CN101850255A - Y-Sb-based composite magnetic particle optical catalyst in nuclear shell structures and application - Google Patents
Y-Sb-based composite magnetic particle optical catalyst in nuclear shell structures and application Download PDFInfo
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- CN101850255A CN101850255A CN201010195781A CN201010195781A CN101850255A CN 101850255 A CN101850255 A CN 101850255A CN 201010195781 A CN201010195781 A CN 201010195781A CN 201010195781 A CN201010195781 A CN 201010195781A CN 101850255 A CN101850255 A CN 101850255A
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- 230000003287 optical effect Effects 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 title claims description 135
- 239000002131 composite material Substances 0.000 title claims description 25
- 239000006249 magnetic particle Substances 0.000 title abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 104
- 230000005291 magnetic effect Effects 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 57
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 22
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 60
- 229910001566 austenite Inorganic materials 0.000 claims description 47
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 238000006555 catalytic reaction Methods 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 230000000593 degrading effect Effects 0.000 claims description 14
- 239000002351 wastewater Substances 0.000 claims description 11
- 238000005273 aeration Methods 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 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 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011941 photocatalyst Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052753 mercury Inorganic materials 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000005286 illumination Methods 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 60
- 239000000758 substrate Substances 0.000 description 56
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 239000007789 gas Substances 0.000 description 36
- 230000005303 antiferromagnetism Effects 0.000 description 34
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- 238000002360 preparation method Methods 0.000 description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 27
- 239000001301 oxygen Substances 0.000 description 27
- 229910052760 oxygen Inorganic materials 0.000 description 27
- 230000001699 photocatalysis Effects 0.000 description 27
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 26
- 238000005245 sintering Methods 0.000 description 24
- 238000000151 deposition Methods 0.000 description 23
- 230000008021 deposition Effects 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 229910052727 yttrium Inorganic materials 0.000 description 21
- 238000009413 insulation Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 20
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- 238000004544 sputter deposition Methods 0.000 description 12
- 229910052769 Ytterbium Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
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- 239000000975 dye Substances 0.000 description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
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- 230000000694 effects Effects 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- 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 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
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- 229960000907 methylthioninium chloride Drugs 0.000 description 4
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- 239000005416 organic matter Substances 0.000 description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229910017771 LaFeO Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 230000005307 ferromagnetism Effects 0.000 description 2
- 230000005426 magnetic field effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- OSCVBYCJUSOYPN-UHFFFAOYSA-K ytterbium(3+);triacetate Chemical compound [Yb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OSCVBYCJUSOYPN-UHFFFAOYSA-K 0.000 description 2
- JRKVGRAQLBXGQB-UHFFFAOYSA-K yttrium(3+);triacetate;hydrate Chemical compound O.[Y+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JRKVGRAQLBXGQB-UHFFFAOYSA-K 0.000 description 2
- MCUFTOFSZFEQMB-UHFFFAOYSA-N 2,3,4,5,6-pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl.OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl MCUFTOFSZFEQMB-UHFFFAOYSA-N 0.000 description 1
- -1 Methylene Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- LDAAFTDRWLUENA-UHFFFAOYSA-N antimony yttrium Chemical compound [Y].[Sb] LDAAFTDRWLUENA-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
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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 relates to a catalytic material in nuclear shell structures, which is shown in the following structural formulas: gama-Fe2O3-Y3-xYbxSbO7 (x is not less than 0.5 and is not more than 1), gama-Fe2O3-Y3-xGaxSbO7 (x is not less than 0.5 and is not more than 1), SiO2- Y3-xYbxSbO7 (x is not less than 0.5 and is not more than 1), SiO2- Y3-xGaxSbO7 (x is not less than 0.5 and is not more than 1), MnO2-Y3-xYbxSbO7 (x is not less than 0.5 and is not more than 1) or MnO2-Y3-xGaxSbO7 (x is not less than 0.5 and is not more than 1). The particle diameters of the gama-Fe2O3, the SiO2 and the MnO2 are 0.06-2 micros and are 0.07-2.1 micros after magnetic particles are coated by the Y3-xYbxSbO7 (x is not less than 0.5 and is not more than 1) and the Y3-xGaxSbO7 (x is not less than 0.5 and is not more than 1) which are used as a catalytic material. Sewage is degraded by a reaction system including a magnetic field device and the optical catalytic material in three nuclear shell structures in an aqueous solution under the conditions that the magnetic field strength is 0.3-0.6 T, a xenon lamp or a high-pressure mercury lamp is used as a light source, and the whole illumination reaction is carried out in a sealed light-tight environment.
Description
Technical field
The present invention relates to a kind of novel photocatalysis agent, preparation and application, especially powder catalytic material Y
3-xYb
xSbO
7(0.5≤x≤1), Y
3-xGa
xSbO
7γ-the Fe of (0.5≤x≤1) and " magnetic-particle nuclear-photochemical catalyst shell " structure
2O
3(ferromagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), γ-Fe
2O
3-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1), SiO
2-Y
3-xGa
xSbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Y
3-xYb
xSbO
7(0.5≤x≤1), MnO-Y
3-xGa
xSbO
7(0.5≤x≤1), the application through the organic pollution in the water body is removed in photocatalysis reaches the application that photochemical catalyzing is produced hydrogen.
Background technology
The processing of poisonous refractory organics organic matter (PTS) is difficult point, the hot subject in the water treatment field always in the water.PTS has characteristics such as pair human body and Ecological Environment Risk height, and therefore, all there is strict control criterion in developed country to this pollutant.Because the routine biochemistry processing method must adopt the specially treated unit process that it is removed targetedly to the poor removal effect (or basic non-processor effect) of this class material.Therefore, the developmental research of the organic novel process technology of refractory organics becomes the focus and the advanced subject in present international environment engineering field in the water.
Semiconductor is (typical in TiO
2) photocatalytic method is exactly the most effective, the technology that market prospects are arranged most of refractory organics organic matter in the countries in the world scholar processing water of generally acknowledging, have huge application potential aspect its refractory organics organic pollution in the degraded water body, have tangible advantage than electro-catalysis, catalytic wet oxidation technology at aspects such as the organic mineralising decomposition of refractory organics.But photocatalysis technology is not industrialization as yet in water treatment and wastewater treatment, mainly there are following two problems: (1) suspension system photocatalysis system photocatalysis efficiency height, there is catalyst post processing problem, reclaim problem if photochemical catalyst is fixed on the separation that can solve photochemical catalyst on the material such as glass, but its photocatalysis efficiency is starkly lower than suspension system; (2) titanium dioxide only can absorb ultraviolet light, in not response of visible-range, utilization rate to sunshine low (4%), and solar spectrum medium ultraviolet light part only accounts for less than 5%, wavelength is that the visible light of 400-750nm then accounts for 43% of solar spectrum, if ultraviolet light wave band and the visible light wave range in the sunshine can be fully utilized simultaneously, photo-quantum efficiency will be greatly improved.Therefore, the recovery of solution photochemical catalyst has become photocatalysis wastewater treatment industry key in application with the quantum efficiency problem under the prerequisite that guarantees higher photocatalysis efficiency.
