CN102941129A - Supported photocatalyst as well as preparation method and application thereof - Google Patents
Supported photocatalyst as well as preparation method and application thereof Download PDFInfo
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- CN102941129A CN102941129A CN2012104397514A CN201210439751A CN102941129A CN 102941129 A CN102941129 A CN 102941129A CN 2012104397514 A CN2012104397514 A CN 2012104397514A CN 201210439751 A CN201210439751 A CN 201210439751A CN 102941129 A CN102941129 A CN 102941129A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000006260 foam Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 66
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 48
- 230000001699 photocatalysis Effects 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 33
- 229910052759 nickel Inorganic materials 0.000 claims description 33
- 238000007146 photocatalysis Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000005416 organic matter Substances 0.000 claims description 27
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000004070 electrodeposition Methods 0.000 claims description 7
- 230000007613 environmental effect Effects 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000012876 carrier material Substances 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000010815 organic waste Substances 0.000 abstract 1
- 239000012855 volatile organic compound Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 39
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 21
- 230000000694 effects Effects 0.000 description 17
- 238000006555 catalytic reaction Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000002604 ultrasonography Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 7
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- 230000003647 oxidation Effects 0.000 description 5
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000001652 electrophoretic deposition Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
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- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention discloses a supported photocatalyst as well as a preparation method and an application thereof. The preparation method comprises the following steps of: taking a foam metal net as an electrode cathode; taking a titanium sheet or a graphite sheet as an electrode anode; immersing the electrode cathode and the electrode anode into photocatalyst sol formed by mixing photocatalyst powder with water according to a distance of 1-20 cm; connecting with a 10-150-V stable-voltage direct-current power supply and continually agitating the sol; after electrifying for 1-50 min, stopping electrifying; and taking out cathode foam metal and drying to obtain the supported photocatalyst. The preparation method provided by the invention can rapidly and efficiently realize large amount of uniform load of the photocatalyst on a carrier material; and the obtained supported photocatalyst is not easy to release and is convenient to recycle and repeatedly utilize. The supported photocatalyst disclosed by the invention can be used for effectively and photo-catalytically degrading volatile organic compounds and can be used for purifying indoor or industrial organic waste gas with different concentrations.
Description
Technical field
The present invention relates to environmental protection technical field, particularly a kind of loaded photocatalyst and preparation method thereof and application.
Background technology
Along with the expanding day of human production activity's scope, it is very serious to the pollution of atmospheric environment to have caused occurring more and more serious problem of environmental pollution, particularly volatile organic matter, has been subject in recent years increasing people's extensive concern.These volatile organic matter great majority are poisonous to human body, and part can also be brought out various serious diseases, has carcinogenic or teratogenesis, simultaneously can also with atmosphere in nitrogen oxide generation photochemical reaction destroy atmospheric ozone layer.Therefore, the improvement of volatile organic matter become in recent years so that from now on decades the atmospheric environment scientific worker research emphasis.
In recent years, photocatalysis oxidation technique is subject to people as a kind of novel high-level oxidation technology and pays close attention to widely.Compare with traditional biology, chemical treatment method, it has simple to operate, mild condition and low energy consumption, does not produce the outstanding features such as secondary pollution, particularly tempting development prospect is arranged aspect the improvement of volatile organic matter in environmental improvement.But this technology still exists the difficult problem in some practical applications to remain further to be solved at present.At first, the low and photochemical catalyst recovery difficulty of light source utilization rate.Photocatalysis oxidation technique employed photochemical catalyst great majority in the processing procedure of organic pollution are powder, this may cause the waste of catalyst in the atmospheric treatment process, and in course of reaction, only have a small amount of photochemical catalyst on surface to absorb ultraviolet light and played the effect of photochemical catalyst, thereby cause photo-quantum efficiency lower, Powdered photochemical catalyst runs off easily in the simultaneous reactions process, the recycling that is unfavorable for photochemical catalyst has been brought certain difficulty to practical application degraded gas phase organic matter.Secondly, the impact that the mutually light-catalysed efficient of gas-solid is subject to the real atmosphere environmental factor easily is larger.The impact such as the concentration of the concentration level of the contaminated thing of photocatalysis technology, relative humidity, oxygen is larger, and particularly in commercial Application, the environmental applications condition is more complicated, often causes photocatalysis efficiency lower.At last, photochemical catalyst long period of activity less stable.Photocatalyst surface deposits the intermediate of hard degradation easily in the photocatalysis to degrade organic matter process, thereby the partition catalyst contacts with ultraviolet light, cause the photochemical catalyst catalytic activity to descend, and can not in-situ regeneration, this affects the commercial Application of photocatalysis oxidation technique greatly.Therefore, a kind of stable, efficiently immobilization photochemical catalyst and application of carrying out its oxidation technology of exploitation is the difficult point of correlative technology field.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of preparation method of loaded photocatalyst with not enough.
