CN105664996A - Preparation method and application of g-C3N4/TiO2 heterojunction photocatalytic film - Google Patents
Preparation method and application of g-C3N4/TiO2 heterojunction photocatalytic film Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 8
- 231100000719 pollutant Toxicity 0.000 claims abstract description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010409 thin film Substances 0.000 claims description 62
- 238000007146 photocatalysis Methods 0.000 claims description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005304 joining Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- -1 TiO2 compound Chemical class 0.000 abstract 3
- 239000007788 liquid Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000005507 spraying Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000005348 self-cleaning glass Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
Abstract
The invention provides a preparation method and application of a g-C3N4/TiO2 heterojunction photocatalytic film.Tetrabutyl titanate is hydrated so that TiO2 sol can be prepared, the TiO2 sol and g-C3N4 ethanol suspension liquid are evenly mixed, and g-C3N4/TiO2 compound sol is obtained; the g-C3N4/TiO2 compound sol is sprayed on a substrate at normal temperature, and the g-C3N4/TiO2 heterojunction photocatalytic film is obtained.The TiO2 sol serves as a carrier, g-C3N4 powder is prepared into a film, and application of g-C3N4 to environment pollution treatment is expanded; g-C3N4/TiO2 serves as the heterojunction photocatalytic film, the sunlight utilizing rate achieved through a TiO2 photocatalyst is increased, the photocatalytic pollutant degradation efficiency is remarkably enhanced under visible light, and the g-C3N4/TiO2 heterojunction photocatalytic film can be used for degradation of NOx and other pollutants in air.In the preparation method, after the g-C3N4/TiO2 compound sol is sprayed on the substrate, natural airing is adopted for drying, and the preparation method is simple and convenient, and popularization is easy.
Description
Technical field
The invention belongs to photocatalysis film field, relate to a kind of g-C3N4/TiO2The preparation method of heterojunction photocatalysis thin film and application thereof.
Background technology
Energy shortage and environmental pollution are the significant challenge that 21 century human society is encountered, and the application of photocatalysis technology brings new opportunity for utilization of energy and environmental conservation. Thin-film material often has the excellent properties not available for bulk material, is more suitable for popularization and application, and therefore photocatalysis film is not only in research field, and in the industrial production and life application in increasingly cause extensive concern. TiO2As field of semiconductor photocatalyst is studied the most extensively, one of the material of most Practical significance, have that non-toxic inexpensive, photocatalysis efficiency be high, steady performance. But, current TiO2The ultraviolet light less than 5% of the ratio in solar spectrum is only had absorption by photocatalysis film, and solar energy utilization ratio is non-normally low, it addition, TiO2Photo-generated carrier recombination rate significantly high, great restricted T iO2Large-scale application.
Non-metal semiconductive g-C3N4Being the material received much concern in the last few years, the triazine circulus of its uniqueness and height polycondensation impart the stability that it is very high, antiacid, alkali resistant, anti-light corrosion. g-C3N4Energy gap 2.7eV, visible ray is had certain absorption, additionally also there is the high-specific surface area same with Graphene, electric transmission speed is exceedingly fast, structure and performance are prone to the advantages such as regulation and control. But, g-C3N4Its powder body is prepared, it is difficult to film forming mainly through thermal polymerization. Currently, thin film g-C is prepared3N4Method be mainly laser splash, vapour deposition and electrochemical method, these method complicated operations, instrument and equipment is required height, energy consumption is big, it is difficult to realize large-scale industrial production and development, limits popularization and application.
Chinese patent CN103464131A is by simple sol method, the reasonably laser modified and successful thin film of titanium oxide being prepared on a ceramic substrate having visible light wave range excellence photocatalysis performance of annealing process. Patent CN102864481A adopts magnetron sputtering, anodic oxidation titanium film and heat treatment to prepare optically catalytic TiO 2 film on glass, there is the advantage such as high light transmittance and high light-catalyzed reaction speed constant, the photocatalysis field demands such as self-cleaning glass, air and purification of waste water can be met. But all there is complicated process of preparation in the photocatalysis film prepared by these patents, it is necessary to the problem such as laser and high-temperature process. Therefore, exploitation preparation technology is simple, economical and energy saving, efficient cryogenic photocatalysis film easy to spread are extremely important for catalysis material application in improving environment.
