CN102107139A - Core-shell structure ferrum-yttrium-stibium-based composite magnetic-particle photocatalyst, and preparation and application thereof - Google Patents
Core-shell structure ferrum-yttrium-stibium-based composite magnetic-particle photocatalyst, and preparation and application thereof Download PDFInfo
- Publication number
- CN102107139A CN102107139A CN2011100337558A CN201110033755A CN102107139A CN 102107139 A CN102107139 A CN 102107139A CN 2011100337558 A CN2011100337558 A CN 2011100337558A CN 201110033755 A CN201110033755 A CN 201110033755A CN 102107139 A CN102107139 A CN 102107139A
- Authority
- CN
- China
- Prior art keywords
- sbo
- powder
- particle
- mno
- sio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 40
- 239000006249 magnetic particle Substances 0.000 title claims description 25
- 239000011941 photocatalyst Substances 0.000 title claims description 8
- 239000011258 core-shell material Substances 0.000 title abstract 4
- 239000003054 catalyst Substances 0.000 claims abstract description 137
- 239000002245 particle Substances 0.000 claims abstract description 116
- 239000000463 material Substances 0.000 claims abstract description 84
- 239000000843 powder Substances 0.000 claims abstract description 81
- 230000005291 magnetic effect Effects 0.000 claims abstract description 72
- 230000001699 photocatalysis Effects 0.000 claims abstract description 42
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 238000000151 deposition Methods 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- 230000000593 degrading effect Effects 0.000 claims abstract description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 239000007790 solid phase Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 60
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 230000005303 antiferromagnetism Effects 0.000 claims description 36
- 230000005298 paramagnetic effect Effects 0.000 claims description 35
- 230000005294 ferromagnetic effect Effects 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 29
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 28
- 238000006555 catalytic reaction Methods 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 229910052786 argon Inorganic materials 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 238000009413 insulation Methods 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 230000008021 deposition Effects 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 18
- 229910052724 xenon Inorganic materials 0.000 claims description 18
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052727 yttrium Inorganic materials 0.000 claims description 18
- 239000010408 film Substances 0.000 claims description 15
- 238000004544 sputter deposition Methods 0.000 claims description 15
- 238000000354 decomposition reaction Methods 0.000 claims description 14
- 229910052787 antimony Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 230000003287 optical effect Effects 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- 238000004549 pulsed laser deposition 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 238000005273 aeration Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 238000003980 solgel method Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000005056 compaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 239000003595 mist Substances 0.000 claims description 5
- 238000000427 thin-film deposition Methods 0.000 claims description 5
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 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 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000001755 magnetron sputter deposition Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 63
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 44
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 34
- 239000005510 Diuron Substances 0.000 description 24
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 24
- 238000007146 photocatalysis Methods 0.000 description 24
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 230000015556 catabolic process Effects 0.000 description 22
- 238000006731 degradation reaction Methods 0.000 description 22
- 230000005855 radiation Effects 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 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 13
- 229940043267 rhodamine b Drugs 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 9
- 239000000975 dye Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 230000033558 biomineral tissue development Effects 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000000694 effects Effects 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
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007857 degradation product Substances 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 229910017771 LaFeO Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005307 ferromagnetism Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000005426 magnetic field effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 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
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- DSDYLDANVNQRMF-UHFFFAOYSA-N [Sb].[Y].[Fe] Chemical compound [Sb].[Y].[Fe] DSDYLDANVNQRMF-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
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 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
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 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
- 229940012189 methyl orange Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a powder catalytic material of which the structural formula is Y[3-x]Fe[x]SbO[7] (0.5<=x<=1) and the particle size is 0.04-0.32 micrometer. The core-shell structure catalytic material can be gamma-Fe[2]O[3]-Y[3-x]Fe[x]SbO[7] (0.5<=x<=1), SiO[2]-Y[3-x]Fe[x]SbO[7] (0.5<=x<=1) or MnO-Y[3-x]-Fe[x]SnO[7] (0.5<=x<=1), wherein the particle sizes of gamma-Fe[2]O[3], SiO[2] and MnO are 0.06-2 micrometers, and the particle size of the coated Y[3-x]Fe[x]SbO[7] (0.5<=x<=1) is 0.08-1.2 micrometers; and the particle size of the Y[3-x]Fe[x]SbO[7] (0.5<=x<=1) powder is 0.04-0.32 micrometer. The core-shell structure catalytic material is used for decomposing water to prepare hydrogen, or degrading wastewater by using a reaction system composed of a magnetic field device and a photocatalytic material. The three magnetic composite photocatalytic materials respectively account for one-third by volume, and the particles of the three magnetic composite catalysts are in gradient distribution in a water solution. A high-temperature solid-phase sintering method is used for preparing the Y[3-x]Fe[x]SbO[7] (0.5<=x<=1) photocatalytic powder material; and a multi-target magnetron sputtering deposition method is used for preparing the core of the core-shell structure catalytic material, gamma-Fe[2]O[3]-Y[3-x]Fe[x]SbO[7] (0.5<=x<=1), SiO[2]-Y[3-x]Fe[x]SbO[7] (0.5<=x<=1) or MnO-Y[3-x]-Fe[x]SnO[7] (0.5<=x<=1).
Description
Technical field
The present invention relates to a kind of novel photocatalysis agent, preparation and application, especially powder catalytic material Y
3-xFe
xSbO
7γ-the Fe of (0.5≤x≤1) and " magnetic-particle nuclear-photochemical catalyst shell " structure
2O
3(ferromagnetic particle nuclear)-Y
3-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xFe
xSbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Y
3-xFe
xSbO
7The application of the preparation of (0.5≤x≤1), the organic pollution in photocatalysis removal water body and the application that photochemical catalyzing is produced hydrogen.
