CN102747404A - 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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- CN102747404A CN102747404A CN2012102430378A CN201210243037A CN102747404A CN 102747404 A CN102747404 A CN 102747404A CN 2012102430378 A CN2012102430378 A CN 2012102430378A CN 201210243037 A CN201210243037 A CN 201210243037A CN 102747404 A CN102747404 A CN 102747404A
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- titanium
- composite film
- titanium alloy
- differential arc
- arc oxidation
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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; Be in titanium or titanium alloy surface preparation; Be composited by zinc oxide nano rod or the nanocone through deposition growth on differential arc oxidation poriferous titanium dioxide bottom and the surperficial hole wall thereof, belong to the field of photocatalytic material that can be used for toxic pollutant purifying treatment, PDT 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 handling a kind of simple and efficient of fluid contaminants, utilizes nano-TiO
2Under ultraviolet and visible light, be formed with the free hydroxy (OH) and the active oxygen (O) of strong oxidative decomposition capacity at material surface, will decompose attached to the organic substance on surface.But in water, under the unglazed or half-light condition, be difficult to obtain satisfied effect.To this problem, studying more at present is to adopt absorption to add photocatalysis technology, generally adopts NACF (ACF) as carrier loaded TiO
2Catalyzer utilizes the absorption property of ACF that pollutent is adsorbed fast, reaches the enrichment of pollutent on the ACF carrier, quickens light-catalyzed reaction speed.But ACF is very low to organic pollutant adsorption index in the water, even in air, when relative humidity was big, ACF also can sharply descend to organic pollutant adsorption capacity such as toluene; Therefore suitable carriers remains the problem that this Technology Need obtains fine solution.
Photo-catalysis function laminated film of the present invention is with absorption and decomposing, purifying function; Also has the peculiar photochemical catalysis reinforcing effect of heterojunction that two kinds of photosensitive materials of semi-conductor are compounded to form simultaneously; Under UV-light or natural light effect; Can carry out sharp separation, efficient absorption, quick degradation treatment to the poisonous liquid organic pollutant of typical cases such as toluene, phenol, even under no optical condition, also can pass through efficient adsorption cleaning water source.
In addition; This photo-catalysis function laminated film also can be used as the photosensitizers of the PDT of treating cancer, after cancer cells contacts in the cancerous tissue of living, externally activates under the specific wavelength rayed; The photosensitizers instability that is in excited state is returned ground state and is emitted energy; With the effect of tumor tissues interior molecules attitude oxygen, produce singlet active oxygen (ROS) and some active radicals of destruction of cancer cells 26S Proteasome Structure and Function, reach the purpose of treatment cancer.Advantages such as this method has the selective killing cancer cells, toxic side effects is few, treatment time is short, auxiliary other treat-ment is noiseless.
Summary of the invention
Technical problem: the purpose 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 to the capable sharp separation of the poisonous liquid organic pollutant of typical case such as toluene, phenol, efficient absorption, quick degradation treatment; Also can be used as a kind of photosensitizers efficiently, be used for the PDT 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 combined with cathode electro-deposition method rod/taper nano zine oxide crystalline composite film of around the bottom hole wall, growing.This laminated film can be applicable to fields such as purifying treatment and the clinical medicine PDT auxiliary for treating cancer of toxic pollutant in the industry under the photochemical catalysis subsidiary conditions.In the differential arc oxidation process, breakdown and pyroceramicization when titanium or titanium alloy surface generate zone of oxidation, the titanium dioxide ceramic bottom of vesicular structure and metallic matrix bonding strength are high; Sedimentary rod/taper nano zine oxide crystal around the pottery bottom hole wall forms the compound photochromics of heterojunction semiconductor with titanium oxide, has the photochemical catalysis reinforcing effect.
The present invention realizes through following technical scheme:
This photo-catalysis function laminated film is the photocatalysis characteristic of composite semiconductor heterojunction under UV-light or natural light irradiation that utilizes the adjustable porous titanium dioxide ceramic bottom of differential arc oxidization technique structure and the rod that distributes along the hole inwall/taper nano zine oxide composition; 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, is composited by the zinc oxide nano rod of deposition growing on poriferous titanium dioxide bottom and the surperficial hole wall thereof; Wherein, The poriferous titanium dioxide bottom generates at the surface of metal titanium in-situ oxidation through differential arc oxidation method, and disperse is distributed with the micron hole of aperture for
in the titanium oxide bottom; Zinc oxide nano rod through the electro-deposition method deposition growing on poriferous titanium dioxide bottom surface hole wall, the zinc oxide nano rod diameter between
, length is between
.