Summary of the invention
For overcoming the problems of the prior art, it is an object of the invention to, it is provided that a kind of g-C3N4/TiO2The preparation method of heterojunction photocatalysis thin film and application thereof, according to hetero-junctions principle, at TiO2Adding on basis can with the g-C of coupling3N4, effectively raise the efficiency of light energy utilization of catalysis material;By the g-C of powder body3N4With TiO2Colloidal sol is carrier, prepares efficient degradation NO under visible lightxG-C3N4/TiO2Heterojunction photocatalysis thin film, has expanded g-C3N4The application space of powder body; It is applied in air by new and effective photocatalysis hetero-junction thin-film NOxDegraded Deng pollutant.
For achieving the above object, the technical solution used in the present invention is:
A kind of g-C3N4/TiO2The preparation method of heterojunction photocatalysis thin film, comprises the following steps:
(1) g-C is prepared3N4/TiO2Complex sol:
Hydrolysis of tetrabutyl titanate prepares TiO2Colloidal sol, by TiO2Colloidal sol with pass through g-C3N4Alcohol suspension is according to volume ratio 1:(1-20) mix homogeneously, obtain g-C3N4/TiO2Complex sol;
(2) g-C is prepared3N4/TiO2Heterojunction photocatalysis thin film:
By g-C3N4/TiO2Complex sol is sprayed in substrate, obtains g-C after drying3N4/TiO2Heterojunction photocatalysis thin film, wherein, described dry by natural air drying or in oven for drying.
TiO2Colloidal sol prepares by the following method: adding butyl titanate in hydrochloric acid solution, under room temperature, hydrolysis, ageing 2～3 weeks, obtain TiO2Colloidal sol; Wherein, hydrochloric acid solution is 10:1 with the volume ratio of butyl titanate.
The concentration of hydrochloric acid solution is 0.12mol/L.
Described g-C3N4Alcohol suspension prepares by the following method: by g-C3N4Joining in ethanol, under 400W power, ultrasonic 4～10h, obtains g-C3N4Alcohol suspension; Wherein, g-C3N4It is (0.001g～1.0) g:100mL with the ratio of ethanol.
By g-C in described step (2)3N4/TiO2Complex sol is sprayed in substrate, obtains g-C3N4/TiO2The detailed process of heterojunction photocatalysis thin film is: by g-C3N4/TiO2Complex sol in high-pressure spray gun watering can, even application 2～4 times in substrate under 6KPa pressure, dried g-C3N4/TiO2Heterojunction photocatalysis thin film.
The temperature of described drying is not higher than 100 DEG C.
Described substrate is glass, pottery or corrosion resistant plate.
A kind of g-C3N4/TiO2The purposes of heterojunction photocatalysis thin film, g-C3N4/TiO2Heterojunction photocatalysis thin film is NO in degraded airxThe application of pollutant.
Compared with prior art, the invention have the benefit that
1. the present invention is by by g-C3N4Alcohol suspension and TiO2Spray after colloidal sol mixing, obtain g-C3N4/TiO2Heterojunction photocatalysis thin film. TiO2Colloidal sol as carrier by g-C high for visible ray utilization rate3N4Powder body makes thin film, overcomes g-C3N4The problem being not easily recycled when processing for environmental contaminants. By g-C in the present invention3N4/TiO2After complex sol is sprayed in substrate, dry adopt natural air drying, overcome the complex process needing laser or high-temperature process in prior art, and this preparation method is easy, initiative by g-C3N4Making thin film, this photocatalysis hetero-junction thin-film has coupled the preparation of photocatalysis heterojunction material and low temperature coating technique (namely baking temperature is relatively low), simple to operate, equipment requirements is low, it is achieved that by the application of plated film in substrate of catalysis material large area;
2. the present invention is with TiO2Colloidal sol is carrier and adhesive, the g-C of preparation3N4/TiO2Heterojunction photocatalysis thin film, improves the efficiency of light energy utilization of catalysis material, has expanded g-C3N4The application space of powder body, improves TiO2The photocatalyst utilization rate to sunlight, it is seen that under light, photocatalytic pollutant degradation efficiency is remarkably reinforced, it is possible to for NO in airxDeng the degraded of pollutant, the degraded of NO can be reached more than 30%, and good stability, repeatable utilization.
Further, substrate is simple glass, pottery, corrosion resistant plate etc., it is possible to the application of extension plated film.
Accompanying drawing explanation
Fig. 1 is FTO substrate of glass, TiO2Thin film, g-C3N4/TiO2The SEM figure of heterojunction photocatalysis thin film;Wherein, (a) is FTO substrate of glass, and (b) is TiO2Thin film, (c) are g-C3N4/TiO2Heterojunction photocatalysis thin film.
