CN105289726A - Magnetic P<3>HT/TNT heterojunction photocatalyst with specific orientation ability and preparation method thereof - Google Patents
Magnetic P<3>HT/TNT heterojunction photocatalyst with specific orientation ability and preparation method thereof Download PDFInfo
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Abstract
The invention provides a magnetic P<3>HT/TNT heterojunction photocatalyst with specific orientation ability and a preparation method thereof. The preparation method includes the steps that polyethylene glycol 4000, deionized water and a prepared TiO<2> nanotube are added into a breaker for ultrasonic treatment, and modified TNT mixed liquid E is obtained; then, poly 3-hexylthiophene is added to trichloromethane for ultrasound till complete dissolution is achieved, then ultrasound is dissolved in the trichloromethane containing the poly 3-hexylthiophene, ultrasonic dissolving is conducted, after tri methylol propane tri methacrylate and azodiisobutyronitrile are added to the trichloromethane, ultrasonic blending is conducted, and mixed liquid F is obtained; the mixed liquid F is slowly added to mixed liquid E, a mixed liquid G is obtained, the mixed liquid G is stirred and subjected to a reaction at the temperature of 80 DEG C under the nitrogen atmosphere, and a product can be obtained. By means of the photocatalyst, sample separation and recovery can be more convenient, faster and efficient, and high selectivity is achieved for photocatalytic degradation of tetracycline.
Description
Technical field
The invention belongs to technical field of environmental material preparation, be specifically related to a kind of preparation method with the magnetic P3HT/TNT heterojunction photocatalyst of single-minded capacity of orientation.
Background technology
Tetracycline (Tetracycline, TC) be from the nutrient solution etc. of actinomyces golden chain clump bacterium separate antibiotic medicine.Having good inhibitory action to gram-positive bacteria, negative bacterium, Richettsia, filterable virus, Spirochaeta and even protozoon class, is a kind of broad-spectrum antibiotic.But tetracycline residual in environment easily causes toxic and side effect, strong drug resistance can be produced by Induction of bacterial, and gene mutation etc. can be produced to other biological, directly have influence on the health of ecology and the mankind.So the tetracycline residue processed rationally and effectively in life, production is an important link.Many experts and scholars remove the tetracycline residue in environment by physics, chemistry and the multiple method such as biological, but due to these method efficiency lower, easily cause secondary pollution again.At present, photocatalysis technology extensive use studies the technology of the wastewater treatment in environment, is a kind of more satisfactory " green " treatment technology.
TiO
2nanotube (TiO
2nanotube, TNT) as the earliest, one of most widely used semiconductor, have nontoxic, cost is low, the advantage such as effective, is a kind of semiconductor light-catalyst with high light catalytic activity.But consider the demand that actual production is lived, general T NT reclaims difficulty, and secondary utilization rate is low, and light induced electron, hole separative efficiency are low, single-minded orientation can not identify and remove development and the application that the problems such as specific pollutants seriously constrain TNT.For reclaiming the defect difficult, secondary utilization rate is low, the present invention introduces magnetic material (Fe on TNT
3o
4), Fe
3o
4be typical magnetic material, there is advantages such as being easy to preparation, quick separating, therefore, Fe
3o
4load can make up well and reclaim the defects such as difficult, secondary utilization rate is low.
In addition, do not have single-minded orientation for general T NT and identify and remove the problem of specific pollutants, the present invention has carried out surface imprinted process to it, realizes it identify and the object of selective removal specific objective thing in multiple pollutant special secondary school one orientation with this.Surface imprinted technology is the covalently or non-covalently effect utilized between template molecule and monomer, prepared the technology having three-dimensional specific structure, template molecule is had to the polymer layer of single-minded directed identity by cross-linked polymeric and wash-out at substrate material surface, the introducing of surface imprinted technology well solves general T NT and identifies without single-minded orientation and the problem of selective removal ability.
But, the introducing of conventional surface imprinted layer greatly covers the photocatalytic activity site of TNT, therefore, the present invention introduces conducting polymer (poly-3-hexyl thiophene, P3HT) in surface imprinted layer, and P3HT is that a kind of dissolubility is large, conductance is high and the novel conductive polymer of good stability, its band gap is lower, energy gap is about 2.0eV, can produce and mate preferably, effectively change luminous energy with sunshine.And this conducting polymer photochemical stability is strong, electron-hole mobility is high, therefore, the introducing of P3HT not only can form heterojunction structure with TNT, improve the separative efficiency of light induced electron and photo-induced hole, thus improve the photocatalytic activity of composite photo-catalyst, but also provide binding site for the formation in trace hole.