At present, the light utilization efficiency of raising photochemical catalyst mainly contains both direction.The one, TiO 2 visible lightization partly replaces oxygen element in the titanium dioxide as nonmetalloids such as N, S, C, can reduce the band-gap energy of catalysis material, has expanded its photoresponse scope, has improved photo-quantum efficiency to a certain extent; The 2nd, research and develop visible light catalyst efficiently.In recent years, researchers have carried out the research work of exploring the novel visible photochemical catalyst, have obtained great achievement: Bi
12GeO
20The powder organic matters such as methyl orange of effectively degrading; Adopt Co
3O
4/ BiVO
4Can degradation of phenol; Adopt Ta
3N
5Particle can the degradation of methylene blue dyestuff; Adopt Na
2Ta
2O
6The Congo red solution of can degrading; Adopt Ga
2BiTaO
7Can the degradation of methylene blue dyestuff.Fu Xixian has developed perovskite composite oxide LaFeO
3, LaFe
1-xCu
xO
3Deng, the result shows LaFeO
3, LaFe
1-xCu
xO
3(x=0.02,0.05) has less band gap, can effectively utilize visible light that the organic matter of aqueous phase is carried out photocatalytic degradation.Zou Zhi has just waited the people successfully to synthesize CaBi
2O
4Deng utilizing visible light degradation water and airborne formaldehyde, acetaldehyde, methylene blue and H effectively
2The novel photocatalysis material of nuisances such as S.Zhu Yongfa, Zhao Jincai etc. utilize homemade new material (as Bi
2WO
6Deng) the aqueous phase rhodamine B of fast and effeciently having degraded, its effect is greatly improved than conventional method.This seminar has successfully prepared In first
2BiTaO
7Methylene blue dye in the powder photocatalytic degradation water body, methylene blue is degraded fully after 135 minutes, and total organic carbon (TOC) clearance is 100%.Therefore, the photoresponse scope of expansion catalysis material is to improve effective ways of photocatalysis quantum efficiency.Mostly the visible-light photocatalysis material of being reported at present is powdered, good photocatalytic activity is arranged in suspension system, therefore the organic pollution in the Powdered catalysis material removal water body of development of new not only can produce remarkable economic efficiency, and can also produce huge environmental benefit and social benefit.
Summary of the invention
The objective of the invention is: propose a kind of powder catalytic material Y
3-xYb
xSbO
7And Y
3-xGa
xSbO
7(0.5≤x≤1) and preparation were established and method, performance characterization and application.γ-the Fe of a kind of " magnetic-particle nuclear-photochemical catalyst shell " structure is also proposed in addition,
2O
3(ferromagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell) preparation technology, performance characterization and application.
Technical scheme of the present invention is: the catalysis material γ-Fe of nucleocapsid structure
2O
3(ferromagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).γ-Fe
2O
3, SiO
2With the particle diameter of MnO be the 0.06-2 micron, Y
3-xYb
xSbO
7, Y
3-xGa
xSbO
7Parcel back particle diameter is the 0.07-2.1 micron.
The catalysis material Y of nucleocapsid structure
3-xYb
xSbO
7(0.5≤x≤1) and Y
3-xGa
xSbO
7(0.5≤x≤1).
The preparation method adopts the preparation method of pulsed laser deposition deposition:
A. target preparation: the method with solid-phase sintering prepares Y
3-xYb
xSbO
7(0.5≤x≤1) and Y
3-xGa
xSbO
7(0.5≤x≤1) target, the target diameter is 10mm, thickness is 2mm;
B. choose substrate: select ferromagnetic particle γ-Fe for use
2O
3, paramagnetic particle SiO
2Or anti-ferromagnetism particle MnO is as substrate;
C. adopt the pulsed laser deposition deposition, laser main wave is long to be 248nm, and laser power density is 2～3J/cm
2, be protective atmosphere with nitrogen, the pressure of nitrogen and oxygen (purity is 99.99%) is 8～10Pa, initial pressure is 6 * 10 in the settling chamber
-5Pa～2 * 10
-3Pa, target is 3～7 centimetres to the distance of substrate, substrate temperature is 300～700 ℃, respectively sputter Y
3-xYb
xSbO
7(0.5≤x≤1) target and Y
3-xGa
xSbO
7(0.5≤x≤1) target is to ferromagnetic particle γ-Fe
2O
3, paramagnetic particle SiO
2Or anti-ferromagnetism particle MnO substrate surface, at γ-Fe
2O
3, SiO
2Or the different film of deposit thickness on the MnO substrate, the thin film deposition time is 90～120 minutes, above-mentioned six kinds of films are handled 60 ± 10min respectively at nitrogen or in argon gas under 1340 ± 10 ℃ and 1340 ± 10 ℃ of temperature, make it crystallization and obtain required magnetic compound catalyze material γ-Fe
2O
3-Y
3-xYb
xSbO
7(0.5≤x≤1), γ-Fe
2O
3-Y
3-xGa
xSbO
7(0.5≤x≤1), SiO
2-Y
3-xYb
xSbO
7(0.5≤x≤1), SiO
2-Y
3-xGa
xSbO
7(0.5≤x≤1), MnO-Y
3-xYb
xSbO
7(0.5≤x≤1) or MnO-Y
3-xGa
xSbO
7(0.5≤x≤1).
Or the method that adopts multi-target magnetic control sputtering to deposit:
A. target preparation: prepare simple metal Yb or Ga and Sb and Y metal targets, the target diameter is 5～6 centimetres;
B. choose substrate: select ferromagnetic particle γ-Fe for use
2O
3,, paramagnetic particle SiO
2Or anti-ferromagnetism particle MnO is as substrate;
C. adopt multi-target magnetic control sputtering, sputtering power is 60～200W, is protective atmosphere with the argon gas, and the pressure of argon gas and oxygen (purity is 99.99%) is 4～32mTorr, the flow-rate ratio (O of oxygen
2/ (O
2+ Ar)) and be 30%～50%, initial pressure is 3.3 * 10 in the settling chamber
-6Torr～1 * 10
-5Torr, target is 4～15 centimetres to the distance of substrate, and substrate temperature is 0～400 ℃, and film deposition rate is 1～2nm/min;
Cosputtering simple metal Y, Yb and Sb target are to ferromagnetic particle γ-Fe in the mist of oxygen and argon gas
2O
3, paramagnetic particle SiO
2Or anti-ferromagnetism particle MnO substrate surface, deposition forms Y on substrate
3-xYb
xSbO
7(0.5≤x≤1) rete is handled 60 ± 10min at 1340 ± 10 ℃ with above-mentioned three kinds of retes in nitrogen or argon gas; Make it crystallization and obtain required photochemical catalyst nucleocapsid structure γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) or MnO (anti-ferromagnetism granular core)-Y
3-xYb
xSbO
7(0.5≤x≤1).
Cosputtering simple metal Y, Ga and Sb target are to ferromagnetic particle γ-Fe in the mist of oxygen and argon gas
2O
3, paramagnetic particle SiO
2Or anti-ferromagnetism particle MnO substrate surface, deposition forms Y on substrate
3-xGa
xSbO
7(0.5≤x≤1) rete is handled 60 ± 10min at 1340 ± 10 ℃ with above-mentioned three kinds of retes in nitrogen or argon gas; Make it crystallization and obtain required γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1) or MnO (anti-ferromagnetism granular core)-Y
3-xGa
xSbO
7(0.5≤x≤1).
