CN102631951A - Method for preparing organic-inorganic hybrid nano-titania hollow ball with high catalytic performance - Google Patents

Method for preparing organic-inorganic hybrid nano-titania hollow ball with high catalytic performance Download PDF

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CN102631951A
CN102631951A CN201210101685XA CN201210101685A CN102631951A CN 102631951 A CN102631951 A CN 102631951A CN 201210101685X A CN201210101685X A CN 201210101685XA CN 201210101685 A CN201210101685 A CN 201210101685A CN 102631951 A CN102631951 A CN 102631951A
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hollow ball
pdma
peo
polymer
organic
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CN102631951B (en
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杜建忠
肖杰
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Tongji University
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Tongji University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention belongs to the technical field of materials, and particularly relates to a method for preparing an organic-inorganic hybrid nano-titania hollow ball with a high catalytic performance. Amphiphilic triblock polymer PEO-b-PDMA-b-PS is obtained by means of atom transfer radical polymerization, polymersomes with uniformly distributed particle sizes are formed by means of macromolecular self-assembly, a settled titanium source is in in-situ sol-gel reaction on the polymersomes, and the organic-inorganic hybrid nano-titania hollow ball is obtained after drying. By the aid of the method, the organic-inorganic hybrid nano-titania hollow ball with the high catalytic performance can be prepared, and the particle sizes of nano-particles can be controlled by means of controlling environmental potential of hydrogen and polymerization of chain segments of the polymer. Moreover, equipment used in the method is simple, the method is fine in technical repeatability, high in controllability and low in cost, and the hollow ball has fine dispersibility in water and can be widely applied to the fields of photocatalytic degradation, solar cells and the like.

Description

A kind of preparation has the method for the organic-inorganic hybrid nanometer titanium dioxide hollow ball of efficient catalytic performance
Technical field
The present invention relates to the method that a kind of preparation has the organic-inorganic hybrid nanometer titanium dioxide hollow ball of efficient catalytic performance.
Background technology
Along with modern society environment pollute serious day by day, particularly the use of the increasing of white garbage, resident's house decorative material and various indoor chemical substances makes environmental quality reduce greatly.The up-to-date report that the Organization of Economy and Cooperation Development announces is claimed, the protection environment if people do not take immediate steps, and environmental pollution will become the maximum killer who causes the mankind early dead.Estimate,, will have 3,600,000 people to die from environmental pollution to the year two thousand fifty.
Titanium dioxide is a kind of novel photocatalysis agent, UV resistant agent as a kind of nontoxic material, causes more and more scientists' concern in recent years.Titanium dioxide not only can be carbon dioxide and water etc. with the organic matter degradation in the waste water waste material; Utilize its strong redox ability can also some harmful substance in the sewage be degraded to innocuous substance; Also have the catalytic degradation white garbage, absorb ultraviolet effect, therefore can be used for curbing environmental pollution.The photocatalytic effect of titania nanoparticles has very big getting in touch with factors such as the dispersive property in water, specific area, size and the uniformitys.And the titanium dioxide hollow ball of organic inorganic hybridization, its high specific area makes it have better photocatalysis performance, thereby obtains research more extensively and profoundly.
Organic inorganic hybridization titanium dioxide is a kind of functional composite material, compares with single organic or inorganic material, and this composite shows better physical and chemical performance.The good combination of organic principle and inorganic constituents make the titanium dioxide of hydridization have better photocatalysis performance, and its structure is more stable.
Polymer vesicle is the nano-hollow ball that is obtained by amphipathic nature polyalcohol self assembly under certain condition; Wherein hydrophilic segment constitutes the shell and the inner casing of vesica; Hydrophobic segment constitutes the double membrane structure of vesica; This polymer vesicle Stability Analysis of Structures, and can realize controllable size, therefore all have the application prospect of very wide model in a lot of fields; Like pharmaceutical carrier, genophore, biomineralization template, microreactor, biological support etc., can also be used as the template of preparation organic-inorganic nano hollow ball.
The innovative point of present technique invention is to utilize the polymer template reaction in-situ to make the titanium dioxide hollow ball of organic inorganic hybridization, and its catalytic efficiency is high, and particle diameter is evenly distributed, controllable size, and method is simple.
