CN105289726B - Magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation and preparation method thereof - Google Patents
Magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation and preparation method thereof Download PDFInfo
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Abstract
The invention provides magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation and preparation method thereof.By Macrogol 4000, deionized water and the TiO prepared2Nanotube, which adds to be ultrasonically treated in beaker, obtains modified magnetic TNT mixed liquors E；Poly- 3 hexyl thiophene is added into chloroform ultrasound to being completely dissolved again, tetracycline is dissolved in the above-mentioned chloroform containing poly- 3 hexyl thiophene again, ultrasonic dissolution, trimethylol-propane trimethacrylate and azodiisobutyronitrile are added after above-mentioned chloroform again, ultrasound mixes, and obtains mixed liquor F, mixed liquor F is slowly added into mixed liquor E and obtains mixed liquor G, by mixed liquor G in nitrogen atmosphere the stirring reaction at 80 DEG C, you can obtain product.The catalyst make it that the separation and recovery of sample is more convenient, efficiently, and has very high selectivity to photocatalytic degradation tetracycline.
Description
Technical field
The invention belongs to technical field of environmental material preparation, and in particular to a kind of magnetic with single-minded capacity of orientation
The preparation method of P3HT/TNT heterojunction photocatalysts.
Background technology
Tetracycline (Tetracycline, TC) is the antibiosis separated from nutrient solution of actinomyces gold chain clump bacterium etc.
Plain medicine.Have well to gram-positive bacteria, negative bacterium, Richettsia, filterable virus, Spirochaeta or even protozoon class
Inhibitory action, it is a kind of broad-spectrum antibiotic.But the tetracycline remained in environment is easily caused toxic side effect, meeting Induction of bacterial produces strong
Drug resistance, and gene mutation etc. can be produced to other biological, directly influence ecology and the health of the mankind.So close
Effectively live, the tetracycline residue in production is an important link by processing for reason.Many experts and scholars by physics,
A variety of methods such as chemistry and biology are made a return journey except the tetracycline residue in environment, but because these methods are less efficient, are easily caused again
Secondary pollution.At present, photocatalysis technology has been widely used the technology for studying the wastewater treatment in environment, is a kind of more satisfactory
" green " treatment technology.
TiO2Nanotube (TiO2Nanotube, TNT) as one of earliest, most widely used semiconductor, there is nontoxic nothing
Evil, the advantages that cost is low, effect is good, be a kind of semiconductor light-catalyst with high light catalytic activity.But in view of actual
The demand of production and living, general T NT recovery is difficult, and secondary use rate is low, light induced electron, hole low separation efficiency, it is impossible to single-minded fixed
To the development and application that TNT is seriously constrained the problems such as identifying and remove specific pollutants.It is low for recovery hardly possible, secondary use rate
The defects of, the present invention introduces magnetic material (Fe on TNT3O4), Fe3O4Typical magnetic material, have it is easily prepared,
The advantages that quick separating, therefore, Fe3O4Load can make up that recovery is difficult, the low defect of secondary use rate well.
In addition, the problem of identifying without single-minded orientation for general T NT and remove specific pollutants, the present invention enters to it
Surface imprinted processing is gone, has realized that it orients identification and selective removal specific objective thing in multiple pollutant special secondary school one with this
Purpose.Surface imprinted technology is using the covalently or non-covalently effect between template molecule and monomer, in substrate material surface
By cross-linked polymeric and elution to prepare with three-dimensional specific structure, to polymer layer of the template molecule with single-minded orientation identity
Technology, the introducing of surface imprinted technology solves general T NT without single-minded orientation identification and selective removal ability well
Problem.
However, the introducing of conventional surface imprinted layer greatly covers TNT photocatalytic activity site, and therefore, the present invention
Conducting polymer (poly- 3- hexyl thiophenes, P3HT) is introduced in surface imprinted layer, P3HT is that a kind of dissolubility is big, conductance is high
The good novel conductive polymer with stability, its band gap is relatively low, and energy gap is about 2.0eV, can be produced with sunshine preferable
Matching, effectively change luminous energy.And this conducting polymer photochemical stability is strong, electron-hole mobility is high, because
This, P3HT introducing not only can form heterojunction structure with TNT, improve the separative efficiency of light induced electron and photo-induced hole,
So as to improve the photocatalytic activity of composite photo-catalyst, but also the formation for trace hole provides binding site.