2, powder catalytic material Y
3-xYb
xSbO
7(0.5≤x≤1) and Y
3-xGa
xSbO
7The preparation method of (0.5≤x≤1): it is characterized in that (1) powder catalytic material Y
3-xYb
xSbO
7(0.5≤x≤1) or Y
3-xGa
xSbO
7The preparation of (0.5≤x≤1): adopt the method for high temperature solid-phase sintering to prepare Y
3-xYb
xSbO
7(0.5≤x≤1) or Y
3-xGa
xSbO
7(0.5≤x≤1) photocatalytic powder material; With purity 99.99% Y
2O
3, Yb
2O
3And Sb
2O
5Or Y
2O
3, Ga
2O
3And Sb
2O
5Be raw material, with Y, Yb and Sb or Y, Ga and Sb Y with the atomic ratio of described molecular formula
2O
3, Yb
2O
3And Sb
2O
5Or Y
2O
3, Ga
2O
3And Sb
2O
5Fully mix, then in grinding in ball grinder, the particle diameter of powder reaches the 1.4-1.8 micron, and 200 ± 40 ℃ of oven dry 4 ± 1 hours, compacting was put into high temperature sintering furnace and fired in flakes.Furnace temperature is risen to 700 ± 20 ℃, be incubated and cool off with stove after 8 ± 2 hours, it is the 1.3-1.6 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 730 ± 20 ℃, be incubated after 6 ± 1 hours and cool off with stove, it is the 1.2-1.5 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. at 400 ℃ of insulation 40 ± 10min; C. be warming up to 730 ℃ by 400 ℃, the heating-up time is 40 ± 10min; D. at 730 ℃ of insulation 480-800min; E. be warming up to 1340 ± 50 ℃ by 730 ℃, the heating-up time is 50 ± 10min; F. at 1340 ± 50 ℃ of insulation 3800 ± 400min, stove is cold.
With the stove cooling, it is the 0.06-0.32 micron that the taking-up pressed powder is crushed to particle diameter to pressed powder behind 1340 ± 50 ℃ of insulations of maximum temperature, 3800 ± 400min, finally prepares successfully pure Y
3-xYb
xSbO
7Or Y
3-xGa
xSbO
7(0.5≤x≤1) powder photocatalytic material;
(2) adopt sol-gel process to prepare powder photocatalytic material Y
3-xYb
xSbO
7(0.5≤x≤1) or Y
3-xGa
xSbO
7(0.5≤x≤1): utilize improved Sol-Gel method, adopt organometallic precursor, preparation Y
3-xYb
xSbO
7(0.5≤x≤1) and Y
3-xGa
xSbO
7(0.5≤x≤1).Presoma ytterbium acetate (Yb (CH
3CO
2)
3) or acetate gallium (Ga (CH
3CO
2)
3) and yttrium acetate hydrate (Y (CH
3CO
2)
3XH
2O) and antimony chloride (SbCl
5) be dissolved in the isopropyl alcohol, and with Y, Yb and Sb or Y, Ga and Sb atomic ratio with described molecular formula, utilize above-mentioned presoma according to the segmented process for preparing sol-gel, the preparation mixed oxide, 200 ± 30 ℃ of oven dry 3 ± 1 hours, compacting was put into high temperature sintering furnace and is fired in flakes then, the intensification condition is as follows: a. is warming up to 400 ℃ by 20 ℃, and the heating-up time is 40 ± 10min; B. at 400 ℃ of insulation 40 ± 10min; C. be warming up to 730 ℃ by 400 ℃, the heating-up time is 40 ± 10min; D. at 730 ℃ of insulation 480-800min; E. be warming up to 1050 ± 30 ℃ by 730 ℃, the heating-up time is 20 ± 10min; F. at 1050 ± 30 ℃ of insulation 2200 ± 400min, stove is cold.With the stove cooling, it is the 0.04-0.20 micron that the taking-up pressed powder is crushed to particle diameter to pressed powder behind 1050 ± 30 ℃ of insulations of maximum temperature, 2200 ± 400min, finally prepares successfully pure Y
3-xYb
xSbO
7(0.5≤x≤1) and Y
3-xGa
xSbO
7(0.5≤x≤1) powder photocatalytic material.
The invention has the beneficial effects as follows: successfully prepared powder catalytic material Y by physical method or sol-gel process
3-xYb
xSbO
7(0.5≤x≤1) and Y
3-xGa
xSbO
7(0.5≤x≤1) has prepared the γ-Fe of novel " magnetic-particle nuclear-photochemical catalyst shell " structure simultaneously
2O
3(ferromagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).And it a series of signs have been carried out, above-mentioned novel photocatalysis material under visible light or UV-irradiation, the degrade efficient and the mechanism of degradation of organic pollution in the contaminated water body have been studied, research decomposition water under visible light or UV-irradiation is produced the efficient and the optical activity of hydrogen, by magnetic field-light-catalyzed reaction system, promoted the gradient of composite magnetic catalysis material in organic wastewater to distribute, also promoted simultaneously the even distribution of magnetic composite photocatalyst material, and then promoted fully contacting of light source and organic pollution, greatly improved the degradation efficiency of organic pollution.
Description of drawings
Figure 1A is Y
2YbSbO
7XRD figure spectrum, Figure 1B. be Y
2GaSbO
7XRD figure spectrum.
Fig. 2 is Y
2YbSbO
7Actual measurement XRD data and simulation XRD data Rietveld software configuration refine collection of illustrative plates (: the XRD experimental data; ...: the XRD analogue data; The difference of---: XRD experimental data and analogue data; |: the reflection position that observes).
Fig. 3 is Y
2GaSbO
7Actual measurement XRD data and simulation XRD data Rietveld software configuration refine collection of illustrative plates (: the XRD experimental data; ...: the XRD analogue data; The difference of---: XRD experimental data and analogue data; |: the reflection position that observes).
Fig. 4 is Y
2YbSbO
7And Y
2GaSbO
7Diffuse reflection absorb collection of illustrative plates.
Fig. 5 is at Y
2YbSbO
7And Y
2GaSbO
7, (α hv)
2Concern collection of illustrative plates with hv.
Fig. 6 is under the radiation of visible light, with Y
2YbSbO
7And Y
2GaSbO
7The absorbance and the lambda1-wavelength that are obtained for the catalyst degradation rhodamine B concern collection of illustrative plates.
Fig. 7 is under radiation of visible light, with Y
2YbSbO
7And Y
2GaSbO
7For rhodamine B concentration and incident light irradiation time chart that the catalyst degradation rhodamine B is obtained are composed.
Fig. 8 is with Y under the radiation of visible light
2YbSbO
7And Y
2GaSbO
7The first order kinetics curve that is obtained for the catalyst degradation rhodamine B.
Fig. 9 is under the radiation of visible light, with Y
2YbSbO
7And Y
2GaSbO
7The CO that is obtained for the catalyst degradation rhodamine B
2Productive rate.
Figure 10 is under the radiation of visible light, with Y
2YbSbO
7And Y
2GaSbO
7During for the catalyst degradation rhodamine B, total organic carbon TOC and incident light irradiation time chart spectrum.
Figure 11 is Y
2YbSbO
7And Y
2GaSbO
7Band structure figure.
The specific embodiment
Powder catalytic material Y
3-xYb
xSbO
7(0.5≤x≤1) and Y
3-xGa
xSbO
7(0.5≤x≤1); In addition, the γ-Fe of novel " magnetic-particle nuclear-photochemical catalyst shell " structure
2O
3(ferromagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).
(1) preparation can be at the novel photocatalysis agent Y of visible light wave range or the response of ultraviolet light wave band
3-xYb
xSbO
7(0.5≤x≤1), Y
3-xGa
xSbO
7(0.5≤x≤1); Preparation can be at the γ-Fe of novel " magnetic-particle nuclear-photochemical catalyst shell " structure of visible light wave range or ultraviolet light wave band response
2O
3(ferromagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).Adopt ultraviolet-visible spectrophotometer and ultraviolet-visible diffuse spectrometer to the new catalyst of above-mentioned preparation visible light (or ultraviolet light) irradiation down the absorption spectra of generation measure, characterized its optical absorption property.Measured above-mentioned new catalyst x-ray photoelectron power spectrum (XPS), inquired into the electron structure feature on above-mentioned new catalyst surface and the transport mechanism in electronics and hole in the catalyst crystal under magnetic field effect, analyzed each microcell element of catalyst of magnetic-particle area load and formed, and binding isotherm result of calculation has been analyzed the level structure and the density of electronic states of above-mentioned new catalyst.
