CN102553534B - 17 beta-estradiol molecular imprinting titanium dioxide (TiO2) nano tube and preparation method thereof - Google Patents
17 beta-estradiol molecular imprinting titanium dioxide (TiO2) nano tube and preparation method thereof Download PDFInfo
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- CN102553534B CN102553534B CN 201110438847 CN201110438847A CN102553534B CN 102553534 B CN102553534 B CN 102553534B CN 201110438847 CN201110438847 CN 201110438847 CN 201110438847 A CN201110438847 A CN 201110438847A CN 102553534 B CN102553534 B CN 102553534B
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Abstract
The invention provides a 17 beta-estradiol molecular imprinting titanium dioxide (TiO2) nano tube and a preparation method thereof. The TiO2 of molecular imprinting can perform selective adsorption and photocatalytic degradation on the 17 beta-estradiol in a water body. The molecular imprinting nano tube is formed by a TiO2 nano tube with holes at two ends and a molecular imprinting polymer, and the mass ratio of the TiO2 nano tube to the molecular imprinting polymer is 63 to 37. The molecular imprinting polymer is prepared by methacrylic acid, trimethylolpropane trimethyl acrylic ester and azo dicyano pentanoic acid according to the molar ratio of 124:123:1. Carbonyl function functional groups are imprinted on the molecular imprinting polymer. The diameter of the molecular imprinting TiO2 nano tube is 90nm, the length is 600nm, the porosity is 0.54cm3/g, and the specific surface area is 300m2/g. The molar ratio of functional monomer methyl acrylic to template molecule estradiol is 124 to 26. The invention further provides the preparation method and application of the 17 beta-estradiol molecular imprinting TiO2 nano tube. The 17 beta-estradiol molecular imprinting TiO2 nano tube is good in estradiol adsorption, has the degradation rate as high as 98%, and can play a positive role on improving sewage reuse water quality.
Description
Technical field
The present invention relates to a kind of photocatalytic nanometer pipe, especially relate to a kind of 17 beta-estradiol molecular engram TiO
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 water resources crisis, 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.In recent years, various emerging pollutants are constantly detected in reused sewage, have brought certain risk to reusing sewage.Wherein a kind ofly be referred to as estrogenic emerging pollutant and just causing widely and to pay close attention to.Estrogen is meant and disturbs 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 extensively is present in the sewage disposal and the active high estrogen of estrogen active and cause the extensive concern of educational circles as a kind of.
At present, utilize TiO
2More and more as the make a return journey research of the incretion interferent in dewatering of catalysis material.Discover TiO
2Characteristics such as nontoxic, environmentally friendly and cheap are arranged, great potential is all arranged in the purified treatment of water body.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 estrogen 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 its removal effect to target contaminant greatly, and this has also influenced its scope of application as a kind of new catalytic material greatly.So at TiO
2Caused more and more scholars' concern in improvement to estrogenic efficient absorption and selectivity degraded.
Summary of the invention
The objective of the invention is to common TiO
2Material makes improvements, and makes it to improve the removal effect to estradiol.
A kind of TiO of 17 beta-estradiol molecular engrams is provided
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 and with its degraded.
A kind of 17 beta-estradiol molecular engram TiO
2Nanotube is characterized in that it is TiO by the two ends perforate
2Nanotube and molecularly imprinted polymer are pressed mass ratio 63:37 and are formed, wherein said molecularly imprinted polymer by methacrylic acid, trimethylol-propane trimethacrylate and azo dicyano valeric acid in molar ratio 124:123:1 form, trace has carbonyl function functional group on this external molecularly imprinted polymer, and the mol ratio of function monomer methacrylic acid and template molecule 17 beta estradiols is 124:26.Described 17 beta-estradiol molecular engram TiO
2The nanotube caliber is 90nm, and pipe range is 600nm, and porosity is 0.54cm
3/ g, specific area is 300m
2/ g.
