CN101983764B - Preparation method of large-area orderly titanium dioxide nanotube film photocatalyst with sheath core structure and application thereof - Google Patents
Preparation method of large-area orderly titanium dioxide nanotube film photocatalyst with sheath core structure and application thereof Download PDFInfo
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- CN101983764B CN101983764B CN2010102881903A CN201010288190A CN101983764B CN 101983764 B CN101983764 B CN 101983764B CN 2010102881903 A CN2010102881903 A CN 2010102881903A CN 201010288190 A CN201010288190 A CN 201010288190A CN 101983764 B CN101983764 B CN 101983764B
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Abstract
The invention relates to a preparation method of large-area orderly titanium dioxide nanotube film photocatalysts with sheath core structure and application thereof.Orderly carbon nanotube film is pulled out of fiber-forming carbon nanotube arrays.The surface of nanotubes is wrapped with a layer of titanium dioxide nano-material by chemical vapor deposition or physical vapor deposition method, with the orderly carbon nanotubes as the template.The orderly sheath core nanotube film is formed with carbon nanotubes as the intermediate layer and titanium dioxide nanotubes as the outer layer. The degradation ability of photocatalysts provided by the invention in the reaction of catalytic degradation of methyl blueness is obviously improved, as compared with that of normal titanium dioxide film photocatalysts under the same condition. The invention effectively facilitates the large-area preparation of titanium dioxide nanotube photocatalyst materials and greatly improves the efficiency of catalysts while overcoming the problem of solidification in real application. The invention is applicable to industrial applications.
Description
Technical field
The present invention relates to photocatalyst material, relate in particular to a kind of preparation method and application thereof of large-area ordered skin-core structure titanic oxide nano tube thin-film photochemical catalyst.
Background technology
Because the environmental pollution degree has exceeded the limit of natural purifying ability, problem of environmental pollution becomes one of current significant problem that influences human survival and development.As the high efficiency method that stains thing in purifying air and in the water, the conductor photocatalysis technology has become present environmental pollution to administer hot research fields.
Conductor photocatalysis Study on Technology emphasis is the well behaved photocatalyst material of development.Existing result of study shows, nano-TiO
2Light urge material to have plurality of advantages: but cost is low, nonhazardous, greatly specific surface, the sensitization of can mixing, good stability and catalytic mechanism research are deep, is the catalysis material of tool application prospect.
Existing preparation nano-TiO
2The major technique of photochemical catalyst comprises: hydro-thermal method, sol-gel process, electrochemistry anodic oxidation, vapor phase method.Use above-mentioned preparation method, obtained the nano-TiO of nano particle, nano wire, nanotube and nano thin-film structure
2Light urge agent material, TiO wherein
2Nanotube light urges agent material because its good architectural feature has shown fabulous photocatalysis performance.But utilize above-mentioned technology of preparing; Can't satisfy application request; Main weak point is: material structure that (1) prepares and dimensional controllability are not high, and (2) can not prepare in enormous quantities, and the structure of the photocatalyst material that (3) prepare and performance are difficult for further modulation; Influence the raising of catalytic efficiency, the TiO of the nanostructured that (4) obtain
2All need further be solidificated on other support materials and just can use.
Summary of the invention
The present invention is directed to the above-mentioned defective of prior art, provide a kind of need not to solidify, but the preparation method of the large-area ordered skin-core structure titanic oxide nano tube thin-film of large-area preparation photocatalyst material.
In order to solve the problems of the technologies described above, the present invention realizes through following technical scheme:
A kind of preparation method of large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material may further comprise the steps: provide one can pull out the ordered nano-tube film carbon nano pipe array; From carbon nano pipe array, pull out the CNT order thin film; Be placed on the CNT order thin film in the passive substrate, perhaps make the periphery of its unsettled fixed carbon nanotube order thin film; Put into reactor to the CNT order thin film; Through physical vapour deposition (PVD) or chemical gaseous phase depositing process; CNT coated outside layer of titanium dioxide shell material in the ordered carbon nanotube film is that CNT, outer shell are the skin-core structure nano-tube films of titania nanotube in the middle of forming.
Wherein, used carbon nano-tube film is the orderly continuous film that from carbon nano pipe array, pulls out.
Wherein, the CNT order thin film of pulling out can be placed one deck in substrate, also can be multilayer; The CNT order thin film is a multilayer, and every layer direction is different, forms braiding structure.
