CN102502484A - Modified titanium dioxide nano particle nanotube and preparation method thereof - Google Patents
Modified titanium dioxide nano particle nanotube and preparation method thereof Download PDFInfo
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Abstract
The invention provides a method for preparing a modified titanium dioxide nano particle nanotube. The method is characterized by comprising the following steps of: providing titanium dioxide nano sol; with chloroauric acid as a raw material, thiol as a surfactant and tetraoctyl ammonium bromide as a phase transfer agent, undergoing a reduction reaction under the action of thiol carboxylic acid and sodium borohydride so as to obtain modified golden nano sol; dispersing the modified golden nano sol and the titanium dioxide nano sol in an organic solvent respectively and then mixing to obtain titanium dioxide sol modified by the golden nano sol; and dropwise adding the titanium dioxide sol modified by the golden nano sol on the surface of an anodic aluminum oxide film, performing vacuum filtration, drying, calcining the composite anodic aluminum oxide film, removing the anodic aluminum oxide film, washing, and performing centrifugal separation to obtain the modified titanium dioxide nano particle nanotube. The modified titanium dioxide nano particle nanotube has a novel and stable structure, high specific surface area and excellent nano particle activity and is easily recovered and repeatedly used.
Description
Technical field
The present invention relates to the inorganic composite materials preparation field, be specifically related to a kind of modifying titanium dioxide nano particle nanotube and preparation method thereof.
Background technology
Titanium dioxide nano sol and golden nanometer particle; Has good multiple sensitiveness; In fields such as chemical industry, medicine, machinery, catalysis, molecular biology, biology sensor, application is arranged all; And along with development of science and technology, titanium dioxide nano sol and gold nano colloidal sol will be applied to more areas.Titanium dioxide nano sol can be used for fields such as sewage disposal, air cleaning processing, product surface antibacterial treatment, coating film on glass processing.
The preparation method of titanium dioxide nano sol of the prior art is: metatitanic acid orthocarbonate (titanium is n-propoxide abbreviation TTIP (iv)) is dispersed in the oil phase of toluene or cyclohexane formation; Tert-butylamine (tert-butylamine) is dispersed in the water; Oil phase and water are added in the same hydrothermal reaction kettle, react 4h down at 180 ℃.Add factors such as volume through adjusting reaction time, reaction temperature and tert-butylamine, can control the size of titanium dioxide nano sol.After hydro-thermal reaction finished, titanium dioxide nano sol need pass through the deposition of methyl alcohol and the dispersion again of organic solvent.
The special construction of nano particle nanotube has its unique advantages, and the reunion that effectively overcomes nano particle reduces the shortcoming of reactivity, its tubular construction, and the active sites of surfaces externally and internally also significantly increases, thereby improves reactivity worth.The nano particle by relative dispersion of nano particle nanotube is formed, and is convenient to Separation of Solid and Liquid, recycle, thereby the utilization efficiency of material that improves has reduced maintenance cost.In the nano particle nano tube structure; Existing more senior structure is the nano particle nanotube; The nano particle conduct is module units independently, still possesses its unique activity, and the tube wall of nano particle nanotube is a loose structure; Further improve the active sites of material, improved the performance of material.The nano particle nanotube of a kind of nano particle preparation is widely used, but prior art is inhomogeneous with the nano particle nanotube surface hole that golden nanometer particle and titanium dioxide nano-particle are mixed with, can't commercialization.
Summary of the invention
The technical problem that the present invention will solve is to provide a kind of surface pore even, the modifying titanium dioxide nano particle nanotube that nano particle is not reunited
In order to solve above technical problem, the invention provides the preparation method that a kind of modifying titanium dioxide nano particle nanotube is provided, comprising:
Titanium dioxide nano sol is provided;
Be raw material with the gold chloride, be surfactant with mercaptan, be consisting of phase-transferring agent, the reduction reaction takes place under mercaptan carboxylic acid and sodium borohydride effect, obtain modification gold nano colloidal sol with four octyl group ammonium bromides;
Said modification gold nano colloidal sol is dispersed in respectively in the organic solvent with said titanium dioxide nano sol will mixes again, obtain with the sol-gel modified TiO 2 sol of gold nano;
Be added drop-wise to the anodic alumina films surface with said with the sol-gel modified TiO 2 sol of gold nano, and carry out vacuum filtration, drying; With compound anodic alumina films calcining; Remove said anodic alumina films, after washing, the centrifugation, obtain modifying titanium dioxide nano particle nanotube.
