CN102502484B - 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 inorganic composite materials preparation field, be specifically related to a kind of modified titanium dioxide nano particle nanotube and preparation method thereof.
Background technology
Titanium dioxide nano sol and golden nanometer particle, there is good multiple sensitiveness, in the fields such as chemical industry, medicine, machinery, catalysis, molecular biology, biology sensor, all there is application, and along with scientific and technological development, titanium dioxide nano sol and gold nano colloidal sol will be applied to more areas.Titanium dioxide nano sol can be 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 (iv) n-propoxide abridge TTIP) is dispersed in the oil phase that toluene or cyclohexane form, tert-butylamine (tert-butylamine) is dispersed in water, oil phase and water are added in same hydrothermal reaction kettle, at 180 ℃, react 4h.Add the factors such as volume by adjusting reaction time, reaction temperature and tert-butylamine, can control the size of titanium dioxide nano sol.After hydro-thermal reaction finishes, titanium dioxide nano sol need to pass through the precipitation of methyl alcohol and disperseing again of organic solvent.
The special construction of nano particle nanotube has its unique superiority, 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 relatively disperseing of nano particle nanotube forms, and is convenient to Separation of Solid and Liquid, recycle, thereby the utilization ratio of the material improving has reduced maintenance cost.In nano particle nanotube structure, existing more senior structure is nano particle nanotube, nano particle is as module units independently, still possesses the activity of its uniqueness, the tube wall of nano particle nanotube is loose structure, further improve the active sites of material, improved the performance of material.Nano particle nanotube prepared by a kind of nano particle is widely used, but the nano particle nanotube surface pore that prior art is mixed with golden nanometer particle and titanium dioxide nano-particle is inhomogeneous, cannot commercialization.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of surface pore even, the modified 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 modified titanium dioxide nano particle nanotube is provided, comprising:
Titanium dioxide nano sol is provided;
Take gold chloride as raw material, take mercaptan as surfactant, take four octyl group ammonium bromides as consisting of phase-transferring agent, issue raw reduction reaction mercaptan carboxylic acid and sodium borohydride effect, obtain modification gold nano colloidal sol;
Described modification gold nano colloidal sol is dispersed in respectively in organic solvent and will be mixed with described titanium dioxide nano sol, obtain with the sol-gel modified TiO 2 sol of gold nano;
Be added drop-wise to anodic alumina films surface by described with the sol-gel modified TiO 2 sol of gold nano, and carry out vacuum filtration, dry, by compound anodic alumina films calcining, remove described anodic alumina films, after washing, centrifugation, obtain modified titanium dioxide nano particle nanotube.
Preferably, described mercaptan carboxylic acid is selected from: TGA, 3-mercaptopropionic acid, 3-sulfydryl butyric acid.
Preferably, described mercaptan carboxylic acid and gold chloride are (1～4) in molar ratio: (1～4).
Preferably, the particle diameter of the golden nanometer particle in described mercaptan carboxylic acid's content and gold nano colloidal sol is inversely proportional to.
Preferably, described in, provide titanium dioxide nano sol to be specially:
Metatitanic acid orthocarbonate and oleic acid are blended in organic solvent, obtain the first solution;
Tert-butylamine is blended in water, obtains the second solution;
Described the first solution and described the second solution are blended in to 150～200 ℃ and issue raw reduction reaction, obtain titanium dioxide nano sol.
Preferably, described organic solvent is toluene or cyclohexane.
Preferably, the general formula of described mercaptan is SR, and wherein R is that carbon atom number is the alkyl of even numbers in 4～20.
Preferably, in described 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 modified titanium dioxide nano particle nanotube, is formed by modified titanium dioxide nano sol particle, and described modified titanium dioxide nano sol particle comprises titanium dioxide nano-particle, mercaptan carboxylic acid, golden nanometer particle.
