CN102747404B - Composite film with photocatalytic function and preparation method thereof - Google Patents
Composite film with photocatalytic function and preparation method thereof Download PDFInfo
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- CN102747404B CN102747404B CN201210243037.8A CN201210243037A CN102747404B CN 102747404 B CN102747404 B CN 102747404B CN 201210243037 A CN201210243037 A CN 201210243037A CN 102747404 B CN102747404 B CN 102747404B
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- titanium
- composite film
- titanium alloy
- differential arc
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Abstract
The invention relates to a composite film with photocatalytic function and a preparation method thereof. The composite film is prepared on the titanium or titanium alloy surface. A nano zinc oxide photosensitizer is uniformly and dispersedly deposited and fixed on a titanium dioxide porous material which is also a semiconductor photosensitive material to form a novel composite film with photocatalytic function. The composite film has the purification functions of adsorption and decomposition, and also has the peculiar photocatalytic enhancement effect of heterojunction compounded by the two semiconductor photosensitive materials. Under the action of ultraviolet or natural light, the composite film can perform quick separation, efficient adsorption and quick degradation on methylbenzene, phenol and other typical toxic liquid organic pollutants, and can also purify the water source through efficient adsorption even under lightless conditions; and the composite film can also be used as an efficient photosensitizer for adjuvantly treating cancers in photodynamic therapy.
Description
Technical field
The present invention relates to a kind of novel photocatalysis function laminated film and preparation method thereof, in titanium or titanium alloy surface preparation, by zinc oxide nano rod or the nanocone by deposition growth on differential arc oxidation poriferous titanium dioxide bottom and surperficial hole wall thereof, be composited, belong to the field of photocatalytic material that can be used for toxic pollutant purifying treatment, photodynamic therapy auxiliary for treating cancer etc.
Background technology
In recent years, nano-TiO
2photocatalysis technology is also being obtained considerable progress aspect the poisonous liquid pollution of improvement.Utilizing photochemical catalysis, adopt living radical liquid towards pollutent to carry out oxygenolysis, is the method for processing a kind of simple and efficient of fluid contaminants, utilizes nano-TiO
2under Uv and visible light, at material surface, be formed with free hydroxy (OH) and the active oxygen (O) of strong oxidative decomposition capacity, by being attached to surperficial organic substance, decompose.But under unglazed or half-light condition, be difficult to obtain satisfied effect in water.For this problem, studying at present more is to adopt absorption to add photocatalysis technology, generally adopts activated carbon fiber (ACF) as carrier loaded TiO
2catalyzer, utilizes the absorption property of ACF to carry out quick adsorption to pollutent, reaches the enrichment of pollutent on ACF carrier, accelerates light-catalyzed reaction speed.But ACF is very low to the adsorption exponent of organic pollutants, even in air, when relative humidity is larger, ACF also can sharply decline to the loading capacity of the organic pollutants such as toluene; Therefore suitable carrier remains the problem that this Technology Need obtains fine solution.
Photo-catalysis function laminated film of the present invention is with Adsorption and decomposition purification function, also there is the peculiar Photocatalytic enhancement effect of heterojunction that two kinds of semiconductor photosensitive Material claddings form simultaneously, under UV-light or natural light effect, can carry out sharp separation, efficient adsorption, fast degradation to the poisonous liquid organic pollutant of the typical cases such as toluene, phenol and process, even without also passing through efficient adsorption purified water source under optical condition.
In addition, this photo-catalysis function laminated film also can be used as treating the photosensitizers of the photodynamic therapy of cancer, after in the cancerous tissue of living, cancer cells contacts, externally under specific wavelength rayed, activate, the unstable ground state of returning of photosensitizers in excited state is emitted energy, with the effect of tumor tissues interior molecules state oxygen, produce singlet active oxygen (ROS) and some Active Radicals Produceds of destruction of cancer cells structure and function, reach the object for the treatment of cancer.The advantages such as the method has selective killing cancer cells, toxic side effects is few, treatment time is short, auxiliary other methods for the treatment of is noiseless.
Summary of the invention
Technical problem: the object of this invention is to provide a kind of laminated film with photo-catalysis function and preparation method thereof, this photo-catalysis function laminated film can be processed the capable sharp separation of the poisonous liquid organic pollutant of typical case, efficient adsorption, fast degradations such as toluene, phenol; Also can be used as a kind of efficient photosensitizers, for photodynamic therapy auxiliary for treating cancer.
