CN102553649B - 17beta-estradiol molecular imprinted silver-doped TiO2 nanotube and preparation method thereof - Google Patents

17beta-estradiol molecular imprinted silver-doped TiO2 nanotube and preparation method thereof Download PDF

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CN102553649B
CN102553649B CN 201110438850 CN201110438850A CN102553649B CN 102553649 B CN102553649 B CN 102553649B CN 201110438850 CN201110438850 CN 201110438850 CN 201110438850 A CN201110438850 A CN 201110438850A CN 102553649 B CN102553649 B CN 102553649B
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estradiol
17beta
nanotube
silver
tio
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CN 201110438850
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CN102553649A (en
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张文龙
李轶
王大伟
罗小勇
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河海大学
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Abstract

The invention provides a 17beta-estradiol molecular imprinted silver-doped TiO2 nanotube and a preparation method thereof. The material can selectively adsorb 17beta-estradiol and degrade 17beta-estradiol and is doped with silver to powerfully kill certain pathogenic microorganisms. The TiO2 nanotube comprises a TiO2 nanotube with two open ends, a molecular imprinting polymer and Ag simple substance, which are formulated in a mass ratio of 58:33:9, wherein the molecular imprinting polymer contains methacrylic acid, trimethylolpropane trimethylacrylate and azo-biscyanopentanoic acid, which are formulated in a mole ratio of 124:123:1, and the molecular imprinting polymer is loaded with carbonyl functional groups; the TiO2 nanotube is 90 nm in diameter, 600 nm in length, 0.51 cm3/g in porosity and 290 m2/g in specific surface area ; and the mole ratio of functional monomer methacrylic acid to template molecule 17beta-estradiol is 124:26. The 17beta-estradiol molecular imprinted silver-doped TiO2 nanotube has a good 17beta-estradiol adsorbing effect, can degrade 17beta-estradiol with high degradation rate up to 98%, can powerfully kill certain pathogenic microorganisms, and is significant in improving the quality of reclaimed water from sewage.

Description

The TiO that 17 beta-estradiol molecular engrams silver mixes 2Nanotube and preparation method thereof

Technical field

The present invention relates to a kind of photocatalytic nanometer pipe, especially relate to the TiO that 17 beta-estradiol molecular engrams silver a kind of molecular imprinting functionalization and that be doped with silver mixes 2Nanotube and preparation method thereof.

Background technology

Along with increase, the development of industrial and agricultural production and being on the rise of water environment pollution degree of population, crisis has appearred in the available water resource in many areas in succession, has seriously restricted society, expanding economy.Reusing sewage is important, the indispensable measure that solves shortage of water resources, also is that cost is low, the effective way of instant effect.Reusing sewage not only can be alleviated the shortage of water resources problem, can also reduce disposal of pollutants simultaneously, also has great importance to improving quality of water environment.Yet the health risk of process and ecological risk can not be ignored in the reusing sewage.But the continuous appearance of various emerging pollutants has but proposed austere requirement because to the reusing sewage technology.At present, a kind ofly be referred to as estrogenic emerging pollutant and just causing widely and to pay close attention to.Estrogen refers to disturb the exogenous material of keeping self stability in the organism, regulating hormonal generation, metabolism, combination, reciprocation and the drainage of reproductive development and other behaviors.These materials can cause internal system, immune system, the nervous system of animal and human's class various anomalies to occur, cause that the organism fecundity descends and offspring's health and survival rate under the degradation problem.Therefore, the estrogen pollution problem has caused global extensive concern.The a lot of zones of China all are subjected to incretion interferent pollution in various degree, and the intrasystem animal of the food chain around the waters is produced harmful effect.Yet the conventional process means do not have too big effect to the removal of this type of polluter, and how removing this material just becomes a problem that presses for solution.Estrogenic kind is more, and wherein estradiol causes the extensive concern of educational circles as the big representative material of a kind of amount.

Often contain microorganisms such as bacterium, virus in the sanitary sewage.Though the pathogenic microorganism in the secondary effluent of municipal sewage plant can be effectively removed in tradition sterilization process such as chlorination, because accessory substance is of a great variety and harm is very big, not best process choice.But at present all disinfection technologies, because ultraviolet disinfection has the unrivaled germicidal efficiency of other technologies, germicidal efficiency can arrive 99%, and almost can both effectively kill all bacteriums, virus.The ultraviolet disinfection non-secondary pollution is safe and reliable to operation in addition, and big yield sterilization continuously safeguards that all ultraviolet disinfections have bigger application prospect undoubtedly easily.Yet ultraviolet disinfection restricts its development because power consumption is huge always.Therefore develop a kind of both effective pathogenic microorganisms in the deactivation sewage, reliably economical, the disinfection technology of non-secondary pollution is very necessary.