Preferably, said mercaptan carboxylic acid is selected from: TGA, 3-mercaptopropionic acid, 3-sulfydryl butyric acid.
Preferably, said mercaptan carboxylic acid and gold chloride are (1～4) in molar ratio: (1～4).
Preferably, the particle diameter of the golden nanometer particle in said mercaptan carboxylic acid's content and the gold nano colloidal sol is inversely proportional to.
Preferably, the said titanium dioxide nano sol that provides is specially:
Metatitanic acid orthocarbonate and oleic acid are blended in the organic solvent, obtain first solution;
Tert-butylamine is blended in the water, obtains second solution;
Said first solution and said second solution are blended in 150～200 ℃ of generation reduction reactions down, obtain titanium dioxide nano sol.
Preferably, said organic solvent is toluene or cyclohexane.
Preferably, the general formula of said mercaptan is SR, and wherein R is the alkyl of even numbers in 4～20 for the carbon atom number.
Preferably, in the said composite, titanium dioxide nano sol, gold nano colloidal sol are (0.3～0.1) in molar ratio: (0.1～1).
The present invention also provides a kind of modifying titanium dioxide nano particle nanotube, is formed by modifying titanium dioxide Nano sol particle, and said modifying titanium dioxide Nano sol particle comprises titanium dioxide nano-particle, mercaptan carboxylic acid, golden nanometer particle.
Preferably, it is characterized in that in the said carbon nano-particles nanotube, titanium dioxide nano sol, gold nano colloidal sol are (0.3～0.1) in molar ratio: (0.1～1).
The invention provides a kind of preparation method of modifying titanium dioxide nano particle nanotube; Use gold nano colloidal sol to mix with existing titanium dioxide nano sol earlier, in preparation gold nano colloidal sol, used the mercaptan carboxylic acid as modifier, the sulfydryl among the mercaptan carboxylic acid has the effect of ADSORPTION OF GOLD nano particle; Carboxyl has the effect that is prone to the absorption titanium dioxide nano-particle; So, interact each other as the better electric charge between balance golden nanometer particle and the titanium dioxide nano-particle of modifier with the mercaptan carboxylic acid, make and form uniform charge field between each particle in the colloidal sol; Keep disperseing uniformly; Thereby make the titanium dioxide nano sol particle diameter after the said modification more even, also can not reunite chemistry and Heat stability is good after receiving environmental stimuli.
Titanium dioxide nano sol with modification drips on anodic alumina films then, carries out vacuum filtration then, calcining; Remove anodic alumina films; Obtain modifying titanium dioxide nano particle nanotube, said modifying titanium dioxide nano particle nanotube has increased the specific area of modifying titanium dioxide nano particle, and novel structure is stable; Nano particle is active high, is prone to reclaim and reuse.The preparation method is convenient and swift, is fit to large-scale industrial production.
Description of drawings
The modifying titanium dioxide nano particle nanotube transmission electron microscope picture that Fig. 1 embodiment of the invention 1 provides;
The modifying titanium dioxide nano particle nanotube transmission electron microscope picture that Fig. 2 embodiment of the invention 2 provides.
The specific embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that these just restriction for further specifying feature and advantage of the present invention rather than patent of the present invention being required is described.
The invention provides a kind of modifying titanium dioxide nano particle nanotube, formed by modifying titanium dioxide Nano sol particle, it is characterized in that, said modifying titanium dioxide Nano sol particle comprises titanium dioxide nano-particle, mercaptan carboxylic acid, golden nanometer particle.
