CN101850255B - 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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- CN101850255B CN101850255B CN2010101957816A CN201010195781A CN101850255B CN 101850255 B CN101850255 B CN 101850255B CN 2010101957816 A CN2010101957816 A CN 2010101957816A CN 201010195781 A CN201010195781 A CN 201010195781A CN 101850255 B CN101850255 B CN 101850255B
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- 239000003054 catalyst Substances 0.000 title claims description 133
- 239000006249 magnetic particle Substances 0.000 title abstract description 22
- 230000003287 optical effect Effects 0.000 title abstract description 4
- 239000002131 composite material Substances 0.000 title description 11
- 239000002245 particle Substances 0.000 claims abstract description 96
- 230000005291 magnetic effect Effects 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims abstract description 55
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 21
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000005286 illumination Methods 0.000 claims abstract description 11
- 229910001566 austenite Inorganic materials 0.000 claims description 47
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 38
- 238000006555 catalytic reaction Methods 0.000 claims description 33
- 230000008878 coupling Effects 0.000 claims description 21
- 238000010168 coupling process Methods 0.000 claims description 21
- 238000005859 coupling reaction Methods 0.000 claims description 21
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- 238000005273 aeration Methods 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 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 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 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
- 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
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- 239000000843 powder Substances 0.000 description 58
- 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
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- 238000002360 preparation method Methods 0.000 description 29
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- 229910052760 oxygen Inorganic materials 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
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- 230000001699 photocatalysis Effects 0.000 description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 21
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- 229910052769 Ytterbium Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 9
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- 239000013077 target material Substances 0.000 description 8
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000005056 compaction Methods 0.000 description 6
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- 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 5
- 238000001816 cooling Methods 0.000 description 5
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- 230000000694 effects Effects 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
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- 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
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- 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
- 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
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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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Classifications
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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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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 photocatalyst, 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 of photochemical catalyzing hydrogen making.
Background technology
The processing of poisonous refractory organic (PTS) is difficult point, the hot subject in the water treatment field always in the water.PTS has pair human body and Ecological Environment Risk high, 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 novel process technology of refractory organic becomes focus and the advanced subject of 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 organic 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 obvious advantage at the aspects such as mineralising decomposition of refractory organic than electro-catalysis, catalytic wet oxidation technology.But photocatalysis technology is not yet industrialization in water treatment and wastewater treatment, mainly have following two problems: (1) suspension system photocatalysis system photocatalysis efficiency is high, 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 absorbing 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 that solves photochemical catalyst under the prerequisite that guarantees higher photocatalysis efficiency has become the key of photocatalysis wastewater treatment industry application with the quantum efficiency problem.
At present, the light utilization efficiency of raising photochemical catalyst mainly contains both direction.The one, TiO 2 visible light partly replaces oxygen element in the titanium dioxide such as nonmetalloids such as N, S, C, can reduce the band-gap energy of catalysis material, has expanded its photoresponse scope, has improved to a certain extent photo-quantum efficiency; The 2nd, research and develop efficient visible light catalyst.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 effectively degradation water and airborne formaldehyde, acetaldehyde, methylene blue and H
2The novel photocatalysis material of the nuisances such as S.Zhu Yongfa, Zhao Jincai etc. utilize homemade new material (such 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
7Powder photocatalytic degradation water body Methylene Blue dyestuff, methylene blue is by degradable 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 reporting 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 significant economic benefit, 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
7Particle diameter is the 0.07-2.1 micron behind the parcel.