At present, utilize TiO 2More and more as the make a return journey research of estrogen in dewatering and pathogenic microorganism of catalysis material.Discover TiO 2Characteristics such as nontoxic, environmentally friendly and cheap are arranged, in the purified treatment of air and water body, great potential is arranged.But this material also has its extensive use of some drawbacks limit, and one of them shortcoming is that reactant must be adsorbed on TiO 2Catalytic reaction could take place in the surface, yet in the secondary effluent of municipal wastewater treatment plant, the estradiol of low concentration is accompanied by the polluter appearance of other high concentration often, at this time utilizes TiO 2Pollutant is carried out light degradation will become and have no purpose, be i.e. TiO 2Target contaminant and other pollutants can not be distinguished when adsorbing, this can reduce it greatly to the removal effect of target contaminant, and this has also influenced it greatly as a kind of scope of application of new catalytic material.So at TiO 2The efficient absorption of estradiol and the improvement of selective degraded are being caused more and more scholars' concern.

Summary of the invention

The objective of the invention is to existing TiO 2Material makes improvements, and makes it to improve the removal effect to estradiol, and effective pathogenic microbe killing.The invention provides the TiO that a kind of 17 beta-estradiol molecular engrams silver mixes 2Nanotube and preparation method thereof.

The purpose of molecular engram is optionally to adsorb, the TiO of molecular engram 2-Can optionally adsorb and degrade, this kind material can optionally adsorb 17 beta estradiols with the estrogen with similar structures and with its degraded, and the purpose that silver mixes is can help to kill the part pathogenic microorganism.The TiO that described 17 beta-estradiol molecular engrams silver mixes 2Nanometer is the TiO by the two ends perforate 2Nanotube and molecularly imprinted polymer and Ag simple substance three parts are that 58:33:9 makes by mass ratio, wherein molecularly imprinted polymer by methacrylic acid, trimethylol-propane trimethacrylate and azo dicyano valeric acid in molar ratio 124:123:1 make, load has carbonyl function functional group on molecularly imprinted polymer, function monomer methacrylic acid and template molecule 17 beta estradiol mol ratios are 124:26, the TiO that described silver mixes 2The nanotube caliber is 90nm, and pipe range is 600nm, and porosity is 0.51cm 3/ g, specific area is 290m 2/ g.The present invention also provides this Preparation of catalysts method and purposes.The present invention is to the excellent adsorption of 17 beta estradiols, and degradation rate is up to 98%, and can strengthen deactivation part pathogenic microorganism, can play positive role to the improvement of reusing sewage water quality.

The TiO that described 17 beta-estradiol molecular engrams silver mixes 2The preparation method of nanotube, its preparation process is as follows:

(1) use the abrasive paper for metallograph grinding and polishing to surperficial no marking the titanium plate, put into distilled water ultrasonic cleaning 15min then, ultrasonic cleaning 15min in the acetone uses distilled water ultrasonic cleaning 15min again, places air drying;

(2) the electrochemistry experiment anode is the titanium plate, and the nickel plate is made negative electrode, and bath composition is ammonium fluoride: oxalic acid: the mass ratio of water is 1:3:200, and anodic oxidation at room temperature continues to carry out magnetic agitation, and the reaction time is 60min, and anode voltage is 20V;

(3) will clean with distilled water through the titanium plate that reactions steps (2) obtain, place air drying;

(4) the nickel plate is made anode, TiO 2/ titanium plate is made negative electrode, contains AgNO 3The mixed liquor of 2g/L and citric acid 20g/L is made electrolyte, feeds DC voltage 1.2V, is taking out drying under the room temperature behind the reaction 3min;

(5) dried titanium plate is put into tube type resistance furnace and is calcined 500 ℃ of calcining heats, 2 ℃ of min of cooling rate at air -1-, calcination time 90min, this is the TiO of silver-doped 2Nanotube;

(6) with the TiO of this silver-doped 2Nanotube carries out molecular engram operation, with methacrylic acid, anhydrous acetonitrile and 17 beta estradiol mol ratios be 124:27:26 as in the quartz ampoule, ultrasonic mixing 5min under the normal temperature; Add trimethylol-propane trimethacrylate and azo dicyano valeric acid again, more than five kinds of material-methacrylic acids: anhydrous acetonitrile: estradiol: trimethylol-propane trimethacrylate: the mol ratio of azo dicyano valeric acid is 124:27:26:123:1, ultrasonic mixing 5min under the normal temperature, synthetic polymer;

