CN103447017B - Laser modification treatment process of titanium oxide photocatalytic film - Google Patents
Laser modification treatment process of titanium oxide photocatalytic film Download PDFInfo
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- CN103447017B CN103447017B CN201310422337.7A CN201310422337A CN103447017B CN 103447017 B CN103447017 B CN 103447017B CN 201310422337 A CN201310422337 A CN 201310422337A CN 103447017 B CN103447017 B CN 103447017B
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- titanium oxide
- film
- thin film
- oxide photocatalytic
- photocatalytic thin
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000008569 process Effects 0.000 title claims abstract description 20
- 230000004048 modification Effects 0.000 title claims abstract description 9
- 238000012986 modification Methods 0.000 title claims abstract description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 56
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- 239000010408 film Substances 0.000 claims description 26
- 239000010409 thin film Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 13
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 12
- 229940043237 diethanolamine Drugs 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 241000931526 Acer campestre Species 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000005457 optimization Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000007146 photocatalysis Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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Abstract
The invention discloses a laser modification treatment process of a titanium oxide photocatalytic film. Influences of process parameters of laser modification treatment to film performance are systematically researched so as to obtain optimal laser modification process parameters to obtain a titanium oxide photocatalytic film with excellent catalytic performance. The result indicates that the process treatment parameters of laser modification have great influence on the photocatalytic performance of the film, and the titanium oxide photocatalytic film with the optimal performance is prepared through reasonable optimization.
Description
Technical field
The present invention relates to titanium oxide photochemical catalyst technical field, particularly a kind of laser modified treatment process of titanium oxide photocatalytic thin film.
Background technology
Titanium oxide (TiO
2) there is excellent UV-irradiation photocatalysis performance, can effective smelly eliminating, antibacterial, antifouling, in addition good stability, nontoxic, with low cost etc. a little, be widely used as catalysis material use and study.But the forbidden band of titanium oxide is wider, the ultraviolet only having wavelength to be less than 380nm just can excite and produce photo-generate electron-hole pair, and for longer visible light-responded poor of wavelength.
In order to expand application and the effect of titanium oxide, carry out modification for titanium oxide in recent years prevailing with the research improving its visible ray utilization rate, wherein main method of modifying comprises noble metal loading, ion doping, semiconductors coupling etc.But these methods are all add certain interpolation adulterant in the preparation process of titanium oxide, improve preparation and the use cost of titanium oxide catalyst, technique is also comparatively complicated.
Laser modified is that one is comparatively effective in titanium oxide inside formation oxygen element defect, thus change its band structure, improve the effective method of photocatalysis performance, such as, disclose a kind of preparation and method of modifying of titanium oxide catalyst in ZL200810201419.8.But its raw material is numerous and diverse, application single (being mainly object with fabric), for laser modified research and for the research of initial film also very superficial, not system, is difficult to carry out effectively applying widely.
Summary of the invention
Namely object of the present invention is preparation method and the modified technique of system research titanium oxide catalyst film, to obtaining the titanium oxide photocatalytic thin film with best catalytic performance.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for titanium oxide photocatalytic thin film, is characterized in that comprising the following steps:
(1) by mol ratio be four titanium isopropoxide and the absolute ethyl alcohol mixture in a reservoir of 1:6-8, adopt electromagnetic agitation 15-20min, obtain A liquid;
(2) be dropwise added drop-wise to by diethanol amine in A liquid, dripping quantity is 0.2-0.25 times of four titanium isopropoxide moles, subsequently by mixed solution electromagnetic agitation 35-40min, obtains B liquid;
(3) be dropwise added drop-wise to by acetic acid in B liquid, dripping quantity is 0.35-0.4 times of four titanium isopropoxide moles, subsequently mixed solution electromagnetic agitation 4-5h is obtained colloidal sol;
(4) adopt pottery as substrate, first by substrate with after acetone ultrasonic cleaning 10min, then under 100-120 DEG C of condition, dry that 10min is simultaneously auxiliary blows N
2, subsequently colloidal sol is dropped on substrate and implements spin coating 1-1.5min with the rotating speed of 2000-2200rpm, obtain wet film;
(5) ceramic substrate of coating wet film is placed in Muffle furnace and is warming up to 400-420 DEG C with the heating rate of 2-2.5 DEG C/min, roasting 2.5-3h;
Preferred further, the mol ratio of four titanium isopropoxide and absolute ethyl alcohol is 1:7.