The invention provides a kind of modifying titanium dioxide nano particle nanotube; At first gold nano colloidal sol and TiO 2 sol are mixed with the modifying titanium dioxide Nano sol; Also can regard the composite of a kind of titanium dioxide nano sol and gold nano colloidal sol as; But the gold nano colloidal sol for preparing in the prior art joins and can't play control titanium dioxide nano sol particle diameter in the titanium dioxide nano sol, improves titanium dioxide nano sol stability, prevent the effect of reuniting, so the inventor considers in preparation gold nano colloidal sol, to add cosurfactant; The group that had both had ability ADSORPTION OF GOLD nano particle in the said cosurfactant; Have the group of absorption titanium dioxide nano-particle again, can increase the binding force of golden nanometer particle said titanium dioxide nano-particle, and charge balance.According to above-mentioned idea; The present invention uses the mercaptan carboxylic acid as cosurfactant; Be preferably TGA, 3-mercaptopropionic acid, 3-sulfydryl butyric acid, the reason of selecting these three kinds of TGAs is can influence adsorption capacity if the chain length of the cocatalyst of selecting is long, causes on the contrary reuniting.
Then said modifying titanium dioxide Nano sol is prepared into modifying titanium dioxide nano particle nanotube, said modifying titanium dioxide nano particle nano tube structure new stable, specific area is high, and the nano particle activity is superior, is prone to reclaim and reuse.
According to the present invention; Gold nano colloidal sol and titanium dioxide nano sol in the said modifying titanium dioxide Nano sol all will be dispersed in the organic solvent; And can carry out proportioning according to the demand difference; But have preferably, titanium dioxide nano-particle and golden nanometer particle are (0.3～0.1) in molar ratio: (0.1～1).Said organic solvent is preferably toluene or cyclohexane.
The present invention also provides a kind of preparation method of modifying titanium dioxide nano particle nanotube, comprising:
Titanium dioxide nano sol is provided;
Be raw material with the gold chloride, be surfactant with mercaptan, be consisting of phase-transferring agent, the reduction reaction takes place under mercaptan carboxylic acid and sodium borohydride effect, obtain modification gold nano colloidal sol with four octyl group ammonium bromides;
Said modification gold nano colloidal sol is dispersed in respectively in the organic solvent with said titanium dioxide nano sol will mixes again, obtain with the sol-gel modified TiO 2 sol of gold nano;
Be added drop-wise to the anodic alumina films surface with said with the sol-gel modified TiO 2 sol of gold nano, and carry out vacuum filtration, drying; With compound anodic alumina films calcining; Remove said anodic alumina films, after washing, the centrifugation, obtain modifying titanium dioxide nano particle nanotube.
According to the present invention, titanium dioxide nano sol is provided at first.Because titanium dioxide nano-particle is divided into Detitanium-ore-type and rutile-type, so when buying and prepare, should be noted that different parameter settings.
The present invention preferably prepares titanium dioxide nano sol voluntarily, and method is:
Metatitanic acid orthocarbonate (TTIP) and oleic acid are blended in the organic solvent, obtain first solution;
Tert-butylamine is blended in the water, obtains second solution;
Said first solution and said second solution are blended in 150～200 ℃ of generation reduction reactions down, obtain titanium dioxide nano sol.
According to the present invention; The time of said first solution and the said second solution hybrid reaction is 3～5h; The oil solution of the said tert-butylamine aqueous solution and said metatitanic acid orthocarbonate reacts at the boundary layer of profit, and said tert-butylamine reduces said metatitanic acid orthocarbonate titanium dioxide nano sol.