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 Gas Sensor Films Deposited by Pulsed Laser Deposition:
A. preparation of target materials: 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
2O
3, paramagnetic particle SiO
2Or anti-ferromagnetism particle MnO is as substrate;
C. adopt Gas Sensor Films Deposited by Pulsed Laser Deposition, laser main wave is long to be 248nm, and laser power density is 2～3J/cm
2, take nitrogen as protective atmosphere, 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 processed 60 ± 10min respectively at nitrogen or in argon gas under 1340 ± 10 ℃ and 1340 ± 10 ℃ of temperature, make it crystallization and obtain required magnetic coupling catalysis 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. preparation of target materials: 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
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, and take argon gas as protective atmosphere, 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, form Y in the substrate deposition
3-xYb
xSbO
7(0.5≤x≤1) rete is processed 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, form Y in the substrate deposition
3-xGa
xSbO
7(0.5≤x≤1) rete is processed 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; Take the Y of purity as 99.99%
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 the 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, Elevated Temperature Conditions 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, finally is successfully prepared pure Y behind 1340 ± 50 ℃ of insulations of maximum temperature, 3800 ± 400min
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 acetic acid 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 the Sb atomic ratio with described molecular formula, utilize above-mentioned presoma according to the segmented process for preparing sol-gel, the preparation mixed oxide, then 200 ± 30 ℃ of oven dry 3 ± 1 hours, compacting was put into high temperature sintering furnace and is fired in flakes, Elevated Temperature Conditions 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, finally is successfully prepared pure Y behind 1050 ± 30 ℃ of insulations of maximum temperature, 2200 ± 400min
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, degrade efficient and the mechanism of degradation of contaminated Organic Pollutants In Water have been studied, efficient and the optical activity of research decomposition water hydrogen making under visible light or UV-irradiation, 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 coupling catalysis 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
7The XRD collection of illustrative plates, Figure 1B. be Y
2GaSbO
7The XRD collection of illustrative plates.
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 for 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 obtain 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 obtains are composed.
Fig. 8 is with Y under the radiation of visible light
2YbSbO
7And Y
2GaSbO
7The first order kinetics curve that obtains for the catalyst degradation rhodamine B.
Fig. 9 is under the radiation of visible light, with Y
2YbSbO
7And Y
2GaSbO
7The CO that obtains 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 photocatalyst 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 UV-Vis DRS spectrometer that the absorption spectra of new catalyst generation under visible light (or ultraviolet light) irradiation of above-mentioned preparation is measured, 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 fields, each microregion element of catalyst of having analyzed the magnetic-particle area load forms, and binding isotherm result of calculation has been analyzed 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 microstructure of novel photocatalyst to the rule that affects of photocatalysis degradation organic contaminant efficient.
Degraded water body inner dye under visible light (or ultraviolet light) irradiation, in the process of the 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 nucleus-shell magnetic coupling catalyst granules effect, the possible approaches of Some Organic Pollutants in the degraded water body has disclosed the water body inner dye under visible light (or ultraviolet light) irradiation, the degradation mechanism of the organic pollution such as Atrazine or pentachlorophenol.
Adopt single wavelength visible light (or ultraviolet light) irradiation water body inner dye, the organic pollution such as Atrazine or pentachlorophenol, successfully derive photogenerated charge (light induced electron or the photohole) quantity that participates in the photocatalytic degradation reaction by experimental study 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 degraded dyes under single wavelength visible light (or ultraviolet light) effect, the photo-quantum efficiency of the organic pollution such as Atrazine or pentachlorophenol.
Table 1Y
2YbSbO
7Atomic Structure Parameters
Table 2Y
2GaSbO
7Atomic Structure Parameters
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.Take the Y of purity as 99.99%
2O
3, Yb
2O
3And Sb
2O
5Be raw material, with Y, Yb, the 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, Elevated Temperature Conditions 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, finally is successfully prepared pure Y behind 1340 ± 50 ℃ of insulations of maximum temperature, 3800 ± 400min
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.Take the Y of purity as 99.99%
2O
3, Ga
2O
3And Sb
2O
5Be raw material, with Y, Ga, the 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, Elevated Temperature Conditions 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, finally is successfully prepared pure Y behind 1340 ± 50 ℃ of insulations of maximum temperature, 3900 ± 400min
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 is adopted 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), acetic acid 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, then 200 ± 30 ℃ of oven dry 3 ± 1 hours, compacting was put into high temperature sintering furnace and is fired in flakes, and Elevated Temperature Conditions 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, finally is successfully prepared pure Y behind 1050 ± 30 ℃ of insulations of maximum temperature, 2200 ± 400min
