CN1762580A - Photocatalytic membrane and its preparation process - Google Patents

Photocatalytic membrane and its preparation process Download PDF

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Publication number
CN1762580A
CN1762580A CNA2005100194629A CN200510019462A CN1762580A CN 1762580 A CN1762580 A CN 1762580A CN A2005100194629 A CNA2005100194629 A CN A2005100194629A CN 200510019462 A CN200510019462 A CN 200510019462A CN 1762580 A CN1762580 A CN 1762580A
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China
Prior art keywords
silane coupler
tio
paint
nano
photocatalysis membrana
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CNA2005100194629A
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CN1322916C (en
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钟家柽
张悦
朱天翔
龚楚清
罗其荣
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Wuhan University WHU
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Wuhan University WHU
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention relates to photocatalysis film, which comprises attaching down-to-up mesh carrier, paint layer, silane coupling agent layer, and nano TiO2 film. The preparation method comprises: coating paint on said carrier; before drying, coating said coupling agent, static in air till solidified; dispersing the nano TiO2 in C1-C4 alcohol water solution to form 1~25wt% suspension or sol; coating the suspension or sol on said coupling agent, drying, and obtaining the film. This product can photocatalytic decompose a plurality organics in water and has wide application.

Description

A kind of photocatalysis membrana and preparation method thereof
Technical field
The present invention relates to a kind of photocatalysis membrana and preparation method thereof.
Background technology
At present, the problem of water pollution is more and more serious, and one of arch-criminal who causes water pollution is exactly some organic matters, and how decomposing these organic pollutions has efficiently become the problem that more and more scientific workers are paid close attention to.
1976, Carey etc. found TiO 2-H 2The O system can non-selectively oxidative degradation organic matter under illumination condition since, the heterogeneous catalysis technique of semiconductor has become an emerging research subject, because TiO 2It is good to have chemical stability, the photocatalytic activity height, and advantage such as cheap and easy to get, it has been widely used in handling various waste water, but in the past, people are with TiO mostly 2Particle is suspended in the liquid phase in order to catalytic decomposition organic matter or other pollutant, but the catalyst of this suspended substance photocatalytic oxidation easily condenses and inactivation in water, the penetration power of light is obstructed, and can the separation of the catalyst after especially handling and the difficult problem of recovery have become this technology practical key.Under the circumstances, how people just improve TiO 2A lot of effort have been made on the photocatalysis efficiency, with TiO 2Make film and be considered to a kind of effective method, thereby in recent years, nano-TiO 2The preparation of particle load film and the research of photocatalytic activity have become important research direction, and the document that annual this respect is delivered is many.Someone adopts polymer is adhesive, and it is coated on the glass plate, forms thin film, with TiO 2Nano-powder is applied on this film, forms the secondary film, as supported titanium 2Photochemical catalyst.But the problem that this method exists is this TiO 2Photochemical catalyst destroys organic its carrier adhesive also can the degraded simultaneously of catalytic decomposition.
Summary of the invention
But the present invention provides organic photocatalysis membrana and preparation method thereof in a kind of decomposition water at the problems referred to above exactly.