Another object of the present invention is to provide the loaded photocatalyst that obtains by above-mentioned preparation method.
A further object of the present invention is to provide the application of described loaded photocatalyst.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of loaded photocatalyst comprises following steps:
(1) preliminary treatment of electrode: the foam metal net is cleaned with hydrochloric acid, absolute ethyl alcohol and water successively, dry rear as electrode cathode; Titanium sheet or graphite flake clean with acetone, second alcohol and water successively, dry rear as electrode anode;
(2) preparation of photocatalyst sol: photocatalyst powder is mixed with water, fully stir, namely get photocatalyst sol after the ultrasonic dispersion again;
(3) electro-deposition prepares loaded photocatalyst: electrode cathode and electrode anode that step (1) preliminary treatment is obtained immerse in the photocatalyst sol of step (2) preparation by spacing 1～20cm, meet constant voltage dc source 10～150V, and constantly stir colloidal sol, behind energising 1～50min, stop energising, take out the negative electrode foam metal, can obtain foam metal loaded optic catalyst, i.e. loaded photocatalyst after drying.
Foam metal described in the step (1) comprises nickel foam, foamed aluminium and alloy thereof etc.;
The size of the foam metal net described in the step (1) is 10～100mm * 50～400mm;
The concentration of the hydrochloric acid described in the step (1) is preferably 0.1～1.0mol/L;
Foam metal network optimization gating described in the step (1) is crossed following concrete steps and is processed: the foam metal net cleaned 3 times in the hydrochloric acid of 0.1～1.0mol/L first, and ultrasonic cleaning 10～100min in absolute ethyl alcohol again, then water cleans 3 times;
Titanium sheet described in the step (1) or graphite flake are preferably processed by following concrete steps: successively in acetone, ethanol respectively behind the ultrasonic 15min, water cleans 3 times with titanium sheet or graphite flake;
Described ultrasonic frequency is 10～100kHz;
Photocatalyst powder described in the step (2) is preferably ZnO or TiO
2
Photocatalyst powder described in the step (2) and described water are joined to get stable sol by 0.1～5:200～1000(g:mL) carry out proportioning;
The well-beaten time described in the step (2) is preferably 10～100min;
Ultrasonic frequency described in the step (2) is 10～100kHz;
The time of the ultrasonic dispersion described in the step (2) is preferably 5～30min;
The water that relates in the above-mentioned steps is deionized water.
A kind of loaded photocatalyst prepares by said method; Wherein, the load capacity that obtains photochemical catalyst is mass percent 0.5～15.0%;
The application of described loaded photocatalyst in environmental protection, volatile organic matter in the atmosphere that is specially adapted to degrade.
A kind of method of high efficiency photocatalysis degraded volatile organic matter may further comprise the steps:
(1) loaded photocatalyst of the present invention is installed in the photo catalysis reactor;
The air that (2) will contain volatile organic matter mixes 1～30min in photo catalysis reactor, under the effect of airflow reflux circulation, Adsorption of Organic is on loaded photocatalyst; Open the ultraviolet lamp irradiation with backward photo catalysis reactor, the organic pollution that is adsorbed on photocatalyst surface carries out light-catalyzed reaction in photocatalyst surface, and along with air constantly circulates, light-catalyzed reaction is carried out continuously, thereby organic pollutant degradation is eliminated;
Described photo catalysis reactor is that gas-solid fixes bed photocatalytic reactor, and detailed construction is seen ZL200820200957.0;
Described volatile organic matter refers to benzene, toluene or styrene etc., and its concentration range is 10～1000ppmv;
The relative humidity of described air is 5～80%, and oxygen concentration is 0～100%;
The irradiation dominant wavelength of described ultraviolet lamp is 254nm;
The method of described high efficiency photocatalysis degraded volatile organic matter can be used for the purification of indoor and industrial variable concentrations organic exhaust gas simultaneously, has wide application potential.
