induction bacterium, and can produce gene mutation etc. to other biological, directly have influence on ecological and the mankind's health.So the residue of ciprofloxacin of processing rationally and effectively in life, production is an important link.Many experts and scholars remove the residue of ciprofloxacin in environment by physics, chemistry and the several different methods such as biological, but because these method efficiency are lower, easily cause again secondary pollution.At present, photocatalysis technology extensive use is studied the technology of the wastewater treatment in environment, is a kind of more satisfactory " green " treatment technology.
CdS is as intrinsic N-shaped semi-conducting material, there is superior photocatalysis performance, it is a kind of visible light-responded photochemical catalyst that has, band gap is 2.3eV, can absorb the energy of visible ray and be excited, can utilize nearly 43%(400nm ~ 750nm) sunshine degradable organic pollutant, there is equally good application prospect.For cost-saving, improve the object of recovery utilization rate, this invention is with magnetic Fe
3o
4for carrier, introduce conduction C layer (improving the light induced electron of CdS and the separative efficiency of photo-induced hole), CdS-loaded again, thereby both improved the photocatalytic activity of this photochemical catalyst under visible ray, also improve the recovery utilization rate of this photochemical catalyst, made it the real not only economy but also practical purpose of having reached.
In addition, for common CdS photochemical catalyst can not be in plurality of target pollutant the shortcoming of degradation selectivity simple target thing, we have introduced surface molecule print technology, surface molecule print technology is the covalently or non-covalently effect utilizing between template molecule and monomer, prepare the technology that has three-dimensional specific structure, template molecule is had to the polymer layer of specific recognition ability by cross-linked polymeric and wash-out at substrate material surface, the introducing of surface molecule print technology has well solved the problem of common CdS photochemical catalyst non-selectivity.
With this, we are not only with magnetic Fe
3o
4for carrier, conduction C layer and CdS semiconductor layer are introduced, also utilize the method for surface molecule print technology and uv-light polymerization to carry out Nanosilica to CdS surface, prepared magnetic surface trace CdS composite photo-catalyst not only has good photocatalytic activity, high recovery utilization rate, but also can be in multiple high density pollution thing the Ciprofloxacin of degradation selectivity low-residual.
Summary of the invention
The present invention is with hydro-thermal method, and the methods such as uv-light polymerization and surface molecule print technology are preparation means, prepare a kind of surface imprinted CdS composite photo-catalyst based on magnetic carbon material.Its advantage is to build one and had not only had a good selectivity but also have the photochemical catalyst system of better photocatalytic activity.
The technical solution used in the present invention is: a kind of surface imprinted CdS composite photo-catalyst based on magnetic carbon material, carries out according to following step:
(1) Fe
3o
4the preparation of nanosphere: first, by Iron(III) chloride hexahydrate, sodium acetate and ethylene glycol join in beaker in proportion, after magnetic agitation to mixture is uniformly dispersed, yellow solution is transferred in autoclave, 200 ℃ are reacted 8 hours, afterwards autoclave are removed, and are cooled to room temperature, the black magnetic particle absolute ethanol washing obtaining, utilize magnet to reclaim black magnetic particle, 30 ℃ of vacuum drying, obtain black Fe
3o
4powder, seals for subsequent use.
(2) C@Fe
3o
4preparation: by the black Fe of preparation in step (1)
3o
4powder, glucose, PEG-4000 (PEG-4000) and distilled water join in reactor in proportion, within ultrasonic 1.5 hours, making solution mix is uniformly dispersed, then reactor is sealed, be positioned in baking oven and slowly heat to 160 ℃, isothermal reaction is after 12 hours, naturally cooling simultaneously, product is collected with magnet, and use respectively distilled water and absolute ethanol washing, vacuum drying at 30 ℃, obtains C@Fe
3o
4.
(3) CdS@C@Fe
3o
4the preparation of composite photo-catalyst:
By C@Fe
3o
4be stirred to completely and dissolve with mixed being incorporated on magnetic force heating stirrer of distilled water, again cadmium sulfate, thiocarbamide and ammoniacal liquor are joined in proportion in above-mentioned reactant liquor and be dissolved to evenly, open magnetic force heating stirrer, be heated to 60 ℃ of isothermal reactions 3 hours, then suspension is collected with magnet, use respectively distilled water and absolute ethanol washing, 30 ℃ of vacuum drying, obtain the CdS@C@Fe of black
3o
4.