Summary of the invention
The purpose of this invention is to provide a kind of preparation simply and easily and have the method for the organic-inorganic hybrid nanometer titanium dioxide hollow ball of efficient catalytic performance.
The preparation that the present invention proposes has the method for the organic-inorganic hybrid nanometer titanium dioxide hollow ball of efficient catalytic performance; Be to utilize polymer template to prepare the organic-inorganic hybrid nanometer titanium dioxide hollow ball, carry out ATRP (ATRP) with bromo polyoxyethylene (PEO-Br), dimethylaminoethyl methacrylate (DMA) and styrene (Styrene) and obtain amphipathic PEO- b-PDMA- b-PS triblock copolymer forms particle diameter homogeneous polymer vesica through big molecule self assembly with this polymer self assembly.The titanium source is dissolved in certain solvent, dropwise splashes in the polymer vesicle solution, promptly obtain the titanium dioxide hollow ball of organic inorganic hybridization after stirring a period of time.
The method of the organic-inorganic hybrid nanometer titanium dioxide hollow ball that the present invention proposes with efficient catalytic performance, concrete steps are following:
(1) the synthetic PEO-of ATRP b-PDMA- b-PS triblock polymer, segment repeats single
Unit is respectively PDMA:10 ~ 40; PS:50 ~ 250 are with gained PEO- b-PDMA- b-PS triblock polymer is dissolved among the good solvent A, control PEO- b-PDMA- b-PS triblock polymer concentration is 1 ~ 50mg/mL, drips poor solvent B then and carries out self assembly and obtain polymer vesicle, control PEO- b-PDMA- b-PS triblock polymer concentration is 0.1 ~ 10mg/mL;
(2) back is diluted in the titanium source in solvent C and dropwise splash in the good polymer vesicle solution of self assembly the solgel reaction of the last tertiary amine functional catalysis titanium that has of PDMA with dimethylaminoethyl methacrylate; The PS segment is used for enough loading titaniums source.Wherein: the mol ratio of titanium source and dimethylaminoethyl methacrylate is (0.5 ~ 10.0): 1;
(3), promptly get the titanium dioxide hollow ball of organic inorganic hybridization with step (2) products therefrom drying.
Among the present invention, the good solvent A of the triblock polymer of the self assembly described in the step (1) is one or more in oxolane, carrene, dimethyl formamide (DMF), chloroform or the methyl-sulfoxide; Poor solvent B is one or more in water, acetone, methyl alcohol, ethanol, glycerine or the butanols.
Among the present invention, employed solvent C is to be in oxolane, methyl alcohol, ethanol, glycerine or the butanols one or more in the step (2).
Among the present invention, the titanium source described in the step (2) is a kind of in butyl titanate, tetraethyl titanate, titanium tetrachloride or the metatitanic acid methyl esters.
The vesica particle diameter that the polymer that utilizes the inventive method to make is assembled is 100～500nm, and the particle diameter of the organic inorganic hybridization titanium dioxide hollow ball that makes is 100 ~ 500nm.The degradation rate of the titanium dioxide hollow ball of hydridization in 1 hour is 90%.
Among the present invention, said amphipathic triblock polymer PEO- b-PDMA- bThe synthetic method of-PS; Be specially: macromole evocating agent PEO-Br, polymerisation catalysts, catalyst ligand and monomer Dimethylaminoethyl Methacrylate (DMA) are with 1:1: (1～5): the mol ratio of (15～150) joins in the round-bottomed flask; Add 1 ~ 100mL solvent methanol, polymerization temperature is 20～100 ℃, reacts after 1～100 hour; Styrene is dissolved in 4 ~ 40mL paraxylene; Join after the degassing and continue reaction in the round-bottomed flask, polymerization temperature is 30～120 ℃, and the time is 12～72 hours; The polymer that makes is revolved steaming, dissolving, peroxidating aluminium pillar, deposition, filtration, vacuum drying, obtain triblock polymer PEO- b-PDMA- b-PS; Wherein: the mol ratio of styrene and PEO-Br is (20 ~ 200): 1.
