CN103071480A - Erbium gadolinium antimony-based composite magnetic particle photocatalyst with core-shell structure, preparation and application - Google Patents
Erbium gadolinium antimony-based composite magnetic particle photocatalyst with core-shell structure, preparation and application Download PDFInfo
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- CN103071480A CN103071480A CN201210433808XA CN201210433808A CN103071480A CN 103071480 A CN103071480 A CN 103071480A CN 201210433808X A CN201210433808X A CN 201210433808XA CN 201210433808 A CN201210433808 A CN 201210433808A CN 103071480 A CN103071480 A CN 103071480A
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- 239000006249 magnetic particle Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title abstract description 8
- 239000011941 photocatalyst Substances 0.000 title abstract description 8
- GBRSYKHFITZFOY-UHFFFAOYSA-N [Sb].[Gd].[Er] Chemical compound [Sb].[Gd].[Er] GBRSYKHFITZFOY-UHFFFAOYSA-N 0.000 title abstract description 3
- 239000011258 core-shell material Substances 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 163
- 239000000463 material Substances 0.000 claims abstract description 96
- 239000002245 particle Substances 0.000 claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000005286 illumination Methods 0.000 claims abstract description 31
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 28
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 19
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 5
- 230000005291 magnetic effect Effects 0.000 claims description 79
- 239000000843 powder Substances 0.000 claims description 68
- 238000006555 catalytic reaction Methods 0.000 claims description 61
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 50
- 229910001566 austenite Inorganic materials 0.000 claims description 46
- 239000007864 aqueous solution Substances 0.000 claims description 45
- 230000005303 antiferromagnetism Effects 0.000 claims description 34
- 230000005298 paramagnetic effect Effects 0.000 claims description 33
- 230000001699 photocatalysis Effects 0.000 claims description 32
- 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 claims description 29
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 29
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 26
- 239000011734 sodium Substances 0.000 claims description 24
- CZIRZNRQHFVCDZ-UHFFFAOYSA-L titan yellow Chemical compound [Na+].[Na+].C1=C(C)C(S([O-])(=O)=O)=C2SC(C3=CC=C(C=C3)/N=N/NC3=CC=C(C=C3)C3=NC4=CC=C(C(=C4S3)S([O-])(=O)=O)C)=NC2=C1 CZIRZNRQHFVCDZ-UHFFFAOYSA-L 0.000 claims description 24
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 claims description 24
- 230000000593 degrading effect Effects 0.000 claims description 23
- 230000008878 coupling Effects 0.000 claims description 22
- 238000010168 coupling process Methods 0.000 claims description 22
- 238000005859 coupling reaction Methods 0.000 claims description 22
- NTGBUUXKGAZMSE-UHFFFAOYSA-N phenyl n-[4-[4-(4-methoxyphenyl)piperazin-1-yl]phenyl]carbamate Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(NC(=O)OC=3C=CC=CC=3)=CC=2)CC1 NTGBUUXKGAZMSE-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 230000005294 ferromagnetic effect Effects 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 238000005273 aeration Methods 0.000 claims description 15
- 230000005611 electricity Effects 0.000 claims description 15
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- 238000000034 method Methods 0.000 claims description 11
- 230000003197 catalytic effect Effects 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
- 240000002853 Nelumbo nucifera Species 0.000 claims description 9
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 9
- 235000006510 Nelumbo pentapetala Nutrition 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000009881 electrostatic interaction Effects 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229920006229 ethylene acrylic elastomer Polymers 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
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- 238000005406 washing Methods 0.000 claims description 3
- KQHKSGRIBYJYFX-UHFFFAOYSA-J Ponceau S Chemical compound [Na+].[Na+].[Na+].[Na+].Oc1c(cc2cc(ccc2c1N=Nc1ccc(cc1S([O-])(=O)=O)N=Nc1ccc(cc1)S([O-])(=O)=O)S([O-])(=O)=O)S([O-])(=O)=O KQHKSGRIBYJYFX-UHFFFAOYSA-J 0.000 claims description 2
- 230000005307 ferromagnetism Effects 0.000 abstract description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052753 mercury Inorganic materials 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 39
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- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 description 4
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
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- 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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- 229910052751 metal Inorganic materials 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 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
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 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 1
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Catalysts (AREA)
Abstract
The invention relates to an erbium gadolinium antimony-based composite magnetic particle photocatalyst with core-shell structure, a preparation and an application. A structural formula of a photocatalyst material is Gd3-xErxSbO7 (0.5<=x<=1), the particle size is 0.04-0.32 micrometers. Gamma-Fe2O3 ferromagnetism particle core-Gd3-xErxSbO7 (0.5<=x<=1), SiO2Gd3-xErxSbO7 (0.5<=x<=1) and MnO-Gd3-xErxSbO7 (0.5<=x<=1) are used; the particle size of Gamma-Fe2O3, SiO2 and MnO is 0.06-1 micrometer, and the particle size of Gd3-xErxSbO7 (0.5<=x<=1) after being wrapped with the core is 0.09-1.30 micrometer. The above material are respectively loaded with a Pt, NiO or RuO2 auxiliary catalyst; the auxiliary catalyst mass ratio is 20-30%, the light source is an xenon lamp or high pressure mercury lamp, and the water decomposition is carried out in an enclosed glass piping internal illumination reactor controlled by a plurality of valves to prepare hydrogen or degrade waste water.