Therefore, inventor is carrier with TNT and to its surface loaded magnetic Fe
3o
4prepare magnetic TNT, then surface imprinted technology is also introduced, and select conducting polymer (P3HT) as function monomer, prepare the magnetic P3HT/TNT heterojunction photocatalyst with single-minded capacity of orientation, this single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst not only has good photochemical stability, higher photo-catalysis capability, and also has very high single-minded orientation to identify and selective light degradation capability.
Summary of the invention
The present invention for preparation means, prepares a kind of magnetic P3HT/TNT heterojunction photocatalyst (single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst) with single-minded capacity of orientation with methods such as hydro-thermal method, solvent-thermal method and surface imprinted technology.Its advantage has good photochemical stability, higher photo-catalysis capability, and also have very high single-minded orientation to identify and selective light degradation capability.
The technical solution used in the present invention is:
Have a magnetic P3HT/TNT heterojunction photocatalyst for single-minded capacity of orientation, this catalyst is by TiO
2nanotube TNT, Fe
3o
4be composited with the P3HT imprinted layer of identifiable design tetracycline; Described TiO
2nanotube TNT is cylindric and the less nano tubular structure of middle cavity, described Fe
3o
4particulate load is in described TiO
2nanotube TNT outer surface; The P3HT imprinted layer of described identifiable design tetracycline is coated on described TiO
2nanotube TNT outer surface, and and TiO
2nanotube TNT forms heterojunction structure; This magnetic P3HT/TNT heterojunction photocatalyst of 0.1g is applied to the Photocatalytic Activity for Degradation of 100mL20mg/L tetracycline, in 120min, reaches the degradation rate of 86%.
There is a preparation method for the magnetic P3HT/TNT heterojunction photocatalyst of single-minded capacity of orientation, carry out according to following step:
Step 1, TiO
2the preparation of nanotube TNT: take P25 powder and join in NaOH solution, obtains suspension A after magnetic agitation is even, is transferred in hydrothermal reaction kettle by the described A of being suspended liquid and carry out constant temp. heating reaction, be cooled to room temperature, open reactor, remove supernatant liquor, obtain titanate nanotube white precipitate; By described washing of precipitate to neutral, with the above-mentioned titanate nanotube of HCl process of 5% under stirring, centrifugal, deionized water cyclic washing is to neutral, and vacuum drying, calcining at constant temperature, obtains TiO
2nanotube TNT;
The preparation of the magnetic TNT of step 2, modification: getting TNT prepared by step 1, to be scattered in volume ratio be that in the absolute ethyl alcohol/water mixed solution of 1:2, ultrasonic process is uniformly dispersed, and obtains suspension B; Get FeCl again
36H
2o and FeCl
24H
2o is dissolved in distilled water, obtains mixed solution C, is joined in described mixed solution C by described suspension B, obtains mixed liquor D; Heating stirring reaction a is carried out to mixed liquor D, adds ammoniacal liquor fast afterwards, proceed stirring reaction b; Finally by obtain product washing, vacuum drying, obtain magnetic TNT; By magnetic TNT, Macrogol 4000 and deionized water mix ultrasonic process, obtain the magnetic TNT mixed liquor E of modification;
The preparation of step 3, single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst: function monomer is added in chloroform, it is ultrasonic until function monomer is dissolved completely in chloroform, again template molecule is dissolved in above-mentioned containing in the chloroform of function monomer, continue ultrasonic to dissolving, again crosslinking agent and initator are added in above-mentioned chloroform, ultrasonic mixing, obtain mixed liquor F, then mixed liquor F is slowly joined in the mixed liquor E of step 2, obtain mixed liquor G, mixed liquor G is heated stirring reaction in nitrogen atmosphere; After completion of the reaction, collect product and cyclic washing product with magnet, finally use apparatus,Soxhlet's eluted template molecule, carry out vacuum drying, obtain single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst.
In addition, the preparation of non-directional type magnetic P3HT/TNT heterojunction photocatalyst is carried out under the same terms and method, just in preparation process, does not add template molecule TC, and do not have template molecule elution step.
In step 1, in described suspension A, the mass ratio of P25 and NaOH is 1:20, and described NaOH solution concentration is 10M.
In step 1, the anti-temperature had of described constant temp. heating is 170 DEG C, and the reaction time is 72h; The temperature of described calcining at constant temperature is 400 DEG C, and calcination time is 2h; Be 1h with the time of the HCl process titanate nanotube of 5%.