Background technology
The processing of poisonous refractory organics organic matter (PTS) is difficult point and the hot subject in the water treatment field always in the water.PTS has great harm to the health of human body, and ecological environment is had very big destruction, and therefore, all there is strict control criterion in developed country to this pollutant.Because the routine biochemistry processing method must adopt photocatalytic advanced oxidation technology and novel photocatalysis material that it is removed targetedly to the poor removal effect or the basic non-processor effect of this class material.Therefore, the developmental research of the organic novel advanced oxidation treatment technology of refractory organics becomes the focus and the advanced subject in present international environment engineering field in the water.In addition, adopting cheap cost to prepare novel energy hydrogen also is present hot subject, and based on this, development can utilize solar energy and have a corresponding novel photocatalysis material of visible light extremely urgent.
Photocatalytic advanced oxidation technology and conductor photocatalysis material are exactly the most effective, technology and the catalysis material that market prospects are arranged most of refractory organics organic matter in the countries in the world scholar processing water of generally acknowledging, has huge application potential aspect its refractory organics organic pollution in the degraded water body, have tangible advantage at aspects such as the organic mineralising decomposition of refractory organics than electro-catalysis, catalytic wet oxidation technology, photocatalytic advanced oxidation technology and conductor photocatalysis material also are technology and the catalysis materials that present decomposition water is produced the cheap and environmental protection of hydrogen in addition.But above-mentioned photocatalysis technology and semiconductor powder catalysis material are produced not industrialization as yet aspect the hydrogen at water treatment and decomposition water, 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 and photochemical catalyzing to produce the key of hydrogen industrial applications 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 conductor photocatalysis material, has expanded its photoresponse scope, has improved photo-quantum efficiency to a certain extent; The 2nd, research and develop visible-light photocatalysis material efficiently.In recent years, scientists has been carried out the research work of exploring the novel visible catalysis material, has obtained great achievement: adopt 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 dyestuff of can degrading; Adopt Bi
2GaTaO
7Can the degradation of methylene blue dyestuff; Adopt In
0.9Ni
0.1TaO
4Can produce hydrogen by decomposition water with visible light.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 the novel photocatalysis material, utilize CaBi
2O
4Deng novel photocatalysis material and visible light degradation water and airborne formaldehyde, acetaldehyde, methylene blue and H effectively
2Nuisances 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.Luan Jing flies seminar and 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 organic pollution in the Powdered catalysis material removal water body of development of new or decomposition water are produced hydrogen and not only can be produced remarkable economic efficiency, and can also produce huge environmental benefit and social benefit.In addition, in order to solve the secondary pollution problem of Powdered catalysis material in the suspension system, be badly in need of preparation nucleocapsid sprills shape catalysis material, purpose is intended to improve the rate of recovery of nucleocapsid sprills shape catalysis material, guarantees that also nucleocapsid sprills shape catalysis material has high photocatalysis quantum efficiency simultaneously.
Summary of the invention
The objective of the invention is: propose a kind of powder catalytic material Y
3-xFe
xSbO
7(0.5≤x≤1), preparation were established and method, performance characterization and application.And the γ-Fe that proposes a kind of " magnetic-particle nuclear-photochemical catalyst shell " structure
2O
3(ferromagnetic particle nuclear)-Y
3-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Y
3-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), preparation technology, performance characterization and application.
Technical scheme of the present invention is: the powder catalytic material, with following structural formula: Y3-xFexSbO7 (0.5≤x≤1), the particle diameter of powder is the 0.04-0.32 micron.
The catalysis material of nucleocapsid structure, γ-Fe2O3 (ferromagnetic particle nuclear)-Y3-xFexSbO7 (0.5≤x≤1) (photochemical catalyst shell), SiO2 (paramagnetic particle nuclear)-Y3-xFexSbO7 (0.5≤x≤1) (photochemical catalyst shell) or MnO (anti-ferromagnetism granular core)-Y3-xFexSbO7 (0.5≤x≤1) (photochemical catalyst shell), the particle diameter of γ-Fe2O3, SiO2 and MnO is the 0.06-2 micron, and Y3-xFexSbO7 (0.5≤x≤1) parcel back particle diameter is the 0.08-1.2 micron; The particle diameter of Y3-xFexSbO7 (0.5≤x≤1) powder is the 0.04-0.32 micron.
The application of powder catalytic material, by Y3-xFexSbO7 (0.5≤x≤1) powder is catalyst, or difference supporting Pt, NiO and RuO2 cocatalyst, light source is xenon lamp or high-pressure sodium lamp, carries out decomposition water and produce hydrogen in the airtight glass piping interior lighting reactor by a plurality of valve controls.
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 0.5～5T (tesla), and light source is xenon lamp or high-pressure sodium lamp; Adopt γ-Fe2O3 (ferromagnetic particle nuclear)-Y3-xFexSbO7 (photochemical catalyst shell), SiO2 (paramagnetic particle nuclear)-Y3-xFexSbO7 (photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y3-xFexSbO7 (photochemical catalyst shell) as catalyst, the 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.
