CN101176842B - Bi2laxv1.6-0.6xO7 or Bi2yxv1.6-0.6xO8 photocatalysis material, preparation method and application - Google Patents
Bi2laxv1.6-0.6xO7 or Bi2yxv1.6-0.6xO8 photocatalysis material, preparation method and application Download PDFInfo
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- CN101176842B CN101176842B CN200710191539XA CN200710191539A CN101176842B CN 101176842 B CN101176842 B CN 101176842B CN 200710191539X A CN200710191539X A CN 200710191539XA CN 200710191539 A CN200710191539 A CN 200710191539A CN 101176842 B CN101176842 B CN 101176842B
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims description 18
- 230000001699 photocatalysis Effects 0.000 title description 21
- 238000007146 photocatalysis Methods 0.000 title description 4
- 239000000843 powder Substances 0.000 claims abstract description 73
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000005056 compaction Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 44
- 239000001257 hydrogen Substances 0.000 abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 9
- 239000000725 suspension Substances 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract 2
- 239000007787 solid Substances 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 56
- 239000010408 film Substances 0.000 description 54
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 46
- 229960000907 methylthioninium chloride Drugs 0.000 description 46
- 230000015556 catabolic process Effects 0.000 description 43
- 238000006731 degradation reaction Methods 0.000 description 43
- 239000003054 catalyst Substances 0.000 description 40
- 239000000243 solution Substances 0.000 description 36
- 229910052760 oxygen Inorganic materials 0.000 description 33
- 239000007864 aqueous solution Substances 0.000 description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 32
- 239000001301 oxygen Substances 0.000 description 32
- 229910052724 xenon Inorganic materials 0.000 description 23
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 23
- 239000007789 gas Substances 0.000 description 21
- 238000005273 aeration Methods 0.000 description 17
- 230000003287 optical effect Effects 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 16
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 16
- 239000000758 substrate Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000013067 intermediate product Substances 0.000 description 10
- 239000010409 thin film Substances 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 9
- 230000033558 biomineral tissue development Effects 0.000 description 9
- 230000007704 transition Effects 0.000 description 9
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 150000004054 benzoquinones Chemical class 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- 239000003595 mist Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 4
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- 238000010792 warming Methods 0.000 description 4
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- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000006652 catabolic pathway Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Catalysts (AREA)
Abstract
The invention provides a photocatalyst powder or a film material of Bi2LaxV(1.6-0.6x)O7 or Bi2YxV(1.6-0.6x)O8 (0.8<=x<=1), or a film of Bi2LaxV(1.6-0.6x)O7 or Bi2YxV(1.6-0.6x)O8 (0.8<=x<=1) doped with N or S. The invention is characterized in that: the photocatalyst powder material is prepared by a method of high-temperature solid sintering; Bi2O3, V2O5, La2O3 or Y2O3 with a purity of 99.99% are used as raw materials; Bi2O3, V2O5 and La2O3 or Y2O3 based on an atom ratio in molecular formulas are mixed; then the mixture is grinded in a ball mill until the grain diameter of the powder reaches 1 to 2 millimeters, and the power is dried for 4 plus or minus 1 hours under the temperature of 200 plus or minus 20 DEG C, pressed into sheets and then sintered. The Bi2LaxV(1.6-0.6-x)O7 or the Bi2YxV(1.6-0.6-x)O8 photocatalyst material is used to degrade waste water or decompose pure water to make hydrogen under light irradiation condition by forming a suspension system or film plate in water solution.
Description
Technical field
The present invention relates to conductor oxidate catalysis material, preparation and application, especially Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder photocatalytic material, N mix or S doping Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film, preparation were established and method, performance characterization and application.
Background technology
Along with economy is serious day by day owing to the water environment pollution problem in recent years, the research and development about the surround lighting catalysis material come into one's own year by year.R.Wang found TiO in 1997
2Film has Superhydrophilic and self-cleaning function, and this has more started the research boom to catalysis material.As everyone knows, solar spectrum medium ultraviolet luminous energy is less than 5%, and wavelength is that the visible light of 400-750nm then accounts for nearly 43%.Can not effectively utilize visible light if utilize catalysis material to solve water pollution problem, then the meaning that exists as the catalysis material that solves problem of environmental pollution can weaken greatly.And with regard to the depollution of environment, also will be restricted for the indoor application that does not have ultraviolet light.Based on this,, need exploitation under visible light, to have the catalysis material of photocatalytic activity, thereby solve extremely urgent water environment pollution problem in order to effectively utilize sunshine.
For the exploitation of visible-light response type surround lighting catalysis material, one of its main flow is to show highly active TiO under UV-irradiation
2In make it to have visible light-responded research with the doping dissimilar metal.Another main flow is to explore the non-oxidized substance semiconductor that band gap width is narrow and have absorption characteristic in the visible region.Sulfur family metallic compounds such as cadmium sulfide, cadmium selenide and organic material etc. are typically arranged.But the oxidized dissolving owing to the effect of the electrified cavity that generates under illumination of these materials, existing does not have stable problems such as function.Therefore, wish that research and development its structure and all stable compound of photoelectrochemical property under illumination come degradation water internal pollution thing as catalysis material.The research that utilizes these powder photocatalytic materials and solar energy to degrade organic pollution in the water body or decompose toxic pollutant causes the scientists keen interest, with regard to purifying contaminated water body environment, these conductor oxidate photocatalytic powder materials will be played the part of extremely important role in future.
The basic design philosophy of novel visible responsive photocatalytic material is control crystal structure and electronic state, and its starting point not only just reduces the size of energy gap, also will be placed on focus on " light " of light-catalyzed reaction.Its photocatalysis principle is when energy is mapped on the semiconductor greater than the illumination of semiconductor energy gap, Electron absorption luminous energy on the semiconductor valence band is excited on the conduction band, thereby on conduction band, produce electronegative high activity electronics, on valence band, produce the hole of positively charged, form light induced electron and the right redox system of photohole.Have an effect in dissolved oxygen, water, electronics and hole, the final generation has highly chemically active hydroxyl radical free radical, utilize the hydroxyl radical free radical of this high activity can oxidize water in multiple hardly degraded organic substance be CO
2With inorganic matters such as water.Perhaps utilizing the photohole that has strong oxidability in the valence band, can be the rapid oxidation Decomposition of organic matter inorganic matters such as carbon dioxide and water.Thereby can be used for organic pollution in the depollution of environment and the degraded water body.Therefore, be to improve the efficient of oxide semiconductor film material degradation organic pollutants in water body, the forbidden band of oxide semiconductor film material should be enough narrow, and the light induced electron that forms behind the solar light irradiation and photohole are compound to being not easy.