The present invention has following advantage and effect with respect to prior art:
(1) the present invention utilizes electrophoretic deposition photocatalyst powder to be loaded on the carrier material of bigger serface, can be fast and realize efficiently a large amount of and uniform load of photochemical catalyst on carrier material, resulting photochemical catalyst is not easy to come off, and is convenient to reclaim and recycling.Compare with existing electro-deposition techniques, at first, colloidal sol electrophoresis of the present invention is simple and fast more; Secondly, the colloidal sol electrophoresis has avoided using environmentally harmful electroplate liquid, more environmental protection; Moreover this method reduces other hetero atoms the doping of catalyst is impacted catalytic activity; At last, in the application of catalyst, the easier catalysqt deactivation that causes of conventional art, but the long period of activity of the loaded photocatalyst that obtains by the method is maintained, and the original position that can realize catalyst in degradable organic pollutant brings back to life, and makes catalyst have more the commercial Application potentiality.
(2) the method medium ultraviolet light distribution homogeneous of high efficiency photocatalysis degraded volatile organic matter provided by the invention, photochemical catalyst can fully contact with volatile organic matter, greatly improve photocatalysis to degraded and the mineralising efficient of volatile organic matter, experimental result shows, initial concentration is that the styrene of 120ppmv can reach degraded in illumination 3min, behind the simultaneous reactions 160min, the cinnamic mineralising efficient of 120ppmv can reach 100%.
Description of drawings
Fig. 1 is X-ray powder diffraction figure; Wherein: curve a is the foamed nickel supported nano-TiO of embodiment 1 preparation
2X-ray powder diffraction figure, curve b be blank nickel foam X-ray powder diffraction figure (●: anatase; Zero: rutile; ★: nickel).
Fig. 2 is the scanning electron microscope (SEM) photograph of sample; Wherein, a is the foamed nickel supported nano-TiO of embodiment 1 preparation
2Scanning electron microscope (SEM) photograph, b is the scanning electron microscope (SEM) photograph of blank nickel foam.
Fig. 3 is photocatalytic degradation and the mineralising efficiency curve diagram of styrene gas; Wherein, (a) be the photocatalytic degradation curve map; (b) be photocatalysis mineralising efficiency curve diagram.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited to this.
Embodiment 1
The preparation method of foam metal loaded optic catalyst:
(1) electrode preliminary treatment: (size is: 50mm * 200mm) clean 3 times in the hydrochloric acid of 0.1mol/L first with Foaming nickel metal mesh, ultrasonic in absolute ethyl alcohol (frequency is the Ultrasound Instrument of 40kHz) 30min again, then use washed with de-ionized water 3 times, dry rear as electrode cathode under the room temperature; With same supersonic frequency, the titanium sheet behind the ultrasonic 15min, puts it into ultrasonic 15min in the ethanol again in acetone, use at last washed with de-ionized water 3 times, naturally dries rear as electrode anode under the room temperature.
(2) TiO
2Colloidal sol preparation: nano-TiO
2Photocatalyst powder and deionized water are by 5:1000(g:mL) mix, fully stir 30min, put into again in the Ultrasound Instrument that supersonic frequency is 40kHz and namely get TiO behind the ultrasonic dispersion 15min
2Colloidal sol.
(3) electro-deposition prepares loaded photocatalyst: the pretreated foam metal of step (1) and titanium sheet are immersed the TiO of step (2) preparation by spacing 6cm
2In the colloidal sol, connect constant voltage dc source 30V, and constantly stir colloidal sol, behind the energising 1min, stop energising, take out the negative electrode foam metal, can obtain foam metal load TiO after naturally drying under the room temperature
2Photochemical catalyst.Draw TiO after weighing by assay balance
2Load capacity be 7.2%.