Preferred further, the dripping quantity of diethanol amine is 0.25 times of four titanium isopropoxide moles.
Preferred further, the dripping quantity of acetic acid is 0.38 times of four titanium isopropoxide moles.
For improving the catalytic performance of the titanium oxide photocatalytic thin film obtained further, carry out laser modified process to the titanium oxide photocatalytic thin film on the ceramic substrate obtained, described laser modified condition is:
Laser vertical irradiation, optical maser wavelength is 800nm, pulse width 160-180fs, frequency 1kHz, spot diameter 300 μm, and sweep speed is 1.5-2mm/s, and overlapping rate is 50-60%, and energy density is 50-60mJ/cm
2; Film after laser modified process is placed in annealing furnace, is warming up to 500-550 DEG C with the heating rate of 5-8 DEG C/min, annealing 1-1.5h, obtains the titanium oxide catalyst film product through modification.
Preferred further, energy density is 55 mJ/cm
2.
Preferred further, annealing temperature is 530 DEG C.
Advantage of the present invention is: preferred raw material and corresponding preparation technology parameter, obtains titanium oxide photocatalytic thin film by simple sol method, and successfully improves the photocatalysis performance of film by rational laser modified and annealing process.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail.
Embodiment 1.
(1) by mol ratio be four titanium isopropoxide and the absolute ethyl alcohol mixture in a reservoir of 1:6, adopt electromagnetic agitation 20min, obtain A liquid;
(2) be dropwise added drop-wise to by diethanol amine in A liquid, dripping quantity is 0.2 times of four titanium isopropoxide moles, subsequently by mixed solution electromagnetic agitation 40min, obtains B liquid;
(3) be dropwise added drop-wise to by acetic acid in B liquid, dripping quantity is 0.35 times of four titanium isopropoxide moles, subsequently mixed solution electromagnetic agitation 4h is obtained colloidal sol;
(4) adopt pottery as substrate, first by substrate with after acetone ultrasonic cleaning 10min, then under 110 DEG C of conditions, dry that 10min is simultaneously auxiliary blows N
2, subsequently colloidal sol is dropped on substrate and implements spin coating 1.5min with the rotating speed of 2000rpm, obtain wet film;
(5) ceramic substrate of coating wet film is placed in Muffle furnace and is warming up to 400 DEG C with the heating rate of 2.5 DEG C/min, roasting 3h;
(6) laser modified process is carried out to the titanium oxide photocatalytic thin film on the ceramic substrate obtained, described laser modified condition is, laser vertical irradiation, optical maser wavelength is 800nm, pulse width 170fs, frequency 1kHz, spot diameter 300 μm, sweep speed is 2mm/s, and overlapping rate is 60%, and energy density is 50mJ/cm
2;
(7) film after laser modified process is placed in annealing furnace, is warming up to 500 DEG C with the heating rate of 6 DEG C/min, annealing 1.5h, obtains final titanium oxide catalyst film product.
Embodiment 2.
Be that the mol ratio of four titanium isopropoxide and absolute ethyl alcohol is 1:7 with the main difference of embodiment 1.
Embodiment 3.
Be that the mol ratio of four titanium isopropoxide and absolute ethyl alcohol is 1:8 with the main difference of embodiment 1.
Comparative example 1.
Be that the mol ratio of four titanium isopropoxide and absolute ethyl alcohol is 1:4 with the main difference of embodiment 1.