Therefore, inventor is using TNT as carrier and to its surface loaded magnetic Fe3O4, magnetic TNT is prepared, is then also introduced
Surface imprinted technology, and select the conducting polymer (P3HT) to be used as function monomer, prepare the magnetic with single-minded capacity of orientation
Property P3HT/TNT heterojunction photocatalysts, the single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts not only have preferable
Photochemical stability, higher photo-catalysis capability, and also have very high single-minded orientation identification and selective light degradation capability.
The content of the invention
The present invention is so that, as preparation means, preparing one kind has the methods of hydro-thermal method, solvent-thermal method and surface imprinted technology
Magnetic P3HT/TNT heterojunction photocatalysts (the single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysis of single-minded capacity of orientation
Agent).Its advantage is that have preferable photochemical stability, higher photo-catalysis capability, and also has very high single-minded orientation
Identification and selective light degradation capability.
The technical solution adopted by the present invention is：
A kind of magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation, the catalyst is by TiO2Nanometer
Pipe TNT, Fe3O4It is combined with the P3HT imprinted layers of recognizable tetracycline；The TiO2Nanotube TNT is cylindrical and middle
The less nano tubular structure of cavity, the Fe3O4Particulate load is in the TiO2Nanotube TNT outer surfaces；Described recognizable four
The P3HT imprinted layers of ring element are coated on the TiO2Nanotube TNT outer surfaces, and and TiO2Nanotube TNT forms heterojunction structure；
0.1g magnetic P3HT/TNT heterojunction photocatalysts are applied to the visible light photocatalysis of 100mL 20mg/L tetracyclines
Degraded, has reached 86% degradation rate in 120min.
A kind of preparation method of the magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation, according to following steps
It is rapid to carry out：
Step 1, TiO2Nanotube TNT preparation：Weigh P25 powder to be added in NaOH solution, after magnetic agitation is uniform
Suspension A is obtained, the suspended A liquid is transferred to progress constant temperature thermal response in hydrothermal reaction kettle, room temperature is cooled to, opens reaction
Kettle, supernatant liquor is removed, obtains titanate nanotube white precipitate；The washing of precipitate to neutrality, stirring is lower with 5%
The above-mentioned titanate nanotube of HCl processing, centrifugation, deionized water are washed to neutrality, vacuum drying, calcining at constant temperature, obtained repeatedly
TiO2Nanotube TNT；
The preparation of step 2, modified magnetic TNT：The TNT for taking step 1 to prepare is scattered in volume ratio for 1:2 anhydrous second
In alcohol/water mixed solution, supersound process is uniformly dispersed, and obtains suspension B；FeCl is taken again3·6H2O and FeCl2·4H2O dissolves
In distilled water, mixed solution C is obtained, the suspension B is added in the mixed solution C, obtains mixed liquor D；To mixed
Close liquid D and carry out heating stirring reaction a, rapidly join ammoniacal liquor afterwards, continue stirring reaction b；Finally obtained product is washed
Wash, be dried in vacuo, obtain magnetic TNT；By magnetic TNT, Macrogol 4000 and deionized water mixing are ultrasonically treated, and are modified
Magnetic TNT mixed liquors E；
The preparation of step 3, single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts：Function monomer is added into three chloromethanes
In alkane, ultrasound until function monomer be dissolved completely in chloroform, then by template molecule be dissolved in it is above-mentioned containing function monomer three
In chloromethanes, continue ultrasound and added to dissolving, then by crosslinking agent and initiator in above-mentioned chloroform, ultrasound mixes, and is mixed
Liquid F is closed, then mixed liquor F is slowly added into the mixed liquor E of step 2, obtains mixed liquor G, by mixed liquor G in nitrogen atmosphere
Middle heating stirring reaction；After completion of the reaction, product and repeatedly washed product are collected with magnet, finally elutes mould with apparatus,Soxhlet's
Plate molecule, is dried in vacuo, and obtains single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts.