Preferably, it is characterized in that, in described 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 modified titanium dioxide nano particle nanotube, first use gold nano colloidal sol to mix with existing titanium dioxide nano sol, in preparation gold nano colloidal sol, use mercaptan carboxylic acid as modifier, sulfydryl in mercaptan carboxylic acid has the effect of ADSORPTION OF GOLD nano particle, carboxyl has the effect of easy absorption titanium dioxide nano-particle, so better electric charge between balance golden nanometer particle and titanium dioxide nano-particle using mercaptan carboxylic acid as modifier, interact each other, make to form uniform charge field between each particle in colloidal sol, keep disperseing uniformly, thereby make the titanium dioxide nano sol particle diameter after described modification more even, be subject to also can not reuniting after environmental stimuli, chemistry and Heat stability is good.
Then the titanium dioxide nano sol of modification is dripped on anodic alumina films, then carry out vacuum filtration, calcining, remove anodic alumina films, obtain modified titanium dioxide nano particle nanotube, described modified titanium dioxide nano particle nanotube has increased the specific area of modified titanium dioxide nano particle, and novel structure is stable, nano particle activity is high, more easily reclaims and reuses.Preparation method is convenient and swift, is applicable to large-scale industrial production.
Accompanying drawing explanation
The modified titanium dioxide nano particle nanotube transmission electron microscope picture that Fig. 1 embodiment of the present invention 1 provides;
The modified titanium dioxide nano particle nanotube transmission electron microscope picture that Fig. 2 embodiment of the present 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 are described is the restriction for further illustrating the features and advantages of the present invention rather than patent of the present invention being required.
The invention provides a kind of modified titanium dioxide nano particle nanotube, formed by modified titanium dioxide nano sol particle, it is characterized in that, described modified titanium dioxide nano sol particle comprises titanium dioxide nano-particle, mercaptan carboxylic acid, golden nanometer particle.
The invention provides a kind of modified titanium dioxide nano particle nanotube, first gold nano colloidal sol and TiO 2 sol are mixed with to modified 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 of preparing in prior art joins in titanium dioxide nano sol and cannot play and control titanium dioxide nano sol particle diameter, improve titanium dioxide nano sol stability, prevent the effect of reuniting, so the inventor considers to add cosurfactant in preparation gold nano colloidal sol, in described cosurfactant, both there is the group of energy ADSORPTION OF GOLD nano particle, there is again the group of absorption titanium dioxide nano-particle, can increase the binding force of golden nanometer particle to described titanium dioxide nano-particle, and charge balance.According to above-mentioned idea, the present invention uses 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 affect adsorption capacity if the chain length of the cocatalyst of selecting is long, causes on the contrary reuniting.
Then described modified titanium dioxide nano sol is prepared into modified titanium dioxide nano particle nanotube, described modified titanium dioxide nano particle nanotube novel structure is stable, and specific area is high, and nano particle activity is superior, more easily reclaims and reuses.
According to the present invention, gold nano colloidal sol in described modified titanium dioxide nano sol and titanium dioxide nano sol all will be dispersed in organic solvent, and difference is carried out proportioning according to demand, but have preferably, titanium dioxide nano-particle and golden nanometer particle are (0.3～0.1) in molar ratio: (0.1～1).Described organic solvent is preferably toluene or cyclohexane.
The present invention also provides a kind of preparation method of modified titanium dioxide nano particle nanotube, comprising:
Titanium dioxide nano sol is provided;
Take gold chloride as raw material, take mercaptan as surfactant, take four octyl group ammonium bromides as consisting of phase-transferring agent, issue raw reduction reaction mercaptan carboxylic acid and sodium borohydride effect, obtain modification gold nano colloidal sol;
Described modification gold nano colloidal sol is dispersed in respectively in organic solvent and will be mixed with described titanium dioxide nano sol, obtain with the sol-gel modified TiO 2 sol of gold nano;
Be added drop-wise to anodic alumina films surface by described with the sol-gel modified TiO 2 sol of gold nano, and carry out vacuum filtration, dry, by compound anodic alumina films calcining, remove described anodic alumina films, after washing, centrifugation, obtain modified titanium dioxide nano particle nanotube.