Japan promptly carries out TiO since the eighties
2Catalysis material is applied to the research of water purified treatment, but because the photocatalytic oxidation degradation water pollutant is the three-dimensional planar reaction of carrying out on the catalysis material surface, pulverous TiO
2The photocatalytic powder material is difficult to separate from water after water treatment, reclaims and reuses difficulty.Based on this, the research of film shape catalysis material just seems particularly important, can avoid the secondary pollution of water in the contaminated water body purification process.And utilize the degrade rarely seen report of research of organic pollution in the water body of oxide semiconductor film catalysis material.
In addition; adopting novel visible responsive photocatalytic material, can make full use of in the solar spectrum 43% visible light, is hydrogen and oxygen with water decomposition; and then obtain hydrogen energy source clean, non-secondary pollution, alleviate oil and natural gas and be about to the exhausted energy crisis of being brought.Utilize these above-mentioned hydrogen energy source can prepare the energy source and power that fuel cell is used for the vehicles such as electric automobile and electric bicycle.
In sum, adopt novel catalysis material, under radiation of visible light, the organic pollution in the water body of not only can degrading can also prepare clean hydrogen energy source, has both solved problem of environmental pollution to a certain extent, has also solved energy crisis.Therefore, preparation novel visible responsive photocatalytic material not only can produce huge economic benefit, can also produce the huge social benefit.
Summary of the invention
The present invention seeks to: propose a kind of Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder photocatalytic material or film, N mix or S doping Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film is the Bi that base embeds metal nanometer cluster (as In, Cu or Au) with the conductor oxidate
2La
xV
1.6-0.6xO
7Film or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film, Bi
2La
xV
1.6-0.6xO
7Monocrystal thin films or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) monocrystal thin films, Bi
2La
xV
1.6-0.6xO
7And Bi
2Y
xV
1.6-0.6xO
8Preparation were established and method, performance characterization and the application of catalysis materials such as (0.8≤x≤1) superlattice film.
Technical scheme of the present invention is: Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) contain V photocatalyst powder or thin-film material; And N mixes or S doping Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film is the Bi that base embeds metal nanometer cluster (as In, Cu or Au) with the conductor oxidate
2La
xV
1.6-0.6xO
7Film or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film, Bi
2La
xV
1.6-0.6xO
7Monocrystal thin films or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) monocrystal thin films, Bi
2La
xV
1.6-0.6xO
7And Bi
2Y
xV
1.6-0.6xO
8Catalysis materials such as (0.8≤x≤1) superlattice film.
To having the different band gap structure and the Bi of the organic pollutants in water body of under visible light, degrading
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8The experiment of the thin-film material that (0.8≤x≤1) is constituted and N doping or S doping film is at Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8Mix N (S) impurity energy level in the forbidden band of (0.8≤x≤1) and carry out hydridization, in broad-band gap, form a series of narrow band gaps, can absorb the different wave length visible light simultaneously, realize that electronics is from the branch order transition of valence band to conduction band, thereby the incident light that makes electronics can absorb longer wavelength is excited to the energy level of higher-energy, and then produces a large amount of photoholes in valence band.Utilize these photoholes organic pollution in the water body of degrading efficiently.In addition, by being embedded in metal nanometer cluster at oxide semiconductor film, be implemented in the film lattice and introduce defective locations, these defective locations finally can become the trap of light induced electron or photohole, thereby suppress the compound of light induced electron or photohole, finally improve the efficient of organic pollution in the film light catalysis material degraded water body and the efficient of raising powder or film light catalysis material hydrogen production by water decomposition gas.
Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Y
xV
1.6-0.6xO
8The preparation of (0.8≤x≤1) photocatalytic powder material, the method for employing high temperature solid-phase sintering.With purity 99.99% Bi
2O
3, V
2O
5, La
2O
3Or Y
2O
3Be raw material, and with Bi, V, La or the Y Bi with the atomic ratio of molecular formula
2O
3, V
2O
5And La
2O
3Or Y
2O
3Fully mix, then in grinding in ball grinder, the particle diameter of powder reaches the 1-2 micron, and 200 ± 20 ℃ of oven dry 4 ± 1 hours, compacting was put into high temperature sintering furnace and fired in flakes.Furnace temperature is risen to 750 ± 20 ℃, be incubated and cool off with stove after 6 ± 2 hours, it is the 0.8-1.6 micron that the pressed powder taking-up is crushed to particle diameter, again that these powder compaction are in blocks, puts into the high temperature sintering furnace sintering, the highest furnace temperature is 750 ± 20 ℃, be incubated after 4 ± 1 hours and cool off with stove, it is the 0.6-1.4 micron that the pressed powder taking-up is crushed to particle diameter, again that these powder compaction are in blocks, put into the high temperature sintering furnace sintering, the intensification condition is as follows:
A.20 ℃ to 400 ℃, the heating-up time is 40 ± 10min; B.400 ℃, insulation 20 ± 10min; C.400 ℃ to 750 ℃, the heating-up time is 40 ± 10min; D.750 ℃ insulation 800 ± 100min; E.750 ℃ to 920 ± 20 ℃, the heating-up time is 30 ± 10min; ℃ f.920 ± 20 insulation 1800 ± 200min, stove is cold.
Pressed powder cools off with stove after 30 hours through 920 ± 20 ℃ of insulations of maximum temperature, and it is the 0.5-1.2 micron that the taking-up pressed powder is crushed to particle diameter.Finally prepare successfully pure single-phase Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) photocatalytic powder material.
Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8The preparation technology of (0.8≤x≤1) photocatalysis film material:
A. target preparation: prepare simple metal Bi, V, La and Y metal targets, and above-mentioned two kinds of powder Bi that make
2La
xV
1.6-0.6xO
7And Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1);
B. choose substrate: select for use YSZ single-crystal substrate, Si base substrate, quartz or ito glass as substrate or the ITO growing epitaxial film of growing thereon;
C.N or S doping Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) rete preparation: adopt high vacuum ion sputtering system or multi-target magnetic control sputtering instrument, sputter Bi in the mist of oxygen, ammonia and argon gas
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) target, at ammonia (or at SO
2Gas), cosputtering simple metal Bi, V, La or Y target in the mist of oxygen and argon gas, the different film of deposit thickness on substrate, with this film in nitrogen or at SO
2Under 750 ℃ to 920 ℃ temperature, handle 30 ± 10min in the gas; Make it crystallization and obtain required N or S doping Bi
2La
xV
1.6-0.6xO
7Rete, or obtain required N or S doping Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) rete.
Bi
2La
xV
1.6-0.6-xO
7Or Bi
2Y
xV
1.6-0.6-xO
8The application of catalysis material powder or film: adopt Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder forms suspension system or thin web is arranged in solution in the aqueous solution, penetrate degrading waste water or decomposition pure water hydrogen under the condition in illumination.The present invention chooses the xenon lamp or the sodium vapor lamp irradiation aqueous solution of 300W, keeps the oxygen saturation state of solution with the mode of oxygenic aeration.Overall optical is carried out according to being reflected under the airtight lighttight environment.
The invention has the beneficial effects as follows: proposed a kind of new material and preparation method, improved the efficient of organic pollution in the film light catalysis material degraded water body and the efficient of raising powder or film light catalysis material hydrogen production by water decomposition gas.
Description of drawings
Fig. 1 is Bi
2La
xV
1.6-0.6xO
7The XRD figure spectrum of (0.8≤x≤1)
Fig. 2 is Bi
2La
xV
1.6-0.6xO
7The SEM collection of illustrative plates of (0.8≤x≤1)
Fig. 3 is Bi
2La
xV
1.6-0.6xO
7The EDX collection of illustrative plates of (0.8≤x≤1)
Fig. 4 is Bi
2La
xV
1.6-0.6xO
7The ultraviolet-visible diffuse reflection absorption spectra of (0.8≤x≤1)
Fig. 5 is Bi
2La
xV
1.6-0.6xO
7In (0.8≤x≤1) (ahv)
1/nRelation curve with hv
Fig. 6 is Bi
2Y
xV
1.6-0.6xO
8The XRD figure spectrum of (0.8≤x≤1) and the indices of crystallographic plane (hkl) of each diffraction maximum
Fig. 7 is Bi
2Y
xV
1.6-0.6xO
8The Rietveld software configuration refine collection of illustrative plates of (0.8≤x≤1)
Fig. 8 is Bi
2Y
xV
1.6-0.6xO
8The structural representation of (0.8≤x≤1)
Fig. 9 is Bi
2Y
xV
1.6-0.6xO
8The SEM collection of illustrative plates of (0.8≤x≤1)
Figure 10 is Bi
2Y
xV
1.6-0.6xO
8The EDX collection of illustrative plates of (0.8≤x≤1)
Figure 11 is Bi
2Y
xV
1.6-0.6xO
8The XPS collection of illustrative plates of oxygen content in (0.8≤x≤1)
Figure 12 is Bi
2Y
xV
1.6-0.6xO
8Bi in (0.8≤x≤1)
3+The XPS collection of illustrative plates of content
Figure 13 is Bi
2Y
xV
1.6-0.6xO
8Bi in (0.8≤x≤1)
5+The XPS collection of illustrative plates of content
Figure 14 is Bi
2Y
xV
1.6-0.6xO
8The ultraviolet-visible diffuse reflection absorption spectra of (0.8≤x≤1)
Figure 15 is Bi
2Y
xV
1.6-0.6xO
8In (0.8≤x≤1) (ahv)
1/nRelation curve with hv
Figure 16 is Bi
2Y
xV
1.6-0.6xO
8The band structure schematic diagram of (0.8≤x≤1)
Figure 17 is with Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) powder is a catalyst, and phenol concentration is change curve in time
Figure 18 is with Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) powder is a catalyst, and the total content of organic carbon of phenol (TOC) is change curve in time
Figure 19 is with Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder is a catalyst, the possible degradation pathway of phenol
Figure 20 is with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder is a catalyst, and phenol concentration is change curve in time
Figure 21 is with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder is a catalyst, and the total content of organic carbon of phenol (TOC) is change curve in time
Figure 22 is with Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) is catalyst, MB concentration changes with time curve
Figure 23 is with Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) is catalyst, and the intermediate product of MB is change curve in time
Figure 24 is with Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) is catalyst, and the total content of organic carbon of MB is change curve in time
Figure 25 is with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) is catalyst, MB concentration changes with time curve
Figure 26 is with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) is catalyst, and the intermediate product of MB is change curve in time
Figure 27 is with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) is catalyst, and the total content of organic carbon of MB (TOC) is change curve in time
Figure 28 is with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder is a catalyst, difference supporting Pt, NiO and RuO
2The composite catalyst MB. that under radiation of visible light, degrades
Figure 29 is with Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) powder is catalyst decomposes pure water hydrogen and oxygen (pure water 300mL, light source are the 400W high-pressure sodium lamp for lambda1-wavelength λ=390nm, catalyst 1g)
Figure 30 is with Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) powder is catalyst decomposes pure water hydrogen and oxygen (pure water 300mL, light source are the xenon lamp of 300W for lambda1-wavelength λ=420nm, catalyst 1g)
Figure 31 is with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder is catalyst decomposes pure water hydrogen and oxygen (pure water 300mL, light source are the 400W high-pressure sodium lamp for lambda1-wavelength λ=390nm, catalyst 1g)
Figure 32 is with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder is catalyst decomposes pure water hydrogen and oxygen (pure water 300mL, light source are the xenon lamp of 300W for lambda1-wavelength λ=420nm, catalyst 1g)
Figure 33 is with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder is a catalyst, difference supporting Pt, NiO and RuO
2Composite catalyst hydrogen production by water decomposition gas (lambda1-wavelength λ=390nm, catalyst 1g, pure water 300mL, 50mL CH
3OH, light source are the 400W high-pressure sodium lamp)
The specific embodiment
1. two kinds of Bi
2La
xV
1.6-0.6xO
7And Bi
2Y
xV
1.6-0.6xO
8The preparation were established of (0.8≤x≤1) photocatalytic powder material is as follows:
A. the method with high temperature solid-phase sintering prepares Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) photocatalytic powder material.With Bi
2O
3, V
2O
5And La
2O
3Be raw material, Bi with 99.99%
2O
3, V
2O
5And La
2O
3Fully mix, then in grinding in ball grinder, the particle diameter of powder reaches the 1-2 micron, and 200 ℃ of oven dry 4 hours, compacting was put into high temperature sintering furnace and fired in flakes.Furnace temperature is risen to 750 ℃, be incubated and cool off with stove after 6 hours, it is the 0.8-1.6 micron that the pressed powder taking-up is crushed to particle diameter, again that these powder compaction are in blocks, puts into the high temperature sintering furnace sintering, the highest furnace temperature is 750 ℃, be incubated after 4 hours and cool off with stove, it is the 0.6-1.4 micron that the pressed powder taking-up is crushed to particle diameter, again that these powder compaction are in blocks, put into the high temperature sintering furnace sintering, concrete technology is:
A.20 ℃ to 400 ℃, the heating-up time is 40min; B.400 ℃ insulation 20min; C.400 ℃ be warming up to 750 ℃, the heating-up time is 40min; D.750 ℃ insulation 800min; E.750 ℃ be warming up to 920 ℃, the heating-up time is 30min; F.920 ℃ insulation 1800min, the g. stove is cold.Pressed powder cools off with stove after 30 hours through 920 ℃ of insulations of maximum temperature, and it is the 0.5-1.2 micron that the taking-up pressed powder is crushed to particle diameter.Finally prepare successfully pure single-phase Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) photocatalytic powder material.