Among the present invention, said catalyst is cuprous bromide or stannous chloride, and said catalyst ligand is PMDETA or bipyridyl.
With respect to scheme of the prior art, advantage of the present invention is:
1) the triblock polymer PEO-that synthesizes b-PDMA- bAmong-the PS, PDMA has the pH response, can regulate the size of controlling polymer vesicle through the pH of environment;
2) the polymer self-assembling technique can access the uniform vesica of particle diameter, and particle diameter distributes and size thereby can effectively control;
3) pass through control vesica size, thereby obtain the hydridization titanium dioxide hollow ball that is evenly distributed of a series of different-grain diameters;
4) catalytic efficiency is high, and dispersive property is good in water, and the preparation method is simple, and the scope of application is wider.
Description of drawings
Fig. 1 is the transmission electron microscope photo of organic inorganic hybridization titanium dioxide hollow ball.Wherein: (a) be nanometer titanium dioxide hybrid material hollow ball under the low range, (b) be the nanometer titanium dioxide hybrid material hollow ball under the high magnification.
Fig. 2 is the degradation rate figure of organic inorganic hybridization titanium dioxide hollow ball degraded rhodamine B.
The specific embodiment
Further specify the present invention through embodiment below.
Embodiment 1
1) amphipathic triblock polymer PEO- b-PDMA- b-PS's is synthetic
With the polyoxyethylene after the 0.500g bromination (PEO-Br) is macromole evocating agent; Catalyst cuprous bromide (CuBr) with 0.036g; 0.044g part PMDETA; 1.580g monomer Dimethylaminoethyl Methacrylate (DMA) and 3mL methanol solvate join in the round-bottomed flask of 50 mL, carry out ATRP (ATRP), temperature 30 oC reacts and after 6 hours 5.430g styrene is dissolved in the 7mL paraxylene, joins to continue reaction 24 hours in the reaction flask, through obtaining amphipathic triblock polymer PEO after the post processing 43- b-PDMA 40- b-PS 200
2) the polymer self assembly forms vesica
Polymer dissolution is prepared the solution of 2mg/mL in oxolane (THF), the speed with 10d/min under stirring condition drips 2 times of methyl alcohol to the oxolane volume in tetrahydrofuran solution, stirred 1 ~ 24 hour, obtains light blue solution.
3) polymer vesicle surface deposition titanium source
Use butyl titanate to be the titanium source, with the concentration of 10mg/mL butyl titanate (TBT) is dissolved in the ethanol, TBT and DMA splash in the solution of polymer vesicle with the mol ratio of 2.0:1, and vigorous stirring obtains nattier blue solution after a period of time.
4) drying obtains the titanium dioxide hollow ball of organic inorganic hybridization
Promptly get the titanium dioxide hollow ball of organic inorganic hybridization after the vesica solution decompression drying with the organic inorganic hybridization that obtains.
As shown in Figure 1, the nano titanium oxide hollow ball structure of organic inorganic hybridization is clear, and grain size is its particle diameter evenly, is approximately 100 ~ 500nm.
As shown in Figure 2, the nano titanium oxide hollow ball of organic inorganic hybridization 90% the rhodamine B of in 1 hour, having degraded.
Embodiment 2
1) amphipathic triblock polymer PEO- b-PDMA- b-PS's is synthetic
0.500g macromole evocating agent PEO 43-Br; 0.036g catalyst cuprous bromide (CuBr), the part PMDETA of 0.044g, monomer Dimethylaminoethyl Methacrylate (DMA) and the 3mL methanol solvate of 1.180g join in the round-bottomed flask of 50mL; Carry out ATRP (ATRP), temperature 30 oC reacts and after 6 hours 3.900g styrene is dissolved in the 6mL paraxylene, joins to continue reaction 24 hours in the reaction flask, obtains block polymer PEO after the post processing 43- b-PDMA 30- b-PS 150
2) the polymer self assembly forms vesica
Polymer dissolution is prepared the solution of 5mg/mL in carrene, the speed with 10d/min under stirring condition drips 4 times to the ethanol of methylene chloride volume in above-mentioned solution, stir and obtain light blue solution after 24 hours.