Technical scheme: this laminated film with photo-catalysis function is to adopt differential arc oxidization technique to prepare the controlled titanium dioxide ceramic bottom of pattern at titanium or titanium alloy surface, the composite film of combined with cathode electro-deposition method growing rod/taper ZnO Nanocrystal around bottom hole wall.This laminated film can be applicable to the fields such as the purifying treatment of industrial toxic pollutant and clinical medicine photodynamic therapy auxiliary for treating cancer under photochemical catalysis subsidiary conditions.In differential arc oxidation process, breakdown and pyroceramic when titanium or titanium alloy surface generate zone of oxidation, titanium dioxide ceramic bottom and the metallic matrix bonding strength of vesicular structure are high; Pottery bottom hole wall is rod/taper ZnO Nanocrystal of deposition around, forms the compound photochromics of heterojunction semiconductor with titanium dioxide, has Photocatalytic enhancement effect.
The present invention is realized by the following technical programs:
This photo-catalysis function laminated film is to utilize composite semiconductor heterojunction that the regulated and controled porous titanium dioxide ceramic bottom that differential arc oxidization technique builds and the rod/taper nano zine oxide distributing along hole inwall the form photocatalysis characteristic under UV-light or natural light irradiation, sharp separation, absorption, degradable organic pollutant, also can be used as the efficient photosensitizers of optical dynamic therapy cancer.
The laminated film that the present invention has a photo-catalysis function is in titanium or titanium alloy surface preparation, by the zinc oxide nano rod of deposition growing on poriferous titanium dioxide bottom and surperficial hole wall thereof, is composited; Wherein, poriferous titanium dioxide bottom generates at surface of metal titanium in-situ oxidation by differential arc oxidation method, and in titanium dioxide bottom, disperse is distributed with aperture and is
micron hole; Zinc oxide nano rod is by electro-deposition method deposition growing on poriferous titanium dioxide bottom surface hole wall, and zinc oxide nano rod diameter exists
between, length exists
between.
The preparation method with the laminated film of photo-catalysis function of the present invention specifically realizes by following step:
A. titanium or titanium alloy pre-treatment: pure titanium or titanium alloy are passed through to mechanical polishing, ultrasonic cleaning, chemical rightenning, deionized water drip washing, dry successively, be placed in drying basin standby;
B. differential arc oxidation electrolyte quota: adopt carbonate system aqueous electrolyte liquid, include the Na of 2 ~ 50g/L
2cO
3, 0.5 ~ 5g/L KOH;
C. differential arc oxidation is processed: in above-mentioned carbonate system electrolyte solution, take titanium or titanium alloy as anode, stainless steel is negative electrode, adopts that bipolar pulse is microarc oxidation equipment provided carries out differential arc oxidation processing to titanium or titanium alloy, at titanium matrix surface, prepares poriferous titanium dioxide bottom;
D. galvanic deposit electrolyte quota: configuration packet is containing the Zn of 0.5～10mM
2+and and Zn
2+the galvanic deposit aqueous electrolyte liquid of the hexamethylenetetramine of equimolar amount (HMT), is placed in thermostat water bath, regulates temperature to be fixed between 65～95 ℃;
E. electrodeposition process: it is negative electrode that the step c of take processes titanium or the titanium alloy that the surface obtaining has poriferous titanium dioxide layer, Graphite Electrodes is anode, adopt two electrode cathode galvanic deposit systems to carry out the deposition growing of zinc oxide nano rod, employing deposition voltage is 1.0～100V, depositing time 10 ~ 100min.
Adopt that bipolar pulse is microarc oxidation equipment provided carries out differential arc oxidation while processing to titanium or titanium alloy, adopt forward voltage 200 ~ 1000V, negative voltage 0 ~ 300V, pulse-repetition regulation range: direct impulse 50Hz ~ 3000Hz, negative-going pulse frequency 1Hz ~ 3000Hz, dutycycle: forward 4% ~ 80%, negative sense 0% ~ 50%, the differential arc oxidation reaction times is 0.5 ~ 120min.
Beneficial effect:
(1) photo-catalysis function laminated film of the present invention is even by nano zine oxide photosensitizers, deposition is fixed on the TiO 2 porous material that is all semiconductor photosensitive material dispersedly, the heterojunction of both compound generations can become the center of bound exciton, both conduction bands, valence band relative position is different, absorbing the hole and the electronics that after luminous energy, produce can shift between both conduction bands and valence band, reduce the recombination probability of photo-generated carrier electron-hole, photoresponse strengthens, improve photocatalysis efficiency, further strongthener surface light catalytic effect, can be used as photodynamic therapy (PDT) photosensitizers, by producing singlet active oxygen (ROS) and some Active Radicals Produceds of destruction of cancer cells structure and function, reach the object for the treatment of cancer.