In addition, the preparation of non-directional type magnetic P3HT/TNT heterojunction photocatalysts is carried out under the same terms and method
, template molecule TC is simply added without in preparation process, and there is no template molecule elution step.
In step 1, P25 and NaOH mass ratio is 1 in the suspension A：20, the NaOH solution concentration is 10M.
In step 1, the anti-temperature having of the constant temperature heating is 170 DEG C, reaction time 72h；The temperature of the calcining at constant temperature
For 400 DEG C, calcination time 2h；The time that titanate nanotube is handled with 5% HCl is 1h.
In step 2, in the suspension B, TNT concentration is 1.4mg/mL；In mixed solution C, FeCl3·6H2O and
FeCl2·4H2O concentration ratio is 91.9mg/mL：35.15mg/mL；Suspension B used, mixed solution C and ammoniacal liquor volume ratio
For 50:2:1；In the mixed liquor E, magnetic TNT, Macrogol 4000 and deionized water quality ratio are 1：1：100.
In step 2, described heating-up temperature is 80 DEG C, and the stirring reaction a times are 30min, and the stirring reaction b times are
20min。
In step 3, the function monomer is poly- 3- hexyl thiophenes P3HT, and template molecule is tetracycline TC, crosslinking agent three
TRIM TRIM, initiator are azodiisobutyronitrile AIBN.
In step 3, when configuring mixed liquor F, described poly- 3- hexyl thiophenes, tetracycline, azodiisobutyronitrile and trichlorine
The amount ratio of methane is 0.01~0.03g：0.05g：0.05g：15mL, trimethylol-propane trimethacrylate used with
The volume ratio of chloroform is 1：150；In mixed liquor G, mixed liquor E used and mixed liquor F volume ratio are 20：3.
In step 3, the 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 effects of the present invention are：
(1) single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts make it that the separation and recovery of sample is more convenient, high
Effect.
(2) single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts prepared by the present invention are to photocatalytic degradation tetracycline
With very high selectivity.
(3) P3HT is coupled with TNT can not only form heterojunction structure, improve light induced electron and photo-induced hole
Separative efficiency, so as to improve the photocatalytic activity of composite photo-catalyst, but also bonding position is provided for the formation in trace hole
Point.
Brief description of the drawings
Fig. 1 is TNT (a), magnetic TNT (b), the TEM of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts (c)
Figure；
Fig. 2 is the EDS spectrograms of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts；
Fig. 3 is TNT (a), magnetic TNT (b), and the XRD of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts (c) is composed
Figure；
Fig. 4 is TNT (a), magnetic TNT (b), the FT-IR of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts (c)
Spectrogram；
Fig. 5 is TNT (a), P3HT (b), the UV-vis of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts (c)
DRS spectrograms；
Fig. 6 is TNT (a), magnetic TNT (b), and the TGA of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts (c) is composed
Figure；
Fig. 7 is the VSM spectrograms of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts；
Fig. 8 is that the adsorption equilibrium of different photochemical catalysts is investigated, wherein a：TNT；b：Single-minded orthotype magnetic P3HT/TNT is different
Matter knot photochemical catalyst)；
Shadow of the addition to single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst photocatalytic activities that Fig. 9 is P3HT
Ring wherein a：0.02g；b：0.025g；c：0.03g；d：0.015g；e：0.01g；
Figure 10 is different polymerization times to single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst photocatalytic activities
Influence wherein a：2h；b：6h；c：12h；d：18h；e：24h；
Figure 11 is different photochemical catalysts to photocatalytic degradation tetracycline (TC) (a, b, c) and Ciprofloxacin (CIP) (d, e, f)
Selectivity investigate (TNT (a, d), wherein, single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts (b, e), non-directional type
Magnetic P3HT/TNT heterojunction photocatalysts (c, f))；
Figure 12 is single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts degraded TC circulation experiment.
Embodiment
With reference to specific implementation example, the present invention will be further described：
Adsorption activity is evaluated：Carried out in DW-01 type photochemical reactions instrument (being purchased from Educational Instrument Factory of Yangzhou University), but not
Open the light source, 100mL 20mg/L tetracyclines (TC) are added in reactor and determine its initial value, the light for then adding 0.1g is urged
Agent, do not turn on light, stuffiness, open magnetic agitation, be spaced 10min sampling analyses, supernatant liquor is taken after being separated with magnet in purple
Its concentration of outer spectrophotometric determination, find out the time of equilibrium adsorption point of photochemical catalyst.