(4) modification CdS@C@Fe
3o
4the preparation of composite photo-catalyst: by above-mentioned CdS@C@Fe
3o
4composite photo-catalyst and PEG-4000 join in the small beaker that contains methyl alcohol, ultrasonic 1 hour, make the CdS@C@Fe of modification
3o
4composite photo-catalyst.
(5) preparation of magnetic surface trace CdS composite photo-catalyst: Ciprofloxacin (CIP) and methacrylic acid (MAA) are added in the beaker that contains distilled water, be stirred to dissolving, again by trimethylol-propane trimethacrylate (TRIM), azodiisobutyronitrile (AIBN) and modification CdS@C@Fe
3o
4composite photo-catalyst joins in above-mentioned solution, and this reaction solution is transferred in the quartz reaction bottle with rotor, at N
2under atmosphere, put into ultraviolet reactor, open magnetic agitation, after UV-irradiation polymerisation, quartz reaction bottle is taken out, product is collected with magnet, respectively with absolute ethyl alcohol and distilled water washing, to remove unreacted material completely, and then add eluent, again put into UV reactive device, 30 ℃ of ultraviolet lighting wash-outs are to remove template molecule, and product is with absolute ethyl alcohol and distilled water wash respectively, 30 ℃ of vacuum drying, obtain magnetic surface trace CdS composite photo-catalyst.
(6) preparation of the non-trace CdS of magnetic surface composite photo-catalyst: MAA is added in the beaker that contains distilled water, is stirred to dissolving, then by TRIM, AIBN, modification CdS@C@Fe
3o
4composite photo-catalyst joins in above-mentioned solution, and this reaction solution is transferred in the quartz reaction bottle with rotor, at N
2under atmosphere, put into ultraviolet reactor, open magnetic agitation, after UV-irradiation polymerization 2 hours (50 ℃ of medium pressure mercury lamp photo catalysis reactors), quartz reaction bottle is taken out, product is collected with magnet, respectively with absolute ethyl alcohol and distilled water washing, to remove unreacted material completely, and then add eluent (distilled water), again put into UV reactive device, 30 ℃ of ultraviolet lighting wash-outs 2 hours are to remove template molecule, absolute ethyl alcohol and distilled water washing respectively for product, 30 ℃ of vacuum drying, obtain the non-trace CdS of magnetic surface composite photo-catalyst.
In described step (1), Iron(III) chloride hexahydrate, the mass ratio of sodium acetate and ethylene glycol is 1:2.7:41.3.
In described step (2), black Fe
3o
4the mass ratio of powder, glucose, PEG4000 and distilled water is 1:8:2:100.
In described step (3), C@Fe
3o
4with distilled water be 1:125 in mass ratio; C@Fe
3o
4, cadmium sulfate, thiocarbamide and ammoniacal liquor mass ratio be 1:1.3:0.75:12.5.
In described step (4), CdS@C@Fe
3o
4the mass ratio of composite photo-catalyst, PEG-4000 and methyl alcohol is 1:5:20.
In described step (5), CIP:MAA: the mol ratio of distilled water is 1:1 ~ 8:833; CIP:TRIM:AIBN: modification CdS@C@Fe
3o
4the mass ratio of composite photo-catalyst is 1:5:0.15:1.5.
In described step (5), described eluent is distilled water, and the addition of distilled water is according to CIP: the mass ratio that distilled water is 1:600 calculates.
In described step (5), UV-irradiation polymeric reaction temperature is 30 ~ 70 ℃, and the reaction time is 0.5 ~ 4 hour; UV-irradiation elution time is 0.5 ~ 4 hour.
In described step (6), MAA: the mol ratio of distilled water is 1:139.
In described step (6), TRIM, AIBN, modification CdS@C@Fe
3o
4the addition of composite photo-catalyst is according to MAA:TRIM:AIBN: modification CdS@C@Fe
3o
4the mass ratio of composite photo-catalyst is that 1:3.3:0.097:0.97 calculates.
In described step (6), described eluent is distilled water, and the addition of distilled water is according to MAA: the mass ratio that distilled water is 1:389 calculates.
