CN101199926B - Preparing process and application ofBi2SbxV1.6-0.6xO7 or Bi2AlxV1.6-0.6xO7 photocatalysis material - Google Patents
Preparing process and application ofBi2SbxV1.6-0.6xO7 or Bi2AlxV1.6-0.6xO7 photocatalysis material Download PDFInfo
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- CN101199926B CN101199926B CN2007101916157A CN200710191615A CN101199926B CN 101199926 B CN101199926 B CN 101199926B CN 2007101916157 A CN2007101916157 A CN 2007101916157A CN 200710191615 A CN200710191615 A CN 200710191615A CN 101199926 B CN101199926 B CN 101199926B
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- 238000007146 photocatalysis Methods 0.000 title description 5
- 239000000843 powder Substances 0.000 claims abstract description 65
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 14
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- 238000009413 insulation Methods 0.000 claims description 12
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- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000005056 compaction Methods 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 51
- 239000003054 catalyst Substances 0.000 abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 29
- 239000001257 hydrogen Substances 0.000 abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 29
- 229910052787 antimony Inorganic materials 0.000 abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 abstract description 9
- 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 2
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- 238000000862 absorption spectrum Methods 0.000 description 4
- 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 4
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- 239000000126 substance Substances 0.000 description 2
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Bi2(Sbx)(V1.6-0.6x)O7 (x: from 0.8 to 1) or Bi2(Alx)(V1.6-0.6x)O7 (x: from 0.8 to 1) The invention relates to a photo-catalytic material, the preparation method and the application. The preparation, with the method of high-temperature solid state sintering, adopts Bi2O3, V2O5, Sb2O3 or Al2O3 with 99.99% of purity as raw material. Bi,V, Sb or Al are fully mixed with the atom ratio of the followingmolecular formulas Bi2O3, V2O5, Sb2O3 or Al2O3, then skived in ball mill, dried at 200+-20 DEG C for 4+-1 hours, pressed to flakes and fired in high-temperature sintering furnace; the furnace temperature rise to 750+-20 DEG C and then cooled; the powder flakes are taken out and crushed to particles of 0.8-1.6microns; and then, the particles are pressed into flakes and sintered in the high-temperature sintering furnace. The application of the catalyst is to degrade waste water under light irradiation or decompose the purified water to produce hydrogen.
Description
Technical field
The present invention relates to Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) powder photocatalytic material, N doping Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film, S doping Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7Preparation were established and method, performance characterization and the application of catalysis materials such as (0.8≤x≤1) film.
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, in order to effectively utilize sunshine, we wish to develop the catalysis material that has photocatalytic activity under visible light, thereby solve extremely urgent water environment pollution problem.
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
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) powder photocatalytic material or film, N or S doping Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film is the Bi that base embeds metal nanometer cluster (as In, Cu or Au) with the conductor oxidate
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7Preparation were established and method, performance characterization and the application of catalysis materials such as (0.8≤x≤1) film.
Technical scheme of the present invention is: Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) contain V photocatalyst powder or thin-film material; And N or S doping Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film.
To having the different band gap structure and the Bi of can under visible light, degrade organic pollutants in water body or hydrogen production by water decomposition gas
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7The thin-film material that (0.8≤x≤1) is constituted and the experiment of N or S doping film are at Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7Mix N in the forbidden band of (0.8≤x≤1) or the S impurity energy level is carried 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, produce a large amount of light induced electrons at conduction band at a large amount of photohole of valence band generation.Utilize these photoholes organic pollution in the water body of degrading efficiently, utilize these light induced electrons to come hydrogen production by water decomposition gas 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
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7The 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, Sb
2O
3Or Al
2O
3Be raw material, and with Bi, V, Sb or the Al Bi with the atomic ratio of molecular formula
2O
3, V
2O
5And Sb
2O
3Or Al
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. be warming up to 400 ℃ by 20 ℃, the heating-up time is 40 ± 10min; B.400 ℃, insulation 20 ± 10min; C. be warming up to 750 ℃ by 400 ℃, the heating-up time is 40 ± 10min; D.750 ℃ insulation 800 ± 100min; E. be warming up to 920 ± 20 ℃ by 750 ℃, 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
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) photocatalytic powder material.
Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7The preparation technology of (0.8≤x≤1) photocatalysis film material:
A. target preparation: prepare simple metal Bi, V, Sb and Al metal targets, and above-mentioned two kinds of powder Bi that make
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) target;
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
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) thin layer 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
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) target is at SO
2Cosputtering simple metal Bi, V, Sb or Al target in the mist of gas, 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
2Sb
xV
1.6-0.6xO
7Rete, or obtain required N or S doping Bi
2Al
xV
1.6-0.6xO
7Rete.
Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7The application of (0.8≤x≤1) catalysis material powder or film: adopt Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(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 400W high voltage mercury lamp radiation aqueous solution of 300W, and the oxygen of keeping solution with the mode of oxygenic aeration is saturation state.Overall optical is carried out according to being reflected under the airtight lighttight environment.The invention has the beneficial effects as follows: successfully prepared Bi by physical method
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) two kinds contains V novel photocatalysis agent powder, and it has been carried out a series of signs, determines N doping Bi on this basis
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film, S doping Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film is the Bi that base embeds metal nanometer cluster (as In, Cu or Au) with the conductor oxidate
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) film or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film can also prepare Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) monocrystal thin films or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) monocrystal thin films, Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) superlattice film, and carried out performance characterization, and study above-mentioned film under radiation of visible light, the degrade efficient and the mechanism of degradation of organic pollution in the contaminated water body, the efficient and the optical activity of research hydrogen production by water decomposition gas under radiation of visible light are by to having the different band gap structure and the Bi of can degrade organic pollutants in water body or hydrogen production by water decomposition gas under visible light
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) thin-film material that is constituted and the research of film super crystal lattice material, band gap overlaps and the hydridization rule between the analyzing semiconductor oxide, at Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7Mix 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, utilize the light induced electron hydrogen production by water decomposition gas of conduction band simultaneously.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 hydrogen production by water decomposition gas.
Description of drawings
Fig. 1 is Bi
2Sb
xV
1.6-0.6xO
7The XRD figure spectrum of (0.8≤x≤1)
Fig. 2 is Bi
2Sb
xV
1.6-0.6xO
7The SEM collection of illustrative plates of (0.8≤x≤1)
Fig. 3 is Bi
2Sb
xV
1.6-0.6xO
7The EDX collection of illustrative plates of (0.8≤x≤1)
Fig. 4 is Bi
2Sb
xV
1.6-0.6xO
7The ultraviolet-visible diffuse reflection absorption spectra of (0.8≤x≤1)
Fig. 5 is Bi
2Sb
xV
1.6-0.6xO
7In (0.8≤x≤1) (ahv)
1/nRelation curve with hv
Fig. 6 is Bi
2Sb
xV
1.6-0.6xO
7The band structure schematic diagram of (0.8≤x≤1)
Fig. 7 is Bi
2Al
xV
1.6-0.6xO
7The XRD figure spectrum of (0.8≤x≤1)
Fig. 8 is Bi
2Al
xV
1.6-0.6xO
7The SEM collection of illustrative plates of (0.8≤x≤1)
Fig. 9 is Bi
2Al
xV
1.6-0.6xO
7The EDX collection of illustrative plates of (0.8≤x≤1)
Figure 10 is Bi
2Al
xV
1.6-0.6xO
7The Rietveld software configuration refine collection of illustrative plates of (0.8≤x≤1)
Figure 11 is Bi
2Al
xV
1.6-0.6xO
7The ultraviolet-visible diffuse reflection absorption spectra of (0.8≤x≤1)
Figure 12 is Bi
2Al
xV
1.6-0.6xO
7In (0.8≤x≤1) (ahv)
1/nRelation curve with hv
Figure 13 is Bi
2Al
xV
1.6-0.6xO
7The band structure schematic diagram of (0.8≤x≤1)
Figure 14 is with Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) powder is a catalyst, and phenol concentration is change curve in time
Figure 15 is with Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) powder is a catalyst, and phenol total content of organic carbon (TOC) is change curve in time
Figure 16 is with Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) powder is a catalyst, the possible degradation pathway schematic diagram of phenol
Figure 17 is with Bi
2Al
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
2Al
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
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) is catalyst, MB concentration changes with time curve
Figure 20 is with Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) is catalyst, and the MB intermediate product is change curve in time
Figure 21 is with Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
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 22 is with Bi
2Sb
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 23 is with Bi
2Sb
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 24 is with Bi
2Al
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 25 is with Bi
2Al
xV
1.6-0.6xO
7Or Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) powder is a catalyst, respectively loaded Pt catalyst hydrogen production by water decomposition gas (pure water 300mL, light source are the xenon lamp of 300W for lambda1-wavelength λ=420nm, catalyst 1g)