Technical scheme provided by the invention is: a kind of photocatalysis membrana, and by mesh carrier, attached to the skin of paint on the mesh carrier, attached to the silane coupling agent layer on the skin of paint with attached to the nano-TiO on the silane coupler coating 2Film is formed.
Above-mentioned paint can select for use the stronger organic polymer paint of cohesive as polyurethane or polyester etc.
Above-mentioned mesh carrier is plastic wire or wire netting (copper mesh, Stainless Steel net, iron net, aluminium net etc.).
Above-mentioned nano-TiO 2Nano-TiO in the film 2Crystal formation be sharp titanium mutually or sharp titanium and rutile mixed crystal mutually, its grain diameter is 5-80nm.
The present invention also provides the preparation method of above-mentioned photocatalysis membrana: coated paint on mesh carrier; Before paint was done, coated thereon silane coupler left standstill the silane coupler curing to material surface in air; With nano-TiO 2Be scattered in C 1-C 4Organic alcohol solution in form suspension or the colloidal sol of 1～25wt%, this suspension or colloidal sol are coated on the silane coupler, oven dry promptly gets required photocatalysis membrana.
The volumetric concentration of above-mentioned organic alcohol solution is 30%～90%.
Above-mentioned organic alcohol is ethanol (available industrial alcohol, or medicinal alcohol), propyl alcohol or isobutanol etc.
Silane coupler recommends to adopt WD-10, WD-20, WD-21, WD-30, WD-40, WD-42, WD-50, WD-51, WD-52, WD-53, WD-54, WD-55, WD-60, WD-70, WD-80, WD-921, WD-922, WD-923, WD-931, WD-932, WD-90A, WD-90, WD-91, WD-92,8510,881, DMC (dimethyl siloxane mixed methylcyclosiloxane), WD-9110, WD-98, WD-941 or WD-942 (the Wuhan University chemical plant is on sale) etc.
The present invention is applied to paint and TiO with being connected with the silane coupler of lipophile group (hydrophobic end) with hydrophilic radical (water-wet side) simultaneously 2Between the nano microcrystalline suspended substance, form " paint-silane coupler-TiO 2Nano-powder " catalytic membrane.The silane coupler role is to intercept paint and TiO 2Nano microcrystalline is to prevent TiO 2Also will paint degraded in the organic while of catalytic decomposition destroys.The inventive method operation is very simple, also can make TiO without high temperature sintering 2What nano-powder was more firm is bonded on the carrier.
The present invention has the following advantages:
1, the preparation method is very easy, need not special installation, need not high temperature sintering.
2, the photocatalysis membrana that makes with the silane coupler (especially the hydrophobic end is the silane coupler of alkyl) that is connected with lipophile group (hydrophobic end) and hydrophilic radical (water-wet side) has extraordinary photocatalytic activity.Under solar light irradiation, can in one to two hour, some organic matter (as methyl orange) almost completely be decomposed.
3, the photocatalysis membrana that makes with above-mentioned silane coupler has lasting light catalytic capability preferably, promptly after photocatalytic decomposing organic matter a period of time, places the dark place, still can continue the catalytic decomposition organic matter in a long time.
4, at certain hour, used photocatalysis membrana is placed clear water, and be placed on irradiation a period of time under the strong sunshine, make its surperficial TiO 2Nano microcrystalline recovers photocatalytic activity, from and can continue to use, and can not lose efficacy.
Description of drawings
Accompanying drawing structural representation of the present invention.
The specific embodiment
Photocatalysis membrana of the present invention is by mesh carrier 4, attached to the skin of paint on the mesh carrier 43, attached to the silane coupler coating 2 that is connected with hydrophobic end 5 and water-wet side 6 on the skin of paint 3 with attached to the nano-TiO on the silane coupler coating 2 2 Film 1 is formed.