Technological merit of the present invention: it is more convenient that the magnetic stalling characteristic of magnetic surface trace CdS composite photo-catalyst reclaims the separation of sample, efficient; The magnetic surface trace CdS composite photo-catalyst of preparing with the method binary mix in phase antibiotic solution photocatalytic degradation Ciprofloxacin is had very high selective; The photocatalytic activity of common trace photochemical catalyst is very weak, and in this invention, due to the introducing of conduction C layer, greatly improve separating of CdS light induced electron and photo-induced hole, prepared magnetic surface trace CdS composite photo-catalyst is not only had good selective, and also have good photocatalytic activity.
Accompanying drawing explanation
Fig. 1: be the preparation flow schematic diagram of magnetic surface trace CdS composite photo-catalyst;
Fig. 2: be Static Adsorption and the photocatalytic degradation design sketch of different samples, a. is without photochemical catalyst, b. CdS C Fe
3o
4composite photo-catalyst, c. magnetic surface trace CdS composite photo-catalyst, the non-trace CdS of d. magnetic surface composite photo-catalyst;
Fig. 3: for different photochemical catalysts mix the photocatalytic degradation design sketch in phase antibiotic waste water, a. CdS@C@Fe in the binary that contains Ciprofloxacin (CIP) and tetracycline (TC)
3o
4composite photo-catalyst, b. magnetic surface trace CdS composite photo-catalyst, the non-trace CdS of c. magnetic surface composite photo-catalyst;
Fig. 4: be 5 circulation light catalytic effect figure of magnetic surface trace CdS composite photo-catalyst photocatalytic degradation ciprofloxacin solution;
Fig. 5: be the fourier infrared spectrogram of different samples, a. Fe
3o
4, b.C/Fe
3o
4, c. CdS@C@Fe
3o
4composite photo-catalyst, d. magnetic surface trace CdS composite photo-catalyst;
Fig. 6: be the X-ray diffraction spectrogram of different samples, a. CdS C Fe
3o
4composite photo-catalyst, b. magnetic surface trace CdS composite photo-catalyst;
Fig. 7: be transmission electron microscope (TEM) figure of different samples, a. Fe
3o
4, b. C@Fe
3o
4, c. CdS@C@Fe
3o
4composite photo-catalyst, d. magnetic surface trace CdS composite photo-catalyst;
Fig. 8: be the solid uv atlas of different samples, a. P25, b. CdS C Fe
3o
4composite photo-catalyst, c. magnetic surface trace CdS composite photo-catalyst;
Fig. 9: be the thermogravimetric analysis spectrogram of different samples, a. CdS@C@Fe
3o
4composite photo-catalyst, b. magnetic surface trace CdS composite photo-catalyst;
Figure 10: be the magnetic stalling characteristic spectrogram of magnetic surface trace CdS composite photo-catalyst.
The specific embodiment
Below in conjunction with concrete embodiment, the present invention will be further described.
Adsorption activity is evaluated: in DW-01 type photochemical reaction instrument (purchased from Educational Instrument Factory of Yangzhou University), carry out, but the source of not opening the light, 100mL 20mg/L Ciprofloxacin simulated wastewater is added in reactor and measures its initial value, then add the photochemical catalyst of 0.1g, do not turn on light, do not open magnetic agitation, stuffiness, interval 5min sample analysis, gets supernatant liquor at ultraviolet specrophotometer λ after separating with magnet
max=276nm place measures its concentration, and passes through formula: Q=(C
0-C) V/m calculates its degradation rate Dr, wherein C
0for ciprofloxacin solution preliminary examination concentration, C is the concentration of the ciprofloxacin solution while reaching adsorption equilibrium, the volume that V is solution, and m is the quality of the catalyst that adds.