The preparation method of powder catalytic material Y3-xFexSbO7 (0.5≤x≤1): the preparation of powder catalytic material Y3-xFexSbO7 (0.5≤x≤1): adopt the method for high temperature solid-phase sintering to prepare Y3-xFexSbO7 (0.5≤x≤1) photocatalytic powder material; With purity is that 99.99% Y2O3, Fe2O3 and Sb2O5 are raw material, Y, Fe and Sb are fully mixed with Y2O3, Fe2O3 and the Sb2O5 of the atomic ratio of described molecular formula, then in grinding in ball grinder, the particle diameter of powder reaches the 1.4-1.8 micron, 200 ± 40 ℃ of oven dry 2 ± 1 hours, compacting is put into high temperature sintering furnace and is fired in flakes.Furnace temperature is risen to 750 ± 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 780 ± 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 800 ℃ by 400 ℃, the heating-up time is 40 ± 10min; D. at 800 ℃ of insulation 480-800min; E. be warming up to 1250 ± 10 ℃ by 800 ℃, the heating-up time is 50 ± 10min; F. at 1250 ± 10 ℃ of insulation 2760 ± 300min, 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 1250 ± 10 ℃ of insulations of maximum temperature, 2760 ± 300min, finally prepares successfully pure Y3-xFexSbO7 (0.5≤x≤1) powder photocatalytic material;
Or adopt sol-gel process to prepare powder photocatalytic material Y3-xFexSbO7 (0.5≤x≤1): to utilize improved Sol-Gel method, adopt organometallic precursor, preparation Y3-xFexSbO7 (0.5≤x≤1).Presoma ferric acetate (Fe (CH3CO2) 3) and yttrium acetate hydrate (Y (CH3CO2) 3xH2O) and antimony chloride (SbCl5) are dissolved in the isopropyl alcohol, and with Y, Fe 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 60 ± 10min; C. be warming up to 750 ℃ by 400 ℃, the heating-up time is 40 ± 10min; D. at 750 ℃ of insulation 480-600min; E. be warming up to 1200 ± 30 ℃ by 750 ℃, the heating-up time is 40 ± 10min; F. at 1200 ± 30 ℃ of insulation 2100 ± 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 1200 ± 30 ℃ of insulations of maximum temperature, 2100 ± 400min, finally prepares successfully pure Y3-xFexSbO7 (0.5≤x≤1) powder photocatalytic material.
The preparation method of the catalysis material magnetic-particle nuclear-Y3-xFexSbO7 (0.5≤x≤1) of nucleocapsid structure:
Adopt the method for pulsed laser deposition deposition:
A. target preparation: the method with solid-phase sintering prepares Y3-xFexSbO7 (0.5≤x≤1) target, and the target diameter is 10mm, and thickness is 2mm;
B. choose substrate: select for use ferromagnetic particle γ-Fe2O3, paramagnetic particle SiO2 or anti-ferromagnetism particle MnO as substrate;
C. adopt the pulsed laser deposition deposition; laser main wave is long to be 248nm; laser power density is 2～3J/cm2; with nitrogen is protective atmosphere; the pressure of nitrogen and oxygen (purity is 99.99%) is 8～10Pa; initial pressure is 6 * 10-5Pa～2 * 10-3Pa in the settling chamber; target to the distance of substrate is 3～7 centimetres; substrate temperature is 300～700 ℃; sputter Y3-xFexSbO7 (0.5≤x≤1) target is to ferromagnetic particle γ-Fe2O3; paramagnetic particle SiO2 or anti-ferromagnetism particle MnO substrate surface; at γ-Fe2O3; the different film of deposit thickness on SiO2 or the MnO substrate; the thin film deposition time is 90～200 minutes; above-mentioned three kinds of films are handled 120 ± 10min respectively at nitrogen or in argon gas under 1250 ± 10 ℃ of temperature, make it crystallization and obtain required magnetic compound catalyze material γ-Fe2O3-Y3-xFexSbO7 (0.5≤x≤1); SiO2-Y3-xFexSbO7 (0.5≤x≤1) and MnO-Y3-xFexSbO7 (0.5≤x≤1).
Or the method that adopts multi-target magnetic control sputtering to deposit:
A. target preparation: prepare pure Fe, Sb and Y metal targets, the target diameter is 5～6 centimetres;
B. choose substrate: select for use ferromagnetic particle γ-Fe2O3,, paramagnetic particle SiO2 or anti-ferromagnetism particle MnO be as substrate;
C. adopt multi-target magnetic control sputtering, sputtering power is 60～200W, with the argon gas is protective atmosphere, the pressure of argon gas and oxygen (purity is 99.99%) is 4～32mTorr, the flow-rate ratio of oxygen (O2/ (O2+Ar)) is 30%～50%, and initial pressure is 3.3 * 10-6Torr～1 * 10--5Torr in the settling chamber, and target to the distance of substrate is 4～15 centimetres, substrate temperature is 0～400 ℃, and film deposition rate is 1～2nm/min;
Cosputtering simple metal Y, Fe and Sb target are to ferromagnetic particle γ-Fe2O3, paramagnetic particle SiO2 or anti-ferromagnetism particle MnO substrate surface in the mist of oxygen and argon gas, deposition forms Y3-xFexSbO7 (0.5≤x≤1) rete on substrate, and above-mentioned three kinds of retes are handled 120 ± 10min at 1250 ± 10 ℃ in nitrogen or argon gas; Make it crystallization and obtain required photochemical catalyst nucleocapsid structure γ-Fe2O3 (ferromagnetic particle nuclear)-Y3-xFexSbO7 (0.5≤x≤1) (photochemical catalyst shell), SiO2 (paramagnetic particle nuclear)-Y3-xFexSbO7 (0.5≤x≤1) or MnO (anti-ferromagnetism granular core)-Y3-xFexSbO7 (0.5≤x≤1).
The invention has the beneficial effects as follows: successfully prepared powder catalytic material Y by physical method or sol-gel process
3-xFe
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-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Y
3-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).And it a series of signs have been carried out, studied above-mentioned novel photocatalysis material and degraded under visible light or UV-irradiation that organic pollution (comprises pentachlorophenol in the contaminated water body, Atrazine and diuron) efficient and mechanism of degradation, 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
Fig. 1 Y
2FeSbO
7The transmission electron microscope collection of illustrative plates.
Fig. 2 .Y
2FeSbO
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. utilize Y
2FeSbO
7Photo-quantum efficiency and the lambda1-wavelength of degraded rhodamine B concern collection of illustrative plates (last figure) under visible light; Y
2FeSbO
7-diffuse reflection absorb collection of illustrative plates (figure below).
Fig. 4. at Y
2FeSbO
7(α hv)
2Concern collection of illustrative plates with hv.
