CN1935379A - Planar photocatalytic device and its preparing method - Google Patents
Planar photocatalytic device and its preparing method Download PDFInfo
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- CN1935379A CN1935379A CN 200610112508 CN200610112508A CN1935379A CN 1935379 A CN1935379 A CN 1935379A CN 200610112508 CN200610112508 CN 200610112508 CN 200610112508 A CN200610112508 A CN 200610112508A CN 1935379 A CN1935379 A CN 1935379A
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Abstract
The present invention provides a full-solid photocatalytic device and its preparation method. The described device includes an insulating base, at least a pair of strip electrodes fixed on said insulating base, and semiconductor photocatalyst loaded on the described insulating base and strip electrodes. Besides, said invention also provides the concrete steps of its preparation method.
Description
Technical field
The present invention relates to a kind of photochemical catalyst and preparation method thereof, especially a kind of all solid state planar photocatalytic device and preparation method thereof belongs to the conductor photocatalysis technical field.
Background technology
Utilize the activity of the resulting photochemical catalyst sample of technology of preparing of existing film photocatalyst all lower, this is because photochemical catalyst (mainly is TiO
2) in the right recombination probability in light induced electron and hole very high, cause the photo-generated carrier utilization ratio lower, restricted the practical application in industry of conductor photocatalysis technology thus.Though to TiO
2Carry out modification (as utilize various metals and nonmetal doping and noble metal loading, multiple oxide bulk is mutually compound, in conjunction with organic dye sensitized and loadization on various bigger serface carriers etc.) can improve the utilization ratio in electronics-hole to a certain extent, improve photocatalytic activity, obvious improved effect is not arranged in essence but all obtain generally.
There is the researcher that " electricity helps photocatalysis technology " studied in recent years, thereby promptly promotes light induced electron and reach a kind of enhancement mode photocatalysis technology that improves the photocatalysis technology treatment effeciency separating of hole by extra electric field.In contrast to photocatalysis, electricity helps photocatalysis to promote separating of light induced electron and hole, and semi-conductive photocurrent response and quantum efficiency are improved, and light-catalysed efficient is increased, and have the photoelectric-synergetic effect, more help utilizing solar energy to carry out the research of photocatalysis aspect.But what currently used electricity helped that photocatalysis technology all adopts is photoelectrochemistrpool pool, according to the electrode number of electrochemical system, can be divided into two electrode systems, three-electrode system even multi-electrode system.In typical three-electrode system, generally be to use the photocatalyst film that loads on the conductive substrates as the light anode, the conduct of Pt electrode is to electrode, and saturated calomel electrode is as reference electrode.For example, Chinese patent 02139272.2 discloses a kind of method at the metal surface loaded titanium dioxide photocatalyst, after the cleaning of metal surface, in acid medium, anodic oxidation, hydrolysis process are carried out in the metal surface, then under the weak base condition, with butyl titanate and titanium dioxide is raw material,---gel---suspending powder method lixiviate of using colloidal sol, applies film forming, handles in steps such as proper temperature calcinations.Resulting product can be used as anode material and photocatalytic reaction device material in the photoelectrocatalysis reaction for the material of oxidation titanium film is arranged in the metal surface set.But these known systems still are confined in the technical field of photoelectrochemistrpool pool.Reaction system needs to form the loop by electrolyte, therefore can not be applied to gas-phase photocatalysis degraded system, also increases production cost simultaneously inevitably and makes complex manufacturingization.
Summary of the invention
At the problems referred to above, the purpose of this invention is to provide a kind of gas, solid, liquid three-phase system all solid state planar photocatalytic device of organic and inorganic pollution and preparation method thereof of degrading that can be applicable to.Design of the present invention is: on dielectric base, fix one or more pairs of strip electrodes, and on this substrate and strip electrode the load semiconductor light-catalyst, just can obtain highly active all solid state planar photocatalytic device.After connecting power supply at the strip electrode two ends, the electric field that produces between two electrodes just can promote electronics and right the separating in hole in the semiconductor light-catalyst between two electrodes, thereby reaches the purpose of the functioning efficiency of raising photochemical catalyst.