Photocatalytic activity is evaluated: in DW-01 type photochemical reaction instrument (purchased from Educational Instrument Factory of Yangzhou University), carry out, xenon lamp (ultraviolet light part is filtered by filter) irradiates, 100mL 20mg/L Ciprofloxacin simulated wastewater is added in reactor and measures its initial value, then add the photochemical catalyst of 0.1g, magnetic agitation is also opened aerator and is passed into air, 10min sample analysis in interval in During Illumination, gets supernatant liquor at ultraviolet specrophotometer λ after separating with magnet
max=276nm place measures its concentration, and passes through formula: Dr=(C
0-C) × 100/C
0calculate its degradation rate Dr, wherein C
0for reaching concentration after adsorption equilibrium, C is the concentration of the ciprofloxacin solution of t chronometry, 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), xenon lamp (ultraviolet light part is filtered by filter) irradiates, the mixed liquor of 100mL (containing 20mg/L Ciprofloxacin and 20mg/L tetracycline) is added in reactor, then add the photochemical catalyst of 0.2g, magnetic agitation is also opened aerator and is passed into air, 10min sample analysis in interval in During Illumination, after separating with magnet, get supernatant liquor and in high-efficient liquid phase chromatogram discuss, measure its concentration, and pass through formula: Dr=(C
0-C) × 100/C
0calculate its degradation rate Dr.
Embodiment 1:(1) Fe
3o
4the preparation of nanosphere: by 1.35g Iron(III) chloride hexahydrate, the sodium acetate of 3.6g joins in the beaker that contains 50mL ethylene glycol, after magnetic agitation to mixture is uniformly dispersed, yellow solution is transferred in autoclave, 200 ℃ are reacted 8 hours, afterwards autoclave is taken out, be cooled to room temperature, absolute ethyl alcohol drip washing 5 times for the black magnetic particle obtaining, utilizes magnet to reclaim black magnetic particle, 30 ℃ of vacuum drying, obtain Fe
3o
4nanosphere.
(2) C@Fe
3o
4preparation: by the Fe of 0.5g
3o
4, the glucose of 4.0g, 1g PEG is dissolved in the beaker that contains 50ml distilled water, after ultrasonic 1.5h, above-mentioned solution is transferred in 100ml reactor, 160 ℃ of reaction 12h, take out reactor afterwards, are cooled to room temperature, at least clean three times with distilled water and ethanol respectively, utilize magnet to reclaim black product, 30 ℃ of vacuum drying, obtain C@Fe
3o
4.
(3) CdS@C@Fe
3o
4the preparation of composite photo-catalyst: by the C/Fe of 0.4g
3o
4put into the single port flask that contains 50ml distilled water, excusing from death disperseed after 10 minutes, transfer in water-bath, add again the cadmium sulfate of 0.513g, the thiocarbamide of 0.3g and the ammoniacal liquor of 5g, 60 ℃ of lower magnetic forces stir 3h, sample is collected with magnet, and clean respectively at least three times with distilled water and ethanol, 30 ℃ of vacuum drying, obtain CdS@C@Fe
3o
4composite photo-catalyst.
(4) modification CdS@C@Fe
3o
4the preparation of composite photo-catalyst: by the CdS@C@Fe of 0.5g
3o
4the PEG-4000 (PEG-4000) of composite photo-catalyst and 2.5g joins in the small beaker that contains 10mL methyl alcohol, ultrasonic to dissolving, and makes the CdS@C@Fe of modification
3o
4composite photo-catalyst.
(5) preparation of magnetic surface trace CdS composite photo-catalyst: by 0.33g Ciprofloxacin (CIP), the methacrylic acid (MAA) of 0.514g joins in the beaker that contains 15ml water, be stirred to dissolving, and then add the trimethylol-propane trimethacrylate (TRIM) of 1.7g, the azodiisobutyronitrile (AIBN) of 0.05g, and the modification CdS@C@Fe of 0.5g
3o
4composite photo-catalyst, above-mentioned solution is transferred in quartz reaction bottle, logical nitrogen, sealing magnetic stirred after 10 minutes, at 50 ℃, quartz reaction bottle is carried out to UV-irradiation polymerization 2 hours (in medium pressure mercury lamp photo catalysis reactor, carrying out), take out afterwards quartz reaction bottle, by absolute ethyl alcohol and the each drip washing of distilled water 3 times for solid sample, add again 200ml distilled water, UV-irradiation wash-out 2 hours at 30 ℃, by product with after absolute ethyl alcohol and the each drip washing of distilled water 3 times, being placed in 30 ℃ of vacuum drying chambers dries, obtain magnetic surface trace CdS composite photo-catalyst.