(2) photo-catalysis function laminated film of the present invention is with Adsorption and decomposition purification function, under UV-light or natural light effect, can carry out the auxiliary sharp separation of chemistry or electrochemistry, efficient adsorption, fast degradation to the poisonous liquid organic pollutant of the typical cases such as toluene, phenol and process, even without also passing through efficient adsorption purified water source under optical condition.Photo-catalysis function laminated film has highly developed microvoid structure and unique nano surface topological framework, and loading capacity is large, high adsorption capacity, and the advantage such as regenerate easy, is a kind of very good Photocatalysis Function Material.
Specific examples mode
1) first pure titanium or titanium alloy surface are passed through to mechanical polishing, ultrasonic cleaning, chemical rightenning, deionized water drip washing, drying and other steps successively, be placed in drying basin standby;
2) special electrolytic solutions of configuration carbonate system;
3) in above-mentioned carbonate system special electrolytic solutions, take titanium or titanium alloy is anode, stainless steel is negative electrode, adopt bipolar pulse differential arc oxidization technique to process sample surfaces, at matrix surface, build poriferous titanium dioxide bioactivity surface layer, change differential arc oxidation processing parameter with adjustment aperture size and pore structure, use successively alcohol and deionized water drip washing, dry, standby;
4) configuration packet is containing the Zn of 0.5～10mM
2+, and Zn
2+the mixed deposit liquid of the HMT of equimolar amount, is placed in thermostat water bath, regulates temperature to be fixed between 65～95 ℃;
5) by 3) in titanium or titanium alloy be negative electrode, Graphite Electrodes is anode, adopts two electrode cathode galvanic deposit systems to prepare rod/taper zinc oxide;
6) above-mentioned materials is taken out, deionized water drip washing, Preservation in sterile condition after sterilization, standby, get final product to such an extent that there is the photo-catalysis function laminated film of poriferous titanium dioxide and nanometer rod/taper zinc oxide semi-conductor heterojunction simultaneously.
The carbonate system special electrolytic solutions of addressing, includes the Na of 2 ~ 50g/L
2cO
3, 0.5 ~ 5g/L KOH.
The differential arc oxidation processing mode operating voltage regulation range of addressing: forward voltage 200 ~ 1000V, negative voltage 0 ~ 300V, pulse-repetition regulation range: direct impulse 50 ~ 3000Hz, negative-going pulse frequency 1 ~ 3000Hz, dutycycle: forward 4% ~ 80%, negative sense 0% ~ 50%, the differential arc oxidation reaction times is 0.5 ~ 120min.
The electrodeposition process mode processing parameter regulation range of addressing: Zn in boosting voltage 1.0～100V, deposit fluid
2+concentration 0.5 ~ 10mM, the concentration of HMT and Zn
2+equate depositing time 10 ~ 100min.
Embodiment 1
(1) first select technical pure Ti to process the body material of photocatalysis to degrade organic matter;
(2) pure titanium pre-treatment: by pure titanium body material use abrasive paper for metallograph that label is followed successively by 600#, 800#, 1000#, 1200# by coarse sand to fine sand sanding and polishing step by step, then use acetone, alcohol, distilled water ultrasonic cleaning, dried for standby.
(3) configuration of electrolytic solution: adopt sodium carbonate solution system, it is the sodium carbonate solution of 15g/L and the potassium hydroxide solution of 2g/L that configuration 10L contains concentration, and 40 ℃ of constant temperature stirring and dissolving are stand-by;
(4) differential arc oxidation of pure titanium: pure titanium matrix is placed in to the microarc oxidation equipment provided electrolyzer of bipolar pulse and adds the electrolytic solution configuring, take pure titanium as anode, stainless steel electrolytic groove is negative electrode, and adjusting process parameter is carried out differential arc oxidation.Processing parameter is: constant voltage mode, operating voltage regulation range forward voltage 300 ~ 600V, negative voltage 0V, pulse-repetition regulation range direct impulse 100 ~ 600Hz, dutycycle forward 12%, negative sense 0%, reaction times 10 ~ 15min;
(5) load of ZnO nanorod: above-mentioned taking-up is pure for titanium after alcohol, distilled water drip washing, be placed in the deposit fluid of electrodeposition apparatus electrolyzer, take pure titanium as negative electrode, and Graphite Electrodes is anode, and adjusting process parameter is at material surface deposition growing ZnO nano-structure.Processing parameter is: constant voltage mode, deposition voltage 1.0 ~ 2.5V, Zn in electrolyte solution
2+concentration is 0.5 ~ 10mM, the concentration of additive HMT and Zn
2+concentration equimolar amount, depositing time 10 ~ 100min;
(6) said sample is taken out, with after alcohol, distilled water drip washing, dry, standby, get final product to such an extent that the dispersed deposition of nano zine oxide photosensitizers of the present invention is fixed on the industrial photochemical catalysis absorption on the poriferous titanium dioxide surface that is all semiconductor photosensitive material, the function laminated film of the liquid organic pollutants such as toluene, phenol of degrading.