Figure 26 is with Bi
2Al
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)
The specific embodiment
1. two kinds of novel B i
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7The preparation were established of (0.8≤x≤1) photocatalytic powder material is as follows: the method with high temperature solid-phase sintering prepares Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) photocatalytic powder material.With Bi
2O
3, V
2O
5And Al
2O
3Being raw material, is 99.99% with purity, by Bi, the Al of molecular formula, the atomic ratio of V, with Bi
2O
3, V
2O
5And Al
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 after 6 hours and cool off with stove, 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, put into the high temperature sintering furnace sintering, the highest furnace temperature is 750 ℃, is incubated after 4 hours to cool off with stove, and 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. is warming up to 400 ℃ by 20 ℃, and the heating-up time is 40min; B.400 ℃ insulation 20min; C. be warming up to 750 ℃ by 400 ℃, the heating-up time is 40min; D.750 ℃ insulation 800min; E. be warming up to 930 ℃ by 750 ℃, the heating-up time is 30min; F.930 ℃ insulation 1800min, the g. stove is cold.Pressed powder cools off with stove after 30 hours through 930 ℃ 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
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) photocatalytic powder material.Sb
2O
3Replace Al
2O
3, obtain Bi with same process
2Sb
xV
1.6-0.6xO
7The photocatalytic powder material.
2. two kinds of Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7The preparation were established of (0.8≤x≤1) photocatalysis film material is as follows: the preparation of a. target: prepare simple metal Bi, V, Sb and Al metal targets, and prepared two kinds of powder Bi in the operation 1
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7(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 study at Si base substrate or other as quartz substrate preparation films such as ito glass.
C.N doping Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(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
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) target, or in the mist of ammonia, oxygen and argon gas cosputtering simple metal Bi, V, Sb and Al target, the different film of deposit thickness on substrate, with this film in nitrogen under higher temperature heat treatment a period of time, make it crystallization and obtain required N doping Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) rete.
D.S doping Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(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
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) target, or at SO
2Cosputtering simple metal Bi, V, Sb and Al target in the mist of gas, oxygen and argon gas, the different film of deposit thickness on substrate, with this film in nitrogen under higher temperature heat treatment a period of time, make it crystallization and obtain required S doping Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) rete.
E. oxide semiconductor film superlattices (Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1)) preparation: in the mist of argon gas and oxygen, carry out magnetic control co-sputtering as target with simple metal Bi, V, Sb and Al target.With [001] crystal orientation YSZ single-crystal substrate is substrate, and YSZ is a cubic structure, cell parameter a=5.148 (2)
Bi
2Sb
xV
1.6-0.6xO
7The space group of (0.8≤x≤1) is I4/mmm, and structure is a tetragonal crystal system, and cell parameter is a=3.9068 (1), b=3.9068 (1), c=15.4385 (7)
Bi
2Al
xV
1.6-0.6xO
7The space group of (0.8≤x≤1) is 14/mmm, and structure is a tetragonal crystal system, and cell parameter is a=3.9294 (1), b=3.9294 (1), c=15.3469 (9)
As calculated, Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7The lattice constant mismatch degree of (0.8≤x≤1) is less than 0.5%, so Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) lattice coupling.Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7The lattice constant mismatch degree of (0.8≤x≤1) and YSZ single-crystal substrate is all less than 7%, thus the YSZ single-crystal substrate can and Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) forms strained super lattice.At first deposition first tunic on substrate carries out magnetic control co-sputtering with simple metal Bi, V and Sb target as target, prepares single-phase Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) film.After rete reaches predetermined thickness, change target, carry out magnetron sputtering with simple metal Bi, V and Al target as target, deposit second tunic, prepare single-phase Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film.Second layer film thickness is identical with the ground floor film thickness.The lattice constant match of this two-layer film.Three-layer thin-film still is Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) film, the 4th layer is Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film.Bi with this rule manufacturing cycle variation
2Sb
xV
1.6-0.6xO
7/ Bi
2Al
xV
1.6-0.6xO
7The plural layers superlattices.Bi
2Sb
xV
1.6-0.6xO
7/ Bi
2Al
xV
1.6-0.6xO
7The plural layers superlattices belong to first kind superlattices, i.e. Bi
2Al
xV
1.6-0.6xO
7Bi is dropped in the forbidden band of (0.8≤x≤1) fully
2Sb
xV
1.6-0.6xO
7In the forbidden band of (0.8≤x≤1).The Bi of lattice coupling
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) is stratification alternately, and its band gap overlaps, and obtains conduction band limit and valence-band edge that one-period changes.