Fig. 5. under the radiation of visible light, with Y
2FeSbO
7The absorbance and the lambda1-wavelength that are obtained for the catalyst degradation rhodamine B concern collection of illustrative plates.
Fig. 6. under the radiation of visible light, with Y
2FeSbO
7For rhodamine B concentration and incident light irradiation time chart that the catalyst degradation rhodamine B is obtained are composed.
Fig. 7. under the radiation of visible light, with Y
2FeSbO
7And In
2FeSbO
7The first order kinetics curve that is obtained for the catalyst degradation rhodamine B.
Fig. 7. under the radiation of visible light, with Y
2FeSbO
7And In
2FeSbO
7The first order kinetics curve that is obtained for the catalyst degradation rhodamine B.
Fig. 8. under the radiation of visible light, with Y
2FeSbO
7The CO that is obtained for the catalyst degradation rhodamine B
2Productive rate.
Fig. 9. under the radiation of visible light, with Y
2FeSbO
7During for the catalyst degradation rhodamine B, total organic carbon TOC and incident light irradiation time chart spectrum.
Figure 10 is Y
2FeSbO
7Band structure.
The specific embodiment
Preparation powder catalytic material Y
3-xFe
xSbO
7(0.5≤x≤1); In addition, the γ-Fe of preparation " magnetic-particle nuclear-photochemical catalyst shell " structure
2O
3(ferromagnetic particle nuclear)-Y
3-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Y
3-xFe
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-xFe
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-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Y
3-xFe
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 the invention described above catalyst has been carried out material phase analysis; Adopt transmission electron microscope (TEM) to analyze the microstructure characteristic of the invention described above catalyst; Utilize ESEM (SEM) that the invention described above 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 of 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, Atrazine, in the process of persistent organic pollutants such as diuron 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, Atrazine, the degradation mechanism of organic pollution such as diuron or pentachlorophenol.
Adopt single wavelength visible light (or ultraviolet light) irradiation water body inner dye, Atrazine, organic pollution such as diuron 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 dyestuff in the water body of under single wavelength visible light (or ultraviolet light) effect, degrading, Atrazine, the photo-quantum efficiency of organic pollution such as diuron or pentachlorophenol.
1. powder catalytic material Y
3-xFe
xSbO
7The preparation were established of (0.5≤x≤1) is as follows:
(1) powder catalytic material Y
3-xFe
xSbO
7The preparation of (0.5≤x≤1): adopt the method for high temperature solid-phase sintering to prepare Y
3-xFe
xSbO
7(0.5≤x≤1) photocatalytic powder material; With purity 99.99% Y
2O
3, Fe
2O
3And Sb
2O
5Be raw material, with Y, Fe and Sb Y with the atomic ratio of described molecular formula
2O
3, Fe
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 2 ± 1 hours, compacting was put into high temperature sintering furnace and fired in flakes.Furnace temperature is risen to 750 ± 20 ℃, be incubated and cool off with stove after 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 780 ± 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 800 ℃ by 400 ℃, the heating-up time is 40 ± 10min; D. at 800 ℃ of insulation 480-800min; E. be warming up to 1250 ± 10 ℃ by 800 ℃, the heating-up time is 50 ± 10min; F. at 1250 ± 10 ℃ of insulation 2760 ± 300min, 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 1250 ± 10 ℃ of insulations of maximum temperature, 2760 ± 300min, finally prepares successfully pure Y
3-xFe
xSbO
7(0.5≤x≤1) powder photocatalytic material;
(2) adopt sol-gel process to prepare Y
3-xFe
xSbO
7(0.5≤x≤1): change the Sol-Gel method that adopts by Garz-Tovar et al, utilize improved Sol-Gel method, adopt organometallic precursor, preparation Y
3-xFe
xSbO
7(0.5≤x≤1).Presoma ferric acetate (Fe (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, Fe 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 60 ± 10min; C. be warming up to 750 ℃ by 400 ℃, the heating-up time is 40 ± 10min; D. at 750 ℃ of insulation 480-600min; E. be warming up to 1200 ± 30 ℃ by 750 ℃, the heating-up time is 40 ± 10min; F. at 1200 ± 30 ℃ of insulation 2100 ± 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 1200 ± 30 ℃ of insulations of maximum temperature, 2100 ± 400min, finally prepares successfully pure Y
3-xFe
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-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xFe
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-xFe
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 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 γ-Fe
2O
3Temperature be 300～700 ℃, sputter Y
3-xFe
xSbO
7(0.5≤x≤1) target is to ferromagnetic particle 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 90～200 minutes, and above-mentioned film is handled 120 ± 10min in nitrogen or in argon gas under 1250 ± 10 ℃ of temperature, makes it crystallization and obtains required magnetic compound catalyze material γ-Fe
2O
3-Y
3-xFe
xSbO
7(0.5≤x≤1).
Adopt the method for multi-target magnetic control sputtering deposition:
A. target preparation: prepare pure Fe, Sb and Y metal targets, the target diameter is 5～6 centimetres;
B. choose substrate: select ferromagnetic particle γ-Fe for use
2O
3, 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 to substrate γ-Fe
2O
3Distance be 4～15 centimetres, substrate γ-Fe
2O
3Temperature be 0～400 ℃, film deposition rate is 1～2nm/min;
Cosputtering simple metal Y, Fe and Sb target are to ferromagnetic particle γ-Fe in the mist of oxygen and argon gas
2O
3Substrate surface, deposition forms Y on substrate
3-xFe
xSbO
7(0.5≤x≤1) rete is handled 120 ± 10min at 1250 ± 10 ℃ with above-mentioned rete in nitrogen or argon gas; Make it crystallization and obtain required photochemical catalyst nucleocapsid structure γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).