Photochemical catalyst characterizes:
Fig. 1 and Fig. 2 have provided respectively pretreated foam metal and foam metal load TiO
2The XRD of photochemical catalyst and SEM characterization result.Can find out foamed nickel supported TiO from Fig. 1 a
2Occurred typical anatase and rutile peak on the XRD spectra of photochemical catalyst, this shows nano-TiO
2Powder successfully loads on the nickel foam, and crystal formation remains unchanged, and this means that its photocatalytic activity is unaffected.In addition, from Fig. 2, can find out more intuitively, by method behind the electrophoretic deposition, form the tight and uniform TiO of one deck on the nickel foam surface
2Film, its load capacity are traditional more than 10 times of dip loading amount.This shows, can be quickly and effectively with powder TiO by electrophoretic deposition
2Load on the nickel foam, and when being used for the degraded volatile organic matter, can avoid too much loss, thereby be convenient to recycling.Similar situation appears according to same on the XRD of the photochemical catalyst of other example preparation and the SEM collection of illustrative plates.
Embodiment 2
(1) electrode preliminary treatment: (size is: 100mm * 400mm) clean 3 times in the hydrochloric acid of 1.0mol/L first with Foaming nickel metal mesh, ultrasonic in absolute ethyl alcohol (frequency is the Ultrasound Instrument of 10kHz) 100min again, then use washed with de-ionized water 3 times, dry rear as electrode cathode under the room temperature; With same supersonic frequency, graphite flake behind the ultrasonic 15min, puts it into ultrasonic 15min in the ethanol again in acetone, use at last washed with de-ionized water 3 times, naturally dries rear as electrode anode under the room temperature.
(2) TiO
2Colloidal sol preparation: with TiO
2Photocatalyst powder and deionized water are by 5:500(g:mL) mix, fully stir 100min, put into again in the Ultrasound Instrument that supersonic frequency is 10kHz and namely get TiO behind the ultrasonic dispersion 30min
2Colloidal sol.
(3) electro-deposition prepares loaded photocatalyst: pretreated nickel foam and graphite flake that step (1) is obtained immerse the TiO of step (2) preparation by spacing 6cm
2In the colloidal sol, connect constant voltage dc source 100V, and constantly stir colloidal sol, behind the energising 5min, stop energising, take out negative electrode nickel foam metal, can obtain foamed nickel supported TiO after naturally drying under the room temperature
2Photochemical catalyst.
Press embodiment 1 method and detect TiO
2Load capacity be 15%; TiO
2Success of powder is in the closely uniformly load of nickel foam surface, and crystal formation remains unchanged.
Embodiment 3
(1) electrode preliminary treatment: (size is: 100mm * 400mm) clean 3 times in the hydrochloric acid of 1.0mol/L first with Foaming nickel metal mesh, ultrasonic in absolute ethyl alcohol (frequency is the Ultrasound Instrument of 10kH z) 100min again, then use washed with de-ionized water 3 times, dry rear as electrode cathode under the room temperature; With same supersonic frequency, graphite flake behind the ultrasonic 15min, puts it into ultrasonic 15min in the ethanol again in acetone, use at last washed with de-ionized water 3 times, naturally dries rear as electrode anode under the room temperature.
(2) TiO
2Colloidal sol preparation: with TiO
2Photocatalyst powder and deionized water are by 0.1:200(g:mL) mix, fully stir 100min, put into again in the Ultrasound Instrument that supersonic frequency is 10kHz and namely get TiO behind the ultrasonic dispersion 30min
2Colloidal sol.
(3) electro-deposition prepares loaded photocatalyst: pretreated nickel foam and graphite flake that step (1) is obtained immerse the TiO of step (2) preparation by spacing 20cm
2In the colloidal sol, connect constant voltage dc source 150V, and constantly stir colloidal sol, behind the energising 50min, stop energising, take out negative electrode nickel foam metal, can obtain foamed nickel supported TiO after naturally drying under the room temperature
2Photochemical catalyst.
Press embodiment 1 method and detect TiO
2Load capacity be 0.5%; TiO
2Success of powder is in the load of nickel foam surface uniform, and crystal formation remains unchanged.
Embodiment 4
(1) electrode preliminary treatment: with foamed aluminium net (size: 10mm * 50mm) in the hydrochloric acid of 0.5mol/L, clean 3 times first, ultrasonic in absolute ethyl alcohol (frequency is the Ultrasound Instrument of 100kHz) 10min again, then use washed with de-ionized water 3 times, dry rear as electrode cathode under the room temperature; With same supersonic frequency, the titanium sheet behind the ultrasonic 15min, puts it into ultrasonic 15min in the ethanol successively again in acetone, use at last washed with de-ionized water 3 times, naturally dries rear as electrode anode under the room temperature.