The gold nano colloidal sol for preparing modification then, raw material are preferably can ionization AuCl
4 -Compound, the present invention selects to use gold chloride, surfactant is SR for the mercaptan structural formula, wherein R is the alkyl of even numbers in 4～20 for the carbon atom number.Reducing agent is a hydroboron, sodium borohydride more preferably, and consisting of phase-transferring agent is four octyl group ammonium bromide N (n-C
8H
17)
4Br is abbreviated as TOAB.The aqueous solution of gold chloride is mixed said AuCl with surfactant, consisting of phase-transferring agent, reducing agent, mercaptan carboxylic acid and organic solvent
4 -Transfer to organic facies from water, in the presence of lauryl mercaptan (DDT) and mercaptan carboxylic acid, said AuCl
4 -The place is reduced to golden nanometer particle at oil-water interfaces, obtains gold nano colloidal sol.Entire reaction course preferably at room temperature uses magnetic stirrer to stir,
According to the present invention, said organic solvent is toluene, xylenes or cyclohexane.
According to the present invention, in the preparation process of said gold nano colloidal sol, said hydroboron, TOAB, DDT and gold dollar element are 5～10: 1～2 in molar ratio: 1: 1.According to the present invention, can control the size of gold nano colloidal sol through the ratio of regulating DDT/Au.After reduction reaction finished, gold nano colloidal sol need pass through the cleaning of ethanol, removes organic substance excessive in the reaction, in organic solvent, disperseed at last (toluene or cyclohexane etc.) again.According to the present invention, said mercaptan carboxylic acid is preferably TGA, 3-mercaptopropionic acid or 3-sulfydryl butyric acid, 3-mercaptopropionic acid more preferably, and said mercaptan carboxylic acid is 1～4: 1～4 with the plain ratio of said gold dollar, more preferably 1～2: 2～4.
Can the titanium dioxide nano sol that prepare and gold nano colloidal sol be dispersed in the organic solvent subsequent usely respectively, the titanium dioxide nano sol after will disperseing again mixes with gold nano colloidal sol, and mixed proportion can be selected different proportionings according to different demands.Preferably, titanium dioxide nano-particle and golden nanometer particle are (0.3～0.1) in molar ratio: (0.1～1).Said organic solvent is toluene, xylenes or cyclohexane.
At last; Use said modifying titanium dioxide Nano sol to prepare the nano particle nanotube, process is specially: 1～2 modifying titanium dioxide Nano sol is added drop-wise to anodic alumina films (AAO) surface, under the vacuum filtration system; Make Nano sol evenly apply drying in the AAO inner wall surface; Preferred aforesaid operations repeats repeatedly, with the composite anode oxide aluminium film of preparation different-thickness.Treat that sample is again behind the vacuum drying 5h; Compound composite anode oxide aluminium film at 400 ℃ of calcining 1h, is taken out the back with diluted sodium hydroxide solution (0.01M) removal anodic alumina films, then use hydrochloric acid and deionized water washes clean after; Centrifugation obtains the nano particle nanotube.
Below be the specific embodiment of the invention, set forth the present invention program in detail.
Embodiment 1
Get 0.15gTTIP and oleic acid 5mL is dispersed in the toluene; Getting the 0.1mL tert-butylamine is dissolved in the water; The aqueous solution of the toluene solution of TTIP and oleic acid and tert-butylamine in the agitated reactor of 50mL, is heated to 180 ℃ of reaction 4h, obtains the titanium dioxide nano sol that average grain diameter is 4nm.
Get 0.09mmol gold chloride, 0.9mmol sodium borohydride, 0.18mmolTOAB, 0.09mmolDDT and 0.09mmol3-mercaptopropionic acid; Gold chloride is dissolved in the water; The aqueous solution of said gold chloride is mixed with said sodium borohydride, TOAB, DDT, 3-mercaptopropionic acid toluene solution; Stir, gold chloride is reduced into golden nanometer particle, and average grain diameter is 2nm.
Get gold nano colloidal sol 0.5mL and titanium dioxide nano sol 0.5mL; Add in the 4mL toluene solution; Obtain stable modifying titanium dioxide Nano sol, get this modifying titanium dioxide Nano sol 0.2ml and add in the 5ml toluene modifying titanium dioxide Nano sol that obtains diluting.