Wherein, physical gas-phase deposite method is vacuum evaporation, vacuum sputtering or vacuum ion membrane plating.
Wherein, the range of reaction temperature during chemical vapour deposition (CVD) is 200 ℃-1200 ℃.
Wherein, the used target of physical gas-phase deposite method is titanium target or titanium dioxide target.
Wherein, when target is the titanium target, after the carbon nano-tube film skin has deposited titanium layer, need further middle oxidation processes, obtain titania nanotube.
Wherein, the skin-core structure nano-tube film for preparing can strip down application from substrate.
The present invention also provides the preparation method of another kind of large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material, and it may further comprise the steps: provide one can pull out the ordered nano-tube film carbon nano pipe array; From carbon nano pipe array, pull out the CNT order thin film, and on the CNT order thin film of pulling out, directly spray titania nanoparticles, forming internal layer is that CNT, skin are the nano-tube films of titania nanoparticles.
The present invention also provides a kind of application of large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material; Because the CNT in the skin-core structure nano-tube film has electric conductivity; In photocatalytic process; Apply a positive bias voltage for the skin-core structure nano-tube film, light induced electron wherein can effectively be separated, can improve light-catalysed efficient.
Can find out from above technical scheme; The present invention is to be the preparation that template is carried out the titanic oxide nano pipe light catalyst material with the continuous carbon nanometer tube film; CNT itself has good physicochemical properties: its tensile strength reaches 50～200Gpa; Be 100 times of steel, density but has only 1/6 of steel; According to the difference of structure, CNT promptly can show semiconductor property, can show conductor nature, when performance during conductor property its electrical conductivity can reach 10,000 times of copper usually; CNT has the good heat transfer performance, and heat exchange performance alongst is the highest in the present known materials; The caliber of CNT is generally 2～20nm, but length can reach the mm magnitude, and pipe shaft is made up of hexagon carbocyclic ring microstructure unit, has perfect crystal structure.And the continuous carbon nanometer tube film that we adopt has outstanding features such as area is big, caliber is long.
Therefore, titanic oxide nano tube thin-film is attached on the continuous carbon nano-tube film solved problem of solidification, easy to use.And because carbon nano-tube film has good physicochemical properties, the structure of the skin-core structure nano-tube film for preparing and size are convenient to control and can not be prepared in enormous quantities.
In sum, technological merit of the present invention is that (1) provides the preparation method of a kind of controlled, large tracts of land, high efficiency, the orderly skin-core structure titanic oxide nano tube thin-film photocatalyst material of the low preparation of cost; (2) this preparation method solves the problem of solidification of titanic oxide nano pipe light catalyst material in practical application;
(3) because the sandwich layer of skin-core structure titanic oxide nano tube thin-film photocatalyst material is a CNT, so carry out photocatalytic degradation when handling pollutant using it, can apply current potential to it, realize optoelectronic integration catalysis.
Description of drawings
Fig. 1 is the preparation flow figure of skin-core structure titanic oxide nano tube thin-film photocatalyst material.
Fig. 2 is when using skin-core structure titanic oxide nano tube thin-film photocatalyst material degradation treatment methyl blue solution, with ordinary titanium dioxide photocatalyst material contrast experiment's curve map under the same conditions.
The specific embodiment
Below in conjunction with the specific embodiment process that the present invention prepares the skin-core structure nano-tube film is done further detailed explanation.
Embodiment one
But from the carbon nano pipe array of membrane, pull out the CNT order thin film, be tiled in the different carbon nano-tube film of multilayer direction on the monocrystalline silicon piece of 2cm * 5cm size, the thickness of silicon chip is 500 microns.Have tiling the silicon chip of carbon nano-tube film to put into 1 inch horizontal pipe furnace middle, feeding flow is the argon gas of 300 standard cubic centimeters per minute, exhaust 10 minutes.Then, begin the stove heating when furnace temperature is raised to 450 ℃, is fed the carrier gas that contains tetraisopropoxy titanium in the stove, the main component of this carrier gas is an argon gas, and flow is 300 standard cubic centimeters per minute.Reaction time is 10 minutes, and reaction is turned off carrier gas earlier after finishing, and keeping argon flow amount is 300 standard cubic centimeters per minute, lets stove cool off naturally, after stove drops to room temperature, from boiler tube, takes out silicon chip.Through above-mentioned experimental procedure, preparing sandwich layer is that CNT, outer shell are the skin-core structure nano-tube film photocatalyst material of titanium dioxide.