Photocatalytic activity evaluation：Carried out in DW-01 type photochemical reactions instrument (being purchased from Educational Instrument Factory of Yangzhou University), will
100mL 20mg/L tetracyclines (TC) add in reactor and determine its initial value, then add 0.1g photochemical catalyst, open
Magnetic agitation simultaneously opens aerator and is passed through air, and first Dynamic Adsorption is to adsorption equilibrium, then with simulated solar light irradiation, illumination
20min sampling analyses are spaced in journey, take supernatant liquor to determine its concentration in ultraviolet specrophotometer after being separated with magnet, and pass through
Formula：DC=[(C0-C1)/C0] × 100% calculates degradation rate.Wherein C0For the absorbance of TC solution after dark absorption, C1For timing
The absorbance of the TC solution of sampling and measuring.
Selective evaluation：Carried out in DW-01 type photochemical reactions instrument (being purchased from Educational Instrument Factory of Yangzhou University), will
100mL20mg/L Ciprofloxacins (CIP) add in reactor and determine its initial value, then add 0.1g photochemical catalyst, beat
Open magnetic agitation and open aerator and be passed through air, first Dynamic Adsorption is to adsorption equilibrium, then with simulated solar light irradiation, illumination
During be spaced 20min sampling analyses, taken after being separated with magnet supernatant liquor survey absorbance.According to formula and pass through formula：DC
=[(C0-C1)/C0] × 100% calculates degradation rate.
Photochemical stability is evaluated：Carried out in DW-01 type photochemical reactions instrument (being purchased from Educational Instrument Factory of Yangzhou University),
100mL 20mg/L tetracyclines (TC) are added in reactor and determine its initial value, then add 0.1g single-minded orthotype magnetic
Property P3HT/TNT heterojunction photocatalysts, open magnetic agitation and open aerator and be passed through air, first Dynamic Adsorption is to adsorbing
Balance, then with simulated solar light irradiation, is spaced 20min sampling analyses in During Illumination, illumination 120 minutes and after sampling, and uses magnetic
Take supernatant liquor to determine its concentration in ultraviolet specrophotometer after iron separation, and pass through formula：DC=[(C0-C1)/C0]×
100% calculates degradation rate；The catalyst absolute ethyl alcohol and water separated are cleaned by ultrasonic repeatedly again, to remove residual Fourth Ring
Plain (TC) and other degraded intermediates, then repeated above-mentioned degradation process, so repeatedly 4 times and calculate its degradation rate.
Embodiment 1：
(1)TiO2The preparation of nanotube (TNT)：Weigh 2g P25 powder and be added to 100ml, in 10M NaOH solution, magnetic
Suspension is obtained after power stirring 6h, above-mentioned suspension is transferred in the hydrothermal reaction kettle with polytetrafluoroethylliner liner, 170 DEG C
Lower reaction 72h, room temperature is cooled to, opens reactor, removed supernatant liquor, obtain white precipitate, the white precipitate is titanate
Nanotube；Wash above-mentioned white precipitate (titanate nanotube) repeatedly with deionized water again, finally obtain the pH value of supernatant about
Equal to 7, above-mentioned white precipitate, magnetic agitation 1h are added with 5% HCl afterwards, centrifugation removes supernatant, then adds deionized water anti-
After backwashing is washed so that the pH of supernatant is approximately equal to 7, is then dried in vacuo at room temperature, finally calcines 2h at 400 DEG C, obtains TiO2
Nanotube (TNT).