In step 2, in described suspension B, the concentration of TNT is 1.4mg/mL; In mixed solution C, FeCl
36H
2o and FeCl
24H
2the concentration ratio of O is 91.9mg/mL:35.15mg/mL; The volume ratio of suspension B used, mixed solution C and ammoniacal liquor is 50:2:1; In described mixed liquor E, magnetic TNT, Macrogol 4000 and deionized water quality are than being 1:1:100.
In step 2, described heating-up temperature is 80 DEG C, and the stirring reaction a time is 30min, and the stirring reaction b time is 20min.
In step 3, described function monomer is poly-3-hexyl thiophene P3HT, and template molecule is tetracycline TC, and crosslinking agent is trimethylol-propane trimethacrylate TRIM, and initator is azodiisobutyronitrile AIBN.
In step 3, during configuration mixed liquor F, the amount ratio of described poly-3-hexyl thiophene, tetracycline, azodiisobutyronitrile and chloroform is 0.01 ~ 0.03g:0.05g:0.05g:15mL, and trimethylol-propane trimethacrylate used and the volume ratio of chloroform are 1:150; In mixed liquor G, mixed liquor E used and the volume ratio of mixed liquor F are 20:3.
In step 3, described heating-up temperature is 80 DEG C, and the time of stirring reaction is 2 ~ 24h.
In step 1 ~ 3, described vacuum drying temperature is 50 DEG C.
Beneficial effect of the present invention is:
(1) single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst makes the separation and recovery of sample more convenient, efficiently.
(2) the single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst prepared of the present invention has very high selective to photocatalytic degradation tetracycline.
(3) P3HT and TNT carries out being coupled and not only can form heterojunction structure, improves the separative efficiency of light induced electron and photo-induced hole, thus improves the photocatalytic activity of composite photo-catalyst, but also provides binding site for the formation in trace hole.
Accompanying drawing explanation
Fig. 1 is the TEM figure of TNT (a), magnetic TNT (b), single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst (c);
Fig. 2 is the EDS spectrogram of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst;
Fig. 3 is the XRD spectra of TNT (a), magnetic TNT (b), single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst (c);
Fig. 4 is TNT (a), magnetic TNT (b), the FT-IR spectrogram of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst (c);
Fig. 5 is TNT (a), P3HT (b), the UV-visDRS spectrogram of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst (c);
Fig. 6 is TNT (a), magnetic TNT (b), the TGA spectrogram of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst (c);
Fig. 7 is the VSM spectrogram of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst;
Fig. 8 is that the adsorption equilibrium of different photochemical catalyst is investigated, wherein a:TNT; B: single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst);
Fig. 9 is that the addition of P3HT is on the impact wherein a:0.02g of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst photocatalytic activity; B:0.025g; C:0.03g; D:0.015g; E:0.01g;
Figure 10 is that different polymerization time is on the impact wherein a:2h of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst photocatalytic activity; B:6h; C:12h; D:18h; E:24h;
Figure 11 is that different photochemical catalyst is to photocatalytic degradation tetracycline (TC) (a, b, and the selective investigation (TNT (a of Ciprofloxacin (CIP) (d, e, f) c), d), wherein, single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst (b, e), non-directional type magnetic P3HT/TNT heterojunction photocatalyst (c, f));
Figure 12 is the circulation experiment of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst degraded TC.
Detailed description of the invention
Below in conjunction with concrete embodiment, the present invention will be further described:
Adsorption activity is evaluated: carry out in DW-01 type photochemical reaction instrument (purchased from Educational Instrument Factory of Yangzhou University), but source of not opening the light, 100mL20mg/L tetracycline (TC) to be added in reactor and to measure its initial value, then add the photochemical catalyst of 0.1g, do not turn on light, stuffiness, open magnetic agitation, interval 10min sample analysis, gets supernatant liquor after being separated and measures its concentration at ultraviolet specrophotometer, find out the time of equilibrium adsorption point of photochemical catalyst with magnet.
Photocatalytic activity evaluation: carry out in DW-01 type photochemical reaction instrument (purchased from Educational Instrument Factory of Yangzhou University), 100mL20mg/L tetracycline (TC) to be added in reactor and to measure its initial value, then the photochemical catalyst of 0.1g is added, open magnetic agitation and open aerator and pass into air, first Dynamic Adsorption is to adsorption equilibrium, irradiate with simulated solar irradiation again, 20min sample analysis in interval in During Illumination, get supernatant liquor after being separated with magnet and measure its concentration at ultraviolet specrophotometer, and pass through formula: D
c=[(C
0-C
1)/C
0] × 100% calculates degradation rate.Wherein C
0for secretly adsorbing the absorbance of rear TC solution, C
1for the absorbance of the TC solution that timing sampling measures.
