CN109794291A - A kind of bionical construction method and application thereof of Ti@BiOI-pDA@CA automatically cleaning film - Google Patents
A kind of bionical construction method and application thereof of Ti@BiOI-pDA@CA automatically cleaning film Download PDFInfo
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- CN109794291A CN109794291A CN201910016781.6A CN201910016781A CN109794291A CN 109794291 A CN109794291 A CN 109794291A CN 201910016781 A CN201910016781 A CN 201910016781A CN 109794291 A CN109794291 A CN 109794291A
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Abstract
The invention belongs to technical field of environment function material preparation, refer in particular to the bionical construction method and purposes of a kind of Ti@BiOI-pDA@CA automatically cleaning film.With poly-dopamine modified lithium CA powder (pDA@CA) for membrane matrix, Ti@BiOI is photochemical catalyst, prepares automatically cleaning film Ti@BiOI-pDA@CA by phase inversion, and for removing the BPA in solution.The resulting membrane material of the present invention improves the compatibility of Ti@BiOI photochemical catalyst Yu pDA@CA film, and further improve the photocatalysis performance, resistance tocrocking and antibacterial ability of automatically cleaning film, photocatalysis technology is coupled to the composite membrane with photo-catalysis function prepared effectively decelerating membrane pollution with membrane separation technique simultaneously, convenient for continuous operation, it is easily recycled, better than powder catalyst, its practical application is promoted.
Description
Technical field
The invention belongs to technical field of environment function material preparation, a kind of the bionical of Ti@BiOI/pDA@CA automatically cleaning film is refered in particular to
Construction method and purposes.
Background technique
Phenol wastewater is the industrial wastewater that a kind of pollution range is wide, water is big, harm is extremely serious, is mainly derived from petroleum
Chemical industry, coal chemical industry, phenol production and phenolic resin factory, coke-oven plant, pharmaceutical factory etc., are the nocuousness that China needs keypoint treatment
One of waste water.The discharge of a large amount of phenol wastewater exacerbates the deterioration of ecological environment, and mankind or animal is taken in environment and food
Phenolic compound, intracorporal function of hormones and physiological system will get muddled, even if very low in content of phenolic compounds
In the case where, still can synthesis, release, effect etc. to biological hormone in vivo have an impact, in turn result in body reproduction, development
And abnormal behavior, it is serious then can carcinogenic, teratogenesis, mutagenesis, threaten the health and existence of the mankind.Currently, there are many processing
The method of first phenol wastewater, it is one of most promising green environment purification techniques that wherein photocatalysis technology, which has been recognized,.So
And in known photochemical catalyst, the efficiency of photochemical catalyst it is highest be usually nano particle, the separation of reaction solution and return
Receipts are the major technical barriers for promoting its business application.
In recent years, the composite membrane with photo-catalysis function that photocatalysis technology is coupled to preparation with membrane separation technique can be efficiently
Ground removes pollutant, environmentally protective.The mode that both technologies are coupled, not only effectively decelerating membrane pollution, and seperation film
It can effectively solve the utilization rate reduction of photochemical catalyst light as supporter, be difficult to reuse problem, to further promote
Its practical application.But traditional photocatalysis membrana coupling process have the shortcomings that it is obvious, as be blended film-forming process in, mostly
The compatibility of number catalyst and membrane material is bad, inorganic if cellulose acetate (CA) film lacks active function groups on polymer
Mutually the weak chemical interaction (such as hydrogen bond, Van der Waals and electrostatic interaction) between polymer substrate may will affect nanometer
Compound adherency causes photochemical catalyst easy to reunite, influences photocatalysis performance.
Summary of the invention
A kind of Ti@BiOI-pDA@CA automatically cleaning is prepared with cellulose acetate, DA, Ti@BiOI the purpose of the present invention is quasi-
Film, and it is applied to the efficient removal of trace contaminant bisphenol-A (BPA).This patent first passage dopamine (DA) modified CA
Powder, the catechol group in DA can ensure that the knot of Ti@BiOI-pDA nano material by chelation combination metal
Structure stability, and inhibit the leaching of Ti@BiOI nano material.Importantly, there is pDA good ultraviolet light, visible light to inhale
Photoconduction under attached ability and good radiation of visible light, is effectively prevented from the electron-hole recombinations of semiconductor catalyst, mentions
Highlight catalytic active.