Fig. 1 is the profile with planar photocatalytic device of a pair of strip electrode, and this device consists of the following components:
Dielectric base I;
Be fixed on the strip electrode II on this dielectric base;
Load on the semiconductor light-catalyst III on dielectric base and the strip electrode.
Wherein, the material used to dielectric base I do not have specific (special) requirements, as long as can realize in manufacturing process, that uses always in the industry has glass and a quartz, cheap.
Wherein, the used material of strip electrode II does not have particular restriction yet, as long as can realize this planar photocatalytic device, preferably can select tin indium oxide (ITO) or fluoro tin oxide (FTO) for use.
Wherein, the semiconductor light-catalyst III of load can be any known or may occur in the future semiconductor light-catalyst material on substrate and strip electrode.Semiconductor light-catalyst material TiO comparatively commonly used in the industry at present
2And porous material, TiO
2/ SnO
2, TiO
2/ Fe
3+, TiO
2/ dyestuffs etc. all can use.Wherein, TiO
2Dyestuff in the/dyestuff can be CuPc, rhodamine B or rose-red in any.
According to another object of the present invention, as shown in Figure 2, the method for preparing above-mentioned planar photocatalytic device comprises the steps:
1) cleaning dielectric base;
2) conductive is fixed on this dielectric base by the chemical sputtering method;
3) method with etching is etched into required strip electrode with this conductive layer;
4) photochemical catalyst is made suspension or colloid, by flooding-lift or the spin-coating method loading on described dielectric base and the strip electrode.
Wherein, chemical sputtering and etching all are the means that those skilled in the art uses always, and lithographic method can also be divided into manual etching and chemical wet etching.Relative chemical wet etching, manual etching operation is simple, and is with low cost.The process of manual etching is: after anchoring at electrode material in the substrate, adopt the method for mask etching, the hydrogen that produces with zinc powder and concentrated hydrochloric acid reaction falls to get final product with unwanted partial corrosion.Manual lithographic method can obtain many to strip electrode equally, and Fig. 3 is the device vertical view with two pairs of strip electrodes, and wherein dash area is an electrode.
Wherein, described photochemical catalyst exists with suspension or colloidal form.The preparation of suspension can be adopted commodity or homemade semiconductor light-catalyst powder, gets final product with ultrasonic being dispersed in the aqueous solution of certain proportion.Colloid generally adopts the sol-gel method preparation.
Wherein, described carrying method can adopt and flood-lift or the spin-coating dual mode.Pull rate is 1～5 cm per minute, and the spin-coating method generally is to adopt sol evenning machine, and even glue speed is 2000～5000 rev/mins.
Technique effect of the present invention is, strip electrode is combined with semiconductor light-catalyst, utilize lateral voltage planar, light induced electron and hole that the semiconductor catalyst film produces are separated effectively the electrode generation, thus the photocatalysis efficiency of raising device.This all solid state planar photocatalytic device has following advantage: (1) does not need working electrode, does not need electrolyte, can be applicable to gas, solid, liquid three individual system; (2) utilize strip electrode, can apply under the situation of small voltage, make light induced electron-hole to abundant separation, thereby photocatalysis efficiency is improved greatly.Therefore, the photochemical catalyst device that can obtain active height, cost is low, technology is simple, be widely used, compatibility is high is easy to promote the use of.
Description of drawings
Fig. 1 is the profile with planar photocatalytic device of a pair of strip electrode, wherein: I-substrate; II-strip electrode; III-photochemical catalyst.
Fig. 2 is the preparation process schematic diagram of planar photocatalytic device.
Fig. 3 is the device vertical view with two pairs of strip electrodes, and wherein dash area is an electrode.