Embodiment 1: with the stainless (steel) wire is carrier, coated high concentrations of toluene diisocyanate on stainless (steel) wire; Before paint was done, coated thereon silane coupler DMC, WD-10, WD-30, WD-50, WD-60 or WD-80 (buying from the Wuhan University chemical plant) left standstill the silane coupler curing to material surface in air; With anatase titanium dioxide, particle diameter is the TiO of 25 nanometers 2Be scattered in the suspension or the colloidal sol that form 20wt% in the industrial alcohol, this suspension or colloidal sol are coated on the silane coupler, oven dry promptly gets photocatalysis membrana under infrared lamp.
Under solar light irradiation, relatively use the effect of the catalyst film photocatalysis Decomposition methyl orange that different silane couplers make:
Silane coupler WD-80 WD-60 WD-50 WD-30 WD-10 DMC
1 hour resolution ratio 28.1％ 73.5％ 60.5％ 71.9％ 50.5％ 69.1％
Embodiment 2: be carrier with the copper mesh, coated polyester paint on copper mesh, coated thereon silane coupled DMC, WD-10, WD-30, WD-50, WD-60 or WD-80 (buying from the Wuhan University chemical plant) leave standstill the silane coupler curing to material surface in air; With anatase titanium dioxide, particle diameter is the TiO of 25 nanometers 2Be scattered in the suspension or the colloidal sol that form 20wt% in the industrial alcohol, this suspension or colloidal sol are coated on the silane coupler, oven dry promptly gets photocatalysis membrana under infrared lamp.
Under solar light irradiation, photocatalysis Decomposition methyl orange half an hour, the comparison that again catalysis system is placed the lasting light catalytic capability of the 2.5 hours rear catalyst films in dark place:
Silane coupler WD-80 WD-60 WD-50 WD-30 WD-10 DMC
0.5 hour resolution ratio of illumination 13.2％ 52.0％ 37.6％ 58.3％ 21.3％ 48.1％
2.5 hours resolution ratios in the camera bellows 21.3％ 86.0％ 62.8％ 77.9％ 39.2％ 78.3％
Embodiment 3: with the plastic wire is carrier, coated high concentrations of toluene diisocyanate on plastic wire; Coated thereon silane coupler WD-60, WD-10, DMC (buying) from the Wuhan University chemical plant, in air, leave standstill silane coupler curing to material surface, crystal formation for based on sharp titanium mutually, is mixed with about 20wt% rutile phase, particle diameter is the TiO of 10 nanometers 2Be scattered in volumetric concentration and be the suspension or the colloidal sol that form 25wt% in the aqueous solution of 80% isobutanol, this suspension or colloidal sol are coated on the silane coupler, oven dry promptly gets photocatalysis membrana under infrared lamp.
Under solar light irradiation, relatively use the effect of the catalyst film photocatalysis Decomposition methyl orange that different silane couplers make:
Silane coupler WD-60 WD-10 DMC
90 minutes resolution ratios 52.3％ 74.3％ 70.6％
Embodiment 4: with the stainless (steel) wire is carrier, coated high concentrations of toluene diisocyanate on stainless (steel) wire; Coated thereon silane coupler WD-60 leaves standstill the silane coupler curing to material surface in air, be the TiO of 5 nanometers with anatase titanium dioxide, particle diameter 2Be scattered in the suspension or the colloidal sol that form 5wt% in the medicinal alcohol (ethanol volumetric concentration 75%), this suspension or colloidal sol are coated on the silane coupler, oven dry promptly gets photocatalysis membrana under infrared lamp.
Under solar light irradiation, methyl orange is just faded fully after about 5 minutes.
Embodiment 5: with the iron net is carrier, in the online coated high concentrations of toluene diisocyanate of iron; Coated thereon silane coupler WD-60 leaves standstill the silane coupler curing to material surface in air, be the TiO of 80 nanometers with anatase titanium dioxide, particle diameter 2Be scattered in the suspension or the colloidal sol that form 1wt% in the aqueous solution of propyl alcohol of volumetric concentration 30%, this suspension or colloidal sol are coated on the silane coupler, oven dry promptly gets photocatalysis membrana under infrared lamp.
Under solar light irradiation, methyl orange is obviously faded after about one day.