B. the method with high temperature solid-phase sintering prepares Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) photocatalytic powder material.With Bi
2O
3, V
2O
5And Y
2O
3Be raw material, with 99.99%, Bi
2O
3, V
2O
5And Y
2O
3Fully mix, then in grinding in ball grinder, the particle diameter of powder reaches the 1-2 micron, and 200 ℃ of oven dry 4 hours, compacting was put into high temperature sintering furnace and fired in flakes.Furnace temperature is risen to 750 ℃, be incubated and cool off with stove after 6 hours, it is the 0.8-1.6 micron that the pressed powder taking-up is crushed to particle diameter, again that these powder compaction are in blocks, puts into the high temperature sintering furnace sintering, the highest furnace temperature is 750 ℃, be incubated after 4 hours and cool off with stove, it is the 0.6-1.4 micron that the pressed powder taking-up is crushed to particle diameter, again that these powder compaction are in blocks, put into the high temperature sintering furnace sintering, concrete technology is:
A.20 ℃ to 400 ℃, the heating-up time is 40min; B.400 ℃ insulation 20min; C.400 ℃ be warming up to 750 ℃, the heating-up time is 40min; D.750 ℃ insulation 800min; E.750 ℃ be warming up to 920 ℃, the heating-up time is 30min; F.940 ℃ insulation 1800min, the g. stove is cold.Pressed powder cools off with stove after 30 hours through 940 ℃ of insulations of maximum temperature, and it is the 0.5-1.2 micron that the taking-up pressed powder is crushed to particle diameter.Finally prepare successfully pure single-phase Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) photocatalytic powder material.
2. two kinds of novel B i
2La
xV
1.6-0.6xO
7And Bi
2Y
xV
1.6-0.6xO
8The preparation were established of (0.8≤x≤1) photocatalysis film material is as follows:
A. target preparation: prepare simple metal Bi, V, La and Y metal targets, and prepared two kinds of powder Bi in the operation 1
2La
xV
1.6-0.6xO
7And Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1).
B. choose substrate: choose substrate used when carrying out magnetron sputtering.The substrate lattice constant must be complementary or exist the crystallography relation with rete.Generally select for use the YSZ single-crystal substrate as substrate (can consider to grow ITO or the some other suitable electrode material) epitaxial film of growing thereon.Also can be at Si base substrate or other as quartz, substrate preparation films such as ito glass.
C.N doping Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) rete preparation: adopt high vacuum ion sputtering system or multi-target magnetic control sputtering instrument, sputter Bi in the mist of oxygen, ammonia and argon gas
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) target, or in the mist of ammonia, oxygen and argon gas cosputtering simple metal Bi, V, La and Y target, the different film of deposit thickness on substrate is handled 30min with this film under 920 ℃ of temperature in nitrogen, make it crystallization and obtain required N doping Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) rete.
D.S doping Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) rete preparation: adopt high vacuum ion sputtering system or multi-target magnetic control sputtering instrument, at oxygen, SO
2Sputter Bi in the mist of gas and argon gas
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) target, or at SO
2Cosputtering simple metal Bi, V, La and Y target in the mist of gas, oxygen and argon gas, the different film of deposit thickness on substrate is handled 30min with this film under 880 ℃ of temperature in nitrogen, make it crystallization and obtain required S doping Bi
2La
xV
1.6-0.6xO
7Or Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) rete.
3.Bi
2La
xV
1.6-0.6xO
7And Bi
2Y
xV
1.6-0.6xO
8The sign of (0.8≤x≤1) catalysis material.
Learn Bi by XRD, SEM-EDX result
2La
xV
1.6-0.6xO
7Be single-phase (seeing Fig. 1-3), and experiment original material height is pure, does not have any impurity phase.Measure Bi by Xray fluorescence spectrometer
2La
xV
1.6-0.6xO
7The average atom ratio be Bi: La: V=2.00: 0.98: 1.02.With Rietveld software to Bi
2La
xV
1.6-0.6xO
7XRD result carry out structure refinement, structure refinement factor R P value is R
P=11.8%.Bi
2La
xV
1.6-0.6xO
7Space group be I4/mmm, structure is a tetragonal crystal system, cell parameter is a=3.9386 (2), b=3.9386 (2), c=15.4527 (3)
Bi
2La
xV
1.6-0.6xO
7The indices of crystallographic plane of each diffraction maximum (hkl) are demarcated.Bi
2La
xV
1.6-0.6xO
7Each atoms in space atom site parameter is determined (as table 1, table 2) in the catalyst.