Fig. 4 has under the ultraviolet lighting situation for to apply certain voltage, and the photoelectric current of device (I) is the change curve of (t) in time.In the system with formaldehyde as target contaminant, Fig. 4 (a) and (b) be respectively not have formaldehyde to exist and have formaldehyde to have the I-t curve of system under the situation.As seen from the figure, under UV-irradiation, the photoelectric current of device is obviously greater than its dark current value, and the existence meeting of target contaminant formaldehyde improves about 400 times to maximum photoelectricity flow valuve.The saturation value (2 μ A) of a system of b system maximum (0.8mA) when not having formaldehyde is big 400 times;
Fig. 5 is formaldehyde-voltage-device (a), the one-level degradation kinetics curve of formaldehyde in formaldehyde-illumination-device (b) and formaldehyde-voltage-illumination-device (c) three individual system, and k is first order reaction speed constant (min
-1).As seen from the figure, the system (a) that only has voltage to exist, formaldehyde is not degraded; And the system (c) that all exists for voltage and illumination, the photocatalysis efficiency of device (the first order reaction speed constant with Degradation Formaldehyde is represented) is that 1.87 times of illumination no-voltage system (b) are arranged.Through calculating the interelectrode TiO of ITO
2Photocatalysis efficiency has improved nearly 23 times.
The specific embodiment
The dielectric base material that uses in the preferred embodiment of the present invention is glass or quartz; ITO on dielectric base material glass or the quartz or FTO conductive layer can obtain by the chemical sputtering mode, and then obtain strip electrode by etching.The used material of etching can be zinc powder, concentrated hydrochloric acid, chloroform, acetone, absolute ethyl alcohol etc.The process of manual etching is: a side that adhesive tape is pasted on ITO of having on glass or FTO, the bar shaped of drawing thereon, tear desire off and will etch away the adhesive tape part of ITO or FTO, etch away the ITO or the FTO of exposure with zinc powder and concentrated hydrochloric acid, tear remaining adhesive tape after the flushing off, clean up then,, obtain substrate and suprabasil bar shaped ITO or FTO electrode after the oven dry such as using chloroform, acetone, ethanol and distilled water supersound washing respectively.
The photochemical catalyst of load need be made suspension or colloid (referring to document: Jing Shang, Wenqing Yao, Yongfa Zhu, Structure and Photocatalytic Performances ofGlass/SnO on dielectric base and electrode
2/ TiO
2Interface Composite Film, Appl.Catal.A:General.2004,257 (1), 25-32, wherein agents useful for same be analyze pure), then by flooding-lift or the spin-coating method being loaded on substrate and the strip electrode.
TiO for example
2The preparation process of photocatalyst film is as follows:
At first prepare TiO
2Colloidal sol or suspension: the 8ml tetrabutyl titanate is under agitation splashed in the 80ml absolute ethyl alcohol, add 1ml diethanol amine (stabilizing agentof sol) wiring solution-forming again, sonic oscillation mixes solution and forms yellow transparent solution.The aqueous alcohol 40ml that adds 98% concentration then, airtight again preservation a period of time is carried out to gel, makes the TiO of homogeneous transparent
2Colloidal sol.TiO
2The preparation of suspension can adopt commodity (as P-25TiO
2) or homemade TiO
2Powder gets final product with ultrasonic being dispersed in the aqueous solution of certain proportion.
With above-mentioned TiO
2Colloidal sol or suspension be as photochemical catalyst, with flooding-lift or the spin-coating method loading on dielectric base and the strip electrode.
The process of flooding-lifting is: substrate and strip electrode are dipped in TiO
2In colloidal sol or the suspension 2～5 minutes, lift with the speed of 1～5 cm per minute, after 60-90 ℃ of dry 10-30 minute, place TiO more then
2Lift in the colloidal sol, so repeat 2～5 times, low temperature (300-500 ℃) was calcined 0.5～1 hour under the air atmosphere condition at last, naturally cooled to room temperature, promptly formed to have certain thickness TiO in substrate
2Film.