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 coupling catalysis 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 Gas Sensor Films Deposited by Pulsed Laser Deposition:
A. preparation of target materials: 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
2O
3As substrate;
C. adopt the Gas Sensor Films Deposited by Pulsed Laser Deposition instrument, laser main wave is long to be 248nm, and laser power density is 2～3J/cm
2, take nitrogen as protective atmosphere, 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 processed 60 ± 10min respectively at nitrogen or in argon gas under 1340 ± 10 ℃ and 1340 ± 10 ℃ of temperature, make it crystallization and obtain required magnetic coupling catalysis 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. preparation of target materials: prepare simple metal Yb, Ga, Sb, Y metal targets, the target diameter is 5～6 centimetres;
B. choose substrate: select ferromagnetic particle γ-Fe
2O
3As substrate;
C. adopt the multi-target magnetic control sputtering instrument, sputtering power is 60～200W, and take argon gas as protective atmosphere, 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 forms Y in the substrate deposition
3-xYb
xSbO
7(0.5≤x≤1) rete is processed 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 forms Y in the substrate deposition
3-xGa
xSbO
7(0.5≤x≤1) rete is processed 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 Gas Sensor Films Deposited by Pulsed Laser Deposition:
A. preparation of target materials: 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
2As substrate;
C. adopt the Gas Sensor Films Deposited by Pulsed Laser Deposition instrument, laser main wave is long to be 248nm, and laser power density is 2～3J/cm
2, take nitrogen as protective atmosphere, 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 processed 60 ± 10min respectively at nitrogen or in argon gas under 1340 ± 10 ℃ and 1340 ± 10 ℃ of temperature, make it crystallization and obtain required magnetic coupling catalysis 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. preparation of target materials: prepare simple metal Yb, Ga, Sb, Y metal targets, the target diameter is 5～6 centimetres;
B. choose substrate: select paramagnetic particle SiO
2As substrate;
C. adopt the multi-target magnetic control sputtering instrument, sputtering power is 60～200W, and take argon gas as protective atmosphere, 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 forms Y in the substrate deposition
3-xYb
xSbO
7(0.5≤x≤1) rete is processed 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 forms Y in the substrate deposition
3-xGa
xSbO
7(0.5≤x≤1) rete is processed 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 Gas Sensor Films Deposited by Pulsed Laser Deposition:
A. preparation of target materials: 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 anti-ferromagnetism particle MnO as substrate;
C. adopt the Gas Sensor Films Deposited by Pulsed Laser Deposition instrument, laser main wave is long to be 248nm, and laser power density is 2～3J/cm
2, take nitrogen as protective atmosphere, 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 processed 60 ± 10min respectively at nitrogen or in argon gas under 1340 ± 10 ℃ and 1340 ± 10 ℃ of temperature, make it crystallization and obtain required magnetic coupling catalysis 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. preparation of target materials: prepare simple metal Yb, Ga, Sb, Y metal targets, the target diameter is 5～6 centimetres;
B. choose substrate: select anti-ferromagnetism particle MnO as substrate;
C. adopt the multi-target magnetic control sputtering instrument, sputtering power is 60～200W, and take argon gas as protective atmosphere, 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 form Y to MnO particle substrate surface in the substrate deposition in the mist of oxygen and argon gas
3-xYb
xSbO
7(0.5≤x≤1) rete is processed 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 form Y to the MnO substrate surface in the substrate deposition in the mist of oxygen and argon gas
3-xGa
xSbO
7(0.5≤x≤1) rete is processed 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, 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 0.3～1T (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 coupling catalysis materials respectively accounts for 1/3rd, above-mentioned three kinds of magnetic coupling catalyst granules 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 simultaneously oxygenic aeration.Whole illumination reaction carries out under 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 the organic aqueous solution, utilize the magnetic-particle nuclear of different magnetic (ferromagnetism, paramagnetism and anti-ferromagnetism) to coat novel photocatalyst, these magnetic coupling catalysis materials can promote the mixing of similar magnetic-particle under the directional magnetic field effect, avoid particle agglomeration, make the magnetic coupling catalysis 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 flexibly as required magnetostatic field and alternating magnetic field, can in very large length and composition range, adjust easily the distribution of ferromagnetism and sub magnetic debris, 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 catalyst, or the difference supporting Pt, NiO and RuO
2Cocatalyst, light source are xenon lamp or high-pressure sodium lamp, carry out the decomposition water hydrogen making 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, without 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 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 the space atom site parameter of each atom be determined (seeing Table 1).Adopt the UV-vis DRS 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 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 the space atom site parameter of each atom be determined (seeing Table 2).Adopt the UV-vis DRS 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.Whole illumination reaction carries out under 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.Whole illumination reaction carries out under 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.Whole illumination reaction carries out under 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.Whole illumination reaction carries out under 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 coupling catalysis materials respectively accounts for 1/3rd, selects the Atrazine of typical difficult degradation in the water as the target degradation product.When magnetic field intensity is 0.3～0.6 tesla, above-mentioned three kinds of magnetic coupling catalyst granules 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 this moment, simultaneously the Y of all magnetic-particle surface coatings