According to the present invention, first provide titanium dioxide nano sol.Because titanium dioxide nano-particle is divided into Detitanium-ore-type and rutile-type, so should be noted that different parameter settings in the time buying and prepare.
The present invention preferably prepares titanium dioxide nano sol voluntarily, and method is:
Metatitanic acid orthocarbonate (TTIP) and oleic acid are blended in organic solvent, obtain the first solution;
Tert-butylamine is blended in water, obtains the second solution;
Described the first solution and described the second solution are blended in to 150～200 ℃ and issue raw reduction reaction, obtain titanium dioxide nano sol.
According to the present invention, the time of described the first solution and described the second solution hybrid reaction is 3～5h, the oil solution of the described tert-butylamine aqueous solution and described metatitanic acid orthocarbonate reacts at the boundary layer of profit, and described tert-butylamine reduces described metatitanic acid orthocarbonate titanium dioxide nano sol.
Then be prepared the gold nano colloidal sol of modification, raw material is preferably and can ionizes AuCl
4 -compound, choice for use gold chloride of the present invention, surfactant is that mercaptan structural formula is SR, wherein R is that carbon atom number is the alkyl of even numbers in 4～20.Reducing agent is hydroboron, more preferably sodium borohydride, 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 to described AuCl with surfactant, consisting of phase-transferring agent, reducing agent, mercaptan carboxylic acid and organic solvent
4 -transfer to organic phase from water, under lauryl mercaptan (DDT) and mercaptan carboxylic acid's existence, described AuCl
4 -at oil-water interfaces, place is reduced to golden nanometer particle, obtains gold nano colloidal sol.Whole course of reaction preferably at room temperature, is used magnetic stirrer to stir,
According to the present invention, described organic solvent is toluene, dimethylbenzene or cyclohexane.
According to the present invention, in the preparation process of described gold nano colloidal sol, described hydroboron, TOAB, DDT and gold element are 5～10: 1～2 in molar ratio: 1: 1.According to the present invention, by regulating the ratio of DDT/Au can control the size of gold nano colloidal sol.After reduction reaction finishes, gold nano colloidal sol need to, through the cleaning of ethanol, remove organic substance excessive in reaction, finally in organic solvent, disperses (toluene or cyclohexane etc.) again.According to the present invention, described mercaptan carboxylic acid is preferably TGA, 3-mercaptopropionic acid or 3-sulfydryl butyric acid, more preferably 3-mercaptopropionic acid, and described mercaptan carboxylic acid is 1～4: 1～4 with the ratio of described gold element, more preferably 1～2: 2～4.
The titanium dioxide nano sol preparing and gold nano colloidal sol can be dispersed in respectively in organic solvent for subsequent usely, then the titanium dioxide nano sol after disperseing be mixed with gold nano colloidal sol, 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).Described organic solvent is toluene, dimethylbenzene or cyclohexane.
Finally, use described modified titanium dioxide nano sol to prepare nano particle nanotube, process is specially: the modified titanium dioxide nano sol of 1～2 is added drop-wise to anodic alumina films (AAO) surface, under vacuum filtration system, Nano sol is evenly applied in AAO inner wall surface, dry; Preferably aforesaid operations repeatedly, to prepare the composite anode oxide aluminium film of different-thickness.Until sample again after vacuum drying 5h, compound composite anode oxide aluminium film, at 400 ℃ of calcining 1h, is removed to anodic alumina films with diluted sodium hydroxide solution (0.01M) after taking out, then use after hydrochloric acid and deionized water washes clean, centrifugation, obtains nano particle nanotube.
Be below the specific embodiment of the invention, elaborate the present invention program.
Embodiment 1
Get 0.15gTTIP and oleic acid 5mL is dispersed in toluene, getting 0.1mL tert-butylamine is dissolved in water, the aqueous solution of the toluene solution of TTIP and oleic acid and tert-butylamine, in the 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 water, the aqueous solution of described gold chloride is mixed with described 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 4mL toluene solution, obtain stable modified titanium dioxide nano sol, get this modified titanium dioxide nano sol 0.2ml and add in 5ml toluene, obtain the modified titanium dioxide nano sol of dilution.