Table 1Bi
2La
xV
1.6-0.6xO
7The atom locus of (0.8≤x≤1)
| Atom | x | y | z | Account for distance |
| Bi La V O(1) O(2) O(3) | 0.0000 0.0000 0.0000 0.0000 0.0000 -0.2558 | 0.5000 0.5000 0.5000 0.0000 0.0000 0.5000 | 0.2500 0.0000 0.0000 0.0000 0.3317 0.0000 | 1.0 0.5 0.5 1.0 1.0 1.0 |
Table 2Bi
2La
xV
1.6-0.6xO
7Each atomic distance of (0.8≤x≤1)
| Atom | La，V-O1 | La，V-O2 | La，V-O4 | Bi-O3 | Bi-O4 |
| Spacing | 1.957(3) | 1.957(3) | 1.799(6) | 2.268(1) | 2.021(3) |
Adopt UV, visible light to diffuse spectrometer to Bi
2La
xV
1.6-0.6xO
7(see figure 4) is measured on the characteristic absorption limit that produces under the irradiation of light.The absorption spectra data show, Bi
2La
xV
1.6-0.6xO
7Electronics begins to produce intrinsic transition at the 540nm place.This proof is at very long visible light wave range, Bi
2La
xV
1.6-0.6xO
7Can produce photoresponse.According to following formula α hv=A (hv-Eg)
n(α is an absorption coefficient, and υ is a light frequency, and A is a constant, and Eg is a band gap width.In the equation, n has determined semi-conductive transition feature.If n=0.5 is direct transition, n=2 then is an indirect transition), at first determine n=1.34, and then acquisition (α hv)
2With the graph of a relation (see figure 5) of hv, finally determined Bi
2La
xV
1.6-0.6xO
7Band gap width be 2.54 (0) eV.
Calculate Bi
2La
xV
1.6-0.6xO
7Band structure, conduction band is made of the 3d track of V, the 5d track of La and the 6s track of La, valence band is made of the 6s track of Bi and the 2p track of O.
Learn Bi by XRD, SEM-EDX result
2Y
xV
1.6-0.6xO
8Be single-phase (seeing Fig. 9,10), and experiment original material height is pure, does not have any impurity phase.According to XPS spectrum, SEM-EDX and Xray fluorescence spectrometer (XFS) analysis result, Bi
2Y
xV
1.6-0.6xO
8In each atoms of elements mol ratio be Bi: Y: V: O=2.00: 0.98: 1.03: 7.95.According to XPS analysis result, Bi
2Y
xV
1.6-0.6xO
8In Bi
3+And Bi
5+Mol ratio be 0.53: 0.47, Y, the chemical valence of V and O ion is respectively 3
+, 5
+With 2
-According to XPS spectrum, SEM-EDX and Xray fluorescence spectrometer (XFS) analysis result, Bi
2Y
xV
1.6-0.6xO
8Chemical formula Bi
3+ 1.06Bi
5+ 0.94Y
3+ 0.98V
5+ 1.03O
2- 7.95(seeing Figure 11-13).Structure refinement by Rietveld software is (see figure 7) as a result, Bi
2Y
xV
1.6-0.6xO
8In around each Y (V) ion and Bi ion, 6 O ions the most adjacent are arranged, each ion phase mutual edge distance each other is determined Bi
2Y
xV
1.6-0.6xO
8Average particle diameter is 1.3 μ m (seeing Fig. 8, table 3, table 4).Bi
2Y
xV
1.6-0.6xO
8The structure refinement factor R
P=6.93%, R
WP=9.84%, R
F2=22.75%.Bi
2Y
xV
1.6-0.6xO
8Space group be I4/mmm, structure is a tetragonal crystal system, cell parameter is a=3.9188 (2), b=3.9188 (2), c=15.3105 (9)
Bi
2Y
xV
1.6-0.6xO
8The indices of crystallographic plane of each diffraction maximum (hkl) are demarcated (see figure 6).
Table 3Bi
2Y
xV
1.6-0.6xO
8The atom locus of (0.8≤x≤1)
| Atom | x | y | z | Account for distance |
| Bi Y V O(1) O(2) O(3) | 0.0000 0.0000 0.0000 0.0000 0.0000 0.2001 | 0.5000 0.5000 0.5000 0.0000 0.0000 0.5000 | 0.2500 0.0000 0.0000 0.0000 0.6688 0.0000 | 1.0 0.5 0.5 1.0 1.0 1.0 |
Table 4Bi
2Y
xV
1.6-0.6xO
8Each atomic distance of (0.8≤x≤1)
| Atom | Y，V-O1 | Y，V-O2 | Y，V-O4 | Bi-O3 | Bi-O4 |
| Spacing | 1.959(4) | 1.959(4) | 1.802(6) | 2.273(0) | 2.026(6) |
Adopt UV, visible light to diffuse spectrometer to Bi
2Y
xV
1.6-0.6xO
8(seeing Figure 14) measured on the characteristic absorption limit that produces under the irradiation of light.The absorption spectra data show, Bi
2Y
xV
1.6-0.6xO
8Electronics begins to produce intrinsic transition at the 593nm place.This proof is at very long visible light wave range, Bi
2Y
xV
1.6-0.6xO
8Can produce photoresponse.According to following formula α hv=A (hv-E
g)
n(α is an absorption coefficient, and υ is a light frequency, and A is a constant, E
gBe band gap width.In the equation, n has determined semi-conductive transition feature.If n=0.5 is direct transition, n=2 then is an indirect transition), at first determine n=0.51, and then acquisition (α hv)
2With the graph of a relation (seeing Figure 15) of hv, finally determined Bi
2Y
xV
1.6-0.6xO
8Band gap width be 2.09eV.Calculate Bi
2Y
xV
1.6-0.6xO
8Band structure, conduction band is made of the 3d track of V, valence band is made of the 6s track of Bi and the 2p track of O.(seeing Figure 16)
Application example:
1. adopt Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) powder degradation of phenol aqueous solution: with Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) powder 0.3g puts into the 100ml phenol solution and forms suspension system, and the initial concentration of phenol solution is 5 * 10
-4Mol L
-1, initial pH value is 7.Choose the xenon lamp irradiation phenol solution of 300W, mix edge filter (λ＞420nm).In the experimentation, keep catalyst fines with the mode of magnetic stirring apparatus and oxygenic aeration and be suspended state.Overall optical is carried out according to being reflected under the airtight lighttight environment.Through 550 minutes, phenol was degraded fully, and degradation rate reaches 1.515 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.34%.Intermediate product mainly contains catechol, hydroquinones, resorcinol, benzoquinones in the degradation of phenol process.Can find out that from the data of TOC phenol TOC clearance (mineralization rate) reaches 99.0% in 550 minutes.