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 equally oxygenic aeration.Whole illumination reaction carries out under airtight lighttight environment.Apply flexibly at last magnetostatic field and alternating magnetic field, 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 coupling catalysis materials respectively accounts for 1/3rd, selects the Atrazine of typical difficult degradation in the water as the target degradation product.When magnetic field intensity is 0.3～0.6 tesla, above-mentioned three kinds of magnetic coupling catalyst granules 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 this moment, simultaneously the Y of all magnetic-particle surface coatings
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 equally oxygenic aeration.Whole illumination reaction carries out under airtight lighttight environment.Apply flexibly at last magnetostatic field and alternating magnetic field, 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 coupling catalysis materials respectively accounts for 1/3rd, selects the pentachlorophenol of typical difficult degradation in the water as the target degradation product.When magnetic field intensity is 0.3～0.6 tesla, above-mentioned three kinds of magnetic coupling catalyst granules 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 this moment, simultaneously the Y of all magnetic-particle surface coatings
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 equally oxygenic aeration.Whole illumination reaction carries out under airtight lighttight environment.Apply flexibly at last magnetostatic field and alternating magnetic field, 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 coupling catalysis materials respectively accounts for 1/3rd, selects the pentachlorophenol of typical difficult degradation in the water as the target degradation product.When magnetic field intensity is 0.3～0.6 tesla, above-mentioned three kinds of magnetic coupling catalyst granules 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 this moment, simultaneously the Y of all magnetic-particle surface coatings
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 equally oxygenic aeration.Whole illumination reaction carries out under airtight lighttight environment.Apply flexibly at last magnetostatic field and alternating magnetic field, 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
7The decomposition water hydrogen making
Carry out the experiment of decomposition water hydrogen making 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 with the gas chromatograph-mass spectrometer (GC-MS) of TCD and measures, and this gas chromatograph-mass spectrometer (GC-MS) links to each other with airtight loop interior lighting reactor.Various gases are removed in the airtight loop interior lighting reactor before reaction, and argon gas is charged this reactor, until oxygen and nitrogen in the reactor are completely removed.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 catalyst, difference supporting Pt, NiO and RuO
2Cocatalyst decomposition water hydrogen making, incident light dominant wavelength are 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
7The decomposition water hydrogen making
Carry out the experiment of decomposition water hydrogen making 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 with the gas chromatograph-mass spectrometer (GC-MS) of TCD and measures, and this gas chromatograph-mass spectrometer (GC-MS) links to each other with airtight loop interior lighting reactor.Various gases are removed in the airtight loop interior lighting reactor before reaction, and argon gas is charged this reactor, until oxygen and nitrogen in the reactor are completely removed.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 catalyst, difference supporting Pt, NiO and RuO
2Cocatalyst decomposition water hydrogen making, incident light dominant wavelength are 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 (2)
1. the catalysis material of nucleocapsid structure is characterized in that using following structural formula: γ-Fe
2O
3-Y
3-xYb
xSbO
70.5≤x≤1, γ-Fe
2O
3-Y
3-xGa
xSbO
70.5≤x≤1, SiO
2-Y
3-xYb
xSbO
70.5≤x≤1, SiO
2-Y
3-xGa
xSbO
70.5≤x≤1, MnO-Y
3-xYb
xSbO
70.5≤x≤1 or MnO-Y
3-xGa
xSbO
70.5≤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
7Particle diameter is the 0.07-2.1 micron behind the parcel.
2. the application of the catalysis material of nucleocapsid structure, it is characterized in that the 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 coupling catalysis materials respectively accounts for 1/3rd, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in the aqueous solution, and make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution, adopt edge filter, λ〉420nm, and adopt simultaneously oxygenic aeration; Whole illumination reaction carries out under airtight lighttight environment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101957816A CN101850255B (en) | 2010-06-09 | 2010-06-09 | Y-Sb-based composite magnetic particle optical catalyst in nuclear shell structures and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101957816A CN101850255B (en) | 2010-06-09 | 2010-06-09 | Y-Sb-based composite magnetic particle optical catalyst in nuclear shell structures and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101850255A CN101850255A (en) | 2010-10-06 |
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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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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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