A kind of bionical construction method of Ti@BiOI-pDA@CA automatically cleaning film, includes the following steps:
(1) preparation of composite photo-catalyst (Ti@BiOI):
Weigh five water bismuth nitrate (Bi (NO3)3·5H2O it) is scattered in ethyl alcohol, ultrasound obtains Bi (NO3)3·5H2O dispersion
Liquid；
It weighs KI to be dissolved in deionized water, KI solution is slowly added dropwise to Bi (NO3)3·5H2In O dispersion liquid and acutely stir
A period of time is mixed, titanium tetraisopropylate is then instilled, is stirred, is placed in reaction kettle and carries out hydro-thermal reaction, cool down after reaction, wash
It washs, is centrifugated, it is dry, composite photo-catalyst is finally obtained, Ti@BiOI is denoted as；
(2) preparation of pDA@CA composite material:
Tris-HCl is weighed to be dissolved in deionized water, adjust pH value of solution, then by CA powder, ethyl alcohol, dopamine D A according to
It is secondary to be added in above-mentioned Tris-HCl solution, poly-dopamine pDA modified CA powder is obtained, is dried in vacuo, obtains pDA@CA；
(3) the bionical preparation of Ti@BiOI-pDA@CA automatically cleaning film:
PDA@CA powder made from Ti@BiOI catalyst made from step (1) and step (2) is sequentially added into diformazan Asia
In sulfone (DMSO), mechanical stirring is uniform, obtains casting solution, and knifing is to get arriving blend film Ti@BiOI-pDA@CA.
In step (1), Bi (NO3)3·5H2The molar concentration rate of O and KI is 1:1；
In step (1), stir as magnetic agitation, time 0.5-1.5h；
In step (1), the temperature of hydro-thermal reaction is 170~190 DEG C, and the reaction time is 1.0~3.0h.
In step (2), the concentration of Tris-HCl solution is 0.605mg/mL, pH=8.5, the quality of Tris-HCl, CA, DA
Than for 0.605:20:1, the volume ratio of deionized water and ethyl alcohol is 30:1,4.0~8.0h of modification time, and vacuum drying temperature is
40~60 DEG C, drying time be 12~for 24 hours；
In step (3), the mass ratio of the gross mass and DMSO of Ti@BiOI catalyst and pDA@CA powder is 13:87, wherein
The quality of Ti@BiOI catalyst and pDA@CA powder is 2:11, and the mechanical stirring time is 6.0~10h.
The preparation process of BiOI is identical as above-mentioned steps (1), does not instill titanium tetraisopropylate only；
The preparation method of BiOI-CA is with above-mentioned difference, is not added titanium tetraisopropylate in step (1), in step (2) not
Add dopamine DA；
The preparation method of Ti@BiOI-CA is that dopamine D A is not added in (2) in step with above-mentioned difference；
The preparation method of BiOI-pDA@CA is with above-mentioned difference, and titanium tetraisopropylate is not added in rapid (1)；
The ethyl alcohol, the Tris-HCl that CA powder can be well dispersed in pH=8.5 are molten in the above technical solution
In liquid.
Ti@BiOI-pDA@CA bionic composite catalyst film produced by the present invention is used for the efficient removal of pollutant BPA.
The invention has the benefit that
(1) appropriate Ti doping, Tidxy key can be integrated into the local conduction band of BiOI, to effectively inhibit electronics
Hole pair it is compound, to effectively increase photocatalysis performance, improve the degradation rate to target substance.
(2) using DA to CA powder modification, the catechol group in DA can be by chelation combination metal, guarantee
The structural stability of Ti@BiOI-pDA nano material, and inhibit the leaching of Ti@BiOI nano material.Made from this method
Film solves the problems, such as that catalyst and membrane matrix poor compatibility in catalytic membrane is blended in tradition.And pDA have good ultraviolet light,
Photoconduction under visible light adsorption capacity and good radiation of visible light, is effectively prevented from the electron hole of semiconductor catalyst
It is compound, further increase photocatalytic activity.
(3) photocatalysis technology is combined with membrane separation technique, not only can solve the difficult problem of fine catalyst separation and recovery,
It also can reduce membrane pollution problem simultaneously.
Detailed description of the invention
Fig. 1 (a) and (b) are respectively prepared BiOI and Ti@BiOI transmission electron microscope picture.
Fig. 2 is that Ti@BiOI-pDA@CA automatically cleaning film photocatalytic prepared by various automatically cleaning films and the present invention removes BPA
Experiment.
Fig. 3 is that the anti-microbial property of Ti@BiOI-pDA@CA automatically cleaning film prepared by various automatically cleaning films and the present invention is surveyed
Examination.
Fig. 4 is that the antifouling property of Ti@BiOI-pDA@CA automatically cleaning film prepared by various automatically cleaning films and the present invention is surveyed
Examination.
Specific embodiment
Below with reference to specification and specific implementation example, the present invention will be further described.
The present invention is by taking casting solution gross mass is 10g as an example.