2. adopt Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder degradation of phenol aqueous solution: with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder 0.3g puts into the 100ml phenol solution and forms suspension system, and the initial concentration of phenol solution is 5 * 10
-4Mol L
-1, initial pH value is 7.Choose the xenon lamp irradiation phenol solution of 300W, mix edge filter (λ＞420nm).In the experimentation, keep catalyst fines with the mode of magnetic stirring apparatus and oxygenic aeration and be suspended state.Overall optical is carried out according to being reflected under the airtight lighttight environment.Through 600 minutes, phenol was degraded fully, and degradation rate reaches 1.389 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.31%.Intermediate product mainly contains catechol, hydroquinones, resorcinol, benzoquinones in the degradation of phenol process.Can find out in 550 minutes that from the data of TOC phenol TOC clearance (mineralization rate) reaches that the phenol mineralization rate reaches 97.9% in 91.6%, 600 minute.
3.Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) monocrystal thin films degradation of phenol aqueous solution: with Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) monocrystal thin films is placed in the reactor, and putting into the 100ml initial concentration is 5 * 10
-4Mol L
-3, initial pH value is 7 phenol solution.Choose the xenon lamp irradiation phenol solution of 300W, mix edge filter (λ＞420nm).In the experimentation, keep the oxygen saturation state of solution with the mode of oxygenic aeration.Overall optical is carried out according to being reflected under the airtight lighttight environment.Through 450 minutes, phenol was degraded fully, and degradation rate reaches 1.852 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.41%.Intermediate product mainly contains catechol, hydroquinones, resorcinol, benzoquinones in the degradation of phenol process.Can find out that from the data of TOC phenol TOC clearance (mineralization rate) reaches 98.1% in 450 minutes.
4.Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) monocrystal thin films degradation of phenol aqueous solution: with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) monocrystal thin films is placed in the reactor, and putting into the 100ml initial concentration is 5 * 10
-4Mol L
-1, initial pH value is 7 phenol solution.Choose the xenon lamp irradiation phenol solution of 300W, mix edge filter (λ＞420nm).In the experimentation, keep the oxygen saturation state of solution with the mode of oxygenic aeration.Overall optical is carried out according to being reflected under the airtight lighttight environment.Through 480 minutes, phenol was degraded fully, and degradation rate reaches 1.736 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.38%.Intermediate product mainly contains catechol, hydroquinones, resorcinol, benzoquinones in the degradation of phenol process.Can find out that from the data of TOC phenol TOC clearance (mineralization rate) reaches 97.2% in 480 minutes.
5.N doping Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation phenol solution: with the N Bi that mixes
2La
xV
1.6-0.6xO
7(0.8≤x≤1) film is placed in the reactor, and putting into the 100ml initial concentration is 5 * 10
-4Mol L
-1, initial pH value is 7 phenol solution.Choose the xenon lamp irradiation phenol solution of 300W, mix edge filter (λ＞420nm).In the experimentation, keep the oxygen saturation state of solution with the mode of oxygenic aeration.Overall optical is carried out according to being reflected under the airtight lighttight environment.Through 370 minutes, phenol was degraded fully, and degradation rate reaches 2.252 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.50%.Intermediate product mainly contains catechol, hydroquinones, resorcinol, benzoquinones in the degradation of phenol process.Can find out that from the data of TOC phenol TOC clearance (mineralization rate) reaches 99.8% in 370 minutes.
6.N doping Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film degradation phenol solution: with the N Bi that mixes
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film is placed in the reactor, and putting into the 100ml initial concentration is 5 * 10
-4Mol L
-1, initial pH value is 7 phenol solution.Choose the xenon lamp irradiation phenol solution of 300W, mix edge filter (λ＞420nm).In the experimentation, keep the oxygen saturation state of solution with the mode of oxygenic aeration.Overall optical is carried out according to being reflected under the airtight lighttight environment.Through 390 minutes, phenol was degraded fully, and degradation rate reaches 2.137 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.47%.Intermediate product mainly contains catechol, hydroquinones, resorcinol, benzoquinones in the degradation of phenol process.Can find out that from the data of TOC phenol TOC clearance (mineralization rate) reaches 99.6% in 390 minutes.
7.S doping Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation phenol solution: with the N Bi that mixes
2La
xV
1.6-0.6xO
7(0.8≤x≤1) film is placed in the reactor, and putting into the 100ml initial concentration is 5 * 10
-4Mol L
-1, initial pH value is 7 phenol solution.Choose the xenon lamp irradiation phenol solution of 300W, mix edge filter (λ＞420nm).In the experimentation, keep the oxygen saturation state of solution with the mode of oxygenic aeration.Overall optical is carried out according to being reflected under the airtight lighttight environment.Through 380 minutes, phenol was degraded fully, and degradation rate reaches 2.193 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.49%.Intermediate product mainly contains catechol, hydroquinones, resorcinol, benzoquinones in the degradation of phenol process.Can find out that from the data of TOC phenol TOC clearance (mineralization rate) reaches 99.5% in 380 minutes.
8.S doping Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film degradation phenol solution: with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film is placed in the reactor, and putting into the 100ml initial concentration is 5 * 10
-4Mol L
-1, initial pH value is 7 phenol solution.Choose the xenon lamp irradiation phenol solution of 300W, mix edge filter (λ＞420nm).In the experimentation, keep the oxygen saturation state of solution with the mode of oxygenic aeration.Overall optical is carried out according to being reflected under the airtight lighttight environment.Through 400 minutes, phenol was degraded fully, and degradation rate reaches 2.083 * 10
-8Mols
-1L
-1, photo-quantum efficiency is 0.46%.Intermediate product mainly contains catechol, hydroquinones, resorcinol, benzoquinones in the degradation of phenol process.Can find out that from the data of TOC phenol TOC clearance (mineralization rate) reaches 99.0% in 400 minutes.