(2) adopt X-ray diffractometer (XRD) that above-mentioned new catalyst has been carried out material phase analysis; Adopt transmission electron microscope (TEM) to analyze the microstructure characteristic of above-mentioned new catalyst; Utilize ESEM (SEM) that above-mentioned new catalyst has been carried out tissue topography's analysis, and in conjunction with ESEM power spectrum (SEM-EDS) and x-ray photoelectron power spectrum (XPS) measured they become to be grouped into, disclosed the electron structure feature on new catalyst surface.Profound level has disclosed the influence rule of the microstructure of novel photocatalysis agent to photocatalysis degradation organic contaminant efficient.
Degraded water body inner dye under visible light (or ultraviolet light) irradiation, in the process of persistent organic pollutants such as Atrazine or pentachlorophenol, by liquid chromatography/mass spectrometry (LC/MS) combined instrument and ion chromatograph, intermediate product and the end product in the above-mentioned organic pollution process of degrading followed the tracks of in test, obtained under novel nuclear-shell magnetic composite catalyst particle effect, the possible approach of multiple organic pollution in the degraded water body has disclosed the water body inner dye under visible light (or ultraviolet light) irradiation, the degradation mechanism of organic pollution such as Atrazine or pentachlorophenol.
Adopt organic pollutions such as single wavelength visible light (or ultraviolet light) irradiation water body inner dye, Atrazine or pentachlorophenol, successfully derive photogenerated charge (light induced electron or the photohole) quantity that participates in the photocatalytic degradation reaction by experimental study result and theoretical calculating, and then derive visible light (or ultraviolet light) number of photons that participates in reaction, in conjunction with the total number of photons of the incident light that calculates, finally draw the photo-quantum efficiency of organic pollutions such as dyestuff, Atrazine or pentachlorophenol in the water body of under single wavelength visible light (or ultraviolet light) effect, degrading.
Table 1Y
2YbSbO
7The atomic structure parameter
Table 2Y
2GaSbO
7The atomic structure parameter
The specific embodiment
1. powder catalytic material Y
3-xYb
xSbO
7(0.5≤x≤1) and Y
3-xGa
xSbO
7The preparation were established of (0.5≤x≤1) is as follows:
(1) powder catalytic material Y
3-xYb
xSbO
7The preparation of (0.5≤x≤1): adopt the method for high temperature solid-phase sintering to prepare Y
3-xYb
xSbO
7(0.5≤x≤1) photocatalytic powder material.With purity 99.99% Y
2O
3, Yb
2O
3And Sb
2O
5Be raw material, with Y, Yb, Sb Y with the atomic ratio of described molecular formula
2O
3, Yb
2O
3And Sb
2O
5Fully mix, then in grinding in ball grinder, the particle diameter of powder reaches the 1.4-1.8 micron, and 200 ± 40 ℃ of oven dry 4 ± 1 hours, compacting was put into high temperature sintering furnace and fired in flakes.Furnace temperature is risen to 700 ± 20 ℃, be incubated and cool off with stove after 8 ± 2 hours, it is the 1.3-1.6 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 730 ± 20 ℃, be incubated after 6 ± 1 hours and cool off with stove, it is the 1.2-1.5 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. at 400 ℃ of insulation 40 ± 10min; C. be warming up to 730 ℃ by 400 ℃, the heating-up time is 40 ± 10min; D. at 730 ℃ of insulation 480-800min; E. be warming up to 1340 ± 50 ℃ by 730 ℃, the heating-up time is 50 ± 10min; F. at 1340 ± 50 ℃ of insulation 3800 ± 400min, stove is cold.
With the stove cooling, it is the 0.06-0.32 micron that the taking-up pressed powder is crushed to particle diameter to pressed powder behind 1340 ± 50 ℃ of insulations of maximum temperature, 3800 ± 400min, finally prepares successfully pure Y
3-xYb
xSbO
7(0.5≤x≤1) powder photocatalytic material.
(2) powder catalytic material Y
3-xGa
xSbO
7The preparation of (0.5≤x≤1): adopt the method for high temperature solid-phase sintering to prepare Y
3-xGa
xSbO
7(0.5≤x≤1) photocatalytic powder material.With purity 99.99% Y
2O
3, Ga
2O
3And Sb
2O
5Be raw material, with Y, Ga, Sb Y with the atomic ratio of described molecular formula
2O3, Ga
2O
3And Sb
2O
5Fully mix, then in grinding in ball grinder, the particle diameter of powder reaches the 1.4-1.8 micron, and 200 ± 40 ℃ of oven dry 4 ± 1 hours, compacting was put into high temperature sintering furnace and fired in flakes.Furnace temperature is risen to 700 ± 20 ℃, be incubated and cool off with stove after 8 ± 2 hours, it is the 1.3-1.6 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 730 ± 20 ℃, be incubated after 6 ± 1 hours and cool off with stove, it is the 1.2-1.5 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. at 400 ℃ of insulation 40 ± 10min; C. be warming up to 730 ℃ by 400 ℃, the heating-up time is 40 ± 10min; D. at 730 ℃ of insulation 480-800min; E. be warming up to 1340 ± 50 ℃ by 730 ℃, the heating-up time is 50 ± 10min; F. at 1340 ± 50 ℃ of insulation 3900 ± 400min, stove is cold.
With the stove cooling, it is the 0.06-0.31 micron that the taking-up pressed powder is crushed to particle diameter to pressed powder behind 1340 ± 50 ℃ of insulations of maximum temperature, 3900 ± 400min, finally prepares successfully pure Y
3-xGa
xSbO
7(0.5≤x≤1) powder photocatalytic material.
(3) adopt sol-gel process to prepare Y
3-xYb
xSbO
7(0.5≤x≤1) and Y
3-xGa
xSbO
7(0.5≤x≤1): change the Sol-Gel method that adopts by Garz-Tovar et al, adopt organometallic precursor, preparation Y
3-xYb
xSbO
7(0.5≤x≤1) and Y
3-xGa
xSbO
7(0.5≤x≤1).Buy presoma ytterbium acetate (Yb (CH
3CO
2)
3), acetate gallium (Ga (CH
3CO
2)
3), yttrium acetate hydrate (Y (CH
3CO
2)
3XH
2O), antimony chloride (SbCl
5) be dissolved in the isopropyl alcohol, utilize above-mentioned presoma according to the segmented process for preparing sol-gel, the preparation mixed oxide, 200 ± 30 ℃ of oven dry 3 ± 1 hours, compacting was put into high temperature sintering furnace and is fired in flakes then, and the intensification condition is as follows:.
A. be warming up to 400 ℃ by 20 ℃, the heating-up time is 40 ± 10min; B. at 400 ℃ of insulation 40 ± 10min; C. be warming up to 730 ℃ by 400 ℃, the heating-up time is 40 ± 10min; D. at 730 ℃ of insulation 480-800min; E. be warming up to 1050 ± 30 ℃ by 730 ℃, the heating-up time is 20 ± 10min; F. at 1050 ± 30 ℃ of insulation 2200 ± 400min, stove is cold.With the stove cooling, it is the 0.04-0.20 micron that the taking-up pressed powder is crushed to particle diameter to pressed powder behind 1050 ± 30 ℃ of insulations of maximum temperature, 2200 ± 400min, finally prepares successfully pure Y
3-xYb
xSbO
7(0.5≤x≤1) and Y
3-xGa
xSbO
7(0.5≤x≤1) powder photocatalytic material.