Embodiment 2
(1) first select medical Ti 6Al4V alloy to process photodynamic therapy body material;
(2) titanium alloy pre-treatment: by titanium alloy substrate use abrasive paper for metallograph that label is followed successively by 600#, 800#, 1000#, 1200# by coarse sand to fine sand sanding and polishing step by step, then use acetone, alcohol, distilled water ultrasonic cleaning, dried for standby.
(3) configuration of electrolytic solution: adopt sodium carbonate solution system, it is the sodium carbonate solution of 15g/L and the potassium hydroxide solution of 2g/L that configuration 10L contains concentration, and 40 ℃ of constant temperature stirring and dissolving are stand-by;
(4) differential arc oxidation of titanium alloy: titanium alloy is placed in to the microarc oxidation equipment provided electrolyzer of bipolar pulse and adds the electrolytic solution configuring, take Ti6Al4V alloy as anode, stainless steel electrolytic groove is negative electrode, and adjusting process parameter is carried out differential arc oxidation to titanium alloy.Processing parameter is: constant voltage mode, operating voltage regulation range forward voltage 300V, negative voltage 0V, pulse-repetition regulation range direct impulse 400Hz, dutycycle forward 12%, negative sense 0%, reaction times 15min;
(5) load of ZnO nano cone: by above-mentioned taking-up for sample after alcohol, distilled water drip washing, be placed in the deposit fluid of electrodeposition apparatus electrolyzer, take titanium alloy as negative electrode, and Graphite Electrodes is anode, and adjusting process parameter is at material surface deposition growing ZnO nano-structure.Processing parameter is: constant voltage mode, deposition voltage 2.0V, Zn in electrolytic solution
2+concentration is 2.5mM, the concentration of additive HMT and Zn
2+concentration equimolar amount, depositing time 15min;
(6) said sample is taken out, with after alcohol, distilled water drip washing, vacuum-drying, Preservation in sterile condition after sterilization, standby, get final product to obtain the photo-catalysis function laminated film that nano zine oxide photosensitizers of the present invention is even, dispersed deposition is fixed on the medical use optical dynamic therapy cancer on the poriferous titanium dioxide surface that is all semiconductor photosensitive material.
Embodiment 3
(1) first select industrial Ti6Al4V to process the body material of photocatalysis to degrade organic matter;
(2) Ti6Al4V pre-treatment: by body material use abrasive paper for metallograph that label is followed successively by 600#, 800#, 1000#, 1200# by coarse sand to fine sand sanding and polishing step by step, then use acetone, alcohol, distilled water ultrasonic cleaning, dried for standby.
(3) configuration of electrolytic solution: adopt sodium carbonate solution system, it is the sodium carbonate solution of 15g/L and the potassium hydroxide solution of 2g/L that configuration 10L contains concentration, and 40 ℃ of constant temperature stirring and dissolving are stand-by;
(4) differential arc oxidation of Ti6Al4V matrix: titanium alloy is placed in to the microarc oxidation equipment provided electrolyzer of bipolar pulse and adds the electrolytic solution configuring, take Ti6Al4V as anode, stainless steel electrolytic groove is negative electrode, and adjusting process parameter is carried out differential arc oxidation to titanium alloy.Processing parameter is: constant voltage mode, operating voltage regulation range forward voltage 300V, negative voltage 0V, pulse-repetition regulation range direct impulse 400Hz, dutycycle forward 12%, negative sense 0%, reaction times 15min;
(5) load of ZnO nanorod: said sample is taken out, with after alcohol, distilled water drip washing, be placed in the deposit fluid of electrodeposition apparatus electrolyzer, take titanium alloy as negative electrode, Graphite Electrodes is anode, and adjusting process parameter is at material surface deposition growing ZnO nano-structure.Processing parameter is: constant voltage mode, deposition voltage 1.5V, Zn in electrolytic solution
2+concentration is 5mM, the concentration of additive HMT and Zn
2+concentration equimolar amount, depositing time 15min;
(6) said sample is taken out, with after alcohol, distilled water drip washing, vacuum-drying is standby, gets final product to obtain the function laminated film that zinc oxide nano rod photosensitizers of the present invention is even, the liquid organic pollutants such as toluene, phenol are adsorbed, degrade in industrial photochemical catalysis that dispersed deposition is fixed on the poriferous titanium dioxide surface that is all semiconductor photosensitive material.