The preparation of embodiment 1Ti@BiOI-pDA@CA bionic composite catalyst film
(1) preparation of pDA@CA composite material
Firstly, 0.1815g Tris-HCl is dissolved in 300mL deionized water, the pH=8.5 for adjusting solution is made slow
Rush solution；Then 6.0g CA powder, 10mL dehydrated alcohol, 0.3g DA are placed in above-mentioned solution, stir 6.0h at room temperature, taken out
Filter, gained powder are washed with deionized, and are then dried under vacuum to constant weight for 40 DEG C, obtain the modified CA powder of dopamine.
(2) preparation of Ti@BiOI-pDA@CA bionic composite catalyst film
Firstly, weigh 200mg Ti@BiOI catalyst, 1.1g pDA@CA is dissolved in 8.7g DMSO, then in 50 DEG C of items
Mechanical stirring 8.0h is to being uniformly dissolved to obtain casting solution under part, and heat preservation stands 4.0h at 50 DEG C, sloughs the bubble that stirring generates,
Casting solution is laid on glass plate, the film of 2.0mm thickness is scraped with glass bar, is slowly dipped in deionized water after 30s,
It takes out after impregnating 30min to get Ti@BiOI-pDA@CA bionic composite catalyst film, is stored in spare in deionized water.
(3) under illumination condition, the removal BPA of Ti@BiOI-pDA@CA bionic composite catalyst film is tested
A. compound concentration is bisphenol-A (BPA) solution of 5.0mg/L, and the solution prepared is placed in dark place；
B. it takes a piece of Ti@BiOI-pDA@CA bionic composite catalyst film prepared to be placed in photo catalysis reactor, is added
The target degradation solution that 50mL step a is prepared, opens source of recycled water, and light source carries out removing experiment under illumination condition；
C. every 30min draws the reaction solution in 3-5ml reactor, and the measurement of UV-visible absorbance is used for after centrifugation；
(4) K12 strain Escherichia coli are put people to have got ready in the conical flask equipped with nutrient broth, is shaken under conditions of 37 DEG C
Swing culture 16h.After the completion of culture, removal nutrient solution aseptically is cleaned with physiological saline, then be diluted to original concentration.So
Afterwards aseptically, drawing 8mL note people, sterilization is crossed in the reactor containing 72mL physiological saline, is placed in xenon lamp catalysis
In device, 10~20min is stirred, coli somatic is made to be dispersed in physiological saline
Photocatalysis membrana prepared by 0.2g is accurately weighed, is put into above-mentioned beaker, 10~20min is stirred, in dark reaction item
After reacting 1h under part, xenon lamp is opened, carries out illumination, takes 0.1mL mixed liquor to dilute 10 at interval of 1h6After times, 0.1mL dilution is drawn
Liquid is uniformly applied on culture dish.After experiment, culture dish is put in 37 DEG C of people of constant incubator and cultivate 16h, then united
It counts E. coli clones number, records data (blank in Fig. 3 is that the quantity of the Escherichia coli of photocatalysis membrana is not added).
(5) the pollution resistance experiment of Ti@BiOI-pDA@CA bionic composite catalyst film
A series of BSA curve for preparing concentration first measures them at 280nm with ultra-violet and visible spectrophotometer
Absorbance draws standard curve.Sheet of membrane is taken to be immersed in 10mL, in the BSA solution of 1.0mg/mL, standing adsorption for 24 hours, surveys solution
Absorbance, according to formula (1) calculate BSA adsorption concentration Qe (mg/cm2):
Wherein C0It is the initial and equilibrium concentration of BSA with Ce, V (mL) is the volume of BSA solution, S (cm2) be film absorption
Area.At least measure the average value measured three times.
In the case that embodiment 2 guarantees that other conditions are constant, it is as follows to establish comparative test: in step (2), weighing 200mg
BiOI catalyst is added in casting solution.
In the case that embodiment 3 guarantees that other conditions are constant, it is as follows to establish comparative test: in step (2), weighing 1.1g not
Modified CA is added in casting solution.
In the case that embodiment 4 guarantees that other conditions are constant, it is as follows to establish comparative test: weighing 200mg BiOI catalyst
It is added in casting solution with the unmodified CA powder of 1.1g.
It can be seen that BiOI is flower-like structure from Fig. 1 (a), it is flower-shaped to can be seen that Ti is dispersed in from Fig. 1 (b)
The surface of BiOI.
Fig. 2 is that Ti@BiOI-pDA@CA automatically cleaning film photocatalytic prepared by various automatically cleaning films and the present invention removes BPA
Experiment, by, it can be seen that Ti@BiOI-pDA@CA automatically cleaning film has excellent photocatalytic activity, which reacts in catalysis in Fig. 2
After 60min, 98% is reached to BPA solution removal rate.
Fig. 3 is that the anti-microbial property of Ti@BiOI-pDA@CA automatically cleaning film prepared by various automatically cleaning films and the present invention is surveyed
Examination, can be seen from figure 3, Ti@BiOI-pDA@CA automatically cleaning film antibiotic property is best.