(7) synthetic polymer evenly is applied in the TiO of doping Ag 2Nanotube surface is put into quartz ampoule then, drives away the oxygen in the quartz ampoule, the sealing bottleneck;

(8) with the quartz ampoule of its sealing as for illumination 12h under the 352nm ultraviolet light, in the process of illumination, the temperature of cooling water remains on 4 ℃;

(9) 17 beta estradiol TiO after the mixed liquid dipping step (7) of 9:1 is handled by volume with methyl alcohol and acetic acid 2Nanotube 4 times;

(10) with the TiO of step (9) 2Nanotube soak 24h with methyl alcohol, dry under 45 degree, through anhydrous acetonitrile and 17 beta estradiols on above-mentioned (8), (9) two the step flush away polymer, degradation reaction 15-20min under illumination finally obtains the TiO that 17 beta-estradiol molecular engrams silver mixes again 2Nanotube.

The present invention compared with prior art has the following advantages:

1. 17 beta estradiols are had single-minded identity, can improve TiO 2Nanotube is to the adsorption rate of such material, thereby improves the degradation rate to this polluter, and degradation rate is up to 98%.

2. the new Ti O that mixes of 17 beta-estradiol molecular engrams silver 2Nanotube can be accelerated the removal speed of 17 beta estradiols and strengthen removal effect, and the improvement of water quality is had important function.

3. silver mixes and makes this kind catalyst can strengthen deactivation part pathogenic microorganism, in the short time colibacillary removal is reached 5lg, in addition, can also make catalyst just can partly activate the degradation rate that also can improve catalyst under the visible light condition.

4. the TiO that mixes of 17 beta-estradiol molecular engrams silver 2Nanotube has making can be repeated, and life cycle is long, and is easy to clean, can batch etc. numerous characteristics.

Description of drawings

Fig. 1 is the new Ti O that 17 beta-estradiol molecular engrams silver mixes 2The structural representation of nanotube.

Fig. 2 is the new Ti O that 17 beta-estradiol molecular engrams silver mixes 2The ESEM phenogram of nanotube, multiplication factor are 20000 times.

Reference numeral: 1 is molecularly imprinted polymer between pipe, and 2 is TiO 2Nanotube, 3 is functional group, 4 is silver-colored particle.

The specific embodiment

Embodiment, the TiO that a kind of 17 beta-estradiol molecular engrams silver mixes 2Nanotube is characterized in that it is TiO by the two ends perforate 2Nanotube and molecularly imprinted polymer and Ag simple substance three parts are that 58:33:9 forms by mass ratio, wherein molecularly imprinted polymer by methacrylic acid, trimethylol-propane trimethacrylate and azo dicyano valeric acid in molar ratio 124:123:1 make, load has carbonyl function functional group, wherein TiO on molecularly imprinted polymer 2The nanotube caliber is 90nm, and pipe range is 600nm, and porosity is 0.51cm 3/ g, specific area is 290m 2/ g, function monomer methacrylic acid and template molecule 17 beta estradiol mol ratios are 124:26.The TiO that this example is to use 17 beta-estradiol molecular engrams silver to mix 2It is 25 μ g/L that nanotube is removed 17 beta estradiol concentration, and e. coli concentration is 10 8The sewage of CFU/L is at a 24W(dominant wavelength 365mm), under the ultra violet lamp, with the TiO of 17 beta-estradiol molecular engrams 2Nanotube is put into this sewage, and the catalyst use amount is 40cm 2/ L, the degradation rate to 17 beta estradiols behind the 20min is 98%, and the general T iO that does not have molecular engram silver to mix 2The degradation rate of nanotube is 50%; Be 5 lg to colibacillary clearance behind the 20min, and the general T iO that does not have molecular engram silver to mix 2The clearance of nanotube is 3 lg, therefore we can say the TiO that 17 beta-estradiol molecular engrams silver mixes 2Nanotube all has great lifting to removal and the bactericidal effect of 17 beta estradiols.

The TiO that described 17 beta-estradiol molecular engrams silver mixes 2The preparation method of nanotube, its preparation process is as follows:

(1) use the abrasive paper for metallograph grinding and polishing to surperficial no marking the titanium plate of 3cm * 8cm, put into distilled water ultrasonic cleaning 15min then, ultrasonic cleaning 15min in the acetone uses distilled water ultrasonic cleaning 15min again, places air drying;

(2) the electrochemistry experiment anode is the titanium plate, and the nickel plate is made negative electrode, and bath composition is ammonium fluoride: oxalic acid: the mass ratio of water is 1:3:200, and anodic oxidation at room temperature continues to carry out magnetic agitation, and the reaction time is 60min, and anode voltage is 20V;