3) polymer vesicle surface deposition titanium source
Use tetraethyl titanate to be the titanium source, with the concentration of 10mg/mL tetraethyl titanate is dissolved in the glycerine, tetraethyl titanate and DMA splash in the solution of vesica with the mol ratio of 1.0:1, and vigorous stirring is light blue constant after 24 hours.
4) drying obtains the nano titanium oxide hollow ball of organic inorganic hybridization
Promptly get the nano titanium oxide hollow ball of organic inorganic hybridization after the particle solution drying with the organic inorganic hybridization that obtains.
Embodiment 3
1) amphipathic triblock polymer PEO- b-PDMA- b-PS's is synthetic
With the polyoxyethylene after the 0.500g bromination (PEO-Br) is macromole evocating agent; 0.036g catalyst cuprous bromide (CuBr); 0.044g part PMDETA; 0.790g monomer Dimethylaminoethyl Methacrylate (DMA) and 2mL methanol solvate join in the round-bottomed flask of 50mL, carry out ATRP (ATRP), temperature 30 oC reacts and after 6 hours 3.900g styrene is dissolved in the 6mL paraxylene, removes to join behind the oxygen and continues reaction 24 hours in the reaction flask.After a series of post processings, obtain block polymer PEO 43- b-PDMA 20- b-PS 150
2) the polymer self assembly forms vesica
Polymer dissolution is prepared the solution of 2mg/mL in oxolane (THF), the speed with 10d/min under stirring condition drips 1 times to the methyl alcohol of THF volume in THF solution, stir and obtain light blue solution after 1 ~ 24 hour.
3) polymer vesicle surface deposition titanium source
With the butyl titanate is the titanium source, with the concentration of 20mg/mL butyl titanate (TBT) is dissolved in the ethanol, and TBT and DMA splash in the solution of vesica with the mol ratio of 5:1, and behind vigorous stirring 1 ~ 24h, light blue constant.
4) drying obtains the titanium dioxide hollow ball of organic inorganic hybridization
Promptly get the titanium dioxide hollow ball of organic inorganic hybridization after the vesica solution spray drying with the organic inorganic hybridization that obtains.
Above-mentioned instance only is explanation technical conceive of the present invention and characteristics, and its purpose is to let the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.

Claims (7)

1. method with organic-inorganic hybrid nanometer titanium dioxide hollow ball of efficient catalytic performance is characterized in that concrete steps are following:
(1) the synthetic PEO-of ATRP b-PDMA- b-PS triblock polymer, segment repeats single
Unit is respectively PDMA:10 ~ 40; PS:50 ~ 250 are with gained PEO- b-PDMA- b-PS triblock polymer is dissolved among the good solvent A, control PEO- b-PDMA- b-PS triblock polymer concentration is 1 ~ 50mg/mL, drips poor solvent B then and carries out self assembly and obtain polymer vesicle, control PEO- b-PDMA- b-PS triblock polymer concentration is 0.1 ~ 10mg/mL;
(2) back is diluted in the titanium source in solvent C and dropwise splash in the good polymer vesicle solution of self assembly the solgel reaction of the last tertiary amine functional catalysis titanium that has of PDMA with dimethylaminoethyl methacrylate; The PS segment is used for enough loading titaniums source; Wherein: the mol ratio of titanium source and dimethylaminoethyl methacrylate is (0.5 ~ 10.0): 1;
(3), promptly get the titanium dioxide hollow ball of organic inorganic hybridization with step (2) products therefrom drying.
2. method according to claim 1, the good solvent A that it is characterized in that the triblock polymer of the self assembly described in the step (1) is one or more in oxolane, carrene, dimethyl formamide, chloroform or the methyl-sulfoxide; Poor solvent B is one or more in water, acetone, methyl alcohol, ethanol, glycerine or the butanols.
3. method according to claim 1 is characterized in that employed solvent C in the step (2) is to be in oxolane, methyl alcohol, ethanol, glycerine or the butanols one or more.
4. method according to claim 1 is characterized in that the titanium source described in the step (2) is a kind of in butyl titanate, tetraethyl titanate, titanium tetrachloride or the metatitanic acid methyl esters.