(6) preparation of the non-trace CdS of magnetic surface composite photo-catalyst: the methacrylic acid of 0.514g (MAA) is joined in the beaker that contains 15ml water, be stirred to dissolving, and then add the trimethylol-propane trimethacrylate (TRIM) of 1.7g, the azodiisobutyronitrile (AIBN) of 0.05g, and the modification CdS@C@Fe of 0.5g
3o
4composite photo-catalyst, above-mentioned solution is transferred in quartz reaction bottle, logical nitrogen, sealing magnetic stirred after 10 minutes, at 50 ℃, quartz reaction bottle is carried out to UV-irradiation polymerization 2 hours (in medium pressure mercury lamp photo catalysis reactor, carrying out), take out afterwards quartz reaction bottle, by absolute ethyl alcohol and the each drip washing of distilled water 3 times for solid sample, add again 200ml distilled water, UV-irradiation wash-out 2 hours at 30 ℃, by product with after absolute ethyl alcohol and the each drip washing of distilled water 3 times, being placed in 30 ℃ of vacuum drying chambers dries, obtain the non-trace CdS of magnetic surface composite photo-catalyst.
(7) get 0.1g(5) in sample in photochemical reaction instrument, carry out dark adsorption test, experimental result is analyzed with ultraviolet specrophotometer, record this magnetic surface trace CdS composite photo-catalyst and can reach 6.23mg/g to the adsorption capacity of Ciprofloxacin when the dark absorption of 30min, show that this magnetic surface trace CdS composite photo-catalyst has stronger adsorption activity.
(8) get 0.1g(5) in sample in photochemical reaction instrument, carry out photocatalytic degradation test, experimental result is analyzed with ultraviolet specrophotometer, record this magnetic surface trace CdS composite photo-catalyst and in 60min radiation of visible light, can reach 71.48% to the photodegradation rate of Ciprofloxacin, show that this magnetic surface trace CdS composite photo-catalyst has stronger photocatalytic activity.
(9) get 0.2g(5) in sample in photochemical reaction instrument, carry out photocatalytic degradation test, in 60min radiation of visible light, record the photocatalytic activity of this magnetic surface trace CdS composite photo-catalyst to Ciprofloxacin in Binary Mixtures (CIP) and tetracycline (TC), experimental result is analyzed with high-efficient liquid phase chromatogram discuss.
Embodiment 2: undertaken by the same step of embodiment 1 preparation technology, different is that the middle Ciprofloxacin of step (5) and methacrylic acid proportioning are got five groups of different proportions, 1:1,1:2,1:4,1:6,1:8, prepare different magnetic surface trace CdS composite photo-catalysts, investigate the impact on magnetic surface trace CdS composite photo-catalyst photocatalytic activity of different Ciprofloxacins and methacrylic acid proportioning, investigate the activity of light degradation Ciprofloxacin antibiotic waste water by (8) step in embodiment 1.Photocatalysis effect as shown in Figure 2, the effect that can find out the magnetic surface trace CdS composite photo-catalyst light degradation Ciprofloxacin antibiotic waste water of preparing take proportioning as 1:6 is best, under the radiation of visible light of 60 minutes, can reach 62.29% to the degradation rate of Ciprofloxacin.
Embodiment 3: undertaken by the same step of embodiment 1 preparation technology, different is that step (5) medium ultraviolet irradiation polymerization time is got five groups of different time 0.5h, 1h, 2h, 3h, 4h, prepare different magnetic surface trace CdS composite photo-catalysts, investigate the impact of different UV-irradiation polymerization times on magnetic surface trace CdS composite photo-catalyst photocatalytic activity, investigate the activity of light degradation Ciprofloxacin antibiotic waste water by (8) step in embodiment 1.Experimental result shows: UV-irradiation polymerization time is that the effect of the magnetic surface trace CdS composite photo-catalyst light degradation Ciprofloxacin antibiotic waste water prepared of 2h is best, under the radiation of visible light of 60 minutes, can reach 66.52% to the degradation rate of Ciprofloxacin.
Embodiment 4: undertaken by the same step of embodiment 1 preparation technology, step (5) medium ultraviolet irradiation polymerization temperature gets 30 ℃ of five groups of different temperatures that different is, 40 ℃, 50 ℃, 60 ℃, 70 ℃, prepare different magnetic surface trace CdS composite photo-catalysts, investigate the impact of different UV-irradiation polymerization temperatures on magnetic surface trace CdS composite photo-catalyst photocatalytic activity, investigate the activity of light degradation Ciprofloxacin antibiotic waste water by (8) step in embodiment 1.Experimental result shows: UV-irradiation polymerization temperature is that the effect of 50 ℃ of magnetic surface trace CdS composite photo-catalyst light degradation Ciprofloxacin antibiotic waste waters of preparing is best, under the radiation of visible light of 60 minutes, can reach 69.44% to the degradation rate of Ciprofloxacin.