(2) modified magnetic TNT preparation：0.7g TNT is taken to be dissolved in 500ml volume ratios as 1:2 absolute ethyl alcohols/water mixes
Close in solution, be ultrasonically treated 5h at room temperature, suspension is made；1.838g FeCl are taken again3·6H2O and 0.703g FeCl2·
4H2O is dissolved in 20ml distilled water, then adds above-mentioned suspension thereto, and 80 DEG C of stirring reaction 30min are quick afterwards to add
Enter 10ml ammoniacal liquor, stirring reaction 20min, product is washed for several times repeatedly with water and absolute ethyl alcohol, is finally dried in vacuo, obtains magnetic
Property TNT；1g magnetic TNT, 1g Macrogol 4000 (PEG4000) and 100ml deionized waters are added in beaker and are ultrasonically treated
To modified magnetic TNT solution.
(3) preparation of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts：Again by the poly- 3- hexyl thiophenes of 0.02g
(P3HT) add in the beaker equipped with 15ml chloroforms, ultrasound is until P3HT is dissolved completely in chloroform (solution colour
In limpid bright orange), then 0.05g tetracyclines (TC) are dissolved in the above-mentioned chloroform containing P3HT, continue ultrasound and extremely dissolve,
0.1mL trimethylol-propane trimethacrylates (TRIM) and 0.05g azodiisobutyronitriles (AIBN) are added above-mentioned three again
After chloromethanes, it is ultrasonically treated 10 minutes, is then slowly added in the magnetic TNT solution of above-mentioned modification, by reactant 80
12h is stirred under DEG C nitrogen atmosphere.Collected with magnet and use deionized water, absolute ethyl alcohol washed product repeatedly, finally carried with Soxhlet
Device eluted template molecule is taken, after vacuum drying, obtains single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts.It is in addition, non-
The preparation of orthotype magnetic P3HT/TNT heterojunction photocatalysts is carried out under the same terms and method, is simply being prepared
Template molecule (TC) is added without in journey, and without template molecule (TC) elution step.
(4) sample in 0.1g (3) is taken to carry out dark adsorption test, experimental result ultraviolet spectrometry light in photochemical reaction instrument
Degree meter analysis, measures the single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts and the adsorption capacity of tetracycline (TC) is existed
0.6mg/g can be reached during 30min dark absorption, show that the single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts have
Preferable adsorption activity.
(5) sample in 0.1g (3) is taken to carry out photocatalytic degradation experiment in photochemical reaction instrument, experimental result is with ultraviolet point
Light luminometric analysis, measure photodegradation rate of the single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts to tetracycline (TC)
86% can be reached in 120min radiation of visible light, show the single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts tool
There is stronger photocatalytic activity.
(6) take sample in 0.1g (3) to carry out photocatalytic degradation experiment in photochemical reaction instrument, shone in 120min visible rays
In penetrating, the single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts are measured to tetracycline (TC) and Ciprofloxacin (CIP)
Photocatalytic activity.
Embodiment 2：
Carried out by the same step of the preparation technology of embodiment 1, the difference is that P3HT dosage is respectively 0.02g in step (3),
0.025g, 0.03g, 0.015g, 0.01g, to prepare different single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts, examine
Influence of the P3HT different amounts to single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst photocatalytic activities is examined, by embodiment
(5) step investigates the activity of light degradation tetracycline (TC) solution in 1.Photocatalysis effect is as shown in Figure 9, it can be seen that when P3HT's
The effect for the single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst light degradation tetracyclines (TC) that dosage is prepared when being 0.02g
Preferably, under the radiation of visible light of 120 minutes, 86% can be reached to the degradation rate of tetracycline (TC).
Embodiment 3：
Carried out by the same step of the preparation technology of embodiment 1, the difference is that polymerization time takes five groups of different times in step (3)
2h, 6h, 12h, 18h, 24h, to prepare different single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts, investigate different poly-
Influence of the time to single-minded orthotype magnetic P3HT/TNT heterojunction photocatalyst photocatalytic activities is closed, by (5) step in embodiment 1
The rapid activity for investigating light degradation tetracycline (TC) solution.Experimental result such as Figure 10：When being 12h between upon polymerization into the photocatalysis
The catalytic activity of agent is best.Under the radiation of visible light of 120 minutes, 86% can be reached to the degradation rate of tetracycline (TC).