(2) SiO
2(paramagnetic particle nuclear)-Y
3-xFe
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-xFe
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 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 Si O
2Temperature be 300～700 ℃, sputter Y
3-xFe
xSbO
7(0.5≤x≤1) target is to paramagnetic particle SiO
2Substrate surface is at SiO
2The different film of deposit thickness on the substrate, the thin film deposition time is 90～200 minutes, and above-mentioned film is handled 120 ± 10min in nitrogen or in argon gas under 1250 ± 10 ℃ of temperature, makes it crystallization and obtains required magnetic compound catalyze material SiO
2-Y
3-xFe
xSbO
7(0.5≤x≤1).
Adopt the method for multi-target magnetic control sputtering deposition:
A. target preparation: prepare pure Fe, Sb and Y metal targets, the target diameter is 5～6 centimetres;
B. choose substrate: select paramagnetic particle SiO for use
2As 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 to substrate Si O
2Distance be 4～15 centimetres, substrate Si O
2Temperature be 0～400 ℃, film deposition rate is 1～2nm/min;
Cosputtering simple metal Y, Fe and Sb target are to paramagnetic particle SiO in the mist of oxygen and argon gas
2Substrate surface, deposition forms Y on substrate
3-xFe
xSbO
7(0.5≤x≤1) rete is handled 120 ± 10min at 1250 ± 10 ℃ with above-mentioned rete in nitrogen or argon gas; Make it crystallization and obtain required photochemical catalyst nucleocapsid structure SiO
2(paramagnetic particle nuclear)-Y
3-xFe
xSbO
7(0.5≤x≤1).
(3) MnO (anti-ferromagnetism granular core)-Y
3-xFe
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-xFe
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 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, the temperature of substrate MnO is 300～700 ℃, sputter Y
3-xFe
xSbO
7(0.5≤x≤1) target is to anti-ferromagnetism particle MnO substrate surface, the different film of deposit thickness on the MnO substrate, the thin film deposition time is 90～200 minutes, above-mentioned film is handled 120 ± 10min in nitrogen or in argon gas under 1250 ± 10 ℃ of temperature, make it crystallization and obtain required magnetic compound catalyze material MnO-Y
3-xFe
xSbO
7(0.5≤x≤1).
Adopt the method for multi-target magnetic control sputtering deposition:
A. target preparation: prepare pure Fe, Sb and Y metal targets, the target diameter is 5～6 centimetres;
B. choose substrate: select for use anti-ferromagnetism particle MnO 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 MnO is 4～15 centimetres to the distance of substrate, and the temperature of substrate MnO is 0～400 ℃, and film deposition rate is 1～2nm/min;
Cosputtering simple metal Y, Fe and Sb target are to anti-ferromagnetism particle MnO substrate surface in the mist of oxygen and argon gas, and deposition forms Y on substrate
3-xFe
xSbO
7(0.5≤x≤1) rete is handled 120 ± 10min at 1250 ± 10 ℃ with above-mentioned rete in nitrogen or argon gas; Make it crystallization and obtain required photochemical catalyst nucleocapsid structure MnO (anti-ferromagnetism granular core)-Y
3-xFe
xSbO
7(0.5≤x≤1).
Table 1Y
2FeSbO
7The atomic structure parameter
Table 2Y
2FeSbO
7The XPS collection of illustrative plates in the binding energy peak value (eV) of each essential element
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 0.3～5T (tesla), and light source is xenon lamp or high-pressure sodium lamp; Adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xFe
xSbO
7(photochemical catalyst shell) (0.5≤x≤1), SiO
2(paramagnetic particle nuclear)-Y
3-xFe
xSbO
7(photochemical catalyst shell) (0.5≤x≤1) and MnO (anti-ferromagnetism granular core)-Y
3-xFe
xSbO
7(photochemical catalyst shell) (0.5≤x≤1) is as catalyst, the 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 0.05～5T (tesla).Light source is 300W xenon lamp and 400W high-pressure sodium lamp.Typical hardly degraded organic substance pentachlorophenol Pentachlorophenol, dyestuff, diuron Diuron 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 space 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
2FeSbO
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
2FeSbO
7Performance characterization
Learn Y by XRD, XPS result
2FeSbO
7For single-phase, and experiment original material height is pure, does not have any impurity phase.
Measure Y by Xray fluorescence spectrometer
2FeSbO
7The average atom molar percentage be Y: Fe: Sb: O=2.00: 0.98: 1.02: 6.99.With Rietveld software to Y
2FeSbO
7XRD result carry out structure refinement, the structure refinement factor R
PValue is R
P=10.03%.Y
2FeSbO
7Space group be Fd-3m, structure is a cubic system, pyrochlore constitution, cell parameter a is
Y
2FeSbO
7The indices of crystallographic plane such as (222) of each diffraction maximum, (400), (440), (622), (444), (800), (662), (840), (844) are demarcated.Y
2FeSbO
7In each atoms in space atom site parameter be determined (seeing Table 1).Adopt UV, visible light to diffuse spectrometer to Y
2FeSbO
7The characteristic absorption limit that produces under the irradiation of light is measured, and obtains Y
2FeSbO
7Band gap width be 2.129eV, obtain Y
2FeSbO
7Band structure, conduction band is made of the 4d track of Y, the 3d track of Fe and the 5p track of Sb, valence band is made of the 2p track of O.Under radiation of visible light, with Y
2FeSbO
7Be catalyst, the initial concentration of rhodamine B is 0.0293mM, and initial soln 300mL, radiation of visible light are after 245 minutes, and the clearance of rhodamine B is 100%; The photo-quantum efficiency of degraded rhodamine B is 0.04740%; Rhodamine B concentration changes with time dynamics Changshu KC is 0.0142min
-1Rhodamine B total organic carbon concentration changes with time dynamics Changshu K
TOCBe 0.0121min
-1Behind the radiation of visible light 200 minutes, CO
2Spill-out be 0.21835mmol, the clearance of total organic carbon is 88.74%.