Fig. 4 is that the antifouling property of Ti@BiOI-pDA@CA automatically cleaning film prepared by various automatically cleaning films and the present invention is surveyed
Examination, in Fig. 4 as can be seen that prepared by film after Static Adsorption BSA24h, absorbance does not have a significant change, prepared by explanation
Antipollution automatically cleaning film pollution resistance it is good.
Claims (7)
1. a kind of bionical construction method of Ti@BiOI-pDA@CA automatically cleaning film, which is characterized in that sequentially include the following steps:
(1) preparation of composite photo-catalyst (Ti@BiOI):
It weighs five water bismuth nitrates to be scattered in ethyl alcohol, ultrasound obtains Bi (NO3)3·5H2O dispersion liquid；Weigh KI be dissolved in from
In sub- water, KI solution is slowly added dropwise to Bi (NO3)3·5H2In O dispersion liquid and it is vigorously stirred a period of time, then instills four isopropyls
Alcohol titanium, stirring, is placed in reaction kettle and carries out hydro-thermal reaction, cool down after reaction, washs, and is centrifugated, dry, finally obtains
Composite photo-catalyst is denoted as Ti@BiOI；
(2) preparation of pDA@CA composite material:
It weighs Tris-HCl to be dissolved in deionized water, adjusts pH value of solution, then sequentially add CA powder, ethyl alcohol, dopamine
In above-mentioned Tris-HCl solution, the drying of poly-dopamine pDA modified CA powder under vacuum is obtained, pDA@CA is obtained；
(3) the bionical preparation of Ti@BiOI-pDA@CA automatically cleaning film:
PDA@CA powder made from Ti@BiOI catalyst made from step (1) and step (2) is sequentially added into dimethyl sulfoxide
(DMSO) in, mechanical stirring is uniform, obtains casting solution, and knifing is to get arriving blend film Ti@BiOI-pDA@CA.
2. a kind of bionical construction method of Ti@BiOI-pDA@CA automatically cleaning film according to claim 1, which is characterized in that
In step (1), Bi (NO3)3·5H2The molar concentration rate of O and KI is 1:1.
3. a kind of bionical construction method of Ti@BiOI-pDA@CA automatically cleaning film according to claim 1, which is characterized in that
In step (1), stir as magnetic agitation, time 0.5-1.5h.
4. a kind of bionical construction method of Ti@BiOI-pDA@CA automatically cleaning film according to claim 1, which is characterized in that
In step (1), the temperature of hydro-thermal reaction is 170~190 DEG C, and the reaction time is 1.0~3.0h.
5. a kind of bionical construction method of Ti@BiOI-pDA@CA automatically cleaning film according to claim 1, which is characterized in that
In step (2), the concentration of Tris-HCl solution is 0.605mg/mL, pH=8.5, and the mass ratio of Tris-HCl, CA, DA are
The volume ratio of 0.605:20:1, deionized water and ethyl alcohol be 30:1,4.0~8.0h of modification time, vacuum drying temperature be 40~
60 DEG C, drying time be 12~for 24 hours.
6. a kind of bionical construction method of Ti@BiOI-pDA@CA automatically cleaning film according to claim 1, which is characterized in that
In step (3), the mass ratio of the gross mass and DMSO of Ti@BiOI catalyst and pDA@CA powder is 13:87, wherein Ti@BiOI
The quality of catalyst and pDA@CA powder is 2:11.
7. a kind of bionical construction method of Ti@BiOI-pDA@CA automatically cleaning film according to claim 1, which is characterized in that
In step (3), the mechanical stirring time is 6.0~10h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112522862A (en) * | 2020-11-13 | 2021-03-19 | 南通大学 | Visible light driven antibacterial nanofiber and preparation method and application thereof |
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| CN103566776A (en) * | 2013-11-06 | 2014-02-12 | 复旦大学 | Photocatalytic inorganic nanoparticle/polydopamine/polymer self-cleaning composite film and preparation method thereof |
| CN108283932A (en) * | 2017-12-21 | 2018-07-17 | 江苏大学 | A kind of C3N4@Ag3PO4The preparation and application thereof of/PDA@PVDF bionic composite catalyst films |
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| CN103566776A (en) * | 2013-11-06 | 2014-02-12 | 复旦大学 | Photocatalytic inorganic nanoparticle/polydopamine/polymer self-cleaning composite film and preparation method thereof |
| CN108283932A (en) * | 2017-12-21 | 2018-07-17 | 江苏大学 | A kind of C3N4@Ag3PO4The preparation and application thereof of/PDA@PVDF bionic composite catalyst films |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112522862A (en) * | 2020-11-13 | 2021-03-19 | 南通大学 | Visible light driven antibacterial nanofiber and preparation method and application thereof |
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