(2) ZnO colloidal sol preparation: with ZnO photocatalyst powder and water by 2:500(g:mL) mix, fully stir 10min, put into again in the Ultrasound Instrument that supersonic frequency is 100kHz and obtain ZnO colloidal sol behind the ultrasonic dispersion 5min.
(3) electro-deposition prepares loaded photocatalyst: pretreated foam metal and titanium sheet that step (1) is obtained immerse in the ZnO colloidal sol of step (2) preparation by spacing 1cm, connect constant voltage dc source 10V, and constantly stir colloidal sol, behind the energising 20min, stop energising, take out the negative electrode foam metal, can obtain foam metal loading ZnO photochemical catalyst after naturally drying under the room temperature.
Press embodiment 1 method and detect, the load capacity of ZnO is 6.7%; Success of ZnO powder is in the closely uniformly load of foamed aluminium net surface, and crystal formation remains unchanged.
Application Example 1
The method of high efficiency photocatalysis degraded volatile organic matter comprises the steps:
(1) the foamed nickel supported TiO that embodiment 1 is prepared
2The gas-solid that photochemical catalyst is installed on structure such as ZL200820200957.0 to be provided fixes bed photocatalytic reactor.
(2) will contain concentration is that the cinnamic air of 120ppmv (air humidity is 5%, and oxygen concentration is 20%) mixes, and under the effect of airflow reflux circulation, Adsorption of Organic is in the foam metal supported titanium
2On (load capacity is 7.2%), absorption 15min back balance.
(3) opening dominant wavelength to photo catalysis reactor simultaneously is the 254nm UV-irradiation, and styrene gas is at foamed nickel supported TiO
2Light-catalyzed reaction is carried out on the surface, and along with air constantly circulates, the light-catalyzed reaction continuous circulation carries out, thereby styrene-degrading is eliminated.
Photocatalytic degradation styrene gas effect:
Fig. 3 provided styrene under ultraviolet excitation under the catalyst of preparation photocatalytic degradation (a) and mineralising (b) curve.By degradation curve (a) as can be known, the time of styrene gas 100% photocatalytic degradation of 120ppmv is 3min only, illustrates that styrene has good degradation efficiency under the method; (b) can find out by the mineralising curve, and behind the reaction 160min, the complete photocatalysis mineralising of 120ppmv styrene becomes CO
2And H
2O.By the above results explanation, method of the present invention not only has good catalytic decomposition efficient to styrene, and can be with the styrene permineralization, this means the increase along with the reaction time, the intermediate product that is deposited on catalyst surface also can permineralization, therefore photochemical catalyst not only can keep its photocatalytic activity for a long time under this system, and can realize in-situ regeneration.
Loaded photocatalyst provided by the present invention has good degradation effect to styrene, and styrene can be converted into CO fully
2And H
2O.
Application Example 2
Organic purification method comprises the steps: in the air
(1) the foamed nickel supported TiO that embodiment 2 is prepared
2The gas-solid that photochemical catalyst is installed on structure such as ZL200820200957.0 to be provided fixes bed photocatalytic reactor.
(2) will contain concentration is that the cinnamic air of 120ppmv (air humidity is 5%, and oxygen concentration is 20%) mixes, and under the effect of airflow reflux circulation, Adsorption of Organic is in the foam metal supported titanium
2On (load capacity is 15%), absorption 15min back balance.
(3) opening simultaneously dominant wavelength is the 254nm UV-irradiation, and styrene gas is at foamed nickel supported TiO
2Light-catalyzed reaction is carried out on the surface, and along with air constantly circulates, the light-catalyzed reaction continuous circulation carries out, thereby styrene-degrading is eliminated.The photocatalytic degradation effect shows that the time of styrene gas 100% photocatalytic degradation of 120ppmv is 6min, and behind the reaction 360min, its mineralization rate only is 70%, compares with application example 1, and its photocatalysis efficiency descends greatly.
Application Example 3
The method of high efficiency photocatalysis degraded volatile organic matter comprises the steps:
(1) the foamed nickel supported TiO that embodiment 1 is prepared
2The gas-solid that photochemical catalyst is installed on structure such as ZL200820200957.0 to be provided fixes bed photocatalytic reactor.