Selective evaluation: carry out in DW-01 type photochemical reaction instrument (purchased from Educational Instrument Factory of Yangzhou University), 100mL20mg/L Ciprofloxacin (CIP) to be added in reactor and to measure its initial value, then the photochemical catalyst of 0.1g is added, open magnetic agitation and open aerator and pass into air, first Dynamic Adsorption is to adsorption equilibrium, irradiate with simulated solar irradiation again, 20min sample analysis in interval in During Illumination, get supernatant liquor after being separated with magnet and survey absorbance.Formula is passed through: D according to formula
c=[(C
0-C
1)/C
0] × 100% calculates degradation rate.
Photochemical stability is evaluated: carry out in DW-01 type photochemical reaction instrument (purchased from Educational Instrument Factory of Yangzhou University), 100mL20mg/L tetracycline (TC) to be added in reactor and to measure its initial value, then the single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst of 0.1g is added, open magnetic agitation and open aerator and pass into air, first Dynamic Adsorption is to adsorption equilibrium, irradiate with simulated solar irradiation again, 20min sample analysis in interval in During Illumination, after illumination also samples for 120 minutes, get supernatant liquor after being separated with magnet and measure its concentration at ultraviolet specrophotometer, and pass through formula: D
c=[(C
0-C
1)/C
0] × 100% calculates degradation rate, again by the catalyst absolute ethyl alcohol separated and water ultrasonic cleaning repeatedly, to remove residual tetracycline (TC) and other degraded intermediate, then repeated above-mentioned degradation process, 4 times and calculate its degradation rate so repeatedly.
Embodiment 1:
(1) TiO
2the preparation of nanotube (TNT): take 2gP25 powder and join 100ml, in the NaOH solution of 10M, suspension is obtained after magnetic agitation 6h, above-mentioned suspension is transferred in the hydrothermal reaction kettle with polytetrafluoroethylliner liner, react 72h at 170 DEG C, be cooled to room temperature, open reactor, remove supernatant liquor, obtain white precipitate, this white precipitate is titanate nanotube; Use the above-mentioned white precipitate of deionized water cyclic washing (titanate nanotube) again, the pH value finally obtaining supernatant approximates 7, above-mentioned white precipitate is added afterwards with the HCl of 5%, magnetic agitation 1h, centrifugal segregation supernatant, then add deionized water cyclic washing, the pH of supernatant is made to approximate 7, then ambient temperature in vacuum is dry, finally at 400 DEG C, calcines 2h, obtains TiO
2nanotube (TNT).
(2) preparation of the magnetic TNT of modification: it is in 1:2 absolute ethyl alcohol/water mixed solution that the TNT getting 0.7g is dissolved in 500ml volume ratio, ultrasonic process 5h under room temperature, obtained suspension; Get 1.838gFeCl again
36H
2o and 0.703gFeCl
24H
2o is dissolved in 20ml distilled water, then adds above-mentioned suspension wherein, and 80 DEG C of stirring reaction 30min, add 10ml ammoniacal liquor afterwards fast, stirring reaction 20min, and by products in water and absolute ethyl alcohol cyclic washing several, last vacuum drying, obtains magnetic TNT; 1g magnetic TNT, 1g Macrogol 4000 (PEG4000) and 100ml deionized water are added the magnetic TNT solution that ultrasonic process in beaker obtains modification.
(3) preparation of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst: again 0.02g is gathered 3-hexyl thiophene (P3HT) and add in the beaker that 15ml chloroform is housed, it is ultrasonic until P3HT is dissolved completely in (solution colour is limpid bright orange) in chloroform, again 0.05g tetracycline (TC) is dissolved in above-mentioned containing in the chloroform of P3HT, continue ultrasonic to dissolving, after again 0.1mL trimethylol-propane trimethacrylate (TRIM) and 0.05g azodiisobutyronitrile (AIBN) being added above-mentioned chloroform, ultrasonic process 10 minutes, then slowly join in the magnetic TNT solution of above-mentioned modification, reactant is stirred 12h under 80 DEG C of nitrogen atmospheres.Collect with magnet and use deionized water, absolute ethyl alcohol cyclic washing product, finally using apparatus,Soxhlet's eluted template molecule, after vacuum drying, obtaining single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst.In addition, the preparation of non-directional type magnetic P3HT/TNT heterojunction photocatalyst is carried out under the same terms and method, just in preparation process, does not add template molecule (TC), and do not have the elution step of template molecule (TC).