Mixed sols is added drop-wise to the mixed sols that 1-2 is dripped is added drop-wise to anodic alumina films (AAO) surface, under the vacuum filtration system, make Nano sol evenly apply drying in the AAO inner wall surface; Repeat 2 times, to prepare certain thickness composite anode oxide aluminium film.Treat that sample is again behind the vacuum drying 5h; Compound composite anode oxide aluminium film at 400 ℃ of calcining 1h, is taken out the back with diluted sodium hydroxide solution (0.01M) removal AAO anodic alumina films, then use hydrochloric acid and deionized water washes clean after; Centrifugation obtains nano particle nanotube sample.
Be illustrated in figure 1 as the modifying titanium dioxide nano particle nanotube transmission electron microscope picture of present embodiment preparation; As can be seen from the figure; Said nano particle nanotube outer wall is smooth, and golden nanometer particle and titanium dioxide nano-particle mix, in the tube wall side; Can clearly see dark golden nanometer particle, not with the titanium dioxide nano granule layering.
Embodiment 2
Get 0.15gTTIP and oleic acid 5mL is dispersed in the toluene; Getting the 0.1mL tert-butylamine is dissolved in the water; The aqueous solution of the toluene solution of TTIP and oleic acid and tert-butylamine in the agitated reactor of 50mL, is heated to 180 ℃ of reaction 4h, obtains the titanium dioxide nano sol that average grain diameter is 4nm.
Get 0.09mmol gold chloride, 0.9mmol sodium borohydride, 0.18mmolTOAB, 0.09mmolDDT and 0.09mmol 3-mercaptopropionic acid; Gold chloride is dissolved in the water; The aqueous solution of said gold chloride is mixed with said sodium borohydride, TOAB, DDT, 3-mercaptopropionic acid toluene solution; Stir, gold chloride is reduced into golden nanometer particle, and average grain diameter is 2nm.
Get gold nano colloidal sol 0.5mL and titanium dioxide nano sol 0.5mL; Add in the 4mL toluene solution; Obtain stable modifying titanium dioxide Nano sol, get this modifying titanium dioxide Nano sol 0.5ml and add in the 0.5ml toluene, obtain the modifying titanium dioxide Nano sol of high concentration.
Mixed sols is added drop-wise to the mixed sols that 1-2 is dripped is added drop-wise to anodic alumina films (AAO) surface, under the vacuum filtration system, make Nano sol evenly apply drying in the AAO inner wall surface; Repeat 2 times, to prepare certain thickness composite anode oxide aluminium film.Treat that sample is again behind the vacuum drying 5h; Compound composite anode oxide aluminium film at 400 ℃ of calcining 1h, is taken out the back with diluted sodium hydroxide solution (0.01M) removal AAO anodic alumina films, then use hydrochloric acid and deionized water washes clean after; Centrifugation obtains nano particle nanotube sample.
Be illustrated in figure 2 as the modifying titanium dioxide nano particle nanotube transmission electron microscope picture of present embodiment preparation; The solubility of the modifying titanium dioxide Nano sol of present embodiment is high, and as can be seen from the figure, said nano particle nanotube outer wall is smooth; Golden nanometer particle and titanium dioxide nano-particle mix; In the tube wall side, can clearly see dark golden nanometer particle, not high-visible with the titanium dioxide nano granule layering and the mouth of pipe.
Embodiment 3
Get 0.15gTTIP and oleic acid 5mL is dispersed in the toluene; Getting the 0.1mL tert-butylamine is dissolved in the water; The aqueous solution of the toluene solution of TTIP and oleic acid and tert-butylamine in the agitated reactor of 50mL, is heated to 180 ℃ of reaction 4h, obtains the titanium dioxide nano sol that average grain diameter is 4nm.
Get 0.09mmol gold chloride, 0.9mmol sodium borohydride, 0.18mmolTOAB, 0.09mmolDDT and 0.09mmol 3-mercaptopropionic acid; Gold chloride is dissolved in the water; The aqueous solution of said gold chloride is mixed with said sodium borohydride, TOAB, DDT, 3-mercaptopropionic acid toluene solution; Stir, gold chloride is reduced into golden nanometer particle, and average grain diameter is 2nm.