The spin-coating method generally is to adopt sol evenning machine, gets 1～3 TiO
2Colloidal sol or suspension, drip on substrate and the strip electrode, even glue speed with 2000～5000 rev/mins is got rid of unnecessary colloidal sol or suspension by centrifugal action, so repeat 2～5 times, low temperature (300～500 ℃) was calcined 0.5～1 hour under the air atmosphere condition at last, naturally cool to room temperature, promptly formation has certain thickness TiO in substrate
2Film.
Above-mentioned preparation TiO
2Colloidal sol or suspension also are equally applicable to other semiconductor light-catalysts with its method that loads on dielectric base and the strip electrode, as TiO
2Porous material, TiO
2/ SnO
2, TiO
2/ Fe
3+, TiO
2/ dyestuff.
Embodiment one:
The TiO of the wide strip electrode of 1 couple of 1mm of etching in the ito glass substrate
2Photocatalytic device and photocatalytic activity thereof.
(1) preparation of manual etching ITO strip electrode photocatalytic device
Adhesive tape is pasted on a side with ITO, tear the wide adhesive tape of 1mm off in the centre, be placed in the beaker, add zinc powder and concentrated hydrochloric acid respectively, the H2 that produces etches away the wide ITO of 1mm of exposure, tear remaining adhesive tape after the flushing off, use chloroform, acetone, ethanol and distilled water supersound washing respectively, obtain having the ito glass conductive substrates of the wide strip electrode of 1mm after the oven dry.The ito glass of this 1mm strip electrode is dipped in TiO
2In the colloidal sol, carry out plated film, behind 90 ℃ of dry 10min, place TiO again with czochralski method
2Lift in the colloidal sol, so repeat 4 times, 450 ℃ of calcining 1h naturally cool to room temperature under the air atmosphere condition, promptly form the 1mm planar photocatalytic device.
(2) electrical modulation base plane type photocatalytic device photocatalytic degradation experiment
Apply the 20V DC voltage at the two ends of this planar photocatalytic device, monitor its current characteristics with Keithley2400 simultaneously.Fig. 4 has under the ultraviolet lighting situation for to apply certain voltage, and the photoelectric current of device (I) is the change curve of (t) in time.In the system with formaldehyde as target contaminant, a and b do not have formaldehyde to exist and have formaldehyde to have the I-t curve of system under the situation.As seen from the figure, under UV-irradiation, the photoelectric current of device is obviously greater than its dark current value, and the existence meeting of target contaminant formaldehyde improves about 400 times to maximum photoelectricity flow valuve.The saturation value (2 μ A) of a system of b system maximum (0.8mA) when not having formaldehyde is big 400 times.Fig. 5 is formaldehyde-voltage-device (a), the one-level degradation kinetics curve of formaldehyde in formaldehyde-illumination-device (b) and formaldehyde-voltage-illumination-device (c) three individual system, and k is first order reaction speed constant (min
-1).As seen from the figure, the system (a) that only has voltage to exist, formaldehyde is not degraded; And the system (c) that all exists for voltage and illumination, the photocatalysis efficiency of device (the first order reaction rate constants k with Degradation Formaldehyde is represented) is that 1.87 times of illumination no-voltage system (b) are arranged.Through calculating the interelectrode TiO of ITO
2Photocatalysis efficiency has improved nearly 23 times.
Claims (9)
1. planar photocatalytic device comprises:
One dielectric base;
At least one pair of is fixed on the strip electrode on this dielectric base;
Load on the semiconductor light-catalyst on described dielectric base and the strip electrode.
2. planar photocatalytic device as claimed in claim 1 is characterized in that, described base material is glass or quartz.
3. planar photocatalytic device as claimed in claim 1 is characterized in that, described strip electrode material is tin indium oxide or fluoro tin oxide.
4. planar photocatalytic device as claimed in claim 1 is characterized in that, described semiconductor light-catalyst material is selected from TiO
2, TiO
2Porous material, TiO
2/ SnO
2, TiO
2/ Fe
3+, TiO
2In/the dyestuff any.