Obviously, the above embodiment of the present invention is only used to clearly demonstrate example of the present invention, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field; also can make other changes in different forms on the basis of the above description; here exhaustive without also giving all embodiments, and these belong to apparent variation that spirit of the present invention amplified out or change still in protection scope of the present invention.
Claims (3)
1. a laminated film with photo-catalysis function, is characterized in that this film is in the preparation of titanium or titanium alloy surface, by the zinc oxide nano rod of deposition growing on poriferous titanium dioxide bottom and surperficial hole wall thereof, is composited; Wherein, poriferous titanium dioxide bottom generates at surface of metal titanium in-situ oxidation by differential arc oxidation method, and in titanium dioxide bottom, disperse is distributed with the micron hole that aperture is 0.5 μ m-500 μ m; Zinc oxide nano rod by electro-deposition method deposition growing on poriferous titanium dioxide bottom surface hole wall, zinc oxide nano rod diameter between 0.05 μ m～1.5 μ m, length is between 0.1 μ m～10 μ m.
2. a preparation method with the laminated film of photo-catalysis function as claimed in claim 1, is characterized in that the method specifically realizes by following step:
A. titanium or titanium alloy pre-treatment: pure titanium or titanium alloy are passed through to mechanical polishing, ultrasonic cleaning, chemical rightenning, deionized water drip washing, dry successively, be placed in drying basin standby;
B. differential arc oxidation electrolyte quota: adopt carbonate system aqueous electrolyte liquid, include the Na of 2～50g/L
2cO
3, 0.5～5g/L KOH;
C. differential arc oxidation is processed: in above-mentioned carbonate system electrolyte solution, take titanium or titanium alloy as anode, stainless steel is negative electrode, adopts that bipolar pulse is microarc oxidation equipment provided carries out differential arc oxidation processing to titanium or titanium alloy, at titanium matrix surface, prepares poriferous titanium dioxide bottom;
D. galvanic deposit electrolyte quota: configuration packet is containing the Zn of 0.5～10mM
2+and and Zn
2+the galvanic deposit aqueous electrolyte liquid of the hexamethylenetetramine of equimolar amount (HMT), is placed in thermostat water bath, regulates temperature to be fixed between 65～95 ℃;
E. electrodeposition process: it is negative electrode that the step c of take processes titanium or the titanium alloy that the surface obtaining has poriferous titanium dioxide layer, Graphite Electrodes is anode, adopt two electrode cathode galvanic deposit systems to carry out the deposition growing of zinc oxide nano rod, employing deposition voltage is 1.0～100V, depositing time 10～100min.
3. a preparation method with the laminated film of photo-catalysis function as claimed in claim 2, it is characterized in that adopting that bipolar pulse is microarc oxidation equipment provided that titanium or titanium alloy are carried out to differential arc oxidation while processing, adopt forward voltage 200～1000V, negative voltage 0～300V, pulse-repetition regulation range: direct impulse 50Hz～3000Hz, negative-going pulse frequency 1Hz～3000Hz, dutycycle: forward 4%～80%, negative sense 0%～50%, the differential arc oxidation reaction times is 0.5～120min.
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| CN102090982A (en) * | 2011-01-21 | 2011-06-15 | 东南大学 | Artificial tooth root or joint material and microarc oxidation preparation method thereof |
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| CN102090982A (en) * | 2011-01-21 | 2011-06-15 | 东南大学 | Artificial tooth root or joint material and microarc oxidation preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 付薇.纳米结构ZnO在TiO2薄膜上的电化学沉积及其光电性能.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2009,(第2期),34-55. |
| 纳米结构ZnO在TiO2薄膜上的电化学沉积及其光电性能;付薇;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20090115(第2期);34-55 * |
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