(4) get sample in 0.1g (3) and carry out dark adsorption test in photochemical reaction instrument, experimental result ultraviolet specrophotometer is analyzed, record this single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst and can reach 0.6mg/g to the adsorption capacity of tetracycline (TC) when the dark absorption of 30min, show that this single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst has good adsorption activity.
(5) get sample in 0.1g (3) and carry out photocatalytic degradation test in photochemical reaction instrument, experimental result ultraviolet specrophotometer is analyzed, record the photodegradation rate of this single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst to tetracycline (TC) and can 86% be reached in 120min radiation of visible light, show that this single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst has stronger photocatalytic activity.
(6) get sample in 0.1g (3) and carry out photocatalytic degradation test in photochemical reaction instrument, in 120min radiation of visible light, record the photocatalytic activity of this single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst to tetracycline (TC) and Ciprofloxacin (CIP).
Embodiment 2:
Undertaken by the same step of embodiment 1 preparation technology, 0.02g is respectively unlike the consumption of P3HT in step (3), 0.025g, 0.03g, 0.015g, 0.01g, prepare different single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts, investigate P3HT different amounts to the impact of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst photocatalytic activity, investigate the activity of light degradation tetracycline (TC) solution by (5) step in embodiment 1.Photocatalysis effect as shown in Figure 9, can find out that the effect of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst light degradation tetracycline (TC) of preparing when the consumption of P3HT is 0.02g is best, under the radiation of visible light of 120 minutes, can 86% be reached to the degradation rate of tetracycline (TC).
Embodiment 3:
Undertaken by the same step of embodiment 1 preparation technology, five groups of different times 2h, 6h, 12h, 18h, 24h are got unlike polymerization time in step (3), prepare different single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts, investigate the impact of different polymerization time on single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst photocatalytic activity, investigate the activity of light degradation tetracycline (TC) solution by (5) step in embodiment 1.Experimental result is as Figure 10: the catalytic activity for this photochemical catalyst become during 12h is upon polymerization best.Under the radiation of visible light of 120 minutes, can 86% be reached to the degradation rate of tetracycline (TC).
Undertaken by the same step of embodiment 1 preparation technology, prepare different photochemical catalysts, investigate the absorption property of different photochemical catalyst.Fig. 8 is with the design sketch of different photochemical catalyst tetracycline adsorption (TC), and result display is compared with TNT, and single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst prepared in the present invention has good single-minded directed recognition capability.The adsorption capacity of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst is better than TNT, because single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst has surface imprinted layer, and the trace hole in surface imprinted layer has single-minded directed recognition capability, can Selective recognition tetracycline (TC).
Undertaken by the same step of embodiment 1 preparation technology, prepare different photochemical catalysts, the single-minded orientation of different photochemical catalyst and degradation selectivity ability are investigated.Figure 11 is the single-minded orientation of different photochemical catalyst and the light degradation design sketch of degradation selectivity ability investigation, the degrading activity of result display TNT and non-directional type magnetic P3HT/TNT heterojunction photocatalyst degraded tetracycline (TC) does not all have single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst high, this is because (1) single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst has surface imprinted layer, and the trace hole in surface imprinted layer has single-minded directed recognition capability, can specific recognition and degradation selectivity tetracycline (TC); (2) P3HT and TNT can form heterojunction structure, which greatly improves the photocatalytic activity of composite photo-catalyst.In addition, the degradation rate of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst degraded Ciprofloxacin (CIP) is very low, the Ciprofloxacin (CIP) this is because the trace hole in surface imprinted layer can not identify and degrade.The above results shows that single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst has very high single-minded orientation and degradation selectivity ability and photocatalytic activity to tetracycline (TC).
Undertaken by the same step of embodiment 1 preparation technology, prepare single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst, investigate the photochemical stability of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst.Figure 12 is the design sketch of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst circulation degraded tetracycline (TC), as can be seen from the figure after 4 circulations, the photocatalytic activity of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst does not obviously reduce, and this shows that single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst has good photochemical stability.