Comparative example 2.
Be that the mol ratio of four titanium isopropoxide and absolute ethyl alcohol is 1:10 with the main difference of embodiment 1.
The mol ratio of four titanium isopropoxide and absolute ethyl alcohol adopts the acetaldehyde of original concentration 100ppm as decomposition object for the impact of film light catalytic performance see table 1(, uses the visible light exposure of the ultraviolet B radiation of 320nm and 700nm to measure residual acetaldehyde concentration after 2 hours as evaluation criterion respectively).
As shown in Table 1, the mol ratio of four titanium isopropoxide and absolute ethyl alcohol has the impact of outbalance for the photocatalysis performance of film, too high absolute ethyl alcohol blend amount too will suppress four titanium isopropoxide active thus affect preparation quality and the photocatalysis performance of thin film of titanium oxide, and too low absolute ethyl alcohol blend amount will cause thin film of titanium oxide quality uneven owing to not playing corresponding inhibitory action and affects its photocatalytic activity, the limited proportion of the two is 1:6-8 by the application, preferred 1:7.
Embodiment 4.
Be that the dripping quantity of diethanol amine is 0.25 times of four titanium isopropoxide moles with the main difference of embodiment 1.
Comparative example 3.
Be that the dripping quantity of diethanol amine is 0.3 times of four titanium isopropoxide moles with the main difference of embodiment 1.
Comparative example 4.
Be that the dripping quantity of diethanol amine is 0.1 times of four titanium isopropoxide moles with the main difference of embodiment 1.
The dripping quantity of diethanol amine is identical with table 1 see table 2(appreciation condition for the impact of film light catalytic performance).
As shown in Table 2, the addition of diethanol amine is for the impact of film catalyst performance and obvious not as ethanol, but still need reasonably to add, too high diethanol amine dripping quantity can't promote the formation of colloidal sol and film better, and too low diethanol amine dripping quantity affects preparation quality and the photocatalysis performance of thin film of titanium oxide by causing the insufficient of hydrolysis, the dripping quantity of diethanol amine is 0.2-0.25 times of four titanium isopropoxide moles by the application, is preferably 0.25 times.
Embodiment 5.
Be that the dripping quantity of acetic acid is 0.38 times of four titanium isopropoxide moles with the main difference of embodiment 1.
Embodiment 6.
Be that the dripping quantity of acetic acid is 0.4 times of four titanium isopropoxide moles with the main difference of embodiment 1.
Comparative example 5.
Be that the dripping quantity of acetic acid is 0.3 times of four titanium isopropoxide moles with the main difference of embodiment 1.
Comparative example 6.
Be that the dripping quantity of acetic acid is 0.5 times of four titanium isopropoxide moles with the main difference of embodiment 1.
The dripping quantity of acetic acid is identical with table 1 see table 3(appreciation condition for the impact of film light catalytic performance).
As shown in Table 3, the addition of acetic acid is very important for the impact of film catalyst performance, the addition of too high acetic acid will make hydrolysis too violent and cause the uniformity of thin film of titanium oxide to be deteriorated and then catalytic performance variation, and the generation being difficult to the reaction of effective facilitation of hydrolysis causes thin film of titanium oxide of poor quality and affects its photocatalytic activity by the addition of too low acetic acid, the dripping quantity of acetic acid is 0.35-0.4 times of four titanium isopropoxide moles by the application, is preferably 0.38 times.
Embodiment 7.
Be that energy density is 55mJ/cm with the main difference of embodiment 1
2.
Embodiment 8.
Be that energy density is 60mJ/cm with the main difference of embodiment 1
2.
Comparative example 7.
Be that energy density is 40mJ/cm with the main difference of embodiment 1
2.
Comparative example 8.
Be that energy density is 70mJ/cm with the main difference of embodiment 1
2.
Comparative example 9.
Modification and the annealing in process of not implementation step (6), (7) is with the main difference of embodiment 1.