Embodiment 5: undertaken by the same step of embodiment 1 preparation technology, different is that step (5) medium ultraviolet irradiation elution time is got five groups of different time 0.5h, 1h, 2h, 3h, 4h, prepare different magnetic surface trace CdS composite photo-catalysts, investigate the impact of different UV-irradiation elution times on magnetic surface trace CdS composite photo-catalyst photocatalytic activity, investigate the activity of light degradation Ciprofloxacin antibiotic waste water by (8) step in embodiment 1.Experimental result shows: UV-irradiation elution time is that the effect of the magnetic surface trace CdS composite photo-catalyst light degradation Ciprofloxacin antibiotic waste water prepared of 2h is best, under the radiation of visible light of 60 minutes, can reach 71.38% to the degradation rate of Ciprofloxacin.
Undertaken by the same step of embodiment 1 preparation technology, prepare different photochemical catalysts, investigate the photocatalytic activity of different photochemical catalysts, press (7) step in embodiment 1 and investigate the activity of absorption Ciprofloxacin antibiotic waste water, and press the activity of (8) step investigation light degradation Ciprofloxacin antibiotic waste water in embodiment 1.Fig. 2 is that result shows that the adsorption capacity of prepared magnetic surface trace CdS composite photo-catalyst is than CdS@C@Fe with the design sketch of different photochemical catalyst absorption and light degradation Ciprofloxacin waste water
3o
4composite photo-catalyst is high, and this is in the surface imprinted layer due to magnetic surface trace CdS composite photo-catalyst, to contain trace hole to cause, and shows that surface imprinted layer has been coated successfully; In addition, the photocatalytic degradation effect of magnetic surface trace CdS composite photo-catalyst is than CdS@C@Fe
3o
4composite photo-catalyst is lower slightly, and this shows in the introducing of surface imprinted layer little on the photocatalytic activity impact of magnetic surface trace CdS composite photo-catalyst.
Undertaken by (9) step in embodiment 1, investigate the activity that binary that different photochemical catalyst light degradation contain Ciprofloxacin (CIP) and tetracycline (TC) is mixed phase antibiotic waste water, the photocatalytic activity figure being calculated by high efficiency liquid phase data as shown in Figure 3, can draw in the time that photocatalytic degradation binary is mixed phase antibiotic waste water from data, magnetic surface trace CdS composite photo-catalyst to the degradation effect of Ciprofloxacin a little less than CdS@C@Fe
3o
4composite photo-catalyst, higher than the non-trace CdS of magnetic surface composite photo-catalyst, and magnetic surface trace CdS composite photo-catalyst is minimum to the degradation effect of tetracycline.The above results shows that mixing magnetic surface trace CdS composite photo-catalyst in phase antibiotic waste water in binary has higher selective to Ciprofloxacin.
Press the photochemical stability of 5 circulation photocatalytic degradation Ciprofloxacin antibiotic waste waters of (8) step investigation magnetic surface trace CdS composite photo-catalyst in embodiment 1, result as shown in Figure 4, as can be seen from the figure after 5 circulations, the variation of the photocatalytic activity of magnetic surface trace CdS composite photo-catalyst is very little, illustrates that prepared magnetic surface trace CdS composite photo-catalyst has good photochemical stability.
As can be seen from Figure 5 Fe
3o
4and C/Fe
3o
4absworption peak almost identical, and CdS/C/Fe
3o
4composite photo-catalyst is than C/Fe
3o
4at 2130cm
-1left and right and 2000cm
-1left and right place has had more two characteristic absorption peaks, 2130cm
-1the absworption peak that the absworption peak at left and right place is CdS, and 2000cm
-1to be that Cd-S key or thiocarbamide are residual cause the absworption peak at left and right place, load of above-mentioned characteristic peak explanation CdS success; In addition, compare with Fig. 5 c, in Fig. 5 d, had more many absworption peaks, wherein 1715cm
-1left and right is to being C=O stretching vibration peak, 1457cm
-1the characteristic absorption peak that left and right place is the two keys of C=C, 1151cm
-1, 1089cm
-1, 1047cm
-1deng the characteristic absorption peak that is C-O-C, the above results illustrates that surperficial imprinted layer has successfully been coated on CdS C Fe
3o
4the surface of composite photo-catalyst.