Preparing method with laminated film of photo-catalysis function of the present invention specifically realizes through following step:
A. titanium or titanium alloy pre-treatment: pure titanium or titanium alloy are passed through mechanical polishing, ultrasonic cleaning, chemical rightenning, deionized water drip washing, drying successively, place drying basin subsequent use;
B. differential arc oxidation electrolyte quota: adopt the carbonate system aqueous electrolyte liquid, include the Na of 2 ~ 50g/L
2CO
3, 0.5 ~ 5g/L KOH;
C. differential arc oxidation is handled: in above-mentioned carbonate system electrolyte solution; With titanium or titanium alloy is anode; Stainless steel is a negative electrode, and the employing bipolar pulse is microarc oxidation equipment provided to carry out the differential arc oxidation processing to titanium or titanium alloy, prepares the poriferous titanium dioxide bottom at the titanium matrix surface;
D. galvanic deposit electrolyte quota: configuration comprises the Zn of 0.5～10mM
2+And and Zn
2+The galvanic deposit aqueous electrolyte liquid of the hexamethylenetetramine of equimolar amount (HMT) places thermostat water bath, and attemperation is fixed between 65～95 ℃;
E. electrodeposition process: handling titanium or the titanium alloy that the surface that obtains has the poriferous titanium dioxide layer with step c is negative electrode; Graphite Electrodes is an anode; Adopt two electrode cathode galvanic deposit systems to carry out the deposition growing of zinc oxide nano rod; The employing deposition voltage is 1.0～100V, depositing time 10 ~ 100min.
Adopt that bipolar pulse is microarc oxidation equipment provided to carry out differential arc oxidation when handling 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 deposits the nano zine oxide photosensitizers evenly, dispersedly and is fixed on the TiO 2 porous material that is all the photosensitive material of semi-conductor; The heterojunction of both compound generations can become the center of bound exciton; Both conduction bands, valence band relative position difference, absorbing the hole and the electronics that produce behind the luminous energy can shift between both conduction bands and valence band, reduces the recombination probability in photo-generated carrier electronics-hole; Photoresponse strengthens; Improve photocatalysis efficiency, further strongthener surface light catalytic effect, can be used as PDT (PDT) photosensitizers; Through producing singlet active oxygen (ROS) and some active radicals of destruction of cancer cells 26S Proteasome Structure and Function, reach the purpose of treatment cancer.
(2) photo-catalysis function laminated film of the present invention is with absorption and decomposing, purifying function; Under UV-light or natural light effect; Can carry out the auxiliary sharp separation of chemistry or electrochemistry, efficient absorption, degradation treatment fast to the poisonous liquid organic pollutant of typical cases such as toluene, phenol, even under no optical condition, also can pass through efficient adsorption cleaning water source.Advantages such as the photo-catalysis function laminated film has highly developed microvoid structure and unique nano surface topological framework, and loading capacity is big, high adsorption capacity, and it is easy to regenerate are a kind of very good photo-catalysis function materials.
The specific examples mode
1) at first pure titanium or titanium alloy surface are passed through mechanical polishing, ultrasonic cleaning, chemical rightenning, deionized water drip washing, drying and other steps successively, place drying basin subsequent use;
2) special electrolytic solutions of configuration carbonate system;
3) in above-mentioned carbonate system special electrolytic solutions, be anode with titanium or titanium alloy; Stainless steel is a negative electrode, adopts the bipolar pulse differential arc oxidization technique that sample surfaces is handled, and makes up poriferous titanium dioxide bioactivity surface layer at matrix surface; Change the differential arc oxidation processing parameter with adjustment aperture size and pore structure; Use alcohol and deionized water drip washing successively, drying, subsequent use;
4) configuration comprises the Zn of 0.5～10mM
2+, and Zn
2+The mixed deposit liquid of the HMT of equimolar amount places thermostat water bath, and attemperation is fixed between 65～95 ℃;
5) with 3) in titanium or titanium alloy be negative electrode, Graphite Electrodes is an 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, the sterilization aseptic preservation in back, subsequent use, get final product to such an extent that have 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 being addressed includes the Na of 2 ~ 50g/L
2CO
3, 0.5 ~ 5g/L KOH.
The differential arc oxidation processing mode WV regulation range of being addressed: 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 being addressed: Zn in boosting voltage 1.0～100V, the deposit fluid
2+Concentration 0.5 ~ 10mM, the concentration of HMT and Zn
2+Equate depositing time 10 ~ 100min.
