CN102941129B - 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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- CN102941129B CN102941129B CN201210439751.4A CN201210439751A CN102941129B CN 102941129 B CN102941129 B CN 102941129B CN 201210439751 A CN201210439751 A CN 201210439751A CN 102941129 B CN102941129 B CN 102941129B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 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
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- 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
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- 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 24
- 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
- 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
- 238000007654 immersion Methods 0.000 claims description 3
- 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
- 239000007789 gas Substances 0.000 abstract description 14
- 239000012876 carrier material Substances 0.000 abstract description 3
- 239000010815 organic waste Substances 0.000 abstract 1
- 239000012855 volatile organic compound Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 39
- 230000000694 effects Effects 0.000 description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 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
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000008030 elimination Effects 0.000 description 5
- 238000003379 elimination reaction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 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
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 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
- 230000008901 benefit Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
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- 238000005286 illumination Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
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Classifications
-
- 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, cause occurring that more and more serious problem of environmental pollution, particularly volatile organic matter are very serious to the pollution of atmospheric environment, be 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 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.Compared 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 has tempting development prospect aspect the improvement of volatile organic matter in environmental improvement.But this technology still exists the difficult problem in some practical applications to need further to be solved at present.First, light source utilization rate is low reclaims difficulty with photochemical catalyst.The photochemical catalyst great majority that photocatalysis oxidation technique uses in the processing procedure of organic pollution are powder, this may cause the waste of catalyst in 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, in simultaneous reactions process, Powdered photochemical catalyst easily runs off, be unfavorable for the recycling of photochemical catalyst, brought certain difficulty to practical application degraded gas phase organic matter.Secondly, the impact that the mutually light-catalysed efficiency of gas-solid is easily subject to real atmosphere environmental factor is larger.The impacts such as the concentration of the concentration level of the contaminated thing of photocatalysis technology, relative humidity, oxygen are larger, and particularly, in commercial Application, environmental applications condition is more complicated, often causes photocatalysis efficiency lower.Finally, photochemical catalyst long period of activity less stable.Photocatalyst surface easily deposits the intermediate of hard degradation in photocatalysis to degrade organic matter process, thereby partition catalyst contacts with ultraviolet light, cause photochemical catalyst catalytic activity to decline, and can not in-situ regeneration, this affects the commercial Application of photocatalysis oxidation technique greatly.Therefore, developing a kind of stable, immobilization photochemical catalyst and application of carrying out its oxidation technology is efficiently the difficult point of correlative technology field.
Summary of the invention
Primary and foremost purpose of the present invention is that the shortcoming that overcomes prior art, with not enough, provides a kind of preparation method of loaded photocatalyst.
Another object of the present invention is to provide the loaded photocatalyst obtaining by above-mentioned preparation method.
A further object of the present invention is the application of the loaded photocatalyst that provides described.
Object of the present invention is achieved through the following technical solutions: a kind of preparation method of loaded photocatalyst, comprises following steps:
(1) pretreatment of electrode: 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, more obtain photocatalyst sol after ultrasonic dispersion;
(3) loaded photocatalyst is prepared in electro-deposition: in the photocatalyst sol that the electrode cathode that step (1) pretreatment is obtained and electrode anode are prepared by spacing 1～20cm immersion step (2), meet constant voltage dc source 10～150V, and constantly stir colloidal sol, after energising 1～50min, stop energising, take out negative electrode foam metal, after drying, can obtain foam metal loaded optic catalyst, i.e. loaded photocatalyst.