F. monocrystal thin films preparation: by multi-target magnetic control sputtering and mask technique, select different backing materials, in the mist of argon gas and oxygen, carry out magnetron sputtering with simple metal Bi, V, Sb and Al target as target, along certain index crystal face epitaxial growth one deck monocrystalline Bi of different substrates
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) film or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film.
G. embed the Bi of metal nanometer cluster (as In, Cu or Au)
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) film or Bi
2Al
xV
1.6-0.6xO
7The preparation of (0.8≤x≤1) film: adopt the multi-target magnetic control sputtering instrument, prepare targets such as simple metal In, Cu or Au.The method synthetic with solid phase reaction prepares Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) target.Work atmosphere is an argon gas, with ready Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) (or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1)) and In (or Cu, Au) carry out cosputtering as target respectively, finally being prepared into what embed metal nanometer cluster is the Bi of base with the conductor oxidate
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) film or Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film.
3. two kinds of novel B i
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7The sign of (0.8≤x≤1) catalysis material
Learn Bi by XRD, SEM-EDX result
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) is 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
2Sb
xV
1.6-0.6xO
7The average atom ratio of (0.8≤x≤1) is Bi: Sb: V=2.00: 0.99: 1.01.With Rietveld software to Bi
2Sb
xV
1.6-0.6xO
7The XRD result of (0.8≤x≤1) carries out structure refinement, the structure refinement factor R
PValue is R
P=13.7%.Bi
2Sb
xV
1.6-0.6xO
7The space group of (0.8≤x≤1) is I4/mmm, and structure is a tetragonal crystal system, and cell parameter is a=3.9068 (1), b=3.9068 (1), c=15.4385 (7)
Bi
2Sb
xV
1.6-0.6xO
7The indices of crystallographic plane (hkl) of (0.8≤x≤1) each diffraction maximum are demarcated.Bi
2Sb
xV
1.6-0.6xO
7Each atoms in space atom site parameter is determined (as table 1, table 2) in (0.8≤x≤1) catalyst.
Table 1 Bi
2Sb
xV
1.6-0.6xO
7The atom locus of (0.8≤x≤1)
| Atom | x | y | z | Occupy attitude |
| Bi Sb 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 2 Bi
2Sb
xV
1.6-0.6xO
7Each atomic distance of (0.8≤x≤1)
| Atom | Sb，V-O1 | Sb，V-O2 | Sb，V-O4 | Bi-O3 | Bi-O4 |
| Atomic distance (dust) | 1.936(4) | 1.936(4) | 1.765(3) | 2.266(2) | 2.015(4) |
Adopt UV, visible light to diffuse spectrometer to Bi
2Sb
xV
1.6-0.6xO
7(see figure 4) is measured on the characteristic absorption limit that (0.8≤x≤1) produces under the irradiation of light.The absorption spectra data show, Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) begins to produce intrinsic transition at 532nm place electronics.This proof is at very long visible light wave range, Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) can 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=0.52, and then acquisition (α hv)
2With the graph of a relation (see figure 5) of hv, finally determined Bi
2Sb
xV
1.6-0.6xO
7The band gap width of (0.8≤x≤1) is 2.33eV.
Calculate Bi
2Sb
xV
1.6-0.6xO
7The band structure of (0.8≤x≤1), conduction band is made of the 3d track of V, the 5p track of Sb, and valence band constitutes (see figure 6) by the 6s track of Bi and the 2p track of O.