Fig. 1 is the TEM figure of different photochemical catalyst.Can find out that from Fig. 1 a TNT is cylindric and the less nano tubular structure of middle cavity.The many nano particles of load can be found out on TNT pipe, the surface that shows TNT successfully load magnetic Fe from Fig. 1 b
3o
4.Compared with Fig. 1 b, the surface of Fig. 1 c is slightly different, this is because the P3HT imprinted layer of magnetic TNT Surface coating identifiable design tetracycline causes, and through magnetic Fe
3o
4load and surface imprinted layer coated after, single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst still presents nano tubular structure.
Fig. 2 is that the EDS of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst can spectrogram.As can be seen from the figure, single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst is made up of C, O, Fe, Ti, S element, the wherein successful preparation that there is indirect proof magnetic TNT of Ti, Fe, O, C, S then indirection table understand the existence of surface imprinted layer, and wherein S element comes from P3HT.To sum up show, single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst is successfully prepared.
Fig. 3 is the XRD spectra of different photochemical catalyst.The peak of 2 θ=25.2 ° in Fig. 3 a, 48.1 ° and 53.9 ° is anatase TiO
2characteristic peak (PDF#01-0562), and peak type is sharp-pointed, illustrates that the crystal formation of the TNT of generation is good.The peak of 2 θ=35.4 ° in figure b, 43.4 °, 57.5 ° and 62.5 ° is Fe
3o
4the principal character peak (PDF#03-0862) of nano particle.Compare with Fig. 3 b with Fig. 3 a, the characteristic peak of Fig. 3 c reduces, but peak type does not all have change, and this is because surface imprinted layer is coated on caused by its surface, also illustrate that surface imprinted layer has just carried out finishing to magnetic TNT, does not change the crystal formation of magnetic TNT.
Fig. 4 is the FT-IR spectrogram of different photochemical catalyst.As shown in Figure 4,2972cm
-1the absworption peak at place is aliphatic C-H stretching vibration peak, 1650cm
-1, 1465cm
-1, 1265cm
-1, 1150cm
-1the characteristic absorption peak of vicinity is the vibration absorption peak of thiphene ring, is the characteristic absorption peak of C=C in thiphene ring and the absworption peak of=C-H plane deformation vibration respectively.820cm
-1near peak be the=out-of-plane bending vibration peak of C-H in thiphene ring.1735cm
-1the absworption peak of vicinity is the characteristic absorption peak of-C=O group, and this may be the absworption peak that the existence of crosslinking agent causes.The above results shows that surface imprinted layer has successfully been coated on the surface of catalyst.
Fig. 5 is the UV-visDRS spectrogram of different photochemical catalyst.Fig. 5 can reflect optical absorption properties and the band structure thereof of photochemical catalyst.TNT has very strong absorption in ultra-violet (UV) band, extremely weak, almost nil in the absorption of visible region.P3HT has absorption in Uv and visible light district, but absorbs all more weak.And single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst all has certain absorption at ultraviolet region and visible region, therefore, prepared in the application single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst has good light absorpting ability.
Fig. 6 is the TGA spectrogram of different photochemical catalyst.From 0 DEG C to 1000 DEG C, quality have lost about 16.45% and 19.71% to TNT and magnetic TNT respectively as can be seen from Figure 6, and this loss being water and surface hydroxyl remove causes.And when temperature is higher than 800 DEG C, still undecomposed, show that they have higher heat endurance.The TGA curve of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst is different from TNT and magnetic TNT, experienced by the mass change of three phases from 0 DEG C to 1000 DEG C.First stage occurs in room temperature to 375 DEG C, and Mass lost about 34.65%, this may be the loss of water and impurity.Second stage occurs in 375 DEG C to 500 DEG C, and Mass lost 31.19%, this is the loss due to some organic residue when imprinted polymer synthesizes.10.83% of phase III loss may be caused by surface imprinted layer P3HT pyrolytic.In sum, single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst has good heat endurance.
Fig. 7 is the VSM spectrogram of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst, and the symmetry of the B-H loop of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst is higher as can be seen from Figure 7.Its magnetic saturation intensity (Ms) is about 4.5emu/g, shows that the single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst prepared by the application has good Magneto separate characteristic.And hysteresis curve is S-shaped, show the feature of typical superparamagnetism, be conducive to sample recovery after a procedure and be separated.