9. adopt Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) powder degraded aqueous solution of methylene blue: with Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) powder 0.3g puts into the 100ml aqueous solution of methylene blue and forms suspension system, and the initial concentration of aqueous solution of methylene blue is 0.0506molm
-3(5.06 * 10
-5Mol L
-1), initial pH value is 7.Choose the xenon lamp irradiation aqueous solution of methylene blue of 300W, mix edge filter (λ＞420nm).In the experimentation, keep catalyst fines with the mode of magnetic stirring apparatus and oxygenic aeration and be suspended state.Overall optical is carried out according to being reflected under the airtight lighttight environment.Use ultraviolet-visible spectrophotometer, in the methylene blue concentration of 670nm place working sample, through 150 minutes, methylene blue was degraded fully, and degradation rate reaches 5.622 * 10
-9Mol s
-1L
-1, the TOC clearance is 98.9%, photo-quantum efficiency is 0.12%.
10. adopt Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder degraded aqueous solution of methylene blue: with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder 0.3g puts into the 100ml aqueous solution of methylene blue and forms suspension system, and the initial concentration of aqueous solution of methylene blue is 0.0506molm
-3(5.06 * 10
-5Mol L
-1), initial pH value is 7.Choose the xenon lamp irradiation aqueous solution of methylene blue of 300W, mix edge filter (λ＞420nm).In the experimentation, keep catalyst fines with the mode of magnetic stirring apparatus and oxygenic aeration and be suspended state.Overall optical is carried out according to being reflected under the airtight lighttight environment.Use ultraviolet-visible spectrophotometer, in the methylene blue concentration of 670nm place working sample, through 170 minutes, methylene blue was degraded fully, and degradation rate reaches 4.961 * 10
-9Mol s
-1L
-1, the TOC clearance is 99.9%, photo-quantum efficiency is 0.11%.Through 150 minutes, the TOC clearance was 93.4%.
With Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder is a catalyst, difference supporting Pt, NiO and RuO
2Compound; The catalyst methylene blue dyestuff of under radiation of visible light, degrading.Adopt 0.2wt%-Pt/Bi
2Y
xV
1.6-0.6xO
8Composite catalyst, through 120 minutes, methylene blue was degraded fully, and degradation rate reaches 7.03 * 10
-6MM s
-1, the TOC clearance is 99.8%, photo-quantum efficiency is 0.16%.Adopt 1.0wt%-NiO/Bi
2Y
xV
1.6-0.6xO
8Composite catalyst, through 140 minutes, methylene blue was degraded fully, and degradation rate reaches 6.02 * 10
-6MM s
-1, the TOC clearance is 98.2%, photo-quantum efficiency is 0.13%.Adopt 1.0wt%-RuO
2/ Bi
2Y
xV
1.6-0.6xO
8Composite catalyst, through 150 minutes, methylene blue was degraded fully, and degradation rate reaches 5.62 * 10
-6MM s
-1, the TOC clearance is 97.5%, photo-quantum efficiency is 0.13%.
11.Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation aqueous solution of methylene blue: with Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) film is placed in the reactor, and putting into the 100ml initial concentration is 0.0506mol m
-3(5.06 * 10
-5Mol L
-1), initial pH value is 7 aqueous solution of methylene blue.Choose the xenon lamp irradiation aqueous solution of methylene blue of 300W, mix edge filter (λ＞420nm).In the experimentation, keep the oxygen saturation state of solution with the mode of oxygenic aeration.Overall optical is carried out according to being reflected under the airtight lighttight environment.Use ultraviolet-visible spectrophotometer, in the methylene blue concentration of 670nm place working sample, through 140 minutes, methylene blue was degraded fully, and degradation rate reaches 6.024 * 10
-9Mol s
-1L
-1, photo-quantum efficiency is 0.13%, the TOC clearance is 97.1%.
12.Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film degradation aqueous solution of methylene blue: with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film is placed in the reactor, and putting into the 100ml initial concentration is 0.0506mol m
-3(5.06 * 10
-5Mol L
-1), initial pH value is 7 aqueous solution of methylene blue.Choose the xenon lamp irradiation aqueous solution of methylene blue of 300W, mix edge filter (λ＞420nm).In the experimentation, keep the oxygen saturation state of solution with the mode of oxygenic aeration.Overall optical is carried out according to being reflected under the airtight lighttight environment.Use ultraviolet-visible spectrophotometer, in the methylene blue concentration of 670nm place working sample, through 160 minutes, methylene blue was degraded fully, and degradation rate reaches 5.271 * 10
-9Mol s
-1L
-1, photo-quantum efficiency is 0.12%, the TOC clearance is 96.8%.
13.N doping Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation aqueous solution of methylene blue: with the N Bi that mixes
2La
xV
1.6-0.6xO
7(0.8≤x≤1) film is placed in the reactor, and putting into the 100ml initial concentration is 0.0506mol m
-3(5.06 * 10
-5Mol L
-1), initial pH value is 7 aqueous solution of methylene blue.Choose the xenon lamp irradiation aqueous solution of methylene blue of 300W, mix edge filter (λ＞420nm).In the experimentation, keep the oxygen saturation state of solution with the mode of oxygenic aeration.Overall optical is carried out according to being reflected under the airtight lighttight environment.Use ultraviolet-visible spectrophotometer, in the methylene blue concentration of 670nm place working sample, through 110 minutes, methylene blue was degraded fully, and degradation rate reaches 7.667 * 10
-9Mol s
-1L
-1, photo-quantum efficiency is 0.17%, the TOC clearance is 98.6%.
14.N doping Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film degradation aqueous solution of methylene blue: with the N Bi that mixes
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film is placed in the reactor, and putting into the 100ml initial concentration is 0.0506mol m
-3(5.06 * 10
-5MolL
-1), initial pH value is 7 aqueous solution of methylene blue.Choose the xenon lamp irradiation aqueous solution of methylene blue of 300W, mix edge filter (λ＞420nm).In the experimentation, keep the oxygen saturation state of solution with the mode of oxygenic aeration.Overall optical is carried out according to being reflected under the airtight lighttight environment.Use ultraviolet-visible spectrophotometer, in the methylene blue concentration of 670nm place working sample, through 120 minutes, methylene blue was degraded fully, and degradation rate reaches 7.028 * 10
-9Mol s
-1L
-1, photo-quantum efficiency is 0.16%, the TOC clearance is 97.9%.