Application example
1. adopt Y
2FeSbO
7Diuron in the powder degrading waste water
With Y
2FeSbO
7Powder 0.8g puts into the 300mL diuron aqueous solution and forms suspension system, and the initial concentration of the diuron aqueous solution is 0.1mmolL
-1, initial pH value is 7.Choose the xenon lamp irradiation diuron 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.With Y
2FeSbO
7Powder is a catalyst, under radiation of visible light, along with the prolongation of irradiation time, the concentration of diuron reduces gradually, and total organic carbon (TOC) concentration also reduced gradually, through 400 minutes, the clearance of diuron is 86.30%, and the clearance of total organic carbon TOC (mineralization rate) reaches 84.93%, CO
2Productive rate be 0.22904mmol, first order kinetics Changshu K of diuron concentration and time
cBe 0.0040026min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.0038403min
-1Detailed data see Table 3.
Table 3 is with Y
2FeSbO
7Powder is the related data that the catalyst degradation Atrazine is obtained
2. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2FeSbO
7Diuron 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 0.5～5T (tesla).Light source is the 300W xenon lamp.Adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2FeSbO
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 diuron of selecting typical difficult degradation in the water is as the target degradation product.When magnetic field intensity is 2.5～3.2 teslas, above-mentioned three kinds of magnetic composite catalyst particles distribution gradient in containing the aqueous solution of diuron, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Select the 900mL diuron aqueous solution, the Y of all magnetic-particle surface-coated simultaneously this moment
2FeSbO
7Weight is near 2.4g, and the initial concentration of the diuron aqueous solution is 0.1mmol L
-1, initial pH value is 7.Choose the xenon lamp irradiation diuron 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.The result shows with γ-Fe
2O
3(magnetic-particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2FeSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, prolongation along with irradiation time, the concentration of diuron reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 400 minutes, the clearance of diuron reaches 89.80%, and the clearance of total organic carbon TOC (mineralization rate) reaches 88.92%, CO
2Productive rate be 0.72001mmol, first order kinetics Changshu K of diuron concentration and time
cBe 0.0045484min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.0043839min
-1Detailed data see Table 4.
Table 4 adopts γ-Fe
2O
3-Y
2FeSbO
7, SiO
2-Y
2FeSbO
7And MnO-Y
2FeSbO
7The related data that is obtained for the catalyst degradation diuron
3. adopt Y
2FeSbO
7Atrazine in the powder degrading waste water
With Y
2FeSbO
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.With Y
2FeSbO
7Powder is a catalyst, under radiation of visible light, along with the prolongation of irradiation time, the concentration of Atrazine reduces gradually, and total organic carbon (TOC) concentration also reduced gradually, through 400 minutes, the clearance of Atrazine is 68.80%, and the clearance of total organic carbon TOC (mineralization rate) reaches 66.79%, CO
2Productive rate be 0.16003mmol, first order kinetics Changshu Kc of Atrazine concentration and time is 0.0023521min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.0022431min
-1, detailed data see Table 5.
Table 5 is with Y
2FeSbO
7Powder is the related data that the catalyst degradation Atrazine is obtained
4. adopt Y
2FeSbO
7Pentachlorophenol in the powder degrading waste water
With Y
2FeSbO
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.With Y
2FeSbO
7Powder be catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of pentachlorophenol reduces gradually, total organic carbon (TOC) concentration also reduces gradually, and through 400 minutes, the clearance of pentachlorophenol was 78.50%, the clearance of total organic carbon TOC (mineralization rate) reaches 76.53%, CO
2Productive rate be 0.13719mmol, first order kinetics Changshu Kc of pentachlorophenol concentration and time is 0.0031959min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.0030588min
-1Detailed data see Table 6.
Table 6 is with Y
2FeSbO
7Powder is the related data that the catalyst degradation pentachlorophenol is obtained
5. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2FeSbO
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 0.5～5T (tesla).Light source is the 300W xenon lamp.Adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2FeSbO
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 2.5～3.2 teslas, 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
2FeSbO
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.The result shows with γ-Fe
2O
3(magnetic-particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2FeSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, prolongation along with irradiation time, the concentration of Atrazine reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 400 minutes, the clearance of Atrazine reaches 74.1%, and the clearance of total organic carbon TOC (mineralization rate) reaches 71.69%, CO
2Productive rate be 0.51573mmol, first order kinetics Changshu K of Atrazine concentration and time
cBe 0.0027392min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.0026064min
-1Detailed data see Table 7.
Table 7 adopts γ-Fe
2O
3-Y
2FeSbO
7, SiO
2-Y
2FeSbO
7And MnO-Y
2FeSbO
7The related data that is obtained for the catalyst degradation Atrazine
6. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2FeSbO
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 0.5～5T (tesla).Light source is the 300W xenon lamp.Adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2FeSbO
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 1.9～2
.During 6 teslas, 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
2FeSbO
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.The result shows with γ-Fe
2O
3(magnetic-particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2FeSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2FeSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, prolongation along with irradiation time, the concentration of pentachlorophenol reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 400 minutes, the clearance of pentachlorophenol reaches 84.5%, and the clearance of total organic carbon TOC (mineralization rate) reaches 81.63%, CO
2Productive rate be 0.44053mmol, first order kinetics Changshu K of pentachlorophenol concentration and time
cBe 0.003769min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.0035391min
-1Detailed data see Table 8.
Table 8 adopts γ-Fe
2O
3-Y
2FeSbO
7, SiO
2-Y
2FeSbO
7And MnO-Y
2FeSbO
7The related data that pentachlorophenol obtained in the degrading waste water
7. adopt Y
2FeSbO
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 6.01 * * 10
-6Einstein L
-1s
-1, the 390nm edge filter) high-pressure sodium lamp, in the 300mL pure water, put into Y
2FeSbO
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 801.6 micromoles, and the output of oxygen is 399.7 micromoles; After 24 hours, the output of hydrogen is 2218.2 micromoles under high voltage mercury lamp radiation, and the output of oxygen is 1108.4 micromoles.