Foam metal described in step (1) comprises nickel foam, foamed aluminium and alloy thereof etc.;
The size of the foam metal net described in step (1) is 10～100mm × 50～400mm;
The concentration of the hydrochloric acid described in step (1) is preferably 0.1～1.0mol/L;
Foam metal network optimization gating described in step (1) is crossed following concrete steps and is processed: foam metal net first cleaned 3 times in the hydrochloric acid of 0.1～1.0mol/L, then ultrasonic cleaning 10～100min, then water cleaning 3 times in absolute ethyl alcohol;
Titanium sheet described in step (1) or graphite flake are preferably processed by following concrete steps: titanium sheet or graphite flake are distinguished after ultrasonic 15min successively in acetone, ethanol, and water cleans 3 times;
Described ultrasonic frequency is 10～100kHz;
Photocatalyst powder described in step (2) is preferably ZnO or TiO
2;
Photocatalyst powder described in step (2) and described water are by 0.1～5:200～1000(g:mL) carry out proportioning and join to obtain stable sol;
The well-beaten time described in step (2) is preferably 10～100min;
Ultrasonic frequency described in step (2) is 10～100kHz;
The time of the ultrasonic dispersion described in step (2) is preferably 5～30min;
The water relating in 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 method for high efficiency photocatalysis degraded volatile organic matter, comprises the following steps:
(1) loaded photocatalyst of the present invention is installed in photo catalysis reactor;
(2) air that contains volatile organic matter is mixed to 1～30min in photo catalysis reactor, under the effect of airflow reflux circulation, Adsorption of Organic is on loaded photocatalyst; Open ultraviolet lamp with backward photo catalysis reactor and irradiate, 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 structure is shown in 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, simultaneously for the purification of indoor and industrial variable concentrations organic exhaust gas, have 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 realize fast and efficiently a large amount of the and uniform load of photochemical catalyst on carrier material, the photochemical catalyst obtaining is not easy to come off, and is convenient to reclaim and recycling.Compared with existing electro-deposition techniques, first, more simple and fast of colloidal sol electrophoresis of the present invention; Secondly, colloidal sol electrophoresis has avoided using environmentally harmful electroplate liquid, more environmental protection; Moreover this method reduces the doping of other hetero atoms to catalyst and catalytic activity is impacted; Finally, in the application of catalyst, conventional art more easily causes catalysqt deactivation, but the long period of activity of the loaded photocatalyst obtaining by the method is maintained, and in degradable organic pollutant, can realize catalyst original position bring back to life, make catalyst have more 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 degraded and the mineralising efficiency of photocatalysis to volatile organic matter, experimental result shows, initial concentration is that the styrene of 120ppmv can reach degraded in illumination 3min, after simultaneous reactions 160min, the cinnamic mineralising efficiency of 120ppmv can reach 100%.
Brief description of the drawings
Fig. 1 is X-ray powder diffraction figure; Wherein: curve a is foamed nickel supported nano-TiO prepared by embodiment 1
2x-ray powder diffraction figure, X-ray powder diffraction figure that curve b is blank nickel foam (●: anatase; Zero: rutile; ★: nickel).
Fig. 2 is the scanning electron microscope (SEM) photograph of sample; Wherein, a is foamed nickel supported nano-TiO prepared by embodiment 1
2scanning electron microscope (SEM) photograph, the scanning electron microscope (SEM) photograph that b is blank nickel foam.
Fig. 3 is photocatalytic degradation and the mineralising efficiency curve diagram of styrene gas; Wherein, (a) be photocatalytic degradation curve map; (b) be photocatalysis mineralising efficiency curve diagram.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
The preparation method of foam metal loaded optic catalyst:
(1) electrode pretreatment: Foaming nickel metal mesh (size is: 50mm × 200mm) is first cleaned 3 times in the hydrochloric acid of 0.1mol/L, ultrasonic in absolute ethyl alcohol (Ultrasound Instrument that frequency is 40kHz) 30min again, then use washed with de-ionized water 3 times, under room temperature, dry rear as electrode cathode; By same supersonic frequency, titanium sheet in acetone after ultrasonic 15min, then puts it into ultrasonic 15min in ethanol, finally uses washed with de-ionized water 3 times, naturally dries rear as electrode anode under room temperature.
(2) TiO
2colloidal sol preparation: nano-TiO
2photocatalyst powder with deionized water by 5:1000(g:mL) mix, fully stir 30min, then put in the Ultrasound Instrument that supersonic frequency is 40kHz and obtain TiO after ultrasonic dispersion 15min
2colloidal sol.
(3) loaded photocatalyst is prepared in electro-deposition: the pretreated foam metal of step (1) and titanium sheet are immersed to TiO prepared by step (2) by spacing 6cm
2in colloidal sol, connect constant voltage dc source 30V, and constantly stir colloidal sol, after energising 1min, stop energising, take out negative electrode foam metal, after naturally drying under room temperature, can obtain foam metal load TiO
2photochemical catalyst.After weighing by assay balance, draw TiO
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
2on the XRD spectra of photochemical catalyst, occurred typical anatase and rutile peak, this shows nano-TiO
2powder successfully loads in 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 after electrophoretic deposition, form the tight and uniform TiO of one deck on nickel foam surface
2film, its load capacity is traditional the more than 10 times of dip loading amount.This shows, can be quickly and effectively by powder TiO by electrophoretic deposition
2load in nickel foam, and when degrading volatile organic matter, can avoid too much loss, thereby be convenient to recycling.The XRD of the photochemical catalyst of preparing according to other example and the similar situation of same appearance on SEM collection of illustrative plates.