Claims (7)

1, a kind of photocatalysis membrana is characterized in that: by mesh carrier, attached to the skin of paint on the mesh carrier, attached to the silane coupler coating on the skin of paint with attached to the nano-TiO on the silane coupler coating 2Film is formed.
2, photocatalysis membrana according to claim 1 is characterized in that: painting is that polyurethane or polyesters are painted.
3, photocatalysis membrana according to claim 1 and 2 is characterized in that: mesh carrier is plastic wire or wire netting.
4, photocatalysis membrana according to claim 1 and 2 is characterized in that: nano-TiO 2Nano-TiO in the film 2Crystal formation be sharp titanium mutually or sharp titanium and rutile mixed crystal mutually, its grain diameter is 5-80nm.
5, the preparation method of the described photocatalysis membrana of claim 1 is characterized in that: coated paint on mesh carrier; Before paint was done, coated thereon silane coupler left standstill the silane coupler curing to material surface in air; With nano-TiO 2Be scattered in C 1-C 4Organic alcohol solution in form suspension or the colloidal sol of 1～25wt%, this suspension or colloidal sol are coated on the silane coupler, oven dry promptly gets required photocatalysis membrana.
6, preparation method according to claim 5 is characterized in that: the volumetric concentration of organic alcohol solution is 30%～90%.
7, according to claim 5 or 6 described preparation methods, it is characterized in that: organic alcohol is ethanol, propyl alcohol or isobutanol.
CNB2005100194629A 2005-09-21 2005-09-21 Photocatalytic membrane and its preparation process Expired - Fee Related CN1322916C (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102580740A (en) * 2011-12-31 2012-07-18 广东工业大学 Method for preparing multidimensional photocatalytic material
CN103638915A (en) * 2013-12-16 2014-03-19 复旦大学 High-catalytic-property TiO2 nano powder/porous material as well as preparation method and application of high-catalytic-property TiO2 nano powder/porous material
CN103774131A (en) * 2012-10-25 2014-05-07 深圳富泰宏精密工业有限公司 Preparation method of housing, and housing prepared with method
CN104870731A (en) * 2012-12-21 2015-08-26 瓦林格光催化股份有限公司 Method for coating a building panel and a building panel
CN105195236A (en) * 2015-09-25 2015-12-30 河海大学 High pressure vibration film plating device for loading photocatalytic film on surface of porous ceramic material
CN106732495A (en) * 2016-12-30 2017-05-31 哈尔滨工业大学深圳研究生院 A kind of method of immobilized titanium dioxide and its application
CN108927225A (en) * 2018-06-27 2018-12-04 浙江工业大学膜分离与水处理协同创新中心湖州研究院 A kind of photocatalysis membrana preparation method for dyestuff degradation
US11045798B2 (en) 2011-07-05 2021-06-29 Valinge Photocatalytic Ab Coated wood products and method of producing coated wood products
US11666937B2 (en) 2012-12-21 2023-06-06 Valinge Photocatalytic Ab Method for coating a building panel and a building panel

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CN1239223C (en) * 2001-05-28 2006-02-01 北京二元世纪技术有限公司 Nano-interface separating net with self-cleaning function and its making process and use
CN1634653A (en) * 2004-12-02 2005-07-06 上海大学 Method for preparing loaded nano titanium dioxide photocatalysis film

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11045798B2 (en) 2011-07-05 2021-06-29 Valinge Photocatalytic Ab Coated wood products and method of producing coated wood products
CN102580740A (en) * 2011-12-31 2012-07-18 广东工业大学 Method for preparing multidimensional photocatalytic material
CN103774131A (en) * 2012-10-25 2014-05-07 深圳富泰宏精密工业有限公司 Preparation method of housing, and housing prepared with method
CN104870731A (en) * 2012-12-21 2015-08-26 瓦林格光催化股份有限公司 Method for coating a building panel and a building panel
US11666937B2 (en) 2012-12-21 2023-06-06 Valinge Photocatalytic Ab Method for coating a building panel and a building panel
CN103638915A (en) * 2013-12-16 2014-03-19 复旦大学 High-catalytic-property TiO2 nano powder/porous material as well as preparation method and application of high-catalytic-property TiO2 nano powder/porous material
CN105195236A (en) * 2015-09-25 2015-12-30 河海大学 High pressure vibration film plating device for loading photocatalytic film on surface of porous ceramic material
CN105195236B (en) * 2015-09-25 2017-11-10 河海大学 High pressure for porous ceramic film material area load photocatalysis membrana vibrates coating apparatus
CN106732495A (en) * 2016-12-30 2017-05-31 哈尔滨工业大学深圳研究生院 A kind of method of immobilized titanium dioxide and its application
CN106732495B (en) * 2016-12-30 2020-03-10 哈尔滨工业大学深圳研究生院 Method for immobilizing titanium dioxide and application thereof
CN108927225A (en) * 2018-06-27 2018-12-04 浙江工业大学膜分离与水处理协同创新中心湖州研究院 A kind of photocatalysis membrana preparation method for dyestuff degradation

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