Claims (10)
1. have a magnetic P3HT/TNT heterojunction photocatalyst for single-minded capacity of orientation, it is characterized in that, this catalyst is by TiO
2nanotube TNT, Fe
3o
4be composited with the P3HT imprinted layer of identifiable design tetracycline; Described TiO
2nanotube TNT is cylindric and the less nano tubular structure of middle cavity, described Fe
3o
4particulate load is in described TiO
2nanotube TNT outer surface; The P3HT imprinted layer of described identifiable design tetracycline is coated on described TiO
2nanotube TNT outer surface, and and TiO
2nanotube TNT forms heterojunction structure; This magnetic P3HT/TNT heterojunction photocatalyst of 0.1g is applied to the Photocatalytic Activity for Degradation of 100mL20mg/L tetracycline, in 120min, reaches the degradation rate of 86%.
2. there is a preparation method for the magnetic P3HT/TNT heterojunction photocatalyst of single-minded capacity of orientation, it is characterized in that, carry out according to following step:
Step 1, TiO
2the preparation of nanotube TNT: take P25 powder and join in NaOH solution, obtains suspension A after magnetic agitation is even, is transferred in hydrothermal reaction kettle by the described A of being suspended liquid and carry out constant temp. heating reaction, be cooled to room temperature, open reactor, remove supernatant liquor, obtain titanate nanotube white precipitate; By described washing of precipitate to neutral, with the above-mentioned titanate nanotube of HCl process of 5% under stirring, centrifugal, deionized water cyclic washing is to neutral, and vacuum drying, calcining at constant temperature, obtains TiO
2nanotube TNT;
The preparation of the magnetic TNT of step 2, modification: getting TNT prepared by step 1, to be scattered in volume ratio be that in the absolute ethyl alcohol/water mixed solution of 1:2, ultrasonic process is uniformly dispersed, and obtains suspension B; Get FeCl again
36H
2o and FeCl
24H
2o is dissolved in distilled water, obtains mixed solution C, is joined in described mixed solution C by described suspension B, obtains mixed liquor D; Heating stirring reaction a is carried out to mixed liquor D, adds ammoniacal liquor fast afterwards, proceed stirring reaction b; Finally by obtain product washing, vacuum drying, obtain magnetic TNT; By magnetic TNT, Macrogol 4000 and deionized water mix ultrasonic process, obtain the magnetic TNT mixed liquor E of modification;
The preparation of step 3, single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst: function monomer is added in chloroform, it is ultrasonic until function monomer is dissolved completely in chloroform, again template molecule is dissolved in above-mentioned containing in the chloroform of function monomer, continue ultrasonic to dissolving, again crosslinking agent and initator are added in above-mentioned chloroform, ultrasonic mixing, obtain mixed liquor F, then mixed liquor F is slowly joined in the mixed liquor E of step 2, obtain mixed liquor G, mixed liquor G is heated stirring reaction in nitrogen atmosphere; After completion of the reaction, collect product and cyclic washing product with magnet, finally use apparatus,Soxhlet's eluted template molecule, carry out vacuum drying, obtain single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst.
3. a kind of preparation method with the magnetic P3HT/TNT heterojunction photocatalyst of single-minded capacity of orientation according to claim 2, it is characterized in that, in step 1, in described suspension A, the mass ratio of P25 and NaOH is 1:20, and described NaOH solution concentration is 10M.
4. a kind of preparation method with the magnetic P3HT/TNT heterojunction photocatalyst of single-minded capacity of orientation according to claim 2, is characterized in that, in step 1, the anti-temperature had of described constant temp. heating is 170 DEG C, and the reaction time is 72h; The temperature of described calcining at constant temperature is 400 DEG C, and calcination time is 2h; Be 1h with the time of the HCl process titanate nanotube of 5%.
5. a kind of preparation method with the magnetic P3HT/TNT heterojunction photocatalyst of single-minded capacity of orientation according to claim 2, is characterized in that, in step 2, in described suspension B, the concentration of TNT is 1.4mg/mL; In mixed solution C, FeCl
36H
2o and FeCl
24H
2the concentration ratio of O is 91.9mg/mL:35.15mg/mL; The volume ratio of suspension B used, mixed solution C and ammoniacal liquor is 50:2:1; In described mixed liquor E, magnetic TNT, Macrogol 4000 and deionized water quality are than being 1:1:100.
6. a kind of preparation method with the magnetic P3HT/TNT heterojunction photocatalyst of single-minded capacity of orientation according to claim 2, it is characterized in that, in step 2, described heating-up temperature is 80 DEG C, the stirring reaction a time is 30min, and the stirring reaction b time is 20min.
7. a kind of preparation method with the magnetic P3HT/TNT heterojunction photocatalyst of single-minded capacity of orientation according to claim 2, it is characterized in that, in step 3, described function monomer is poly-3-hexyl thiophene P3HT, template molecule is tetracycline TC, crosslinking agent is trimethylol-propane trimethacrylate TRIM, and initator is azodiisobutyronitrile AIBN.