Embodiment 2
(1) electrode pretreatment: Foaming nickel metal mesh (size is: 100mm × 400mm) is first cleaned 3 times in the hydrochloric acid of 1.0mol/L, ultrasonic in absolute ethyl alcohol (Ultrasound Instrument that frequency is 10kHz) 100min again, then use washed with de-ionized water 3 times, under room temperature, dry rear as electrode cathode; By same supersonic frequency, graphite flake in acetone after ultrasonic 15min, then puts it into ultrasonic 15min in ethanol, finally uses washed with de-ionized water 3 times, naturally dries rear as electrode anode under room temperature.
(2) TiO
2colloidal sol preparation: by TiO
2photocatalyst powder with deionized water by 5:500(g:mL) mix, fully stir 100min, then put in the Ultrasound Instrument that supersonic frequency is 10kHz and obtain TiO after ultrasonic dispersion 30min
2colloidal sol.
(3) loaded photocatalyst is prepared in electro-deposition: the pretreated nickel foam that step (1) is obtained and graphite flake immerse TiO prepared by step (2) by spacing 6cm
2in colloidal sol, connect constant voltage dc source 100V, and constantly stir colloidal sol, after energising 5min, stop energising, take out negative electrode nickel foam metal, after naturally drying under room temperature, can obtain foamed nickel supported TiO
2photochemical catalyst.
Press embodiment 1 method and detect, TiO
2load capacity be 15%; TiO
2success of powder is in the closely load uniformly of nickel foam surface, and crystal formation remains unchanged.
Embodiment 3
(1) electrode pretreatment: Foaming nickel metal mesh (size is: 100mm × 400mm) is first cleaned 3 times in the hydrochloric acid of 1.0mol/L, ultrasonic in absolute ethyl alcohol (frequency is the Ultrasound Instrument of 10kH z) 100min again, then use washed with de-ionized water 3 times, under room temperature, dry rear as electrode cathode; By same supersonic frequency, graphite flake in acetone after ultrasonic 15min, then puts it into ultrasonic 15min in ethanol, finally uses washed with de-ionized water 3 times, naturally dries rear as electrode anode under room temperature.
(2) TiO
2colloidal sol preparation: by TiO
2photocatalyst powder with deionized water by 0.1:200(g:mL) mix, fully stir 100min, then put in the Ultrasound Instrument that supersonic frequency is 10kHz and obtain TiO after ultrasonic dispersion 30min
2colloidal sol.
(3) loaded photocatalyst is prepared in electro-deposition: the pretreated nickel foam that step (1) is obtained and graphite flake immerse TiO prepared by step (2) by spacing 20cm
2in colloidal sol, connect constant voltage dc source 150V, and constantly stir colloidal sol, after energising 50min, stop energising, take out negative electrode nickel foam metal, after naturally drying under room temperature, can obtain foamed nickel supported TiO
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 pretreatment: foamed aluminium net (size: 10mm × 50mm) is first cleaned 3 times in the hydrochloric acid of 0.5mol/L, ultrasonic in absolute ethyl alcohol (Ultrasound Instrument that frequency is 100kHz) 10min again, then use washed with de-ionized water 3 times, under room temperature, dry rear as electrode cathode; By same supersonic frequency, titanium sheet successively in acetone after ultrasonic 15min, then puts it into ultrasonic 15min in ethanol, finally uses washed with de-ionized water 3 times, naturally dries rear as electrode anode under room temperature.
(2) ZnO colloidal sol preparation: by ZnO photocatalyst powder with water by 2:500(g:mL) mix, fully stir 10min, then put in the Ultrasound Instrument that supersonic frequency is 100kHz and obtain ZnO colloidal sol after ultrasonic dispersion 5min.
(3) loaded photocatalyst is prepared in electro-deposition: in the ZnO colloidal sol that the pretreated foam metal that step (1) is obtained and titanium sheet are prepared by spacing 1cm immersion step (2), connect constant voltage dc source 10V, and constantly stir colloidal sol, after energising 20min, stop energising, take out negative electrode foam metal, after naturally drying under room temperature, can obtain foam metal loading ZnO photochemical catalyst.
Press embodiment 1 method and detect, the load capacity of ZnO is 6.7%; Success of ZnO powder is in the closely load uniformly 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 being prepared by embodiment 1
2photochemical catalyst is installed on structure and fixes bed photocatalytic reactor as the gas-solid that ZL200820200957.0 provided.