With Y
2FeSbO
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
2FeSbO
7Be composite catalyst, the output of hydrogen is 4.96mmol after 24 hours; With 1.0wt%-NiO/Y
2FeSbO
7Be composite catalyst, the output of hydrogen is 3.18mmol after 24 hours; With 1.0wt%-RuO
2/ Y
2FeSbO
7Be composite catalyst, the output of hydrogen is 2.55mmol after 24 hours, and detailed data see Table 9 and table 10.
Table 9 is with Y
2FeSbO
7Powder is a catalyst, and decomposition water is produced the related data that hydrogen obtains under UV-irradiation
Table 10 is with Y
2FeSbO
7Powder is a catalyst, and decomposition water is produced the related data that hydrogen obtains under radiation of visible light
Claims (6)
1. the powder catalytic material is characterized in that with following structural formula: Y
3-xFe
xSbO
7(0.5≤x≤1), the particle diameter of powder are the 0.04-0.32 micron.
2. the catalysis material of nucleocapsid structure is characterized in that using following structural formula: γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell) or MnO (anti-ferromagnetism granular core)-Y
3-xFe
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-xFe
xSbO
7(0.5≤x≤1) parcel back particle diameter is the 0.08-1.2 micron; Y
3-xFe
xSbO
7The particle diameter of (0.5≤x≤1) powder is the 0.04-0.32 micron.
3. the application of powder catalytic material is characterized in that passing through Y
3-xFe
xSbO
7(0.5≤x≤1) powder 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. 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 0.5～5T (tesla), and light source is xenon lamp or high-pressure sodium lamp; Adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xFe
xSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xFe
xSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
3-xFe
xSbO
7(photochemical catalyst shell) is as catalyst, the 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.
5. powder catalytic material Y
3-xFe
xSbO
7The preparation method of (0.5≤x≤1): it is characterized in that powder catalytic material Y
3-xFe
xSbO
7The preparation of (0.5≤x≤1): adopt the method for high temperature solid-phase sintering to prepare Y
3-xFe
xSbO
7(0.5≤x≤1) photocatalytic powder material; With purity 99.99% Y
2O
3, Fe
2O
3And Sb
2O
5Be raw material, with Y, Fe and Sb Y with the atomic ratio of described molecular formula
2O
3, Fe
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 2 ± 1 hours, compacting was put into high temperature sintering furnace and fired in flakes.Furnace temperature is risen to 750 ± 20 ℃, be incubated and cool off with stove after 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 780 ± 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 800 ℃ by 400 ℃, the heating-up time is 40 ± 10min; D. at 800 ℃ of insulation 480-800min; E. be warming up to 1250 ± 10 ℃ by 800 ℃, the heating-up time is 50 ± 10min; F. at 1250 ± 10 ℃ of insulation 2760 ± 300min, 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 1250 ± 10 ℃ of insulations of maximum temperature, 2760 ± 300min, finally prepares successfully pure Y
3-xFe
xSbO
7(0.5≤x≤1) powder photocatalytic material;
Or employing Prepared by Sol Gel Method powder photocatalytic material Y
3-xFe
xSbO
7(0.5≤x≤1): utilize improved Sol-Gel method, adopt organometallic precursor, preparation Y
3-xFe
xSbO
7(0.5≤x≤1).Presoma ferric acetate (Fe (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, Fe and Sb atomic ratio with described molecular formula, utilize above-mentioned presoma according to the segmented sol-gel process for preparing, 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 60 ± 10min; C. be warming up to 750 ℃ by 400 ℃, the heating-up time is 40 ± 10min; D. at 750 ℃ of insulation 480-600min; E. be warming up to 1200 ± 30 ℃ by 750 ℃, the heating-up time is 40 ± 10min; F. at 1200 ± 30 ℃ of insulation 2100 ± 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 1200 ± 30 ℃ of insulations of maximum temperature, 2100 ± 400min, finally prepares successfully pure Y
3-xFe
xSbO
7(0.5≤x≤1) powder photocatalytic material.
6. the catalysis material magnetic-particle nuclear-Y of nucleocapsid structure
3-xFe
xSbO
7The preparation method of (0.5≤x≤1): the method that it is characterized in that adopting the pulsed laser deposition deposition:
A. target preparation: the method with solid-phase sintering prepares Y
3-xFe
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 ℃, sputter Y
3-xFe
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 90～200 minutes, above-mentioned three kinds of films are handled 120 ± 10min respectively at nitrogen or in argon gas under 1250 ± 10 ℃ of temperature, make it crystallization and obtain required magnetic compound catalyze material γ-Fe
2O
3-Y
3-xFe
xSbO
7(0.5≤x≤1), SiO
2-Y
3-xFe
xSbO
7(0.5≤x≤1) and MnO-Y
3-xFe
xSbO
7(0.5≤x≤1).