Embodiment 1
(1) at first select for use technical pure Ti to process the body material of photocatalysis to degrade organic matter;
(2) pure titanium pre-treatment: with 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, use acetone, alcohol, zero(ppm) water ultrasonic cleaning then, dried for standby.
(3) configuration of electrolytic solution: adopt the 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 for use;
(4) differential arc oxidation of pure titanium: pure titanium matrix is placed the microarc oxidation equipment provided electrolyzer of bipolar pulse and adds the electrolytic solution that configures, and is anode with pure titanium, and the stainless steel electrolytic groove is a negative electrode, regulates processing parameter and carries out differential arc oxidation.Processing parameter is: constant voltage mode, WV 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 nanometer rod: with the pure titanium of above-mentioned taking-up with alcohol, zero(ppm) water drip washing after; Be placed in the deposit fluid of electrodeposition apparatus electrolyzer; With pure titanium is negative electrode, and Graphite Electrodes is an anode, regulates processing parameter in material surface deposition growing ZnO nanostructure.Processing parameter is: constant voltage mode, deposition voltage 1.0 ~ 2.5V, Zn in the electrolyte solution
2+Concentration is 0.5 ~ 10mM, the concentration of additive HMT and Zn
2+The concentration equimolar amount, depositing time 10 ~ 100min;
(6) said sample is taken out; After alcohol, zero(ppm) water drip washing; Dry; Subsequent use, get final product to such an extent that nano zine oxide photosensitizers homodisperse deposition of the present invention is fixed on the industrial photochemical catalysis absorption on the poriferous titanium dioxide surface that is all the photosensitive material of semi-conductor, the function laminated film of the liquid organic pollutants such as toluene, phenol of degrading.
Embodiment 2
(1) at first select for use medical Ti 6Al4V alloy to process the PDT body material;
(2) titanium alloy pre-treatment: with 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, use acetone, alcohol, zero(ppm) water ultrasonic cleaning then, dried for standby.
(3) configuration of electrolytic solution: adopt the 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 for use;
(4) differential arc oxidation of titanium alloy: titanium alloy is placed the microarc oxidation equipment provided electrolyzer of bipolar pulse and adds the electrolytic solution that configures, and is anode with the Ti6Al4V alloy, and the stainless steel electrolytic groove is a negative electrode, regulates processing parameter titanium alloy is carried out differential arc oxidation.Processing parameter is: constant voltage mode, WV 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 nanocone: with above-mentioned taking-up sample with alcohol, zero(ppm) water drip washing after; Be placed in the deposit fluid of electrodeposition apparatus electrolyzer; With the titanium alloy is negative electrode, and Graphite Electrodes is an anode, regulates processing parameter in material surface deposition growing ZnO nanostructure.Processing parameter is: constant voltage mode, deposition voltage 2.0V, Zn in the electrolytic solution
2+Concentration is 2.5mM, the concentration of additive HMT and Zn
2+The concentration equimolar amount, depositing time 15min;
(6) said sample is taken out; After alcohol, zero(ppm) water drip washing; Vacuum-drying; The aseptic preservation in sterilization back, subsequent use, get final product nano zine oxide photosensitizers of the present invention evenly, dispersed deposition is fixed on the photo-catalysis function laminated film of the medical use optical dynamic therapy cancer on the poriferous titanium dioxide surface that is all the photosensitive material of semi-conductor.
Embodiment 3
(1) at first select for use industrial Ti6Al4V to process the body material of photocatalysis to degrade organic matter;
(2) Ti6Al4V pre-treatment: with 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, use acetone, alcohol, zero(ppm) water ultrasonic cleaning then, dried for standby.
(3) configuration of electrolytic solution: adopt the 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 for use;
(4) differential arc oxidation of Ti6Al4V matrix: titanium alloy is placed the microarc oxidation equipment provided electrolyzer of bipolar pulse and adds the electrolytic solution that configures; With Ti6Al4V is anode; The stainless steel electrolytic groove is a negative electrode, regulates processing parameter titanium alloy is carried out differential arc oxidation.Processing parameter is: constant voltage mode, WV 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 nanometer rod: said sample is taken out; After alcohol, zero(ppm) water drip washing, be placed in the deposit fluid of electrodeposition apparatus electrolyzer, with the titanium alloy negative electrode; Graphite Electrodes is an anode, regulates processing parameter in material surface deposition growing ZnO nanostructure.Processing parameter is: constant voltage mode, deposition voltage 1.5V, Zn in the electrolytic solution
2+Concentration is 5mM, the concentration of additive HMT and Zn
2+The concentration equimolar amount, depositing time 15min;
(6) said sample is taken out; After alcohol, zero(ppm) water drip washing; Vacuum-drying is subsequent use, get final product zinc oxide nano rod photosensitizers of the present invention evenly, dispersed deposition is fixed on the function laminated film of the liquid organic pollutants such as industrial photochemical catalysis absorption, degraded toluene, phenol on the poriferous titanium dioxide surface that is all the photosensitive material of semi-conductor.