Fig. 2 is TiO2Powder body, g-C3N4Powder body, g-C3N4/TiO2The UV, visible light of heterojunction photocatalysis powder body-diffuse-reflectance figure; Wherein, (a) is TiO2Powder body, (b) are g-C3N4Powder body, (c) are g-C3N4/TiO2Heterojunction photocatalysis powder body.
Fig. 3 is TiO under visible light2Thin film, g-C3N4Thin film, g-C3N4/TiO2Heterojunction photocatalysis thin film is to NO degradation efficiency figure. Wherein, (a) is TiO2Thin film, (b) is g-C3N4Thin film, (c) is g-C3N4/TiO2Heterojunction photocatalysis thin film.
Detailed description of the invention
Below in conjunction with detailed description of the invention and accompanying drawing, the present invention is described in detail, but protection scope of the present invention is not limited in the following example.
Embodiment 1
A kind of efficiently g-C3N4/TiO2The preparation of heterojunction photocatalysis thin film, comprises the following steps:
(1) adopting peptisation, added by 12mL butyl titanate in 120mL0.12mol/L hydrochloric acid solution, under room temperature, hydrolysis, ageing 2 weeks, obtain TiO2Colloidal sol;
Ultrasonic Pulverization method is adopted to prepare g-C3N4Alcohol suspension: by g-C3N4Being scattered in ethanol, under 400W power, continuous ultrasound 4h, obtains g-C3N4Alcohol suspension; Wherein, g-C3N4It is 0.001g:100mL with the ratio of ethanol.
By TiO2Colloidal sol and g-C3N4Suspension, according to volume ratio 1:1 mix homogeneously, obtains g-C3N4/TiO2Complex sol;
(2) by g-C3N4/TiO2Complex sol adopts air spraying method, in 10*10cm under 6KPa pressure2Substrate of glass sprays 2～4 times, natural air drying, obtain g-C3N4/TiO2Heterojunction photocatalysis thin film.
Embodiment 2
Different from embodiment 1 are in that TiO2Colloidal sol and g-C3N4Suspension vol compares 1:5.
Embodiment 3
Different from embodiment 1 are in that TiO2Colloidal sol and g-C3N4Suspension vol compares 1:10.
Embodiment 4
Different from embodiment 1 are in that TiO2Colloidal sol and g-C3N4Suspension vol compares 1:20.
Embodiment 5
Adding butyl titanate in the hydrochloric acid solution that mass concentration is 0.12mol/L, under room temperature, hydrolysis, ageing 3 weeks, obtain TiO2Colloidal sol; Wherein, hydrochloric acid solution is 10:1 with the volume ratio of butyl titanate.
By g-C3N4Joining in ethanol, under 400W power, ultrasonic 10h, obtains g-C3N4Alcohol suspension; Wherein, g-C3N4It is 0.01g:100mL with the ratio of ethanol.
By TiO2Colloidal sol with pass through g-C3N4Alcohol suspension, according to volume ratio 1:7 mix homogeneously, obtains g-C3N4/TiO2Complex sol;
By g-C3N4/TiO2Complex sol in high-pressure spray gun watering can, even application 2 times on a ceramic substrate under 6KPa pressure, after drying at 100 DEG C in an oven g-C3N4/TiO2Heterojunction photocatalysis thin film.
Embodiment 6
Adding butyl titanate in the hydrochloric acid solution that mass concentration is 0.12mol/L, under room temperature, hydrolysis, ageing 2 weeks, obtain TiO2Colloidal sol; Wherein, hydrochloric acid solution is 10:1 with the volume ratio of butyl titanate.
By g-C3N4Joining in ethanol, under 400W power, ultrasonic 4h, obtains g-C3N4Alcohol suspension; Wherein, g-C3N4It is 0.1g:100mL with the ratio of ethanol.
By TiO2Colloidal sol with pass through g-C3N4Alcohol suspension, according to volume ratio 1:15 mix homogeneously, obtains g-C3N4/TiO2Complex sol;
By g-C3N4/TiO2Complex sol in high-pressure spray gun watering can, even application 3 times in corrosion resistant plate substrate under 6KPa pressure, after drying at 40 DEG C in an oven g-C3N4/TiO2Heterojunction photocatalysis thin film.
Embodiment 7
Adding butyl titanate in the hydrochloric acid solution that mass concentration is 0.12mol/L, under room temperature, hydrolysis, ageing 3 weeks, obtain TiO2Colloidal sol;Wherein, hydrochloric acid solution is 10:1 with the volume ratio of butyl titanate.
By g-C3N4Joining in ethanol, under 400W power, ultrasonic 6h, obtains g-C3N4Alcohol suspension; Wherein, g-C3N4It is 1.0g:100mL with the ratio of ethanol.