(3) will clean with distilled water through the titanium plate that reactions steps (2) obtain, place air drying;

(4) the nickel plate is made anode, TiO 2/ titanium plate is made negative electrode, contains AgNO 3The mixed liquor of 2g/L and citric acid 20g/L is made electrolyte, feeds DC voltage 1.2V, is taking out drying under the room temperature behind the reaction 3min;

(5) dried titanium plate is put into tube type resistance furnace and is calcined 500 ℃ of calcining heats, 2 ℃ of min of cooling rate at air -1-, calcination time 90min, this is the TiO of silver-doped 2Nanotube;

(6) carry out the molecular engram operation with the nanotube of this silver-doped, with methacrylic acid, anhydrous acetonitrile and 17 beta estradiol mol ratios be 124:27:26 as in the quartz ampoule, ultrasonic mixing 5min under the normal temperature; Add trimethylol-propane trimethacrylate and azo dicyano valeric acid again, more than five kinds of material-methacrylic acids: anhydrous acetonitrile: estradiol: trimethylol-propane trimethacrylate: the mol ratio of azo dicyano valeric acid is 124:27:26:123:1, ultrasonic mixing 5min under the normal temperature, synthetic polymer;

(7) synthetic polymer evenly is applied in the TiO of doping Ag 2Nanotube surface is put into quartz ampoule then, drives away the oxygen in the quartz ampoule, the sealing bottleneck;

(8) with the quartz ampoule of its sealing as for illumination 12h under the 352nm ultraviolet light, in the process of illumination, the temperature of cooling water remains on 4 ℃;

(9) 17 beta estradiol TiO after the mixed liquid dipping step (7) of 9:1 is handled by volume with methyl alcohol and acetic acid 2Nanotube 4 times;

(10) with the TiO of step (9) 2Nanotube soak 24h with methyl alcohol, dry under 45 degree, through anhydrous acetonitrile and 17 beta estradiols on above-mentioned (8), (9) two the step flush away polymer, degradation reaction 15-20min under illumination finally obtains the TiO that 17 beta-estradiol molecular engrams silver mixes again 2Nanotube.

Claims (1)

1. the TiO that mixes of beta-estradiol molecular engram silver 2Nanotube is characterized in that it is TiO by the two ends perforate 2Nanotube and molecularly imprinted polymer and Ag simple substance three parts are that 58:33:9 makes by mass ratio, wherein molecularly imprinted polymer by methacrylic acid, trimethylol-propane trimethacrylate and azo dicyano valeric acid in molar ratio 124:123:1 make, load has carbonyl function functional group on molecularly imprinted polymer, function monomer methacrylic acid and template molecule 17 beta estradiol mol ratios are 124:26, the TiO that described silver mixes 2The nanotube caliber is 90nm, and pipe range is 600nm, and porosity is 0.51cm 3/ g, specific area is 290m 2/ g, described molecularly imprinted polymer are to be that 124:27:26 places quartz ampoule with methacrylic acid, anhydrous acetonitrile and 17 beta estradiol mol ratios, ultrasonic mixing 5min under the normal temperature; Add trimethylol-propane trimethacrylate and azo dicyano valeric acid again, more than five kinds of material-methacrylic acids: anhydrous acetonitrile: estradiol: trimethylol-propane trimethacrylate: the mol ratio of azo dicyano valeric acid is 124:27:26:123:1, ultrasonic mixing 5min under the normal temperature, synthetic polymer.
CN 201110438850 2011-12-26 2011-12-26 17beta-estradiol molecular imprinted silver-doped TiO2 nanotube and preparation method thereof CN102553649B (en)

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CN103212410A (en) * 2013-04-19 2013-07-24 河海大学 Catalyst, preparation method of catalyst and water treatment device containing catalyst
CN104558409A (en) * 2013-10-22 2015-04-29 北京林业大学 Surface molecular imprinting polymer made from nanoflower material, and preparation and application of surface molecular imprinting polymer
CN104022295B (en) * 2014-05-07 2016-10-19 南通大学 A kind of DMFC PdAg/TiO2the preparation method of nanotube electrode
CN104037428B (en) * 2014-05-07 2017-02-15 南通大学 Direct methanol fuel cell with alloy-TiO2 nanotube/Ti anode and preparation method thereof
CN108855154A (en) * 2018-06-15 2018-11-23 云南民族大学 A kind of mesoporous carbon-TiO with excellent absorption and photocatalysis performance2(B)-BiOI material and preparation method thereof
CN108654652A (en) * 2018-06-15 2018-10-16 云南民族大学 A kind of TiO2 (B)-Bi5O7I photochemical catalysts and preparation method thereof

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