Or the method that adopts multi-target magnetic control sputtering to deposit:
A. target preparation: prepare pure Fe, 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, Fe 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-xFe
xSbO
7(0.5≤x≤1) rete is handled 120 ± 10min at 1250 ± 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-xFe
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xFe
xSbO
7(0.5≤x≤1) or MnO (anti-ferromagnetism granular core)-Y
3-xFe
xSbO
7(0.5≤x≤1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100337558A CN102107139A (en) | 2011-01-31 | 2011-01-31 | Core-shell structure ferrum-yttrium-stibium-based composite magnetic-particle photocatalyst, and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100337558A CN102107139A (en) | 2011-01-31 | 2011-01-31 | Core-shell structure ferrum-yttrium-stibium-based composite magnetic-particle photocatalyst, and preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102107139A true CN102107139A (en) | 2011-06-29 |
Family
ID=44171485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100337558A Pending CN102107139A (en) | 2011-01-31 | 2011-01-31 | Core-shell structure ferrum-yttrium-stibium-based composite magnetic-particle photocatalyst, and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102107139A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104874401A (en) * | 2014-12-26 | 2015-09-02 | 南京大学 | Preparation and application of Nd3-xCoxTaO7-zeolite composite porous nano-catalyst material |
| CN107837805A (en) * | 2017-11-09 | 2018-03-27 | 南京大学（苏州）高新技术研究院 | The preparation and application of a kind of powder catalytic material, film catalyst material, composite Nano catalysis material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311057A (en) * | 2000-02-22 | 2001-09-05 | 韩国化学研究所 | CdZnMS photocatalyst used for water decomposition and its prepn. method, and method for hydrogen prodn. |
| CN101850255A (en) * | 2010-06-09 | 2010-10-06 | 南京大学 | Y-Sb-based composite magnetic particle optical catalyst in nuclear shell structures and application |
-
2011
- 2011-01-31 CN CN2011100337558A patent/CN102107139A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311057A (en) * | 2000-02-22 | 2001-09-05 | 韩国化学研究所 | CdZnMS photocatalyst used for water decomposition and its prepn. method, and method for hydrogen prodn. |
| CN101850255A (en) * | 2010-06-09 | 2010-10-06 | 南京大学 | Y-Sb-based composite magnetic particle optical catalyst in nuclear shell structures and application |
Non-Patent Citations (2)
| Title |
|---|
| 《Solid State Sciences》 20101112 Jingfei Luan et al., Preparation and property characterization of new Y2FeSbO7 and In2FeSbO7 photocatalysts 185-194 1 第13卷, * |
| 《Solid State Sciences》 20101112 Jingfei Luan et al., Preparation and property characterization of new Y2FeSbO7 and In2FeSbO7 photocatalysts 185-194 2-6 第13卷, * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104874401A (en) * | 2014-12-26 | 2015-09-02 | 南京大学 | Preparation and application of Nd3-xCoxTaO7-zeolite composite porous nano-catalyst material |
| CN104874401B (en) * | 2014-12-26 | 2018-07-31 | 南京大学 | Nd3-xCoxTaO7The preparation and application of the compound porous nano catalytic material of zeolite |
| CN107837805A (en) * | 2017-11-09 | 2018-03-27 | 南京大学（苏州）高新技术研究院 | The preparation and application of a kind of powder catalytic material, film catalyst material, composite Nano catalysis material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101850255B (en) | Y-Sb-based composite magnetic particle optical catalyst in nuclear shell structures and application | |
| CN101757926B (en) | Magnetic-particle photocatalyst with core-shell structure, preparation and application thereof | |
| CN101850256B (en) | Preparation method of Y-Sb-based composite magnetic particle optical catalyst in nuclear-shell structures | |
| CN101797500B (en) | Gd3-xBixSbO7, Gd3-xYxSbO7 and In2BiTaO7 photocatalyst as well as preparation and application | |
| CN105214709B (en) | Interlayer bimetallic ion doping carbonitride catalysis material and its preparation and application | |
| CN104646003B (en) | Nd3-xCoxNbO7The preparation and application of the compound porous nano catalytic material of Si-Zn molecular sieve | |
| CN104645966A (en) | Preparation of Tb<3-x>PrxTaO7-zeolite molecular sieve composite porous nanometer catalyst material and application thereof | |
| Du et al. | Black lead molybdate nanoparticles: facile synthesis and photocatalytic properties responding to visible light | |
| CN101204651B (en) | Ti2LaxBi2-xO7 or Bi2SnxTi2-xO7 photocatalysis material, preparation method and application thereof | |
| CN102151572A (en) | Iron-gadolinium-antimony based composite magnetic particle photo-catalyst in core-shell structure as well as preparation and application thereof | |
| CN102145288A (en) | Bismuth iron niobium-based composite magnetic particle photocatalyst with core-shell structure, preparation and application of bismuth iron niobium-based composite magnetic particle photocatalyst | |
| CN102139208A (en) | Niobium bismuth yttrium-based composite magnetic particle photocatalysts with core-shell structures as well as preparation methods and applications thereof | |
| CN104689812B (en) | Ce3-xSbxTaO7The compound porous catalysis material of coal ash zeolite prepares and application | |
| CN102139209B (en) | Core-shell gadolinium indium antimony base composite magnetic-particle photochemical catalyst as well as preparation and application thereof | |
| CN102107139A (en) | Core-shell structure ferrum-yttrium-stibium-based composite magnetic-particle photocatalyst, and preparation and application thereof | |
| CN104645968A (en) | Preparation of Tb<3-x>PrxNbO7-zeolite composite porous nanometer catalyst material and application thereof | |
| CN103071480B (en) | Erbium gadolinium antimony-based composite magnetic particle photocatalyst with core-shell structure, preparation and application | |
| CN101199926B (en) | Preparing process and application ofBi2SbxV1.6-0.6xO7 or Bi2AlxV1.6-0.6xO7 photocatalysis material | |
| CN102151563B (en) | Gadolinium-yttrium-antimony based composite magnetic particle photo catalyst of core-shell structure, preparation and application thereof | |
| CN107837805B (en) | Preparation and application of powder catalytic material, thin film catalytic material and composite nano catalytic material | |
| CN102626650A (en) | Preparation method of nanometer porous nitrogen doped titanium oxide visible photocatalyst | |
| CN104874401A (en) | Preparation and application of Nd3-xCoxTaO7-zeolite composite porous nano-catalyst material | |
| CN102139210A (en) | Gadolinium-ytterbium-stibium based composite magnetic particle photocatalyst with core-shell structure, preparation and application | |
| CN102107140A (en) | Indium, ferrum and stibium composite magnetic-particle optical catalyst of nuclear-shell structure as well as preparation and application thereof | |
| CN102166513A (en) | Antimony, ytterbium and indium based composite magnetic particle photocatalyst with core-shell structure, preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110629 |