Learn Bi by XRD, SEM-EDX result
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) is single-phase (seeing Fig. 7-9), and experiment original material height is pure, does not have any impurity phase.Measure Bi by Xray fluorescence spectrometer
2Al
xV
1.6-0.6xO
7The average atom ratio of (0.8≤x≤1) is Bi: Al: V=2.00: 0.98: 1.02.With Rietveld software to Bi
2Al
xV
1.6-0.6xO
7The XRD result of (0.8≤x≤1) carries out structure refinement, the structure refinement factor R
PValue is R
P=12.9% (see figure 10).Bi
2Al
xV
1.6-0.6xO
7The space group of (0.8≤x≤1) is I4/mmm, and structure is a tetragonal crystal system, and cell parameter is a=3.9294 (1), b=3.9294 (1), c=15.3469 (9)
Bi
2Al
xV
1.6-0.6xO
7The indices of crystallographic plane (hkl) of (0.8≤x≤1) each diffraction maximum are demarcated.Bi
2Al
xV
1.6-0.6xO
7Each atoms in space atom site parameter is determined (as table 3, table 4) in (0.8≤x≤1) catalyst.
Table 3 Bi
2Al
xV
1.6-0.6xO
7The atom locus of (0.8≤x≤1)
| Atom | x | y | z | Occupy attitude |
| Bi Al 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 4 Bi
2Al
xV
1.6-0.6xO
7Each atomic distance of (0.8≤x≤1)
| Atom | Al，V-O1 | Al，V-O2 | Al，V-O4 | Bi-O3 | Bi-O4 |
| Atomic distance (dust) | 1.931(2) | 1.931(2) | 1.752(3) | 2.259(2) | 2.007(5) |
Adopt UV, visible light to diffuse spectrometer to Bi
2Al
xV
1.6-0.6xO
7(seeing Figure 11) measured on the characteristic absorption limit that (0.8≤x≤1) produces under the irradiation of light.The absorption spectra data show, Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) begins to produce intrinsic transition at 609nm place electronics.This proof is at very long visible light wave range, Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) can 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=0.64, and then acquisition (α hv)
2With the graph of a relation (seeing Figure 12) of hv, finally determined Bi
2Al
xV
1.6-0.6xO
7The band gap width of (0.8≤x≤1) is 2.03eV.
Calculate Bi
2Al
xV
1.6-0.6xO
7The band structure of (0.8≤x≤1), conduction band is made of the 3d track of V and the 3s track of Al, and valence band is made of the 6s track of Bi and the 2p track of O.(seeing Figure 13)
Application example
1. adopt Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) powder degradation of phenol aqueous solution: with Bi
2Sb
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 475 minutes, phenol was degraded fully, and degradation rate reaches 1.754 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.39%.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 475 minutes.
2. adopt Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) powder degradation of phenol aqueous solution: with Bi
2Al
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 400 minutes, phenol was degraded fully, and degradation rate reaches 2.083 * 10
-8Mol s
-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 98.2% in 400 minutes.
3.Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) monocrystal thin films degradation of phenol aqueous solution: with Bi
2Sb
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 340 minutes, phenol was degraded fully, and degradation rate reaches 2.451 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.54%.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 98.3% in 340 minutes.
4.Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) monocrystal thin films degradation of phenol aqueous solution: with Bi
2Al
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
-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 320 minutes, phenol was degraded fully, and degradation rate reaches 2.604 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.58%.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 98.7% in 320 minutes.
5.N doping Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation phenol solution
With the N Bi that mixes
2Sb
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 315 minutes, phenol was degraded fully, and degradation rate reaches 2.646 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.59%.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 99.1% in 315 minutes.
6.N doping Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation phenol solution
With the N Bi that mixes
2Al
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 300 minutes, phenol was degraded fully, and degradation rate reaches 2.778 * 10
-8Mols
-1L
-1, photo-quantum efficiency is 0.62%.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 300 minutes.
7.S doping Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation phenol solution: with the N Bi that mixes
2Sb
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 325 minutes, phenol was degraded fully, and degradation rate reaches 2.564 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.57%.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 99.2% in 325 minutes.
8.S doping Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation phenol solution
With Bi
2Al
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 310 minutes, phenol was degraded fully, and degradation rate reaches 2.688 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.60%.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 98.8% in 310 minutes.