(2) will contain concentration is that the cinnamic air of 400ppmv (air humidity is 5%, and oxygen concentration is 100%) mixes, and under the effect of airflow reflux circulation, Adsorption of Organic is in the foam metal supported titanium
2On (load capacity is 7.2%), absorption 15min back balance.
(3) opening simultaneously dominant wavelength is the 254nm UV-irradiation, and styrene gas is at foamed nickel supported TiO
2Light-catalyzed reaction is carried out on the surface, and along with air constantly circulates, the light-catalyzed reaction continuous circulation carries out, thereby styrene-degrading is eliminated.Photocatalytic degradation is the result show, 400ppmv styrene reaches 100% in 4min eliminates.
Application Example 4
The method of high efficiency photocatalysis degraded volatile organic matter comprises the steps:
(1) the foamed nickel supported TiO that embodiment 1 is prepared
2The gas-solid that photochemical catalyst is installed on structure such as ZL200820200957.0 to be provided fixes bed photocatalytic reactor.
(2) will contain concentration is that the cinnamic air of 400ppmv (air humidity is 5%, and oxygen concentration is 0%) mixes, and under the effect of airflow reflux circulation, Adsorption of Organic is in the foam metal supported titanium
2On (load capacity is 7.2%), absorption 15min back balance.
(3) opening simultaneously dominant wavelength is the 254nm UV-irradiation, and styrene gas is at foamed nickel supported TiO
2Light-catalyzed reaction is carried out on the surface, and along with air constantly circulates, the light-catalyzed reaction continuous circulation carries out, thereby styrene-degrading is eliminated.Photocatalytic degradation is the result show, 400ppmv styrene just can reach 100% in 30min eliminates.
Application Example 5
The method of high efficiency photocatalysis degraded volatile organic matter comprises the steps:
(1) the foamed nickel supported TiO that embodiment 3 is prepared
2The gas-solid that photochemical catalyst is installed on structure such as ZL200820200957.0 to be provided fixes bed photocatalytic reactor.
(2) will contain concentration is that the cinnamic air of 40ppmv (air humidity is 80%, and oxygen concentration is 20%) mixes, and under the effect of airflow reflux circulation, Adsorption of Organic is in the foam metal supported titanium
2On (load capacity is 0.5%), absorption 15min back balance.
(3) opening simultaneously dominant wavelength is the 254nm UV-irradiation, and styrene gas is at foam metal load TiO
2Light-catalyzed reaction is carried out on the surface, and along with air constantly circulates, the light-catalyzed reaction continuous circulation carries out, thereby styrene-degrading is eliminated.Photocatalytic degradation is the result show, 40ppmv styrene reaches 100% in 2min eliminates, and permineralization behind reaction 60min.
Application Example 6
Organic purification method comprises the steps: in the air
(1) gas-solid that the foamed aluminium load ZnO photochemical catalyst of embodiment 4 preparation is installed on structure such as ZL200820200957.0 provides fixes bed photocatalytic reactor.
(2) will contain concentration is that (air humidity is 5% to the cinnamic air of 120ppmv, oxygen concentration is 20%) mix, under the effect of airflow reflux circulation, Adsorption of Organic is 6.7% in foamed aluminium load type ZnO(load capacity) on, absorption 15min back balance.
(3) opening simultaneously dominant wavelength is the 254nm UV-irradiation, and styrene gas is carried out light-catalyzed reaction on foamed aluminium load ZnO surface, and along with air constantly circulates, the light-catalyzed reaction continuous circulation carries out, thereby styrene-degrading is eliminated.The photocatalytic degradation effect shows that 120ppmv styrene reaches 100% in 4min eliminates, and reaches 100% mineralising in the 120min.
Application Example 7
The method of high efficiency photocatalysis degraded volatile organic matter comprises the steps:
(1) the foamed nickel supported TiO that embodiment 1 is prepared
2The gas-solid that photochemical catalyst is installed on structure such as ZL200820200957.0 to be provided fixes bed photocatalytic reactor;
(2) will contain the air that concentration is 400ppmv toluene (air humidity is 5%, and oxygen concentration is 20%) and mix, under the effect of airflow reflux circulation, Adsorption of Organic is in the foam metal supported titanium
2On (load capacity is 7.2%), absorption 15min back balance.