8. a kind of preparation method with the magnetic P3HT/TNT heterojunction photocatalyst of single-minded capacity of orientation according to claim 2 or 7, it is characterized in that, in step 3, during configuration mixed liquor F, the amount ratio of described poly-3-hexyl thiophene, tetracycline, azodiisobutyronitrile and chloroform is 0.01 ~ 0.03g:0.05g:0.05g:15mL, and trimethylol-propane trimethacrylate used and the volume ratio of chloroform are 1:150; In mixed liquor G, mixed liquor E used and the volume ratio of mixed liquor F are 20:3.
9. a kind of preparation method with the magnetic P3HT/TNT heterojunction photocatalyst of single-minded capacity of orientation according to claim 2, is characterized in that, in step 3, described heating-up temperature is 80 DEG C, and the time of stirring reaction is 2 ~ 24h.
10. a kind of preparation method with the magnetic P3HT/TNT heterojunction photocatalyst of single-minded capacity of orientation according to claim 2, is characterized in that, in step 1 ~ 3, described vacuum drying temperature is 50 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383536A (en) * | 2017-08-05 | 2017-11-24 | 福建师范大学 | The preparation method and device of a kind of photocatalysis film |
| CN111686806A (en) * | 2020-05-29 | 2020-09-22 | 黑龙江大学 | Preparation method and application of poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1868580A (en) * | 2006-06-23 | 2006-11-29 | 华中科技大学 | Artificial anitibody type composite photocatalyst and its prepn. method |
| CN102319591A (en) * | 2011-07-15 | 2012-01-18 | 江苏大学 | Preparation method of molecular imprinting modification composite photocatalyst with selective degradation |
| CN102962041A (en) * | 2012-11-07 | 2013-03-13 | 江苏大学 | Preparation method and application of microwave-assisted synthesized chlorine-element-doped surface molecular imprinting photocatalyst |
| CN103223352A (en) * | 2013-04-02 | 2013-07-31 | 江苏大学 | Preparation method of magnetic imprinting composite photocatalyst with good light transmission |
| CN103613719A (en) * | 2013-10-25 | 2014-03-05 | 江苏大学 | Controllable preparation method of magnetic halloysite surface nano imprinting composite material |
| CN103623869A (en) * | 2013-11-04 | 2014-03-12 | 江苏大学 | Preparation method of temperature-sensitive surface molecular imprinting load type composite photocatalyst |
| PL220028B1 (en) * | 2009-02-26 | 2015-08-31 | Univ Jagielloński | Nanokrystalline photocatalyst, active in visible light, in a form of transparent colloidal solutions, method of obtaining it and the application |
-
2015
- 2015-10-28 CN CN201510712027.8A patent/CN105289726B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1868580A (en) * | 2006-06-23 | 2006-11-29 | 华中科技大学 | Artificial anitibody type composite photocatalyst and its prepn. method |
| PL220028B1 (en) * | 2009-02-26 | 2015-08-31 | Univ Jagielloński | Nanokrystalline photocatalyst, active in visible light, in a form of transparent colloidal solutions, method of obtaining it and the application |
| CN102319591A (en) * | 2011-07-15 | 2012-01-18 | 江苏大学 | Preparation method of molecular imprinting modification composite photocatalyst with selective degradation |
| CN102962041A (en) * | 2012-11-07 | 2013-03-13 | 江苏大学 | Preparation method and application of microwave-assisted synthesized chlorine-element-doped surface molecular imprinting photocatalyst |
| CN103223352A (en) * | 2013-04-02 | 2013-07-31 | 江苏大学 | Preparation method of magnetic imprinting composite photocatalyst with good light transmission |
| CN103613719A (en) * | 2013-10-25 | 2014-03-05 | 江苏大学 | Controllable preparation method of magnetic halloysite surface nano imprinting composite material |
| CN103623869A (en) * | 2013-11-04 | 2014-03-12 | 江苏大学 | Preparation method of temperature-sensitive surface molecular imprinting load type composite photocatalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383536A (en) * | 2017-08-05 | 2017-11-24 | 福建师范大学 | The preparation method and device of a kind of photocatalysis film |
| CN111686806A (en) * | 2020-05-29 | 2020-09-22 | 黑龙江大学 | Preparation method and application of poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst |
| CN111686806B (en) * | 2020-05-29 | 2022-09-30 | 黑龙江大学 | Preparation method and application of poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst |
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