9. with the conductor oxidate Bi that base embeds metal nanometer cluster (as In, Cu or Au)
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation phenol solution
To be the Bi that base embeds metal nanometer cluster (as In, Cu or Au) with the conductor oxidate
2Sb
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 330 minutes, phenol was degraded fully, and degradation rate reaches 2.525 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.56%.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 98.7% in 330 minutes.
10. with the conductor oxidate Bi that base embeds metal nanometer cluster (as In, Cu or Au)
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation phenol solution: will be the Bi that base embeds metal nanometer cluster (as In, Cu or Au) with the conductor oxidate
2Al
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 295 minutes, phenol was degraded fully, and degradation rate reaches 2.825 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.63%.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 295 minutes.
11.Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) superlattice film degradation of phenol aqueous solution Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) superlattice 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 280 minutes, phenol was degraded fully, and degradation rate reaches 2.976 * 10
-8Mol s
-1L
-1, photo-quantum efficiency is 0.66%.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 280 minutes.
12. adopt Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) powder degraded aqueous solution of methylene blue: with Bi
2Sb
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 0.0506mol m
-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 160 minutes, the TOC clearance was 74.4%.Through 200 minutes, methylene blue was degraded fully, and degradation rate reaches 4.22 * 10
-9Mol s
-1L
-1, the TOC clearance is 99.6%, photo-quantum efficiency is 0.09%.
13. adopt Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) powder degraded aqueous solution of methylene blue: with Bi
2Al
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 0.0506mol m
-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 160 minutes, methylene blue was degraded fully, and degradation rate reaches 5.27 * 10
-9Mol s
-1L
-1, the TOC clearance is 99.7%, photo-quantum efficiency is 0.12%.
14.Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) monocrystal thin films degraded aqueous solution of methylene blue is with Bi
2Sb
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 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 145 minutes, methylene blue was degraded fully, and degradation rate reaches 5.816 * 10
-9Mol s
-1L
-1, photo-quantum efficiency is 0.13%, the TOC clearance is 97.8%.
15.Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) monocrystal thin films degraded aqueous solution of methylene blue: with Bi
2Al
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 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 125 minutes, methylene blue was degraded fully, and degradation rate reaches 6.747 * 10
-9Mol s
-1L
-1, photo-quantum efficiency is 0.15%, the TOC clearance is 98.1%.
16.N doping Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation aqueous solution of methylene blue: with the N Bi that mixes
2Sb
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 98.4%.
17.N doping Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation aqueous solution of methylene blue: with the N Bi that mixes
2Al
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 105 minutes, methylene blue was degraded fully, and degradation rate reaches 8.032 * 10
-9Mol s
-1L
-1, photo-quantum efficiency is 0.18%, the TOC clearance is 99.2%.
18.S doping Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation aqueous solution of methylene blue
With the N Bi that mixes
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) film is placed in the reactor, and putting into the 100ml initial concentration is 0.0506molm
-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 115 minutes, methylene blue was degraded fully, and degradation rate reaches 7.333 * 10
-9Mol s
-1L
-1, photo-quantum efficiency is 0.16%, the TOC clearance is 98.8%.
19.S doping Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation aqueous solution of methylene blue: with Bi
2Al
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 98.5%.
20. with the conductor oxidate is the Bi that base embeds metal nanometer cluster (as In, Cu or Au)
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation aqueous solution of methylene blue: will be the Bi that base embeds metal nanometer cluster (as In, Cu or Au) with the conductor oxidate
2Sb
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 100 minutes, methylene blue was degraded fully, and degradation rate reaches 8.433 * 10
-9Mol s
-1L
-1, photo-quantum efficiency is 0.19%, the TOC clearance is 98.7%.
21. with the conductor oxidate is the Bi that base embeds metal nanometer cluster (as In, Cu or Au)
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) film degradation aqueous solution of methylene blue: will be the Bi that base embeds metal nanometer cluster (as In, Cu or Au) with the conductor oxidate
2Al
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
-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 85 minutes, methylene blue was degraded fully, and degradation rate reaches 9.922 * 10
-9Mols
-1L
-1, photo-quantum efficiency is 0.22%.The TOC clearance is 99.9%.