The TiO of described 17 beta-estradiol molecular engrams
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 after above-mentioned processing, the nickel plate is made negative electrode, and bath composition is an 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, reaction time is 60min, and anode voltage is 20V;
(3) the titanium plate that reaction obtains through step (2) cleans with distilled water, places air drying;
(4) dried titanium plate is put into tube type resistance furnace and calcine, 500 ℃ of calcining heats, 2 ℃ of min of cooling rate at air
-1-, calcination time 90min generates TiO
2Nanotube;
(5) 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, above-mentioned methacrylic acid: anhydrous acetonitrile: 17 beta estradiols: 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;
(6) above-mentioned synthetic polymer evenly is applied in the TiO that step (4) generates
2Nanotube surface is put into quartz ampoule then, drives away the oxygen in the quartz ampoule, the sealing bottleneck;
(7) with the quartz ampoule of its sealing ultraviolet lighting 12h as for 352nm, in the process of illumination, the temperature of cooling water remains on 4 ℃;
(8) 17 beta estradiol TiO after the mixed liquid dipping step (7) of 9:1 is handled by volume with methyl alcohol and acetate
2Nanotube 4 times;
(9) with the TiO of step (8)
2Nanotube soak 24h with methyl alcohol, dry under 45 degree, anhydrous acetonitrile and 17 beta estradiols through on above-mentioned (8), (9) two the step flush away polymer finally obtain 17 beta-estradiol molecular engram TiO
2Nanotube.
The present invention 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 raising can reach 98% to the degradation rate of this polluter.
2. the new Ti O of 17 beta-estradiol molecular engrams
2Nanotube has making can be repeated, and life cycle is long, and is easy to clean, advantage such as can produce by batch.
3. the TiO of 17 beta-estradiol molecular engrams
2Nanotube can be accelerated the removal speed of 17 beta estradiols and strengthen removal effect, and removal effect doubles than common nanotube, and the improvement of water quality is had important function.
Description of drawings
Fig. 1 is the TiO of 17 beta-estradiol molecular engrams
2The cross sectional representation of nanotube.
Fig. 2 is the TiO of 17 beta-estradiol molecular engrams
2The vertical face structure ESEM schematic diagram of nanotube, multiplication factor is 20000 times.
Fig. 3 is the TiO of 17 beta-estradiol molecular engrams
2The planar structure ESEM schematic diagram of nanotube, multiplication factor is 20000 times.
Reference numeral: 1 is molecularly imprinted polymer between pipe among Fig. 1, and 2 is TiO
2Nanotube, 3 is function functional group.
The specific embodiment
Embodiment, a kind of 17 beta-estradiol molecular engram TiO
2Nanotube is characterized in that it is TiO by the two ends perforate
2Nanotube and molecularly imprinted polymer two parts are pressed mass ratio 63:37 and are formed, wherein said molecularly imprinted polymer by methacrylic acid, trimethylol-propane trimethacrylate and azo dicyano valeric acid in molar ratio 124:123:1 form, trace has carbonyl function functional group on this external molecularly imprinted polymer, the mol ratio of function monomer methacrylic acid and template molecule 17 beta estradiols is 124:26, described 17 beta-estradiol molecular engram TiO
2The nanotube caliber is 90nm, and pipe range is 600nm, and porosity is 0.54cm
3/ g, specific area is 300m
2/ g.
This example is to use the new Ti O of 17 beta-estradiol molecular engrams
2Nanotube removes that 17 beta estradiol concentration are the sewage of 25 μ g/L in the municipal sewage plant, at a 24W(dominant wavelength 365mm) under the ultra violet lamp, with the new Ti O of 17 beta-estradiol molecular engrams
2Nanotube is put into this sewage, and the catalyst use amount is 40cm
2/ L, the clearance to 17 beta estradiols behind the 20min is 98%, and does not have the general T iO of molecular engram
2The degradation rate of nanotube is 50%, this shows the new Ti O of 17 beta-estradiol molecular engrams
2Nanotube has huge lifting to the removal effect of 17 beta estradiols.