Carried out by the same step of the preparation technology of embodiment 1, to prepare different photochemical catalysts, investigate different photochemical catalysts
Absorption property.Fig. 8 is with the design sketch of different photochemical catalyst tetracycline adsorptions (TC), is as a result shown compared with TNT, in the present invention
Prepared single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts have preferable single-minded orientation recognition capability.It is single-minded fixed
It is better than TNT to the adsorption capacity of type magnetic P3HT/TNT heterojunction photocatalysts, it is because single-minded orthotype magnetic P3HT/TNT
Heterojunction photocatalyst has surface imprinted layer, and the trace hole in surface imprinted layer has single-minded orientation recognition capability, can
With Selective recognition tetracycline (TC).
Carried out by the same step of the preparation technology of embodiment 1, to prepare different photochemical catalysts, to the special of different photochemical catalysts
One orientation and degradation selectivity ability are investigated.Figure 11 is that the single-minded orientation of different photochemical catalysts and degradation selectivity ability are examined
The light degradation design sketch examined, as a result show TNT and non-directional type magnetic P3HT/TNT heterojunction photocatalysts degraded tetracycline
(TC) degrading activity is high without single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts, because (1) is single-minded fixed
There is surface imprinted layer to type magnetic P3HT/TNT heterojunction photocatalysts, and the trace hole in surface imprinted layer have it is single-minded
Recognition capability is oriented, can be with specific recognition and degradation selectivity tetracycline (TC)；(2) P3HT and TNT can form hetero-junctions
Structure, which greatly improves the photocatalytic activity of composite photo-catalyst.In addition, single-minded orthotype magnetic P3HT/TNT hetero-junctions
The degradation rate of photocatalyst for degrading Ciprofloxacin (CIP) is very low, because the trace hole in surface imprinted layer can not know
Other and degraded Ciprofloxacin (CIP).The above results show single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts to Fourth Ring
Plain (TC) has very high single-minded orientation and degradation selectivity ability and photocatalytic activity.
Carry out by the same step of the preparation technology of embodiment 1, urged to prepare single-minded orthotype magnetic P3HT/TNT hetero-junctions light
Agent, investigate the photochemical stability of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts.Figure 12 is single-minded orthotype
The design sketch of magnetic P3HT/TNT heterojunction photocatalysts circulation degraded tetracycline (TC), is as can be seen from the figure followed by 4 times
After ring, the photocatalytic activity of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts does not substantially reduce, and this shows single-minded
Orthotype magnetic P3HT/TNT heterojunction photocatalysts have preferable photochemical stability.
Fig. 1 is the TEM figures of different photochemical catalysts.It can be seen that TNT is cylindrical and middle cavity is less from Fig. 1 a
Nano tubular structure.It can be seen that having loaded many nano-particles on TNT pipes from Fig. 1 b, show that TNT surface has succeeded
Ground has loaded magnetic Fe3O4.Compared with Fig. 1 b, Fig. 1 c surface is slightly different, because magnetic TNT Surface coatings can be known
Caused by the P3HT imprinted layers of other tetracycline, and pass through magnetic Fe3O4After the cladding of load and surface imprinted layer, single-minded orthotype
Magnetic P3HT/TNT heterojunction photocatalysts still show nano tubular structure.
Fig. 2 is the EDS energy spectrum diagrams of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts.It can be seen that
Single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts are made up of C, O, Fe, Ti, S element, wherein between Ti, Fe, O presence
The successful preparation for demonstrating magnetic TNT is connect, and C, S then indicate the presence of surface imprinted layer indirectly, wherein S elements come from
P3HT.To sum up show, single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts are successfully prepared.
Fig. 3 is the XRD spectra of different photochemical catalysts.2 θ=25.2 ° in Fig. 3 a, the peak of 48.1 ° and 53.9 ° are anatases
TiO2Characteristic peak (PDF#01-0562), and peak type is sharp, illustrates that the TNT of generation crystal formation is good.Scheme b in 2 θ=35.4 °,
43.4 °, 57.5 ° and 62.5 ° of peak is Fe3O4The principal character peak (PDF#03-0862) of nano-particle.With Fig. 3 a and Fig. 3 b phases
Than Fig. 3 c characteristic peak reduces, but peak type does not all become, and this is due to that surface imprinted layer is coated on caused by its surface, is also illustrated
Surface imprinted layer simply to magnetic TNT has carried out surface modification, does not change magnetic TNT crystal formation.