By TiO2Colloidal sol with pass through g-C3N4Alcohol suspension, according to volume ratio 1:12 mix homogeneously, obtains g-C3N4/TiO2Complex sol;
By g-C3N4/TiO2Complex sol in high-pressure spray gun watering can, even application 4 times in corrosion resistant plate substrate under 6KPa pressure, after drying at 80 DEG C in an oven g-C3N4/TiO2Heterojunction photocatalysis thin film.
The TiO of preparation in the present invention2Colloidal sol as carrier and adhesive, itself and g-C3N4According to different volumes mixing, suspension causes that thin film load capacity on glass is not quite similar, refer to table 1, cause that film performance also has larger difference.
Table 1 is that different volumes is than low temperature TiO2And g-C3N4Complex sol is spray-coated film load capacity on glass
As it can be seen from table 1 volume ratio is the TiO of 1:12Colloidal sol and g-C3N4The load capacity of the photocatalysis film that suspension prepares is up to 65 μ g/cm2。
Comparative example 1
Low temperature TiO2The preparation of thin film:
Low-temperature growth TiO2Colloidal sol, mixs homogeneously with ethanol according to a certain volume by it, ultrasonic 30min, adopts air spraying method, in 10*10cm under 6KPa pressure2The substrates such as simple glass, pottery, corrosion resistant plate spray 2～4 times, natural air drying or oven for drying (dry temperature≤100 DEG C), obtain TiO2Thin film.
Comparative example 2
Low temperature g-C3N4The preparation of thin film:
Direct ultrasonic method prepares g-C3N4Suspension, adopts air spraying method, at 10*10cm2Glass on spraying 2～4 times, natural air drying or oven for drying (dry temperature≤100 DEG C), obtain g-C3N4Thin film.
It will be seen from figure 1 that TiO2Thin film (see figure (b)) covers substrate FTO glass surface than relatively evenly, sees figure (a), g-C3N4/TiO2Heterojunction photocatalysis thin film, is shown in figure (c), relative to TiO2Film surface skewness (the highest thickness reaches 400nm), it was shown that g-C3N4Really FTO surface filming it is supported on.
Figure it is seen that after thin film coatings solution is dried making powder body, g-C3N4/TiO2The visible absorption of heterojunction photocatalysis powder body (see c) strengthens relatively, and light absorption range is between TiO2(see a) and g-C3N4Between (see b).
From figure 3, it can be seen that TiO under visible ray2NO is had certain degraded by thin film, sees a, by g-C3N4Powder suspension directly sprays the g-C obtained in substrate3N4Thin film, is shown in b, due to g-C3N4Load capacity is less, and it is relatively low to NO photodegradation rate, and g-C3N4/TiO2Heterojunction photocatalysis thin film has coupled TiO2And g-C3N4The excellent properties of two kinds of photocatalysts, reaches more than 30% to NO degraded, sees c.
In the present invention, the preparation method of high efficiency photocatalysis thin membrane comprises the following steps: 1) prepare g-C3N4/TiO2Complex sol; 2) g-C is prepared3N4/TiO2Heterojunction photocatalysis thin film. This g-C3N4/TiO2Heterojunction photocatalysis thin film has coupled photocatalysis and low temperature coating technique, it is achieved by the application of plated film in the substrates such as simple glass, pottery, corrosion resistant plate of catalysis material large area. Photocatalysis hetero-junction thin-film of the present invention have prepare simple economy, light transmission is good, reactivity is high and the feature such as repeatable utilization, it is possible to be widely used in air pollution NOxDegraded Deng pollutant.
Claims (8)
1. a g-C3N4/TiO2The preparation method of heterojunction photocatalysis thin film, it is characterised in that comprise the following steps:
(1) g-C is prepared3N4/TiO2Complex sol:
Hydrolysis of tetrabutyl titanate prepares TiO2Colloidal sol, by TiO2Colloidal sol with pass through g-C3N4Alcohol suspension is according to volume ratio 1:(1-20) mix homogeneously, obtain g-C3N4/TiO2Complex sol;
(2) g-C is prepared3N4/TiO2Heterojunction photocatalysis thin film:
By g-C3N4/TiO2Complex sol is sprayed in substrate, obtains g-C after drying3N4/TiO2Heterojunction photocatalysis thin film, wherein, described dry by natural air drying or in oven for drying.
2. a kind of g-C according to claim 13N4/TiO2The preparation method of heterojunction photocatalysis thin film, it is characterised in that TiO2Colloidal sol prepares by the following method: adding butyl titanate in hydrochloric acid solution, under room temperature, hydrolysis, ageing 2～3 weeks, obtain TiO2Colloidal sol; Wherein, hydrochloric acid solution is 10:1 with the volume ratio of butyl titanate.