Be used for the photocatalysis experiment to the nano-tube film photocatalyst material of above-mentioned titanium dioxide/CNT skin-core structure, use the ultra violet lamp of dominant wavelength, the solution that contains methyl blue is carried out photocatalytic degradation handle as 365nm.The methyl blue initial concentration of solution is 50mg/L.Experimental result shows that under the same conditions, the catalytic performance of the titanium dioxide optical catalyst that the present invention prepares is compared with the titanium dioxide that commonsense method prepares, and has improved 2.2 times.
Embodiment two
But from the carbon nano pipe array of membrane, pull out the orderly continuous film of CNT, be tiled in carbon nano-tube film on the monocrystalline silicon piece of 2cm * 5cm size, the thickness of silicon chip is 500 microns.There is tiling the silicon chip of carbon nano-tube film to put into the middle of horizontal pipe furnace second warm area of 1 inch two warm area; A quartz boat is put in middle at first warm area of two warm area horizontal pipe furnaces, the inside tetraisopropoxide titanium solution of packing into, and volume is 10 milliliters.Feeding flow is the argon gas of 300 standard cubic centimeters per minute, exhaust 10 minutes.Then, the temperature of first warm area (putting the zone of tetraisopropoxide titanium solution) of the two warm area horizontal pipe furnaces of control is 120 ℃, and the temperature of second warm area (putting the silicon chip position) is 450 ℃.In process after this, keep argon flow amount is that 300 standard cubic centimeters per minute are constant always, and the reaction time is 20 minutes.After reaction finished, keeping argon flow amount was 300 standard cubic centimeters per minute, lets stove cool off naturally, after furnace temperature drops to room temperature, from boiler tube, takes out silicon chip.Through above-mentioned experimental procedure, preparing sandwich layer is that CNT, outer shell are the skin-core structure nano-tube film photocatalyst material of titanium dioxide.
Embodiment three
But from the carbon nano pipe array of membrane, pull out the CNT order thin film, be tiled in carbon nano-tube film on the monocrystalline silicon piece of 2cm * 5cm size, the thickness of silicon chip is 500 microns.Put into the vacuum chamber of vacuum electron beam evaporation coating appearance to the above-mentioned monocrystalline silicon piece that has tiled one deck carbon nano-tube film, behind system vacuum to 1 * 10-4Pa, the beginning plated film.Target is that diameter of phi 1mm purity is 99.99% metal Ti particle.Keeping watch on sedimentation rate and deposition thickness with film thickness gauge, is 1 minute with constant sedimentation rate
sedimentation time.After deposition finished, preparing sandwich layer was that CNT, outer shell are the skin-core structure nano-tube film of titanium nanotube.
Put into open tube furnace to above-mentioned nano-tube film sample, annealing under air atmosphere.Stove begins to heat up from room temperature, is raised to 400 ℃, and the heating-up time is 40 minutes.Kept 60 minutes at 400 ℃, powered-down lets stove naturally cool to room temperature then.
Through above-mentioned steps, preparing sandwich layer is that CNT, outer shell are the skin-core structure nano-tube film photocatalyst material of titania nanotube.
Embodiment four
But from the carbon nano pipe array of membrane, pull out the CNT order thin film, be tiled in carbon nano-tube film on the monocrystalline silicon piece of 2cm * 5cm size, the thickness of silicon chip is 500 microns.Put into the above-mentioned monocrystalline silicon piece that has tiled one deck carbon nano-tube film the vacuum chamber of magnetron sputtering plating appearance.Target is that diameter of phi 200mm purity is 99.99% metal Ti target, and working gas is the Ar gas of purity 99.999%, and reacting gas is the O2 gas of purity 99.99%, through the nanotube of direct current reaction magnetron sputtering at skin deposition one deck TiO2 of CNT.Sedimentation rate
sedimentation time is 20 minutes.Through above-mentioned steps, preparing sandwich layer is that CNT, outer shell are the skin-core structure nano-tube film photocatalyst material of titania nanotube
Embodiment five
But from the carbon nano pipe array of membrane, pull out the orderly continuous film of CNT, and on the CNT order thin film of pulling out, directly spray titania nanoparticles, forming internal layer is that CNT, skin are the nano-tube films of titania nanoparticles.
The present invention also provides a kind of application of large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material; CNT in this nano-tube film has electric conductivity; Can apply a positive bias voltage to film in use; Implement optoelectronic integration catalysis, light induced electron wherein can effectively be separated, improve light-catalysed efficient.