5. method according to claim 1 is characterized in that the vesica particle diameter of prepared polymer assembling is 100～500nm, and the particle diameter of the organic inorganic hybridization titanium dioxide hollow ball that makes is 100 ~ 500nm; The degradation rate of the titanium dioxide hollow ball of hydridization in 1 hour is 90%.
6. method according to claim 1 is characterized in that amphipathic triblock polymer PEO-described in the step (1) b-PDMA- bThe synthetic method of-PS is specially: macromole evocating agent PEO-Br, catalyst, catalyst ligand and monomer Dimethylaminoethyl Methacrylate are with 1:1: (1～5): the mol ratio of (15～150) joins in the round-bottomed flask, adds 1 ~ 100mL solvent methanol; Polymerization temperature is 20～100 ℃; React after 1～100 hour, styrene is dissolved in 4 ~ 40mL paraxylene, join after the degassing and continue reaction in the round-bottomed flask; Polymerization temperature is 30～120 ℃, and the time is 12～72 hours; The polymer that makes is revolved steaming, dissolving, peroxidating aluminium pillar, deposition, filtration, vacuum drying, obtain triblock polymer PEO- b-PDMA- b-PS; Wherein: the mol ratio of styrene and PEO-Br is (20 ~ 200): 1.
7. method according to claim 6 is characterized in that said catalyst is cuprous bromide or stannous chloride, and said catalyst ligand is PMDETA or bipyridyl.
CN201210101685XA 2012-04-10 2012-04-10 Method for preparing organic-inorganic hybrid nano-titania hollow ball with high catalytic performance Expired - Fee Related CN102631951B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103948546A (en) * 2014-04-14 2014-07-30 同济大学 Method for preparing antioxidant coated polymer nano-vesicle
CN105268477A (en) * 2014-07-23 2016-01-27 中国科学院大连化学物理研究所 Preparation method of macrocyclic compound nano hollow balls
CN107349967A (en) * 2017-09-06 2017-11-17 张永霞 A kind of preparation method of the organic titanium dioxide hollow ball of photocatalysis
CN105268477B (en) * 2014-07-23 2018-08-31 中国科学院大连化学物理研究所 A kind of preparation method of macrocyclic compound nano-hollow ball
CN110950379A (en) * 2019-12-13 2020-04-03 陕西师范大学 Preparation method of titanium dioxide vesicle material with ultrathin shell layer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0376819A (en) * 1989-08-11 1991-04-02 Nippon Soda Co Ltd Production of tio2 hollow fiber
CN101580275A (en) * 2008-05-15 2009-11-18 中国科学院过程工程研究所 Method for preparing titanium dioxide hollow spherical powder
CN102267719A (en) * 2010-06-04 2011-12-07 中国科学院化学研究所 Simple method for preparing titanium dioxide multi-shell hollow spheres and sphere-in-sphere structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0376819A (en) * 1989-08-11 1991-04-02 Nippon Soda Co Ltd Production of tio2 hollow fiber
CN101580275A (en) * 2008-05-15 2009-11-18 中国科学院过程工程研究所 Method for preparing titanium dioxide hollow spherical powder
CN102267719A (en) * 2010-06-04 2011-12-07 中国科学院化学研究所 Simple method for preparing titanium dioxide multi-shell hollow spheres and sphere-in-sphere structure

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103948546A (en) * 2014-04-14 2014-07-30 同济大学 Method for preparing antioxidant coated polymer nano-vesicle
CN103948546B (en) * 2014-04-14 2016-04-06 同济大学 A kind of preparation method of polymer nano vesicle of coated antioxidant
CN105268477A (en) * 2014-07-23 2016-01-27 中国科学院大连化学物理研究所 Preparation method of macrocyclic compound nano hollow balls
CN105268477B (en) * 2014-07-23 2018-08-31 中国科学院大连化学物理研究所 A kind of preparation method of macrocyclic compound nano-hollow ball
CN107349967A (en) * 2017-09-06 2017-11-17 张永霞 A kind of preparation method of the organic titanium dioxide hollow ball of photocatalysis
CN110950379A (en) * 2019-12-13 2020-04-03 陕西师范大学 Preparation method of titanium dioxide vesicle material with ultrathin shell layer

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