Get gold nano colloidal sol 0.5mL and titanium dioxide nano sol 0.5mL; Add in the 4mL toluene solution; Obtain stable modifying titanium dioxide Nano sol, get this modifying titanium dioxide Nano sol 0.2ml and add in the 5ml toluene modifying titanium dioxide Nano sol that obtains diluting.
Mixed sols is added drop-wise to the mixed sols that 1-2 is dripped is added drop-wise to anodic alumina films (AAO) surface, under the vacuum filtration system, make Nano sol evenly apply drying in the AAO inner wall surface; Repeat 5-10 time, with the composite anode oxide aluminium film of preparation different-thickness.Treat that sample is again behind the vacuum drying 5h; Compound composite anode oxide aluminium film at 400 ℃ of calcining 1h, is taken out the back with diluted sodium hydroxide solution (0.01M) removal AAO anodic alumina films, then use hydrochloric acid and deionized water washes clean after; Centrifugation obtains nano particle nanotube sample.
More than a kind of modifying titanium dioxide nano particle nanotube provided by the invention and preparation method thereof has been carried out detailed introduction; Having used concrete example among this paper sets forth principle of the present invention and embodiment; The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. the preparation method of a modifying titanium dioxide nano particle nanotube is characterized in that, comprising:
Titanium dioxide nano sol is provided;
Be raw material with the gold chloride, be surfactant with mercaptan, be consisting of phase-transferring agent, the reduction reaction takes place under mercaptan carboxylic acid and sodium borohydride effect, obtain modification gold nano colloidal sol with four octyl group ammonium bromides;
Said modification gold nano colloidal sol is dispersed in respectively in the organic solvent with said titanium dioxide nano sol will mixes again, obtain with the sol-gel modified TiO 2 sol of gold nano;
Be added drop-wise to the anodic alumina films surface with said with the sol-gel modified TiO 2 sol of gold nano, and carry out vacuum filtration, drying; With compound anodic alumina films calcining; Remove said anodic alumina films, after washing, the centrifugation, obtain modifying titanium dioxide nano particle nanotube.
2. preparation method according to claim 1 is characterized in that, said mercaptan carboxylic acid is selected from: TGA, 3-mercaptopropionic acid, 3-sulfydryl butyric acid.
3. preparation method according to claim 1 is characterized in that, said mercaptan carboxylic acid and gold chloride are (1～4) in molar ratio: (1～4).
4. preparation method according to claim 3 is characterized in that, the particle diameter of the golden nanometer particle in said mercaptan carboxylic acid's content and the gold nano colloidal sol is inversely proportional to.
5. preparation method according to claim 1 is characterized in that, the said titanium dioxide nano sol that provides is specially:
Metatitanic acid orthocarbonate and oleic acid are blended in the organic solvent, obtain first solution;
Tert-butylamine is blended in the water, obtains second solution;
Said first solution and said second solution are blended in 150～200 ℃ of generation reduction reactions down, obtain titanium dioxide nano sol.
6. preparation method according to claim 5 is characterized in that, said organic solvent is toluene or cyclohexane.
7. preparation method according to claim 1 is characterized in that, the general formula of said mercaptan is SR, and wherein R is the alkyl of even numbers in 4～20 for the carbon atom number.
8. preparation method according to claim 1 is characterized in that, in the said composite, titanium dioxide nano sol, gold nano colloidal sol are (0.3～0.1) in molar ratio: (0.1～1).
9. a modifying titanium dioxide nano particle nanotube is formed by modifying titanium dioxide Nano sol particle, it is characterized in that, said modifying titanium dioxide Nano sol particle comprises titanium dioxide nano-particle, mercaptan carboxylic acid, golden nanometer particle.
10. modifying titanium dioxide nano particle nanotube according to claim 9 is characterized in that, in the said carbon nano-particles nanotube, titanium dioxide nano sol, gold nano colloidal sol are (0.3～0.1) in molar ratio: (0.1～1).
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