The above embodiment has only expressed several kinds of embodiments of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with accompanying claims.
Claims (10)
1. the preparation method of a large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material is characterized in that, may further comprise the steps:
Provide one can pull out the ordered nano-tube film carbon nano pipe array;
From carbon nano pipe array, pull out the CNT order thin film;
Be placed on the CNT order thin film in the passive substrate, perhaps make the periphery of its unsettled fixed carbon nanotube order thin film;
Put into reactor to the CNT order thin film; Through physical vapour deposition (PVD) or chemical gaseous phase depositing process; CNT coated outside layer of titanium dioxide shell material in the ordered carbon nanotube film is that CNT, outer shell are the skin-core structure nano-tube films of titania nanotube in the middle of forming.
2. the preparation method of large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material as claimed in claim 1 is characterized in that used carbon nano-tube film is the orderly continuous film that from carbon nano pipe array, pulls out.
3. the preparation method of large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material as claimed in claim 1 is characterized in that the CNT order thin film of pulling out can place one deck in substrate, also can be multilayer; The CNT order thin film is a multilayer, and every layer direction is different, forms braiding structure.
4. the preparation method of large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material as claimed in claim 1 is characterized in that physical gas-phase deposite method is vacuum evaporation, vacuum sputtering or vacuum ion membrane plating.
5. the preparation method of large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material as claimed in claim 1, the range of reaction temperature when it is characterized in that chemical vapour deposition (CVD) is 200 ℃-1200 ℃.
6. the preparation method of large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material as claimed in claim 4 is characterized in that, the used target of physical gas-phase deposite method is titanium target or titanium dioxide target.
7. the preparation method of large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material as claimed in claim 6; It is characterized in that, when target is the titanium target, after the carbon nano-tube film skin has deposited titanium layer; Oxidation processes in needing further obtains titania nanotube.
8. the preparation method of large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material as claimed in claim 1 is characterized in that, the skin-core structure nano-tube film for preparing can strip down application from substrate.
9. the preparation method of a large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material is characterized in that, may further comprise the steps:
Provide one can pull out the ordered nano-tube film carbon nano pipe array;
From carbon nano pipe array, pull out the CNT order thin film, and on the CNT order thin film of pulling out, directly spray titania nanoparticles, forming internal layer is that CNT, skin are the nano-tube films of titania nanoparticles.
10. the application of large-area ordered skin-core structure titanic oxide nano tube thin-film photocatalyst material as claimed in claim 1; It is characterized in that; In photocatalytic process; Apply a positive bias voltage for the skin-core structure nano-tube film, light induced electron wherein can effectively be separated, improve light-catalysed efficient.
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| CN101972641B (en) * | 2010-10-13 | 2012-05-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Large-area titanium dioxide nanotube film as well as preparation method and application thereof |
| CN102643638B (en) * | 2012-04-28 | 2014-07-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Tungsten trioxide carbon nano tube composite film, production process and applications thereof |
| CN106378123B (en) * | 2016-08-17 | 2018-02-27 | 袁沛文 | A kind of preparation method for the array active film for strengthening photocatalytic effect |
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| CN101157521A (en) * | 2007-09-20 | 2008-04-09 | 复旦大学 | Visible light active nano titania coextruded film material and preparation method thereof |
| CN101347725A (en) * | 2008-08-19 | 2009-01-21 | 武汉大学 | Carbon nano-tube/titanic oxide nano compound photocatalyst and preparation method and application thereof |
| CN101723313A (en) * | 2009-11-02 | 2010-06-09 | 浙江大学 | Method for preparing nano titanium dioxide/carbon nano tube composite material |
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| WO2001042140A1 (en) * | 1999-12-13 | 2001-06-14 | Jonathan Sherman | Nanoparticulate titanium dioxide coatings, and processes for the production and use thereof |
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| CN101157521A (en) * | 2007-09-20 | 2008-04-09 | 复旦大学 | Visible light active nano titania coextruded film material and preparation method thereof |
| CN101347725A (en) * | 2008-08-19 | 2009-01-21 | 武汉大学 | Carbon nano-tube/titanic oxide nano compound photocatalyst and preparation method and application thereof |
| CN101723313A (en) * | 2009-11-02 | 2010-06-09 | 浙江大学 | Method for preparing nano titanium dioxide/carbon nano tube composite material |
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