Fig. 4 is the FT-IR spectrograms of different photochemical catalysts.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 that the vibration of thiphene ring is inhaled
Peak is received, is C=C characteristic absorption peak and the absworption peak of=C-H plane deformations vibration in thiphene ring respectively.820cm-1Neighbouring peak
It is=C-H out-of-plane bending vibration peak in thiphene ring.1735cm-1The absworption peak of vicinity is the characteristic absorption peak of-C=O groups,
This is probably absworption peak caused by the presence of crosslinking agent.The above results show that surface imprinted layer is successfully coated on catalyst
Surface.
Fig. 5 is the UV-vis DRS spectrograms of different photochemical catalysts.Fig. 5 can reflect the optical absorption properties of photochemical catalyst
And its band structure.TNT has very strong absorption in ultra-violet (UV) band, extremely weak in the absorption of visible region, almost nil.P3HT is ultraviolet
There is absorption with visible region, but absorb all weaker.And single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts are ultraviolet
Light area and visible region have certain absorption, therefore, prepared single-minded orthotype magnetic P3HT/TNT hetero-junctions in the application
Photochemical catalyst has preferable light absorpting ability.
Fig. 6 is the TGA spectrograms of different photochemical catalysts.As can be seen from Figure 6 TNT and magnetic TNT from 0 DEG C to 1000 DEG C quality
Have lost about 16.45% and 19.71% respectively, this be water and surface hydroxyl removing loss caused by.And when temperature is higher than 800
DEG C when, it is still undecomposed, show that they have higher heat endurance.Single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts
TGA curves be different from TNT and magnetic TNT, the mass change that experienced three phases from 0 DEG C to 1000 DEG C.First stage is sent out
It is raw in room temperature to 375 DEG C, Mass lost about 34.65%, this is probably the loss of water and impurity.Second stage occurs 375
DEG C to 500 DEG C, Mass lost 31.19%, the loss of some organic residues when this is due to imprinted polymer synthesis.3rd
Caused by the 10.83% of stage yield-loss is probably surface imprinted layer P3HT pyrolytics.In summary, single-minded orthotype magnetic
P3HT/TNT heterojunction photocatalysts have good heat endurance.
Fig. 7 is the VSM spectrograms of single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts, single-minded as can be seen from Figure 7
The symmetry of the B-H loop of orthotype magnetic P3HT/TNT heterojunction photocatalysts is higher.Its magnetic saturation intensity (Ms) is about
4.5emu/g, show that the single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts prepared by the application have preferable magnetic point
From characteristic.And hysteresis curve is S-shaped, show the feature of typical superparamagnetism, be advantageous to the recovery of sample after use and
Separation.
Claims (9)
- A kind of 1. magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation, it is characterised in that the catalyst For nano tubular structure, template molecule is tetracycline, and function monomer is poly- 3- hexyl thiophenes P3HT；The catalyst is by TiO2 Nanotube TNT, Fe3O4It is combined with the P3HT imprinted layers of recognizable tetracycline；The TiO2Nanotube TNT it is cylindrical and The less nano tubular structure of middle cavity, the Fe3O4Particulate load is in the TiO2Nanotube TNT outer surfaces；It is described to know The P3HT imprinted layers of other tetracycline are coated on the TiO2Nanotube TNT outer surfaces, and and TiO2Nanotube TNT forms hetero-junctions Structure；0.1g magnetic P3HT/TNT heterojunction photocatalysts are applied to the visible ray light of 100mL 20mg/L tetracyclines Catalytic degradation, 86% degradation rate is reached in 120min.