2. the preparation were established of the magnetic compound catalyze material of " magnetic-particle nuclear-photochemical catalyst shell " structure is as follows:
(1) γ-F
e2O
3(ferromagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell) and γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xGa
xSbO
7The preparation of (0.5≤x≤1) (photochemical catalyst shell):
Adopt the method for pulsed laser deposition deposition:
A. target preparation: the method by the above-mentioned solid phase sintering prepares Y
3-xYb
xSbO
7(0.5≤x≤1) target and Y
3-xGa
xSbO
7(0.5≤x≤1) target, the target diameter is 10mm, thickness is 2mm;
B. choose substrate: select ferromagnetic particle γ-Fe for use
2O
3As substrate;
C. adopt pulsed laser deposition deposition instrument, laser main wave is long to be 248nm, and laser power density is 2～3J/cm
2, be protective atmosphere with nitrogen, the pressure of nitrogen and oxygen (purity is 99.99%) is 8～10Pa, initial pressure is 6 * 10 in the settling chamber
-5Pa～2 * 10
-3Pa, target is 3～7 centimetres to the distance of substrate, substrate temperature is 300～700 ℃, respectively sputter Y
3-xYb
xSbO
7(0.5≤x≤1) target and Y
3-xGa
xSbO
7(0.5≤x≤1) target is to γ-Fe
2O
3Substrate surface is at γ-Fe
2O
3The different film of deposit thickness on the substrate, the thin film deposition time is 90～120 minutes, above-mentioned two kinds of films are handled 60 ± 10min respectively at nitrogen or in argon gas under 1340 ± 10 ℃ and 1340 ± 10 ℃ of temperature, make it crystallization and obtain required magnetic compound catalyze material γ-Fe
2O
3-Y
3-xYb
xSbO
7(0.5≤x≤1) and γ-Fe
2O
3-Y
3-xGa
xSbO
7(0.5≤x≤1).
Adopt the method for multi-target magnetic control sputtering deposition:
A. target preparation: prepare simple metal Yb, Ga, Sb, Y metal targets, the target diameter is 5～6 centimetres;
B. choose substrate: select ferromagnetic particle γ-Fe for use
2O
3As substrate;
C. adopt the multi-target magnetic control sputtering instrument, sputtering power is 60～200W, is protective atmosphere with the argon gas, and the pressure of argon gas and oxygen (purity is 99.99%) is 4～32mTorr, the flow-rate ratio (O of oxygen
2/ (O
2+ Ar)) and be 30%～50%, initial pressure is 3.3 * 10 in the settling chamber
-6Torr～1 * 10
-5Torr, target is 4～15 centimetres to the distance of substrate, and substrate temperature is 0～400 ℃, and film deposition rate is 1～2nm/min.Cosputtering simple metal Y, Yb and Sb target are to γ-Fe in the mist of oxygen and argon gas
2O
3Substrate surface, deposition forms Y on substrate
3-xYb
xSbO
7(0.5≤x≤1) rete is handled 60 ± 10min at 1340 ± 10 ℃ with this rete in nitrogen or argon gas; Make it crystallization and obtain required γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell); Cosputtering simple metal Y, Ga and Sb target are to γ-Fe in the mist of oxygen and argon gas
2O
3Substrate surface, deposition forms Y on substrate
3-xGa
xSbO
7(0.5≤x≤1) rete is handled 60 ± 10min at 1340 ± 10 ℃ with this rete in nitrogen or argon gas; Make it crystallization and obtain required γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).
(2) SiO
2(paramagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell) and SiO
2(paramagnetic particle nuclear)-Y
3-xGa
xSbO
7The preparation of (0.5≤x≤1) (photochemical catalyst shell):
Adopt the method for pulsed laser deposition deposition:
A. target preparation: the method by the above-mentioned solid phase sintering prepares Y
3-xYb
xSbO
7(0.5≤x≤1) target and Y
3-xGa
xSbO
7(0.5≤x≤1) target, the target diameter is 10mm, thickness is 2mm;
B. choose substrate: select paramagnetic particle SiO for use
2As substrate;
C. adopt pulsed laser deposition deposition instrument, laser main wave is long to be 248nm, and laser power density is 2～3J/cm
2, be protective atmosphere with nitrogen, the pressure of nitrogen and oxygen (purity is 99.99%) is 8～10Pa, initial pressure is 6 * 10 in the settling chamber
- -5Pa～2 * 10
-3Pa, target is 3～7 centimetres to the distance of substrate, substrate temperature is 300～700 ℃, respectively sputter Y
3-xYb
xSbO
7(0.5≤x≤1) target and Y
3-xGa
xSbO
7(0.5≤x≤1) target is to SiO
2Substrate surface is at SiO
2The different film of deposit thickness on the substrate, the thin film deposition time is 90～120 minutes, above-mentioned two kinds of films are handled 60 ± 10min respectively at nitrogen or in argon gas under 1340 ± 10 ℃ and 1340 ± 10 ℃ of temperature, make it crystallization and obtain required magnetic compound catalyze material SiO
2-Y
3-xYb
xSbO
7(0.5≤x≤1) and SiO
2-Y
3-xGa
xSbO
7(0.5≤x≤1).
Adopt the method for multi-target magnetic control sputtering deposition:
A. target preparation: prepare simple metal Yb, Ga, Sb, Y metal targets, the target diameter is 5～6 centimetres;
B. choose substrate: select paramagnetic particle SiO for use
2As substrate;
C. adopt the multi-target magnetic control sputtering instrument, sputtering power is 60～200W, is protective atmosphere with the argon gas, and the pressure of argon gas and oxygen (purity is 99.99%) is 4～32mTorr, the flow-rate ratio (O of oxygen
2/ (O
2+ Ar)) and be 30%～50%, initial pressure is 3.3 * 10 in the settling chamber
-6Torr～1 * 10
-5Torr, target is 4～15 centimetres to the distance of substrate, and substrate temperature is 0～400 ℃, and film deposition rate is 1～2nm/min.Cosputtering simple metal Y, Yb and Sb target are to SiO in the mist of oxygen and argon gas
2Substrate surface, deposition forms Y on substrate
3-xYb
xSbO
7(0.5≤x≤1) rete is handled 60 ± 10min at 1340 ± 10 ℃ with this rete in nitrogen or argon gas; Make it crystallization and obtain required SiO
2(paramagnetic particle nuclear)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell); Cosputtering simple metal Y, Ga and Sb target are to SiO in the mist of oxygen and argon gas
2Substrate surface, deposition forms Y on substrate
3-xGa
xSbO
7(0.5≤x≤1) rete is handled 60 ± 10min at 1340 ± 10 ℃ with this rete in nitrogen or argon gas; Make it crystallization and obtain required SiO
2(paramagnetic particle nuclear)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).
(3) MnO (anti-ferromagnetism granular core)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
3-xGa
xSbO
7The preparation of (0.5≤x≤1) (photochemical catalyst shell):
Adopt the method for pulsed laser deposition deposition:
A. target preparation: the method by the above-mentioned solid phase sintering prepares Y
3-xYb
xSbO
7(0.5≤x≤1) target and Y
3-xGa
xSbO
7(0.5≤x≤1) target, the target diameter is 10mm, thickness is 2mm;
B. choose substrate: select for use anti-ferromagnetism particle MnO as substrate;
C. adopt pulsed laser deposition deposition instrument, laser main wave is long to be 248nm, and laser power density is 2～3J/cm
2, be protective atmosphere with nitrogen, the pressure of nitrogen and oxygen (purity is 99.99%) is 8～10Pa, initial pressure is 6 * 10 in the settling chamber
-5Pa～2 * 10
-3Pa, target is 3～7 centimetres to the distance of substrate, substrate temperature is 300～700 ℃, respectively sputter Y
3-xYb
xSbO
7(0.5≤x≤1) target and Y
3-xGa
xSbO
7(0.5≤x≤1) target is to the MnO substrate surface, the different film of deposit thickness on MnO particle substrate, the thin film deposition time is 90～120 minutes, above-mentioned two kinds of films are handled 60 ± 10min respectively at nitrogen or in argon gas under 1340 ± 10 ℃ and 1340 ± 10 ℃ of temperature, make it crystallization and obtain required magnetic compound catalyze material MnO-Y
3-xYb
xSbO
7(0.5≤x≤1) and MnO-Y
3-xGa
xSbO
7(0.5≤x≤1).