(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 foam metal supported titanium
2(load capacity is 7.2%) is upper, absorption 15min back balance.
(3) open dominant wavelength to photo catalysis reactor is 254nm UV-irradiation simultaneously, and styrene gas is at foamed nickel supported TiO
2light-catalyzed reaction is carried out on surface, and along with air constantly circulates, 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.From degradation curve (a), the time of styrene gas 100% photocatalytic degradation of 120ppmv is only 3min, illustrates that styrene has good degradation efficiency under the method; Can be found out by mineralising curve (b), after reaction 160min, the complete photocatalysis of 120ppmv styrene is mineralized into CO
2and H
2o.Illustrate by the above results, method of the present invention not only has good catalytic decomposition efficiency to styrene, and can be by styrene permineralization, this means the increase along with the reaction time, the intermediate product that is deposited on catalyst surface also can permineralization, therefore under this system, photochemical catalyst not only can keep its photocatalytic activity for a long time, 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 completely
2and H
2o.
Application Example 2
In air, organic purification method comprises the steps:
(1) the foamed nickel supported TiO being prepared by embodiment 2
2photochemical catalyst is installed on structure and fixes bed photocatalytic reactor as the gas-solid that ZL200820200957.0 provided.
(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 foam metal supported titanium
2(load capacity is 15%) is upper, absorption 15min back balance.
(3) open dominant wavelength is 254nm UV-irradiation simultaneously, and styrene gas is at foamed nickel supported TiO
2light-catalyzed reaction is carried out on surface, and along with air constantly circulates, light-catalyzed reaction continuous circulation carries out, thereby styrene-degrading is eliminated.The demonstration of photocatalytic degradation effect, the time of styrene gas 100% photocatalytic degradation of 120ppmv is 6min, and after reaction 360min, its mineralization rate is only 70%, and compared with application example 1, its photocatalysis efficiency declines greatly.
Application Example 3
The method of high efficiency photocatalysis degraded volatile organic matter comprises the steps:
(1) the foamed nickel supported TiO being prepared by embodiment 1
2photochemical catalyst is installed on structure and fixes bed photocatalytic reactor as the gas-solid that ZL200820200957.0 provided.
(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 foam metal supported titanium
2(load capacity is 7.2%) is upper, absorption 15min back balance.
(3) open dominant wavelength is 254nm UV-irradiation simultaneously, and styrene gas is at foamed nickel supported TiO
2light-catalyzed reaction is carried out on surface, and along with air constantly circulates, light-catalyzed reaction continuous circulation carries out, thereby styrene-degrading is eliminated.Photocatalytic degradation result shows, 400ppmv styrene reaches 100% elimination in 4min.
Application Example 4
The method of high efficiency photocatalysis degraded volatile organic matter comprises the steps:
(1) the foamed nickel supported TiO being prepared by embodiment 1
2photochemical catalyst is installed on structure and fixes bed photocatalytic reactor as the gas-solid that ZL200820200957.0 provided.
(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 foam metal supported titanium
2(load capacity is 7.2%) is upper, absorption 15min back balance.
(3) open dominant wavelength is 254nm UV-irradiation simultaneously, and styrene gas is at foamed nickel supported TiO
2light-catalyzed reaction is carried out on surface, and along with air constantly circulates, light-catalyzed reaction continuous circulation carries out, thereby styrene-degrading is eliminated.Photocatalytic degradation result shows, 400ppmv styrene just can reach 100% elimination in 30min.
Application Example 5
The method of high efficiency photocatalysis degraded volatile organic matter comprises the steps:
(1) the foamed nickel supported TiO being prepared by embodiment 3
2photochemical catalyst is installed on structure and fixes bed photocatalytic reactor as the gas-solid that ZL200820200957.0 provided.
(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 foam metal supported titanium
2(load capacity is 0.5%) is upper, absorption 15min back balance.
(3) open dominant wavelength is 254nm UV-irradiation simultaneously, and styrene gas is at foam metal load TiO
2light-catalyzed reaction is carried out on surface, and along with air constantly circulates, light-catalyzed reaction continuous circulation carries out, thereby styrene-degrading is eliminated.Photocatalytic degradation result shows, 40ppmv styrene reaches 100% elimination in 2min, and permineralization after reaction 60min.