Mixed sols is added drop-wise to the mixed sols that 1-2 is dripped and is added drop-wise to anodic alumina films (AAO) surface, under vacuum filtration system, Nano sol is evenly applied in AAO inner wall surface, dry; Repeat 2 times, to prepare certain thickness composite anode oxide aluminium film.Until sample again after vacuum drying 5h, compound composite anode oxide aluminium film is calcined to 1h at 400 ℃, after taking out, remove AAO anodic alumina films with diluted sodium hydroxide solution (0.01M), then use after hydrochloric acid and deionized water washes clean, centrifugation, obtains nano particle nanotube sample.
Be illustrated in figure 1 modified titanium dioxide nano particle nanotube transmission electron microscope picture prepared by the present embodiment, as can be seen from the figure, described nano particle nanotube outer wall is smooth, golden nanometer particle and titanium dioxide nano-particle mix, in tube wall side, can clearly see dark golden nanometer particle, not with titanium dioxide nano granule layering.
Embodiment 2
Get 0.15gTTIP and oleic acid 5mL is dispersed in toluene, getting 0.1mL tert-butylamine is dissolved in water, the aqueous solution of the toluene solution of TTIP and oleic acid and tert-butylamine, in the 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 water, the aqueous solution of described gold chloride is mixed with described 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 4mL toluene solution, obtain stable modified titanium dioxide nano sol, get this modified titanium dioxide nano sol 0.5ml and add in 0.5ml toluene, obtain the modified titanium dioxide nano sol of high concentration.
Mixed sols is added drop-wise to the mixed sols that 1-2 is dripped and is added drop-wise to anodic alumina films (AAO) surface, under vacuum filtration system, Nano sol is evenly applied in AAO inner wall surface, dry; Repeat 2 times, to prepare certain thickness composite anode oxide aluminium film.Until sample again after vacuum drying 5h, compound composite anode oxide aluminium film is calcined to 1h at 400 ℃, after taking out, remove AAO anodic alumina films with diluted sodium hydroxide solution (0.01M), then use after hydrochloric acid and deionized water washes clean, centrifugation, obtains nano particle nanotube sample.
Be illustrated in figure 2 modified titanium dioxide nano particle nanotube transmission electron microscope picture prepared by the present embodiment, the solubility of the modified titanium dioxide nano sol of the present embodiment is high, as can be seen from the figure, described nano particle nanotube outer wall is smooth, golden nanometer particle and titanium dioxide nano-particle mix, in tube wall side, can clearly see dark golden nanometer particle, not high-visible with titanium dioxide nano granule layering and the mouth of pipe.
Embodiment 3
Get 0.15gTTIP and oleic acid 5mL is dispersed in toluene, getting 0.1mL tert-butylamine is dissolved in water, the aqueous solution of the toluene solution of TTIP and oleic acid and tert-butylamine, in the 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 water, the aqueous solution of described gold chloride is mixed with described 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 4mL toluene solution, obtain stable modified titanium dioxide nano sol, get this modified titanium dioxide nano sol 0.2ml and add in 5ml toluene, obtain the modified titanium dioxide nano sol of dilution.
Mixed sols is added drop-wise to the mixed sols that 1-2 is dripped and is added drop-wise to anodic alumina films (AAO) surface, under vacuum filtration system, Nano sol is evenly applied in AAO inner wall surface, dry; Repeat 5-10 time, to prepare the composite anode oxide aluminium film of different-thickness.Until sample again after vacuum drying 5h, compound composite anode oxide aluminium film is calcined to 1h at 400 ℃, after taking out, remove AAO anodic alumina films with diluted sodium hydroxide solution (0.01M), then use after hydrochloric acid and deionized water washes clean, centrifugation, obtains nano particle nanotube sample.
Above a kind of modified titanium dioxide nano particle nanotube provided by the invention and preparation method thereof is described in detail; having applied specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the premise without departing from the principles 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 the claims in the present invention.