Adopt the method for multi-target magnetic control sputtering deposition:
A. target preparation: prepare simple metal Yb, Ga, Sb, Y metal targets, the target diameter is 5～6 centimetres;
B. choose substrate: select for use anti-ferromagnetism particle MnO as substrate;
C. adopt the multi-target magnetic control sputtering instrument, sputtering power is 60～200W, is protective atmosphere with the argon gas, and the pressure of argon gas and oxygen (purity is 99.99%) is 4～32mTorr, the flow-rate ratio (O of oxygen
2/ (O
2+ Ar)) and be 30%～50%, initial pressure is 3.3 * 10 in the settling chamber
-6Torr～1 * 10
-5Torr, target is 4～15 centimetres to the distance of substrate, and substrate temperature is 0～400 ℃, and film deposition rate is 1～2nm/min.Cosputtering simple metal Y, Yb and Sb target are to MnO particle substrate surface in the mist of oxygen and argon gas, and deposition forms Y on substrate
3-xYb
xSbO
7(0.5≤x≤1) rete is handled 60 ± 10min at 1340 ± 10 ℃ with this rete in nitrogen or argon gas; Make it crystallization and obtain required MnO (anti-ferromagnetism granular core)-Y
3-xYb
xSbO
7(0.5≤x≤1) (photochemical catalyst shell); Cosputtering simple metal Y, Ga and Sb target are to the MnO substrate surface in the mist of oxygen and argon gas, and deposition forms Y on substrate
3-xGa
xSbO
7(0.5≤x≤1) rete is handled 60 ± 10min at 1340 ± 10 ℃ with this rete in nitrogen or argon gas; Make it crystallization and obtain required MnO (anti-ferromagnetism granular core)-Y
3-xGa
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).
3. the method for building up of magnetic field-light-catalyzed reaction system
The application of the catalysis material of nucleocapsid structure, by the reaction system degrading waste water that magnetic field device and catalysis material constitute, magnetic field device is the adjustable alternating magnetic field generator of intensity, and magnetic field intensity is chosen 0.3～1T (tesla), and light source is xenon lamp or high-pressure sodium lamp; Adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2YbSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2YbSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2YbSbO
7(photochemical catalyst shell) is as catalyst, or employing γ-Fe
2O
3-Y
2GaSbO
7, SiO
2-Y
2GaSbO
7, MnO-Y
2GaSbO
7The percent by volume of above-mentioned three kinds of magnetic composite photocatalyst materials respectively accounts for 1/3rd, above-mentioned three kinds of magnetic composite catalyst particles distribution gradient in the aqueous solution, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution, the employing edge filter (λ＞420nm), and adopt oxygenic aeration simultaneously.Overall optical is carried out according to being reflected under the airtight lighttight environment.Magnetic field intensity also can be 0.05～1.5T (tesla).Light source is 300W xenon lamp and 400W high-pressure sodium lamp.Typical hardly degraded organic substance pentachlorophenol Pentachlorophenol, dyestuff and Atrazine Atrazine are as the target degradation product in the selection water.
By magnetic field control composite magnetic particle distribution gradient in containing aqueous organic, utilize the magnetic-particle nuclear of different magnetic (ferromagnetism, paramagnetism and anti-ferromagnetism) to coat the novel photocatalysis agent, these magnetic compound catalyze materials can promote the mixing of similar magnetic-particle under the directional magnetic field effect, avoid particle agglomeration, make the magnetic compound catalyze material be evenly distributed on upper, middle and lower-ranking in the aqueous solution in the aqueous solution thereby it is evenly dispersed in fully.Also can apply magnetostatic field and alternating magnetic field as required flexibly, can in very big length and composition range, adjust the distribution of ferromagnetism and weak magnetic-particle easily, and then the surface coated photochemical catalyst of magnetic-particle can fully be contacted with organic pollution and light source, organic pollution can be degraded expeditiously under visible light (or ultraviolet light) irradiation.
The application of nucleocapsid structure catalysis material also is to pass through Y
2YbSbO
7Or Y
2GaSbO
7Powder is a catalyst, or the difference supporting Pt, NiO and RuO
2Cocatalyst, light source are xenon lamp or high-pressure sodium lamp, carry out decomposition water and produce hydrogen in the airtight glass piping interior lighting reactor by a plurality of valve controls.
4.Y
2YbSbO
7And Y
2GaSbO
7Performance characterization
Learn Y by XRD, XPS result
2YbSbO
7And Y
2GaSbO
7Be all single-phasely, and experiment original material height is pure, does not have any impurity phase.
Measure Y by Xray fluorescence spectrometer
2YbSbO
7The average atom molar percentage be Y: Yb: Sb: O=2.00: 0.98: 1.01: 6.97.With Rietveld software to Y
2YbSbO
7XRD result carry out structure refinement, structure refinement factor R P value is R
P=10.09%.Y
2YbSbO
7Space group be Fd-3m, structure is a cubic system, pyrochlore constitution, cell parameter a are 10.49977 (8)
Y
2YbSbO
7The indices of crystallographic plane such as (222) of each diffraction maximum, (400), (440), (622), (444), (800), (662), (840), (844) are demarcated.Y
2YbSbO
7In each atoms in space atom site parameter be determined (seeing Table 1).Adopt UV, visible light to diffuse spectrometer to Y
2YbSbO
7The characteristic absorption limit that produces under the irradiation of light is measured, and obtains Y
2YbSbO
7Band gap width be 2.521eV, obtain Y
2YbSbO
7Band structure, conduction band is made of the 4d track of Y, the 4f track of Yb and the 5p track of Sb, valence band is made of the 2p track of O.
Measure Y by Xray fluorescence spectrometer
2GaSbO
7The average atom molar percentage be Y: Ga: Sb: O=2.00: 0.97: 1.02: 6.99.With Rietveld software to Y
2GaSbO
7XRD result carry out structure refinement, the structure refinement factor R
PValue is R
P=12.36%.Y
2GaSbO
7Space group be Fd-3m, structure is a cubic system, pyrochlore constitution, cell parameter a are 10.17981 (1)
Y
2GaSbO
7The indices of crystallographic plane such as (222) of each diffraction maximum, (400), (440), (622), (444), (800), (662), (840), (844) are demarcated.Y
2GaSbO
7In each atoms in space atom site parameter be determined (seeing Table 2).Adopt UV, visible light to diffuse spectrometer to Y
2GaSbO
7The characteristic absorption limit that produces under the irradiation of light is measured, and obtains Y
2GaSbO
7Band gap width be 3.322eV, obtain Y
2GaSbO
7Band structure, conduction band is made of the 4d track of Y, the 4p track of Ga and the 5p track of Sb, valence band is made of the 2p track of O.
Application example
1. adopt Y
2GaSbO
7Atrazine in the powder degrading waste water
With Y
2GaSbO
7Powder 0.8g puts into the 300mL Atrazine aqueous solution and forms suspension system, and the initial concentration of the Atrazine aqueous solution is 0.1mmol L
-1, initial pH value is 7.Choose the xenon lamp irradiation Atrazine 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, the clearance of Atrazine was 92.2%, and photo-quantum efficiency is 0.31%, and the clearance of total organic carbon TOC (mineralization rate) reaches 88.3%.