The TiO of described 17 beta-estradiol molecular engrams
2The preparation method of nanotube 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 then and clean 15min at ultrasonic (15KHz), ultrasonic in the acetone (15KHz) cleans 15min, uses distilled water ultrasonic (15KHz) to clean 15min again, places air drying;
(2) the electrochemistry experiment anode is the titanium plate after above-mentioned processing, the nickel plate is made negative electrode, and bath composition is an 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, reaction time is 60min, and anode voltage is 20V;
(3) the titanium plate that reaction obtains through step (2) cleans with distilled water, places air drying;
(4) dried titanium plate is put into tube type resistance furnace and calcine, 500 ℃ of calcining heats, 2 ℃ of min of cooling rate at air
-1-, calcination time 90min generates TiO
2Nanotube;
(5) 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, above-mentioned methacrylic acid: anhydrous acetonitrile: 17 beta estradiols: 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;
(6) above-mentioned synthetic polymer evenly is applied in the TiO that step (4) generates
2Nanotube surface is put into quartz ampoule then, drives away the oxygen in the quartz ampoule, the sealing bottleneck;
(7) with the quartz ampoule of its sealing ultraviolet lighting 12h as for 352nm, in the process of illumination, the temperature of cooling water remains on 4 ℃;
(8) 17 beta estradiol TiO after the mixed liquid dipping step (7) of 9:1 is handled by volume with methyl alcohol and acetate
2Nanotube 4 times;
(9) with the TiO of step (8)
2Nanotube soak 24h with methyl alcohol, dry under 45 degree, anhydrous acetonitrile and 17 beta estradiols through on above-mentioned (8), (9) two the step flush away polymer finally obtain 17 beta-estradiol molecular engram TiO
2Nanotube.
Claims (2)
1. beta-estradiol molecular engram TiO
2Nanotube is characterized in that it is TiO by the two ends perforate
2Nanotube and molecularly imprinted polymer two parts are made by mass ratio 63:37, wherein said molecularly imprinted polymer by methacrylic acid, trimethylol-propane trimethacrylate and azo dicyano valeric acid in molar ratio 124:123:1 form, trace has carbonyl function functional group on this external molecularly imprinted polymer, the mol ratio of function monomer methacrylic acid and template molecule 17 beta estradiols is 124:26, described 17 beta-estradiol molecular engram TiO
2The nanotube caliber is 90nm, and pipe range is 600nm, and porosity is 0.54cm
3/ g, specific area is 300m
2/ g.
2. one kind prepares the described 17 beta-estradiol molecular engram TiO of claim 1
2The 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 after above-mentioned processing, the nickel plate is made negative electrode, and bath composition is an 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, reaction time is 60min, and anode voltage is 20V;
(3) the titanium plate that reaction obtains through step (2) cleans with distilled water, places air drying;
(4) dried titanium plate is put into tube type resistance furnace and calcine, 500 ℃ of calcining heats, 2 ℃ of min of cooling rate at air
-1-, calcination time 90min generates TiO
2Nanotube;
(5) 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, above-mentioned methacrylic acid: anhydrous acetonitrile: 17 beta estradiols: 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;
(6) above-mentioned synthetic polymer evenly is applied in the TiO that step (4) generates
2Nanotube surface is put into quartz ampoule then, drives away the oxygen in the quartz ampoule, the sealing bottleneck;
(7) quartz ampoule of its sealing is placed the ultraviolet lighting 12h of 352nm, in the process of illumination, the temperature of cooling water remains on 4 ℃;
(8) 17 beta estradiol TiO after the mixed liquid dipping step (7) of 9:1 is handled by volume with methyl alcohol and acetate
2Nanotube 4 times;
(9) with the TiO of step (8)
2Nanotube soaks 24h with methyl alcohol, and dry under 45 degree, anhydrous acetonitrile and 17 beta estradiols through on above-mentioned steps (8) the flush away polymer finally obtain 17 beta-estradiol molecular engram TiO
2Nanotube.
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| CN110523398B (en) * | 2019-09-11 | 2021-08-06 | 山东大学 | Carbon nano-sheet layer loaded TiO2Molecularly imprinted material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607736A (en) * | 2009-04-22 | 2009-12-23 | 湖南大学 | A kind of surface imprinting functionalization TiO 2Nanotube |
| CN102280269A (en) * | 2011-07-07 | 2011-12-14 | 西北工业大学 | TiO2 nanotube array photoanode and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101607736A (en) * | 2009-04-22 | 2009-12-23 | 湖南大学 | A kind of surface imprinting functionalization TiO 2Nanotube |
| CN102280269A (en) * | 2011-07-07 | 2011-12-14 | 西北工业大学 | TiO2 nanotube array photoanode and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| TiO2光催化降解水中内分泌干扰物17β-雌二醇;李青松等;《环境科学》;20070115;第28卷(第1期);第120-125页 * |
| 李青松等.TiO2光催化降解水中内分泌干扰物17β-雌二醇.《环境科学》.2007,第28卷(第1期),第120-125页. |
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