22.Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) superlattice film degraded aqueous solution of methylene blue Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) and Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) superlattice 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 95 minutes, methylene blue was degraded fully, and degradation rate reaches 8.877 * 10
-9Mols
-1L
-1, photo-quantum efficiency is 0.20%, the TOC clearance is 99.8%.
23. adopt Bi
2Sb
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 4.51310 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
2Sb
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 454.26 micromoles, and the output of oxygen is 227.63 micromoles; After 24 hours, the output of hydrogen is 1241.52 micromoles under high voltage mercury lamp radiation, and the output of oxygen is 621.26 micromoles.
24. adopt Bi
2Al
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 4.51310 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
2Al
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 516.26 micromoles, and the output of oxygen is 259.39 micromoles; After 24 hours, the output of hydrogen is 1306.53 micromoles under high voltage mercury lamp radiation, and the output of oxygen is 654.29 micromoles.
With Bi
2Al
xV
1.6-0.6xO
7Or Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) powder is a catalyst, difference loaded Pt catalyst hydrogen production by water decomposition gas, and lambda1-wavelength λ=420nm, catalyst 1g, pure water 300mL, light source is the xenon lamp of 300W, with 0.2wt%-Pt/Bi
2Al
xV
1.6-0.6xO
7(0.8≤x≤1) is composite catalyst, and the output of hydrogen is 609.32 micromoles after 24 hours; With 0.2wt%-Pt/Bi
2Sb
xV
1.6-0.6xO
7(0.8≤x≤1) is composite catalyst, and the output of hydrogen is 579.26 micromoles after 24 hours.
Claims (1)
1.Bi
2Sb
xV
1.6-0.6xO
7Or Bi
2Al
xV
1.6-0.6xO
7The photocatalytic powder preparation methods is characterized in that adopting the method for high temperature solid-phase sintering, is 99.99% Bi with purity
2O
3, V
2O
5And Sb
2O
3Be raw material, press described molecular formula atomic ratio Bi
2O
3, V
2O
5And Sb
2O
3Fully mixing, perhaps is 99.99% Bi with purity
2O
3, V
2O
5And Al
2O
3Be raw material, press described molecular formula atomic ratio Bi
2O
3, V
2O
5And Al
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 after 6 ± 2 hours and cool off with stove, 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, put into the high temperature sintering furnace sintering, the highest furnace temperature is 750 ± 20 ℃, is incubated after 4 ± 1 hours to cool off with stove, and 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: be warming up to 400 ℃ by 20 ℃, the heating-up time is 40 ± 10min; B.400 ℃, insulation 20 ± 10min; C. be warming up to 750 ℃ by 400 ℃, the heating-up time is 40 ± 10min; D.750 ℃ insulation 800 ± 100min; E. be warming up to 920 ± 20 ℃ by 750 ℃, the heating-up time is 30 ± 10min; ℃ f.920 ± 20 insulation 1800min, 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, gets Bi
2Sb
xV
1.6-0.6xO
70.8≤x≤1 or Bi
2Al
xV
1.6-0.6xO
70.8≤x≤1 photocatalytic powder material.
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| CN2007101916157A CN101199926B (en) | 2007-12-14 | 2007-12-14 | Preparing process and application ofBi2SbxV1.6-0.6xO7 or Bi2AlxV1.6-0.6xO7 photocatalysis material |
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|---|---|---|---|
| CN2007101916157A CN101199926B (en) | 2007-12-14 | 2007-12-14 | Preparing process and application ofBi2SbxV1.6-0.6xO7 or Bi2AlxV1.6-0.6xO7 photocatalysis material |
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| CN101199926B true CN101199926B (en) | 2010-08-18 |
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| CN103521211B (en) * | 2013-10-31 | 2015-06-24 | 北京航空航天大学 | Preparation method for photocatalytic material with In mingled with Bi2O3 |
| CN105970247B (en) * | 2016-07-19 | 2018-06-08 | 李国岭 | It is a kind of to prepare hydrogen peroxide single crystal semiconductor oxide anode and electrolytic cell |
| CN105951117B (en) * | 2016-07-19 | 2018-02-02 | 李国岭 | A kind of electrolytic method of low cost production high purity of hydrogen peroxide and hydrogen |
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