2. adopt Y
2YbSbO
7Atrazine in the powder degrading waste water
With Y
2YbSbO
7Powder 0.8g puts into the 300mL Atrazine aqueous solution and forms suspension system, and the initial concentration of the Atrazine aqueous solution is 0.1mmol L
-1, initial pH value is 7.Choose the xenon lamp irradiation Atrazine 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, the clearance of Atrazine was 89.3%, and photo-quantum efficiency is 0.29%, and the clearance of total organic carbon TOC (mineralization rate) reaches 86.2%.
3. adopt Y
2GaSbO
7Pentachlorophenol in the powder degrading waste water
With Y
2GaSbO
7Powder 0.8g puts into the 300mL pentachlorophenol aqueous solution and forms suspension system, and the initial concentration of the pentachlorophenol aqueous solution is 0.1mmol L
-1, initial pH value is 7.Choose the xenon lamp irradiation pentachlorophenol 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, the clearance of pentachlorophenol was 93.4%, and photo-quantum efficiency is 0.33%, and the clearance of total organic carbon TOC (mineralization rate) reaches 89.1%.
4. adopt Y
2YbSbO
7Pentachlorophenol in the powder degrading waste water
With Y
2YbSbO
7Powder 0.8g puts into the 300mL pentachlorophenol aqueous solution and forms suspension system, and the initial concentration of the pentachlorophenol aqueous solution is 0.1mmol L
-1, initial pH value is 7.Choose the xenon lamp irradiation pentachlorophenol 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, the clearance of pentachlorophenol was 91.2%, and photo-quantum efficiency is 0.30%, and the clearance of total organic carbon TOC (mineralization rate) reaches 88.6%.
5. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2GaSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2GaSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2GaSbO
7Atrazine in (photochemical catalyst shell) degrading waste water utilizes homemade magnetic field-light-catalyzed reaction system, and by the adjustable alternating magnetic field generator of magnetic field intensity, magnetic field intensity is chosen 0.3～0.6T (tesla).Light source is the 300W xenon lamp.Adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2GaSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2GaSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2GaSbO
7(photochemical catalyst shell) as catalyst, the percent by volume of above-mentioned three kinds of magnetic composite photocatalyst materials respectively accounts for 1/3rd, and the Atrazine of selecting typical difficult degradation in the water is as the target degradation product.When magnetic field intensity is 0.3～0.6 tesla, above-mentioned three kinds of magnetic composite catalyst particles distribution gradient in containing the aqueous solution of Atrazine, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Select the 900mL Atrazine aqueous solution, the Y of all magnetic-particle surface-coated simultaneously this moment
2GaSbO
7Weight is near 2.4g, and the initial concentration of the Atrazine aqueous solution is 0.1mmol L
-1, initial pH value is 7.Choose the xenon lamp irradiation Atrazine solution of 300W, mix edge filter (λ＞420nm).In the experimentation, adopt oxygenic aeration equally.Overall optical is carried out according to being reflected under the airtight lighttight environment.Apply magnetostatic field and alternating magnetic field at last flexibly, the surface coated photochemical catalyst of magnetic-particle can fully be contacted with organic pollution and light source, at radiation of visible light after 400 minutes, the clearance of Atrazine reaches 96.8%, photo-quantum efficiency is 0.33%, and the clearance of total organic carbon TOC (mineralization rate) reaches 93.2%.
6. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2YbSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2YbSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2YbSbO
7Atrazine in (photochemical catalyst shell) degrading waste water
Utilize homemade magnetic field-light-catalyzed reaction system, by the adjustable alternating magnetic field generator of magnetic field intensity, magnetic field intensity is chosen 0.3～0.6T (tesla).Light source is the 300W xenon lamp.Adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2YbSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2YbSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2YbSbO
7(photochemical catalyst shell) as catalyst, the percent by volume of above-mentioned three kinds of magnetic composite photocatalyst materials respectively accounts for 1/3rd, and the Atrazine of selecting typical difficult degradation in the water is as the target degradation product.When magnetic field intensity is 0.3～0.6 tesla, above-mentioned three kinds of magnetic composite catalyst particles distribution gradient in containing the aqueous solution of Atrazine, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Select the 900mL Atrazine aqueous solution, the Y of all magnetic-particle surface-coated simultaneously this moment
2YbSbO
7Weight is near 2.4g, and the initial concentration of the Atrazine aqueous solution is 0.1mmol L
-1, initial pH value is 7.Choose the xenon lamp irradiation Atrazine solution of 300W, mix edge filter (λ＞420nm).In the experimentation, adopt oxygenic aeration equally.Overall optical is carried out according to being reflected under the airtight lighttight environment.Apply magnetostatic field and alternating magnetic field at last flexibly, the surface coated photochemical catalyst of magnetic-particle can fully be contacted with organic pollution and light source, at radiation of visible light after 400 minutes, the clearance of Atrazine reaches 93.5%, photo-quantum efficiency is 0.31%, and the clearance of total organic carbon TOC (mineralization rate) reaches 90.4%.
7. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2GaSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2GaSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2GaSbO
7Pentachlorophenol in (photochemical catalyst shell) degrading waste water
Utilize homemade magnetic field-light-catalyzed reaction system, by the adjustable alternating magnetic field generator of magnetic field intensity, magnetic field intensity is chosen 0.3～0.6T (tesla).Light source is the 300W xenon lamp.Adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2GaSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2GaSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2GaSbO
7(photochemical catalyst shell) as catalyst, the percent by volume of above-mentioned three kinds of magnetic composite photocatalyst materials respectively accounts for 1/3rd, and the pentachlorophenol of selecting typical difficult degradation in the water is as the target degradation product.When magnetic field intensity is 0.3～0.6 tesla, above-mentioned three kinds of magnetic composite catalyst particles distribution gradient in containing the aqueous solution of pentachlorophenol, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Select the 900mL pentachlorophenol aqueous solution, the Y of all magnetic-particle surface-coated simultaneously this moment
2GaSbO
7Weight is near 2.4g, and the initial concentration of the pentachlorophenol aqueous solution is 0.1mmol L
-1, initial pH value is 7.Choose the xenon lamp irradiation pentachlorophenol solution of 300W, mix edge filter (λ＞420nm).In the experimentation, adopt oxygenic aeration equally.Overall optical is carried out according to being reflected under the airtight lighttight environment.Apply magnetostatic field and alternating magnetic field at last flexibly, the surface coated photochemical catalyst of magnetic-particle can fully be contacted with organic pollution and light source, at radiation of visible light after 400 minutes, the clearance of pentachlorophenol reaches 96.7%, photo-quantum efficiency is 0.35%, and the clearance of total organic carbon TOC (mineralization rate) reaches 93.4%.
8. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2YbSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2YbSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2YbSbO
7Pentachlorophenol in (photochemical catalyst shell) degrading waste water
Utilize homemade magnetic field-light-catalyzed reaction system, by the adjustable alternating magnetic field generator of magnetic field intensity, magnetic field intensity is chosen 0.3～0.6T (tesla).Light source is the 300W xenon lamp.Adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2YbSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2YbSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2YbSbO
7(photochemical catalyst shell) as catalyst, the percent by volume of above-mentioned three kinds of magnetic composite photocatalyst materials respectively accounts for 1/3rd, and the pentachlorophenol of selecting typical difficult degradation in the water is as the target degradation product.When magnetic field intensity is 0.3～0.6 tesla, above-mentioned three kinds of magnetic composite catalyst particles distribution gradient in containing the aqueous solution of pentachlorophenol, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Select the 900mL pentachlorophenol aqueous solution, the Y of all magnetic-particle surface-coated simultaneously this moment
2YbSbO
7Weight is near 2.4g, and the initial concentration of the pentachlorophenol aqueous solution is 0.1mmol L
-1, initial pH value is 7.Choose the xenon lamp irradiation pentachlorophenol solution of 300W, mix edge filter (λ＞420nm).In the experimentation, adopt oxygenic aeration equally.Overall optical is carried out according to being reflected under the airtight lighttight environment.Apply magnetostatic field and alternating magnetic field at last flexibly, the surface coated photochemical catalyst of magnetic-particle can fully be contacted with organic pollution and light source, at radiation of visible light after 400 minutes, the clearance of pentachlorophenol reaches 94.3%, photo-quantum efficiency is 0.32%, and the clearance of total organic carbon TOC (mineralization rate) reaches 91.5%.