- A kind of 2. preparation method of the magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation, it is characterised in that Carry out as steps described below：Step 1, TiO2Nanotube TNT preparation：Weigh P25 powder to be added in NaOH solution, hanged after magnetic agitation is uniform Turbid A, the suspended A liquid is transferred to progress constant temperature thermal response in hydrothermal reaction kettle, room temperature is cooled to, opens reactor, go Except supernatant liquor, titanate nanotube white precipitate is obtained；By the washing of precipitate to neutrality, the HCl processing down with 5% is stirred Above-mentioned titanate nanotube, centrifugation, deionized water are washed to neutrality repeatedly, vacuum drying, calcining at constant temperature, obtain TiO2Nanotube TNT；The preparation of step 2, modified magnetic TNT：The TNT for taking step 1 to prepare is scattered in volume ratio for 1:2 absolute ethyl alcohol/water In mixed solution, supersound process is uniformly dispersed, and obtains suspension B；FeCl is taken again3·6H2O and FeCl2·4H2O is dissolved in distillation In water, mixed solution C is obtained, the suspension B is added in the mixed solution C, obtains mixed liquor D；Mixed liquor D is entered Row heating stirring reacts a, rapidly joins ammoniacal liquor afterwards, continues stirring reaction b；Finally by the washing of obtained product, vacuum Dry, obtain magnetic TNT；By magnetic TNT, Macrogol 4000 and deionized water mixing are ultrasonically treated, and obtain modified magnetic TNT mixed liquors E；The preparation of step 3, single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts：By the poly- 3- hexyl thiophenes of function monomer P3HT is added in chloroform, and ultrasound is until function monomer is dissolved completely in chloroform, then by template molecule of tetracycline TC It is dissolved in the above-mentioned chloroform containing function monomer, continues ultrasound to dissolving, then by crosslinking agent trimethylol propane trimethyl third Olefin(e) acid ester TRIM and initiator azodiisobutyronitrile AIBN is added in above-mentioned chloroform, and ultrasound mixes, and obtains mixed liquor F；Match somebody with somebody When putting mixed liquor F, described poly- 3- hexyl thiophenes P3HT, tetracycline TC, the use of azodiisobutyronitrile AIBN and chloroform It is 0.01 ~ 0.03g to measure ratio： 0.05g：0.05g：15mL, trimethylol-propane trimethacrylate and chloroform used Volume ratio be 1：150；Then mixed liquor F is slowly added into the mixed liquor E of step 2, obtains mixed liquor G, by mixed liquor G in nitrogen atmosphere Heating stirring is reacted；After completion of the reaction, product and repeatedly washed product are collected with magnet, finally with apparatus,Soxhlet's eluted template Molecule, it is dried in vacuo, obtains single-minded orthotype magnetic P3HT/TNT heterojunction photocatalysts.
- A kind of 3. system of magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation according to claim 2 Preparation Method, it is characterised in that in step 1, P25 and NaOH mass ratio is 1 in the suspension A：20, the NaOH solution is dense Spend for 10M.
- A kind of 4. system of magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation according to claim 2 Preparation Method, it is characterised in that in step 1, the temperature of the constant temperature thermal response is 170 DEG C, reaction time 72h；The constant temperature The temperature of calcining is 400 DEG C, calcination time 2h；The time that titanate nanotube is handled with 5% HCl is 1h.
- A kind of 5. system of magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation according to claim 2 Preparation Method, it is characterised in that in step 2, in the suspension B, TNT concentration is 1.4mg/mL；In mixed solution C, FeCl3·6H2O and FeCl2·4H2O concentration ratio is 91.9mg/mL：35.15mg/mL；Suspension B used, mixed solution C and The volume ratio of ammoniacal liquor is 50:2:1；In the mixed liquor E, magnetic TNT, Macrogol 4000 and deionized water quality ratio are 1：1： 100。
- A kind of 6. system of magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation according to claim 2 Preparation Method, it is characterised in that in step 2, described heating-up temperature is 80 DEG C, and the stirring reaction a times are 30min, stirring reaction b Time is 20min.
- A kind of 7. system of magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation according to claim 2 Preparation Method, it is characterised in that in step 3 mixed liquor G, mixed liquor E used and mixed liquor F volume ratio are 20：3.
- A kind of 8. system of magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation according to claim 2 Preparation Method, it is characterised in that in step 3, the heating-up temperature is 80 DEG C, and the time of stirring reaction is 2 ~ 24h.
- A kind of 9. system of magnetic P3HT/TNT heterojunction photocatalysts with single-minded capacity of orientation according to claim 2 Preparation Method, it is characterised in that in step 1 ~ 3, described vacuum drying temperature is 50 DEG C.
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