5. planar photocatalytic device as claimed in claim 4 is characterized in that, the dyestuff in the described TiO2/ dyestuff be CuPc, rhodamine B or rose-red in any.
6. method for preparing planar photocatalytic device comprises step:
1) cleaning dielectric base;
2) conductive is fixed on this dielectric base by the chemical sputtering method;
3) method with etching is etched into required strip electrode with this conductive layer;
4) photochemical catalyst is made suspension or colloid, by flooding-lift or the spin-coating method loading on described dielectric base and the strip electrode.
7. the method for preparing planar photocatalytic device as claimed in claim 6, it is characterized in that, described lithographic method is manual etching or chemical wet etching, wherein, the operating process of manual etching is: after anchoring at electrode material in the substrate, adopt the method for mask etching, the hydrogen that produces with zinc powder and concentrated hydrochloric acid reaction falls unwanted partial corrosion.
8. the method for preparing planar photocatalytic device as claimed in claim 6 is characterized in that, described photochemical catalyst is suspension or colloidal form.
9. the method for preparing planar photocatalytic device as claimed in claim 6 is characterized in that, the pull rate of described dipping-lift is 1～5 cm per minute; Described spin-coating method is to adopt sol evenning machine, and even glue speed is 2000～5000 rev/mins.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108190996A (en) * | 2018-01-03 | 2018-06-22 | 京东方科技集团股份有限公司 | A kind of degradation module and cleaning equipment |
| CN109226240A (en) * | 2018-10-17 | 2019-01-18 | 广州市花林景观工程有限公司 | A kind of catalytic type contaminated soil remediation device |
| CN115253672A (en) * | 2022-08-17 | 2022-11-01 | 中国科学院生态环境研究中心 | Photoelectric catalytic device for gas-solid reaction and application |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0923988B1 (en) * | 1995-06-19 | 2008-04-09 | Nippon Soda Co., Ltd. | Photocatalyst-carrying structure and photocatalyst coating material |
| JP3446985B2 (en) * | 1996-08-14 | 2003-09-16 | 株式会社荏原製作所 | Gas cleaning method and apparatus |
| CN1104938C (en) * | 1998-07-29 | 2003-04-09 | 中国科学院感光化学研究所 | Organic substrate double-layer film capable of photocatalytically purifying air and sterilizing, and preparation method thereof |
| JP2004122301A (en) * | 2002-10-03 | 2004-04-22 | Okuma Corp | Filtration device for mist lubrication exhaust |
| US20050147543A1 (en) * | 2004-01-07 | 2005-07-07 | Lin Pi C. | Photocatalysis water-supply device |
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2006
- 2006-08-22 CN CNB2006101125086A patent/CN100406124C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108190996A (en) * | 2018-01-03 | 2018-06-22 | 京东方科技集团股份有限公司 | A kind of degradation module and cleaning equipment |
| CN108190996B (en) * | 2018-01-03 | 2020-11-17 | 京东方科技集团股份有限公司 | Degradation module and cleaning equipment |
| CN109226240A (en) * | 2018-10-17 | 2019-01-18 | 广州市花林景观工程有限公司 | A kind of catalytic type contaminated soil remediation device |
| CN115253672A (en) * | 2022-08-17 | 2022-11-01 | 中国科学院生态环境研究中心 | Photoelectric catalytic device for gas-solid reaction and application |
| CN115253672B (en) * | 2022-08-17 | 2024-05-10 | 中国科学院生态环境研究中心 | Photoelectrocatalysis device for gas-solid phase reaction and application |
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| CN100406124C (en) | 2008-07-30 |
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Effective date of registration: 20161019 Address after: 100085, room 4, building 1, building 12, information road, Haidian District, Beijing, Patentee after: BEIJING LINGKESHENGSHI ENVIRONMENT PROTECTION TECHNOLOGY CO., LTD. Address before: 100871 Beijing the Summer Palace Road, Haidian District, No. 5 Patentee before: Peking University |
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