Claims (9)
1. a preparation method for modified titanium dioxide nano particle nanotube, is characterized in that, comprising:
Titanium dioxide nano sol is provided, is specially:
Metatitanic acid orthocarbonate and oleic acid are blended in organic solvent, obtain the first solution;
Tert-butylamine is blended in water, obtains the second solution;
Described the first solution and described the second solution are blended in to 150～200 ℃ and issue raw reduction reaction, obtain titanium dioxide nano sol;
Take gold chloride as raw material, take mercaptan as surfactant, take four octyl group ammonium bromides as consisting of phase-transferring agent, issue raw reduction reaction mercaptan carboxylic acid and sodium borohydride effect, obtain modification gold nano colloidal sol;
Described modification gold nano colloidal sol is dispersed in organic solvent and is mixed respectively with described titanium dioxide nano sol, obtain with the sol-gel modified TiO 2 sol of gold nano;
Be added drop-wise to anodic alumina films surface by described with the sol-gel modified TiO 2 sol of gold nano, and carry out vacuum filtration, dry, by compound anodic alumina films calcining, remove described anodic alumina films, after washing, centrifugation, obtain modified titanium dioxide nano particle nanotube.
2. preparation method according to claim 1, is characterized in that, described 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, described 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 described mercaptan carboxylic acid's content and gold nano colloidal sol is inversely proportional to.
5. preparation method according to claim 1, is characterized in that, described organic solvent is toluene or cyclohexane.
6. preparation method according to claim 1, is characterized in that, the general formula of described mercaptan is SR, and wherein R is that carbon atom number is the alkyl of even numbers in 4～20.
7. preparation method according to claim 1, is characterized in that, described with in the sol-gel modified TiO 2 sol of gold nano, titanium dioxide nano sol, gold nano colloidal sol are (0.3～0.1) in molar ratio: (0.1～1).
8. a modified titanium dioxide nano particle nanotube, formed by modified titanium dioxide nano sol particle, it is characterized in that, described modified titanium dioxide nano sol particle forms by modification gold nano is sol-gel modified, described modification gold nano colloidal sol is by take gold chloride as raw material, take mercaptan as surfactant, take four octyl group ammonium bromides as consisting of phase-transferring agent, issues raw reduction reaction obtain in mercaptan carboxylic acid and sodium borohydride effect.
9. modified titanium dioxide nano particle nanotube according to claim 8, it is characterized in that, in described modified titanium dioxide nano particle nanotube, titanium dioxide nano sol, gold nano colloidal sol are (0.3～0.1) in molar ratio: (0.1～1).
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| CN103817321B (en) * | 2014-02-19 | 2016-03-30 | 南京林业大学 | A kind of preparation method of modified Nano silver powder |
| CN107217285A (en) * | 2017-02-10 | 2017-09-29 | 江苏城乡建设职业学院 | A kind of method in regulation and control titania nanotube footpath |
| CN107217276A (en) * | 2017-02-10 | 2017-09-29 | 江苏城乡建设职业学院 | A kind of method in regulation and control titania nanotube footpath |
| CN107217288A (en) * | 2017-02-10 | 2017-09-29 | 江苏城乡建设职业学院 | A kind of method in regulation and control titania nanotube footpath |
| CN107217286A (en) * | 2017-02-10 | 2017-09-29 | 江苏城乡建设职业学院 | A kind of method in regulation and control titania nanotube footpath |
| CN108253422B (en) * | 2018-03-20 | 2023-10-13 | 苏州新耀环保科技有限公司 | Plasma garbage incinerator |
| CN109233521A (en) * | 2018-09-20 | 2019-01-18 | 徐冬 | A kind of exterior wall heat-insulating paint |
| CN110316764A (en) * | 2019-04-01 | 2019-10-11 | 复旦大学 | A method of nanocrystalline superstructure pipe or superstructure stick are prepared based on the assembling of template extension |
| CN110127722B (en) * | 2019-06-11 | 2022-04-15 | 吉林师范大学 | Hydrophobic surface defect modified TiO2Preparation method of visible light nitrogen fixation catalyst |
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