3. a kind of g-C according to claim 23N4/TiO2The preparation method of heterojunction photocatalysis thin film, it is characterised in that the concentration of hydrochloric acid solution is 0.12mol/L.
4. a kind of g-C according to claim 13N4/TiO2The preparation method of heterojunction photocatalysis thin film, it is characterised in that described g-C3N4Alcohol suspension prepares by the following method: by g-C3N4Joining in ethanol, under 400W power, ultrasonic 4～10h, obtains g-C3N4Alcohol suspension; Wherein, g-C3N4It is (0.001g～1.0) g:100mL with the ratio of ethanol.
5. a kind of g-C according to claim 13N4/TiO2The preparation method of heterojunction photocatalysis thin film, it is characterised in that by g-C in described step (2)3N4/TiO2Complex sol is sprayed in substrate, obtains g-C3N4/TiO2The detailed process of heterojunction photocatalysis thin film is: by g-C3N4/TiO2Complex sol in high-pressure spray gun watering can, even application 2～4 times in substrate under 6KPa pressure, dried g-C3N4/TiO2Heterojunction photocatalysis thin film.
6. a kind of g-C according to claim 13N4/TiO2The preparation method of heterojunction photocatalysis thin film, it is characterised in that the temperature of described drying is not higher than 100 DEG C.
7. a kind of g-C according to claim 13N4/TiO2The preparation method of heterojunction photocatalysis thin film, it is characterised in that described substrate is glass, pottery or corrosion resistant plate.
8. a g-C3N4/TiO2The purposes of heterojunction photocatalysis thin film, it is characterised in that g-C3N4/TiO2Heterojunction photocatalysis thin film is NO in degraded airxThe application of pollutant.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179441A (en) * | 2016-07-01 | 2016-12-07 | 陕西科技大学 | A kind of carbonitride carbon-doped mesoporous TiO 2 composite photo-catalyst and preparation method thereof |
| CN106190511A (en) * | 2016-07-05 | 2016-12-07 | 武汉理工大学 | A kind of photocatalysis concrete parting agent and preparation method thereof |
| CN107159289A (en) * | 2017-04-20 | 2017-09-15 | 西北大学 | A kind of preparation g C in situ3N4‑TiO2The method of nano heterojunction photocatalysis film |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3550947B2 (en) * | 1997-06-09 | 2004-08-04 | 住友金属工業株式会社 | Method for producing and using photocatalytic multifunctional member |
| CN103602976A (en) * | 2013-11-28 | 2014-02-26 | 中国科学院金属研究所 | Method and device for preparing visible-light responsive TiO2 photocatalytic coating by cold spraying |
| CN103736512A (en) * | 2014-01-03 | 2014-04-23 | 北京工业大学 | Preparation method of TiO2 (titanium dioxide) mesoporous monocrystal microsphere and g-C3N4 heterojunction photocatalyst |
| CN104785232A (en) * | 2015-03-17 | 2015-07-22 | 珠海全程科技有限公司 | Low-temperature preparation method for high-activity nano titanium dioxide thin film loaded on ceramic |
-
2016
- 2016-03-09 CN CN201610134111.0A patent/CN105664996B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3550947B2 (en) * | 1997-06-09 | 2004-08-04 | 住友金属工業株式会社 | Method for producing and using photocatalytic multifunctional member |
| CN103602976A (en) * | 2013-11-28 | 2014-02-26 | 中国科学院金属研究所 | Method and device for preparing visible-light responsive TiO2 photocatalytic coating by cold spraying |
| CN103736512A (en) * | 2014-01-03 | 2014-04-23 | 北京工业大学 | Preparation method of TiO2 (titanium dioxide) mesoporous monocrystal microsphere and g-C3N4 heterojunction photocatalyst |
| CN104785232A (en) * | 2015-03-17 | 2015-07-22 | 珠海全程科技有限公司 | Low-temperature preparation method for high-activity nano titanium dioxide thin film loaded on ceramic |
Non-Patent Citations (1)
| Title |
|---|
| 臧梦樵: "C3/N4/TiO2复合光催化剂对污染物可见光降解性能研究", 《中国优秀硕士学位论文全文数据库（电子期刊）》 * |
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| CN106179441A (en) * | 2016-07-01 | 2016-12-07 | 陕西科技大学 | A kind of carbonitride carbon-doped mesoporous TiO 2 composite photo-catalyst and preparation method thereof |
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