(3) opening simultaneously dominant wavelength is the 254nm UV-irradiation, and toluene gas is at foamed nickel supported TiO
2Light-catalyzed reaction is carried out on the surface, and along with air constantly circulates, the light-catalyzed reaction continuous circulation carries out, thereby degradation of toluene is eliminated.Photocatalytic degradation is the result show, 400ppmv toluene reaches 100% in 30min eliminates.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a loaded photocatalyst is characterized in that comprising following steps:
(1) preliminary treatment of electrode: the foam metal net is cleaned with hydrochloric acid, absolute ethyl alcohol and water successively, dry rear as electrode cathode; Titanium sheet or graphite flake clean with acetone, second alcohol and water successively, dry rear as electrode anode;
(2) preparation of photocatalyst sol: photocatalyst powder is mixed with water, fully stir, namely get photocatalyst sol after the ultrasonic dispersion again;
(3) electro-deposition prepares loaded photocatalyst: electrode cathode and electrode anode that step (1) preliminary treatment is obtained immerse in the photocatalyst sol of step (2) preparation by spacing 1～20cm, meet constant voltage dc source 10～150V, and constantly stir colloidal sol, behind energising 1～50min, stop energising, take out the negative electrode foam metal, can obtain loaded photocatalyst after drying.
2. the preparation method of loaded photocatalyst according to claim 1 is characterized in that: the foam metal described in the step (1) is a kind of in nickel foam, foamed aluminium and the alloy thereof.
3. the preparation method of loaded photocatalyst according to claim 1, it is characterized in that: the size of the foam metal net described in the step (1) is 10～100mm * 50～400mm.
4. the preparation method of loaded photocatalyst according to claim 1, it is characterized in that: the foam metal Netcom described in the step (1) crosses following concrete steps and processes: the foam metal net is cleaned 3 times in the hydrochloric acid of 0.1～1.0mol/L first, ultrasonic cleaning 10～100min in absolute ethyl alcohol again, then water cleans 3 times;
Titanium sheet described in the step (1) or graphite flake are processed by following concrete steps: successively in acetone, ethanol respectively behind the ultrasonic 15min, water cleans 3 times with titanium sheet or graphite flake.
5. the preparation method of loaded photocatalyst according to claim 1, it is characterized in that: the photocatalyst powder described in the step (2) is ZnO or TiO
2
Photocatalyst powder described in the step (2) and described water are by the proportioning of 0.1～5:200～1000(g:mL);
The well-beaten time described in the step (2) is 10～100min;
Ultrasonic frequency described in the step (2) is 10～100kHz;
The time of the ultrasonic dispersion described in the step (2) is 5～30min.
6. loaded photocatalyst, each described preparation method obtains by claim 1～5.
7. the application of loaded photocatalyst claimed in claim 6 in environmental protection is characterized in that: described loaded photocatalyst is used for the degraded volatile organic matter.
8. the method for high efficiency photocatalysis degraded volatile organic matter is characterized in that may further comprise the steps:
(1) loaded photocatalyst claimed in claim 6 is installed in the photo catalysis reactor;
The air that (2) will contain volatile organic matter mixes 1～30min in photo catalysis reactor; Open the ultraviolet lamp irradiation with backward photo catalysis reactor.
9. the method for high efficiency photocatalysis according to claim 8 degraded volatile organic matter, it is characterized in that: described photo catalysis reactor fixes bed photocatalytic reactor for the gas-solid that utility model patent ZL200820200957.0 provides;
Described volatile organic matter is benzene, toluene or styrene, and its concentration range is 10～1000ppmv;
The relative humidity of described air is 5～80%, and oxygen concentration is 0～100%;
The irradiation dominant wavelength of described ultraviolet lamp is 254nm.
10. the application of the method for high efficiency photocatalysis degraded volatile organic matter claimed in claim 9 is characterized in that: the method for described high efficiency photocatalysis degraded volatile organic matter can be used for the purification of indoor or industrial variable concentrations organic exhaust gas.
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| CN114849742B (en) * | 2022-06-21 | 2024-02-20 | 常州大学 | Bi for deeply purifying VOCs 5 O 7 I/WO 3 Ni foam photocatalytic film and preparation method thereof |
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