Laser modified energy density is identical with table 1 see table 4(appreciation condition for the impact of film light catalytic performance).
As shown in Table 4, the test result of No. 9, the comparative example of non-modified process, although photocatalysis performance change is little after ultraviolet irradiation, visible light part impact clearly.In addition, although along with the rising of irradiation energy density, the photocatalysis performance of film raises gradually, but cross senior general due to energy density and material impact is produced to the mechanical property of film and profile, and consider that too high energy density can not obtain more significant performance change, therefore the laser energy density upper limit is set as 60 mJ/cm
2, lower limit set is 50 mJ/cm
2, preferably 55 mJ/cm
2.
In addition, consider to compare annealed process and the sample without annealing in process, find to be warming up to 500-550 DEG C with the heating rate of 5-8 DEG C/min, annealing 1-1.5h, can be good at mechanical property and the stability of improving film, particularly preferably the heating rate of 6 DEG C/min is warming up to 500 DEG C, annealing 1.5h.
Claims (2)
1. a laser modified treatment process for titanium oxide photocatalytic thin film, is characterized in that comprising the following steps:
(1) adopt pottery as substrate, prepare titanium oxide photocatalytic thin film on its surface;
(2) further laser modified process is carried out to the titanium oxide photocatalytic thin film on the ceramic substrate obtained, described laser modified condition is: laser vertical irradiation, optical maser wavelength is 800nm, pulse width 160-180fs, frequency 1kHz, spot diameter 300 μm, sweep speed is 1.5-2mm/s, overlapping rate is 50-60%, and energy density is 55mJ/cm
2; Film after laser modified process is placed in annealing furnace, is warming up to 500-550 DEG C with the heating rate of 5-8 DEG C/min, annealing 1-1.5h, obtains the titanium oxide catalyst film product through modification;
Wherein, prepare titanium oxide photocatalytic thin film specifically at ceramic base plate surface: four titanium isopropoxide and the absolute ethyl alcohol mixture in a reservoir that by mol ratio are 1:7, adopt electromagnetic agitation 15-20min, obtain A liquid; Dropwise be added drop-wise to by diethanol amine in A liquid, dripping quantity is 0.25 times of four titanium isopropoxide moles, subsequently by mixed solution electromagnetic agitation 35-40min, obtains B liquid; Dropwise be added drop-wise to by acetic acid in B liquid, dripping quantity is 0.38 times of four titanium isopropoxide moles, subsequently mixed solution electromagnetic agitation 4-5h is obtained colloidal sol; By ceramic substrate with after acetone ultrasonic cleaning 10min, then under 100-120 DEG C of condition, dry that 10min is simultaneously auxiliary blows N
2, subsequently colloidal sol is dropped on substrate and implements spin coating 1-1.5min with the rotating speed of 2000-2200rpm, obtain wet film; The ceramic substrate of coating wet film is placed in Muffle furnace and is warming up to 400-420 DEG C with the heating rate of 2-2.5 DEG C/min, roasting 2.5-3h.
2. the laser modified treatment process of titanium oxide photocatalytic thin film according to claim 1, is characterized in that: annealing temperature is 530 DEG C.
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| CN110230084B (en) * | 2019-04-15 | 2020-09-11 | 清华大学 | Titanium surface polycrystalline structure forming method and system based on femtosecond laser annealing treatment |
| CN112844349B (en) * | 2019-11-28 | 2023-05-05 | 桂林理工大学 | Method for preparing TiOx photo-anode by utilizing laser etching Ti sheet |
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| CN101391210A (en) * | 2008-10-21 | 2009-03-25 | 东华大学 | Preparation method of laser modified titanium dioxide photocatalyst |
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| JP特开2002-356650A 2002.12.13 * |
| 涂亚芳 等.Ce掺杂TiO2纳米薄膜的制备及其光催化性能研究.《江汉大学学报(自然科学版)》.2012,第40卷(第6期),第17-20页. * |
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