Six diffraction maximums from Fig. 6 a (2 θ=30.1 °, 35.5 °, 43.1 °, 53.4 °, 62.5 ° of 57 ° of and) can find out that we have successfully prepared magnetic Fe
3o
4, and 2 θ=26.5 °, 43.7 °, to locate for 51.8 °, corresponding crystal face is respectively (002), (110) and (112), with the comparison of international standard card, determines it is CdS crystal, and crystal formation is hexagonal crystal; In addition, the curve of Fig. 6 a and Fig. 6 b is almost identical, and coated CdS and the Fe of not changing through surface imprinted layer is described
3o
4crystal formation.
From Fig. 7 a, can find out the Fe synthetic by hydro-thermal method
3o
4have good spherical structure and dispersiveness, particle size is about 250nm left and right; Can find out Fe from Fig. 7 b
3o
4the coated C layer in surface after prepared C/Fe
3o
4have good nucleocapsid structure, particle size is in 260nm left and right, and this illustrates that the average thickness of coated conduction C layer is about 10nm(and sees illustration in Fig. 7 b); Fig. 7 c is CdS/C/Fe
3o
4composite photo-catalyst can clearly be seen and have many particles to occur, and be distributed in C/Fe from figure
3o
4the surface of nucleocapsid structure, illustrates that CdS has successfully loaded on C/Fe
3o
4the surface of nucleocapsid structure; Fig. 7 d is magnetic surface trace CdS composite photo-catalyst, there is the material that one deck is very thin (being mainly surface imprinted layer) on the surface that can see this material, and the particle diameter of this material is approximately 300nm left and right, and this illustrates that surperficial imprinted layer has successfully been coated on CdS/C/Fe
3o
4the surface of composite photo-catalyst.
As can be seen from Figure 8 than commercially available P25 photochemical catalyst, no matter at ultraviolet region or at visible region, CdS/C/Fe
3o
4composite photo-catalyst and magnetic surface trace CdS composite photo-catalyst all have good absorption, and magnetic surface trace CdS composite photo-catalyst and CdS/C/Fe
3o
4the curve of composite photo-catalyst is almost identical, and the coated not to CdS/C/Fe of surperficial imprinted layer is described
3o
4the activity of composite photo-catalyst produces a very large impact.
As can be seen from Figure 9, in being warmed up to 800 degree, CdS/C/Fe
3o
4the loss in weight of composite photo-catalyst is 24.64%, and the loss in weight of magnetic surface trace CdS composite photo-catalyst is 33.75%, this is to cause because molecular engram layer decomposes, and illustrates that the surface imprinted layer in magnetic surface trace CdS composite photo-catalyst has been coated successfully.
As can be seen from Figure 10 prepared magnetic surface trace CdS composite photo-catalyst has good magnetic stalling characteristic, and magnetic saturation intensity can reach 30.05emu/g.