15.S doping Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation aqueous solution of methylene blue: with the N Bi that mixes
2La
xV
1.6-0.6xO
7(0.8≤x≤1) film is placed in the reactor, and putting into the 100ml initial concentration is 0.0506mol m
-3(5.06 * 10
-5Mol L
-1), initial pH value is 7 aqueous solution of methylene blue.Choose the xenon lamp irradiation aqueous solution of methylene blue of 300W, mix edge filter (λ＞420nm).In the experimentation, keep the oxygen saturation state of solution with the mode of oxygenic aeration.Overall optical is carried out according to being reflected under the airtight lighttight environment.Use ultraviolet-visible spectrophotometer, in the methylene blue concentration of 670nm place working sample, through 120 minutes, methylene blue was degraded fully, and degradation rate reaches 7.028 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.16%, the TOC clearance is 98.2%.
16.S doping Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film degradation aqueous solution of methylene blue: with Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) film is placed in the reactor, and putting into the 100ml initial concentration is 0.0506mol m
-3(5.06 * 10
-5Mol L
-1), initial pH value is 7 aqueous solution of methylene blue.Choose the xenon lamp irradiation aqueous solution of methylene blue of 300W, mix edge filter (λ＞420nm).In the experimentation, keep the oxygen saturation state of solution with the mode of oxygenic aeration.Overall optical is carried out according to being reflected under the airtight lighttight environment.Use ultraviolet-visible spectrophotometer, in the methylene blue concentration of 670nm place working sample, through 130 minutes, methylene blue was degraded fully, and degradation rate reaches 6.487 * 10
-9Mol s
-1L
-1, photo-quantum efficiency is 0.14%, the TOC clearance is 97.5%.
17. adopt Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) powder decomposes the pure water hydrogen: carry out in the airtight glass piping interior lighting reactor by a plurality of valve controls, (incident flux is 4.513 * 10 to the xenon lamp of radiation source employing 300W
-6Einstein L
-1s
-1, the 420nm edge filter) or 400W (incident flux is 6.013 * 10
-6Einstein L
-1s
-1, the 390nm edge filter) high-pressure sodium lamp, put into Bi
2La
xV
1.6-0.6xO
7(0.8≤x≤1) powder 1g, pure water 300ml.The hydrogen that overflows adopts the gas chromatograph that has TCD, and this gas chromatograph links to each other with airtight loop interior lighting reactor.All gases is removed in the airtight loop interior lighting reactor before reaction, and argon gas is charged into this reactor, and oxygen in reactor and nitrogen are removed fully.After under the xenon lamp irradiation 24 hours, the output of hydrogen is 438.9 micromoles, and the output of oxygen is 220.3 micromoles; After 24 hours, the output of hydrogen is 1217.7 micromoles under high voltage mercury lamp radiation, and the output of oxygen is 609.2 micromoles.
18. adopt Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder decomposes the pure water hydrogen: carry out in the airtight glass piping interior lighting reactor by a plurality of valve controls, (incident flux is 4.513 * 10 to the xenon lamp of radiation source employing 300W
-6Einstein L
-1s
-1, the 420nm edge filter) or 400W (incident flux is 6.013 * 10
-6Einstein L
-1s
-1, the 390nm edge filter) high-pressure sodium lamp, put into Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder 1g, pure water 300ml.The hydrogen that overflows adopts the gas chromatograph that has TCD, and this gas chromatograph links to each other with airtight loop interior lighting reactor.All gases is removed in the airtight loop interior lighting reactor before reaction, and argon gas is charged into this reactor, and oxygen in reactor and nitrogen are removed fully.After under the xenon lamp irradiation 24 hours, the output of hydrogen is 399.1 micromoles, and the output of oxygen is 199.8 micromoles; After 24 hours, the output of hydrogen is 977.8 micromoles under high voltage mercury lamp radiation, and the output of oxygen is 496.8 micromoles.
With Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) powder is a catalyst, difference supporting Pt, NiO and RuO
2Compound: catalyst decomposes water hydrogen, lambda1-wavelength λ=390nm, catalyst 1g of the present invention, pure water 300mL, 50mL CH
3OH, light source are the 400W high-pressure sodium lamp, adopt with 0.2wt%-Pt/Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) is composite catalyst, and the output of hydrogen is 5.65mmol after 14 hours; With 1.0wt%-NiO/Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) is composite catalyst, and the output of hydrogen is 4.18mmol after 14 hours; With 1.0wt%-RuO
2/ Bi
2Y
xV
1.6-0.6xO
8(0.8≤x≤1) is composite catalyst, and the output of hydrogen is 1.74mmol after 14 hours.
Claims (1)
1.Bi
2La
xV
1.6-0.6xO
7The preparation method of catalysis material is characterized in that adopting the method for high temperature solid-phase sintering to prepare Bi
2La
xV
1.6-0.6xO
7, 0.8≤x≤1; With purity 99.99% Bi
2O
3, V
2O
5, La
2O
3Be raw material, and by the atomic ratio of described molecular formula with Bi
2O
3, V
2O
5And La
2O
3Mix, then in grinding in ball grinder, the particle diameter of powder reaches the 1-2 micron, and 200 ± 20 ℃ of oven dry 4 ± 1 hours, compacting was put into high temperature sintering furnace and fired in flakes; Furnace temperature is risen to 750 ± 20 ℃, be incubated and cool off with stove after 6 ± 2 hours, it is the 0.8-1.6 micron that the pressed powder taking-up is crushed to particle diameter, again that these powder compaction are in blocks, puts into the high temperature sintering furnace sintering, the highest furnace temperature is 750 ± 20 ℃, be incubated after 4 ± 1 hours and cool off with stove, it is the 0.6-1.4 micron that the pressed powder taking-up is crushed to particle diameter, again that these powder compaction are in blocks, put into the high temperature sintering furnace sintering, the intensification condition is as follows:
A.20 ℃ to 400 ℃, the heating-up time is 40 ± 10min; B.400 ℃, insulation 20 ± 10min; C.400 ℃ to 750 ℃, the heating-up time is 40 ± 10min; D.750 ℃ insulation 800 ± 100min; E.750 ℃ to 920 ± 20 ℃, the heating-up time is 30 ± 10min; ℃ f.920 ± 20 insulation 1800 ± 200min, stove is cold.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710191539XA CN101176842B (en) | 2007-12-12 | 2007-12-12 | Bi2laxv1.6-0.6xO7 or Bi2yxv1.6-0.6xO8 photocatalysis material, preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710191539XA CN101176842B (en) | 2007-12-12 | 2007-12-12 | Bi2laxv1.6-0.6xO7 or Bi2yxv1.6-0.6xO8 photocatalysis material, preparation method and application |
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