Obviously, the above embodiment of the present invention only be for clearly demonstrate that the present invention does for example, and be not to be qualification to embodiment of the present invention.Those of ordinary skill for affiliated field; Also can on the basis of above-mentioned explanation, make other multi-form variation or change; Here need not also can't give all embodiments exhaustive, and these belong to conspicuous variation or the change that spirit of the present invention amplified out and still are in protection scope of the present invention.
Claims (3)
1. laminated film with photo-catalysis function is characterized in that this film is in titanium or titanium alloy surface preparation, is composited by the zinc oxide nano rod of deposition growing on poriferous titanium dioxide bottom and the surperficial hole wall thereof; Wherein, The poriferous titanium dioxide bottom generates at the surface of metal titanium in-situ oxidation through differential arc oxidation method, and disperse is distributed with the micron hole of aperture for
in the titanium oxide bottom; Zinc oxide nano rod through the electro-deposition method deposition growing on poriferous titanium dioxide bottom surface hole wall, the zinc oxide nano rod diameter between
, length is between
.
2. preparation method with laminated film of photo-catalysis function as claimed in claim 1 is characterized in that this method is specifically through following step realization:
A. titanium or titanium alloy pre-treatment: pure titanium or titanium alloy are passed through mechanical polishing, ultrasonic cleaning, chemical rightenning, deionized water drip washing, drying successively, place drying basin subsequent use;
B. differential arc oxidation electrolyte quota: adopt the carbonate system aqueous electrolyte liquid, include the Na of 2 ~ 50g/L
2CO
3, 0.5 ~ 5g/L KOH;
C. differential arc oxidation is handled: in above-mentioned carbonate system electrolyte solution; With titanium or titanium alloy is anode; Stainless steel is a negative electrode, and the employing bipolar pulse is microarc oxidation equipment provided to carry out the differential arc oxidation processing to titanium or titanium alloy, prepares the poriferous titanium dioxide bottom at the titanium matrix surface;
D. galvanic deposit electrolyte quota: configuration comprises the Zn of 0.5～10mM
2+And and Zn
2+The galvanic deposit aqueous electrolyte liquid of the hexamethylenetetramine of equimolar amount (HMT) places thermostat water bath, and attemperation is fixed between 65～95 ℃;
E. electrodeposition process: handling titanium or the titanium alloy that the surface that obtains has the poriferous titanium dioxide layer with step c is negative electrode; Graphite Electrodes is an anode; Adopt two electrode cathode galvanic deposit systems to carry out the deposition growing of zinc oxide nano rod; The employing deposition voltage is 1.0～100V, depositing time 10 ~ 100min.
3. preparation method with 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 differential arc oxidation when handling; Adopt forward voltage 200～1000V, negative voltage 0 ~ 300V; The 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109655443A (en) * | 2019-01-14 | 2019-04-19 | 中国人民解放军火箭军工程大学 | Silver-colored carried titanium dioxide nano-array laminated film, preparation method and its application in trace materials detection |
Citations (2)
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|---|---|---|---|---|
| US20030059742A1 (en) * | 2001-09-24 | 2003-03-27 | Webster Thomas J. | Osteointegration device and method |
| CN102090982A (en) * | 2011-01-21 | 2011-06-15 | 东南大学 | Artificial tooth root or joint material and microarc oxidation preparation method thereof |
-
2012
- 2012-07-13 CN CN201210243037.8A patent/CN102747404B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030059742A1 (en) * | 2001-09-24 | 2003-03-27 | Webster Thomas J. | Osteointegration device and method |
| 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 (1)
| 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》, no. 2, 15 January 2009 (2009-01-15), pages 34 - 55 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109655443A (en) * | 2019-01-14 | 2019-04-19 | 中国人民解放军火箭军工程大学 | Silver-colored carried titanium dioxide nano-array laminated film, preparation method and its application in trace materials detection |
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