Claims (8)
1. the preparation method of the surface imprinted CdS composite photo-catalyst based on magnetic carbon material, is characterized in that carrying out according to following step:
(1) Fe
3o
4the preparation of nanosphere: first, by Iron(III) chloride hexahydrate, sodium acetate and ethylene glycol join in beaker in proportion, after magnetic agitation to mixture is uniformly dispersed, yellow solution is transferred in autoclave, 200 ℃ are reacted 8 hours, afterwards autoclave are removed, and are cooled to room temperature, the black magnetic particle absolute ethanol washing obtaining, utilize magnet to reclaim black magnetic particle, 30 ℃ of vacuum drying, obtain black Fe
3o
4powder, seals for subsequent use;
(2) C@Fe
3o
4preparation: by the black Fe of preparation in step (1)
3o
4powder, glucose, PEG-4000 (PEG-4000) and distilled water join in reactor in proportion, within ultrasonic 1.5 hours, making solution mix is uniformly dispersed, then reactor is sealed, be positioned in baking oven and slowly heat to 160 ℃, isothermal reaction is after 12 hours, naturally cooling simultaneously, product is collected with magnet, and use respectively distilled water and absolute ethanol washing, vacuum drying at 30 ℃, obtains C@Fe
3o
4;
(3) CdS@C@Fe
3o
4the preparation of composite photo-catalyst: by C@Fe
3o
4be stirred to completely and dissolve with mixed being incorporated on magnetic force heating stirrer of distilled water, again cadmium sulfate, thiocarbamide and ammoniacal liquor are joined in proportion in above-mentioned reactant liquor and be dissolved to evenly, open magnetic force heating stirrer, be heated to 60 ℃ of isothermal reactions 3 hours, then suspension is collected with magnet, use respectively distilled water and absolute ethanol washing, 30 ℃ of vacuum drying, obtain the CdS@C@Fe of black
3o
4;
(4) modification CdS@C@Fe
3o
4the preparation of composite photo-catalyst: by above-mentioned CdS@C@Fe
3o
4composite photo-catalyst and PEG-4000 join in the small beaker that contains methyl alcohol, ultrasonic 1 hour, make the CdS@C@Fe of modification
3o
4composite photo-catalyst;
(5) preparation of magnetic surface trace CdS composite photo-catalyst: Ciprofloxacin (CIP) and methacrylic acid (MAA) are added in the beaker that contains distilled water, be stirred to dissolving, again by trimethylol-propane trimethacrylate (TRIM), azodiisobutyronitrile (AIBN) and modification CdS@C@Fe
3o
4composite photo-catalyst joins in above-mentioned solution, and this reaction solution is transferred in the quartz reaction bottle with rotor, at N
2under atmosphere, put into ultraviolet reactor, open magnetic agitation, after UV-irradiation polymerisation, quartz reaction bottle is taken out, product is collected with magnet, respectively with absolute ethyl alcohol and distilled water washing, to remove unreacted material completely, and then add eluent, again put into UV reactive device, 30 ℃ of ultraviolet lighting wash-outs are to remove template molecule, and product is with absolute ethyl alcohol and distilled water wash respectively, 30 ℃ of vacuum drying, obtain magnetic surface trace CdS composite photo-catalyst.
2. the preparation method of the surface imprinted CdS composite photo-catalyst based on magnetic carbon material as claimed in claim 1, is characterized in that: in step (1), and Iron(III) chloride hexahydrate, the mass ratio of sodium acetate and ethylene glycol is 1:2.7:41.3.
3. the preparation method of the surface imprinted CdS composite photo-catalyst based on magnetic carbon material as claimed in claim 1, is characterized in that: in step (2), and black Fe
3o
4the mass ratio of powder, glucose, PEG4000 and distilled water is 1:8:2:100.
4. the preparation method of the surface imprinted CdS composite photo-catalyst based on magnetic carbon material as claimed in claim 1, is characterized in that: in step (3), and C@Fe
3o
4with distilled water be 1:125 in mass ratio; C@Fe
3o
4, cadmium sulfate, thiocarbamide and ammoniacal liquor mass ratio be 1:1.3:0.75:12.5.
5. the preparation method of the surface imprinted CdS composite photo-catalyst based on magnetic carbon material as claimed in claim 1, is characterized in that: in step (4), and CdS@C@Fe
3o
4the mass ratio of composite photo-catalyst, PEG-4000 and methyl alcohol is 1:5:20.
6. the preparation method of the surface imprinted CdS composite photo-catalyst based on magnetic carbon material as claimed in claim 1, is characterized in that: in step (5), and CIP:MAA: the mol ratio of distilled water is 1:1 ~ 8:833; CIP:TRIM:AIBN: modification CdS@C@Fe
3o
4the mass ratio of composite photo-catalyst is 1:5:0.15:1.5.
7. the preparation method of the surface imprinted CdS composite photo-catalyst based on magnetic carbon material as claimed in claim 1, it is characterized in that: in step (5), described eluent is distilled water, and the addition of distilled water is according to CIP: the mass ratio that distilled water is 1:600 calculates.
8. the preparation method of the surface imprinted CdS composite photo-catalyst based on magnetic carbon material as claimed in claim 1, is characterized in that: in step (5), UV-irradiation polymeric reaction temperature is 30 ~ 70 ℃, and the reaction time is 0.5 ~ 4 hour; UV-irradiation elution time is 0.5 ~ 4 hour.
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