Application Example 6
In air, organic purification method comprises the steps:
(1) the foamed aluminium load ZnO photochemical catalyst of being prepared by embodiment 4 is installed on structure and fixes bed photocatalytic reactor as the gas-solid that ZL200820200957.0 provided.
(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) upper, absorption 15min back balance.
(3) open dominant wavelength is 254nm UV-irradiation simultaneously, and styrene gas is carried out light-catalyzed reaction on foamed aluminium load ZnO surface, and along with air constantly circulates, light-catalyzed reaction continuous circulation carries out, thereby styrene-degrading is eliminated.The demonstration of photocatalytic degradation effect, 120ppmv styrene reaches 100% elimination in 4min, reaches 100% mineralising in 120min.
Application Example 7
The method of high efficiency photocatalysis degraded volatile organic matter comprises the steps:
(1) the foamed nickel supported TiO being prepared by embodiment 1
2photochemical catalyst is installed on structure and fixes bed photocatalytic reactor as the gas-solid that ZL200820200957.0 provided;
(2) mix containing the air that concentration is 400ppmv toluene (air humidity is 5%, and oxygen concentration is 20%), under the effect of airflow reflux circulation, Adsorption of Organic is in foam metal supported titanium
2(load capacity is 7.2%) is upper, absorption 15min back balance.
(3) open dominant wavelength is 254nm UV-irradiation simultaneously, and toluene gas is at foamed nickel supported TiO
2light-catalyzed reaction is carried out on surface, and along with air constantly circulates, light-catalyzed reaction continuous circulation carries out, thereby degradation of toluene is eliminated.Photocatalytic degradation result shows, 400ppmv toluene reaches 100% elimination in 30min.
Above-described embodiment is preferably 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 principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a preparation method for loaded photocatalyst, is characterized in that comprising following steps:
(1) pretreatment of electrode: 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, more obtain photocatalyst sol after ultrasonic dispersion;
(3) loaded photocatalyst is prepared in electro-deposition: in the photocatalyst sol that the electrode cathode that step (1) pretreatment is obtained and electrode anode are prepared by spacing 1～20cm immersion step (2), meet constant voltage dc source 10～150V, and constantly stir colloidal sol, after energising 1～50min, stop energising, take out negative electrode foam metal, after drying, can obtain loaded photocatalyst;
Photocatalyst powder described in step (2) is ZnO or TiO
2.
2. the preparation method of loaded photocatalyst according to claim 1, is characterized in that: the foam metal described in step (1) is the one in nickel foam, foamed aluminium and alloy thereof.
3. the preparation method of loaded photocatalyst according to claim 1, is characterized in that: the size of the foam metal net described in 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 step (1) crosses following concrete steps and processes: foam metal net is first cleaned 3 times in the hydrochloric acid of 0.1～1.0mol/L, ultrasonic cleaning 10～100min in absolute ethyl alcohol again, then water cleans 3 times;
Titanium sheet described in step (1) or graphite flake are processed by following concrete steps: titanium sheet or graphite flake are distinguished after ultrasonic 15min successively in acetone, ethanol, and water cleans 3 times.
5. the preparation method of loaded photocatalyst according to claim 1, is characterized in that:
Photocatalyst powder described in step (2) and described water are by 0.1～5g:200～1000mL proportioning;
The well-beaten time described in step (2) is 10～100min;
Ultrasonic frequency described in step (2) is 10～100kHz;
The time of the ultrasonic dispersion described in step (2) is 5～30min.
6. a loaded photocatalyst, obtains by the preparation method described in claim 1～5 any one.
7. the application of loaded photocatalyst claimed in claim 6 in environmental protection, is characterized in that: described loaded photocatalyst is used for the volatile organic matter of degrading.
8. a method for high efficiency photocatalysis degraded volatile organic matter, is characterized in that comprising the following steps:
(1) loaded photocatalyst claimed in claim 6 is installed in photo catalysis reactor;
(2) air that contains volatile organic matter is mixed to 1～30min in photo catalysis reactor; Opening ultraviolet lamp with backward photo catalysis reactor irradiates.
9. the method for high efficiency photocatalysis according to claim 8 degraded volatile organic matter, 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%;
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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| CN113385160A (en) * | 2021-07-15 | 2021-09-14 | 广东工业大学 | Photocatalyst with nonmetal substrate loaded with P25 titanium dioxide and preparation method and application thereof |
| CN114345338B (en) * | 2021-12-24 | 2023-11-14 | 广东工业大学 | High-selectivity catalyst for converting mercaptan compound and preparation method and application thereof |
| 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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