9. adopt Y
2GaSbO
7Decomposition water is produced hydrogen
Carry out decomposition water and produce the hydrogen experiment 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, in the 300mL pure water, put into Y
2GaSbO
7Powder 0.8g.The hydrogen yield that overflows adopts the gas chromatograph-mass spectrometer (GC-MS) that has TCD to measure, and this gas chromatograph-mass spectrometer (GC-MS) 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 762.4 micromoles, and the output of oxygen is 378.5 micromoles; After 24 hours, the output of hydrogen is 2148.8 micromoles under high voltage mercury lamp radiation, and the output of oxygen is 1069.2 micromoles.
With Y
2GaSbO
7Powder is a catalyst, difference supporting Pt, NiO and RuO
2The cocatalyst decomposition water is produced hydrogen, and incident light dominant wavelength is λ=360nm, catalyst 0.8g, pure water 300mL, 50mL CH
3OH, light source is the 400W high-pressure sodium lamp, with 0.2wt%-Pt/Y
2GaSbO
7Be composite catalyst, the output of hydrogen is 5.46mmol after 24 hours; With 1.0wt%-NiO/Y
2GaSbO
7Be composite catalyst, the output of hydrogen is 4.12mmol after 24 hours; With 1.0wt%-RuO
2/ Y
2GaSbO
7Be composite catalyst, the output of hydrogen is 3.18mmol after 24 hours.
10. adopt Y
2YbSbO
7Decomposition water is produced hydrogen
Carry out decomposition water and produce the hydrogen experiment 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, in the 300mL pure water, put into Y
2YbSbO
7Powder 0.8g.The hydrogen yield that overflows adopts the gas chromatograph-mass spectrometer (GC-MS) that has TCD to measure, and this gas chromatograph-mass spectrometer (GC-MS) 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 658.6 micromoles, and the output of oxygen is 326.1 micromoles; After 24 hours, the output of hydrogen is 1836.5 micromoles under high voltage mercury lamp radiation, and the output of oxygen is 915.8 micromoles.
With Y
2YbSbO
7Powder is a catalyst, difference supporting Pt, NiO and RuO
2The cocatalyst decomposition water is produced hydrogen, and incident light dominant wavelength is λ=360nm, catalyst 0.8g, pure water 300mL, 50mL CH
3OH, light source is the 400W high-pressure sodium lamp, with 0.2wt%-Pt/Y
2YbSbO
7Be composite catalyst, the output of hydrogen is 4.72mmol after 24 hours; With 1.0wt%-NiO/Y
2YbSbO
7Be composite catalyst, the output of hydrogen is 3.89mmol after 24 hours; With 1.0wt%-RuO
2/ Y
2YbSbO
7Be composite catalyst, the output of hydrogen is 2.63mmol after 24 hours.
Claims (4)
1. the catalysis material of nucleocapsid structure is characterized in that using following structural formula: γ-Fe
2O
3-Y
3-xYb
xSbO
7(0.5≤x≤1), γ-Fe
2O
3-Y
3-xGa
xSbO
7(0.5≤x≤1), SiO
2-Y
3-xYb
xSbO
7(0.5≤x≤1), SiO
2-Y
3-xGa
xSbO
7(0.5≤x≤1), MnO-Y
3-xYb
xSbO
7(0.5≤x≤1) or MnO-Y
3-xGa
xSbO
7(0.5≤x≤1), γ-Fe
2O
3, SiO
2With the particle diameter of MnO be the 0.06-2 micron, Y
3-xYb
xSbO
7, Y
3-xGa
xSbO
7Parcel back particle diameter is the 0.07-2.1 micron.
2. catalysis material is characterized in that structural formula: Y
3-xYb
xSbO
7(0.5≤x≤1) and Y
3-xGa
xSbO
7(0.5≤x≤1), the particle diameter of above-mentioned powder are the 0.04-0.32 micron.
3. the application of the catalysis material of nucleocapsid structure, it is characterized in that reaction system degrading waste water by magnetic field device and catalysis material formation, magnetic field device is the adjustable alternating magnetic field generator of intensity, and magnetic field intensity is chosen 0.3～0.6T, and light source is xenon lamp or high-pressure sodium lamp; Adopt γ-Fe
2O
3-Y
2YbSbO
7, SiO
2-Y
2YbSbO
7And MnO-Y
2YbSbO
7As catalyst, or adopt γ-Fe
2O
3-Y
2GaSbO
7, SiO
2-Y
2GaSbO
7, MnO-Y
2GaSbO
7The percent by volume of above-mentioned three kinds of magnetic composite photocatalyst materials respectively accounts for 1/3rd, above-mentioned three kinds of magnetic composite catalyst particles distribution gradient in the aqueous solution, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution, adopt edge filter, λ＞420nm, and adopt oxygenic aeration simultaneously.Overall optical is carried out according to being reflected under the airtight lighttight environment.
4. the application of the catalysis material of nucleocapsid structure is characterized in that passing through Y
2YbSbO
7Or Y
2GaSbO
7Powder is a catalyst, or the difference supporting Pt, NiO and RuO
2Cocatalyst, light source are xenon lamp or high-pressure sodium lamp, carry out decomposition water and produce hydrogen in the airtight glass piping interior lighting reactor by a plurality of valve controls.
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| CN102107139A (en) * | 2011-01-31 | 2011-06-29 | 南京大学 | Core-shell structure ferrum-yttrium-stibium-based composite magnetic-particle photocatalyst, and preparation and application thereof |
| CN102107140A (en) * | 2011-01-31 | 2011-06-29 | 南京大学 | Indium, ferrum and stibium composite magnetic-particle optical catalyst of nuclear-shell structure as well as preparation and application thereof |
| CN102139210A (en) * | 2011-02-23 | 2011-08-03 | 南京大学 | Gadolinium-ytterbium-stibium based composite magnetic particle photocatalyst with core-shell structure, preparation and application |
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| CN102107139A (en) * | 2011-01-31 | 2011-06-29 | 南京大学 | Core-shell structure ferrum-yttrium-stibium-based composite magnetic-particle photocatalyst, and preparation and application thereof |
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| CN102139208A (en) * | 2011-02-23 | 2011-08-03 | 南京大学 | Niobium bismuth yttrium-based composite magnetic particle photocatalysts with core-shell structures as well as preparation methods and applications thereof |
| CN102145288A (en) * | 2011-02-23 | 2011-08-10 | 南京大学 | Bismuth iron niobium-based composite magnetic particle photocatalyst with core-shell structure, preparation and application of bismuth iron niobium-based composite magnetic particle photocatalyst |
| CN102151572A (en) * | 2011-02-23 | 2011-08-17 | 南京大学 | Iron-gadolinium-antimony based composite magnetic particle photo-catalyst in core-shell structure as well as preparation and application thereof |
| CN102166513A (en) * | 2011-02-23 | 2011-08-31 | 南京大学 | Antimony, ytterbium and indium based composite magnetic particle photocatalyst with core-shell structure, preparation and application |
| CN102188968A (en) * | 2011-02-23 | 2011-09-21 | 南京大学 | Core-shell constructed indium-yttrium-antimony-based composite magnetic particle photocatalyst, its preparation and its application |
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