Description
Technical field
The present invention relates to a kind of novel photocatalyst, preparation and application, especially powder catalytic material Gd
3-xEr
xSbO
7γ-the Fe of (0.5≤x≤1) and " magnetic-particle nuclear-photochemical catalyst shell " structure
2O
3-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2-Gd
3-xEr
xSbO
7(0.5≤x≤1), MnO-Gd
3-xEr
xSbO
7(0.5≤x≤1), preparation technology, the application through the organic pollution in the water body is removed in photocatalysis reaches the application of photochemical catalyzing hydrogen making.
Background technology
Along with economic development, the water environment pollution problem is day by day serious in recent years.In water body environment, the processing that is difficult to biodegradable organic pollution is difficult point and the hot subject in the water treatment field always.Being difficult to biodegradable organic pollution has great harm to the health of human body, and ecological environment is had huge destruction, therefore should seek good technology and technique and remove this pollutant in the water body.Because the routine biochemistry processing method must adopt photocatalytic advanced oxidation technology and novel photocatalysis material that it is removed targetedly to poor removal effect or the basic non-processor effect of this class material.Research and development about the novel photocatalysis material come into one's own year by year.As everyone knows, solar spectrum medium ultraviolet luminous energy is less than 5%, and wavelength is that the visible light of 400-750nm then accounts for nearly 43%.Can not effectively utilize visible light if utilize catalysis material to solve water pollution problem, the meaning that then exists as the catalysis material that solves problem of environmental pollution can weaken greatly.And with regard to the depollution of environment, also will be restricted for the indoor application that does not have ultraviolet light.In addition, the energy hydrogen that adopts cheap cost to prepare novel clean also is present hot subject.Based on this, in order to effectively utilize sunshine, we wish to develop the catalysis material that has photocatalytic activity under visible light, thereby solve extremely urgent water environment pollution and energy scarcity problem.
For the exploitation of visible-light response type surround lighting catalysis material, one of its main flow is to show highly active TiO under UV-irradiation
2In make it to have visible light-responded research with the doping dissimilar metal.Another main flow is to explore the non-oxidized substance semiconductor that band gap width is narrow and have absorption characteristic in the visible region.The sulfur family metallic compounds such as cadmium sulfide, cadmium selenide and organic material etc. are typically arranged.But the oxidized dissolving owing to the effect of the electrified cavity that generates under illumination of these materials, existing does not have the stable problems such as function.Therefore, wish research and development under illumination its structure and photoelectrochemical property all stable compound come degradation water internal pollution thing as catalysis material.The research that utilizes these powder photocatalytic materials and solar energy to degrade organic pollution in the water body or decompose toxic pollutant causes the scientists keen interest, with regard to purifying contaminated water body environment, these conductor oxidate photocatalytic powder materials will be played the part of extremely important role in future.
The fundamental design idea of novel visible responsive photocatalytic material is control crystal structure and electronic state.Its photocatalysis principle is when energy is mapped on the semiconductor greater than the illumination of semiconductor energy gap, Electron absorption luminous energy on the semiconductor valence band is excited on the conduction band, thereby at the electronegative high activity electronics of conduction band generation, produce the hole of positively charged in valence band, form light induced electron and the right redox system of photohole.Have an effect in dissolved oxygen, water, electronics and hole, the final generation has highly chemically active hydroxyl radical free radical, utilize the hydroxyl radical free radical of this high activity can oxidize water in multiple hardly degraded organic substance be CO
2With little molecule inorganic matters such as water; Perhaps utilizing the photohole that has strong oxidability in the valence band, can be the rapid oxidation Decomposition of organic matter the inorganic matters such as carbon dioxide and water.Thereby can be used for organic pollution in the depollution of environment and the degraded water body.Therefore, be to improve the efficient of oxide semiconductor film material degradation organic pollutants in water body, the forbidden band of oxide semiconductor film material should be enough narrow, and the light induced electron that forms behind the solar light irradiation and photohole are compound to being not easy.
Japan namely carries out TiO since the eighties
2Catalysis material is applied to the research of purifying water process, but because the photocatalytic oxidation degradation water pollutant is the three-dimensional planar reaction of carrying out on the catalysis material surface, pulverous TiO
2The photocatalytic powder material is difficult to separate from water after water treatment, reclaims and reuses difficulty.Based on this, it is particularly important that the research of film-form catalysis material just seems, can avoid the secondary pollution of water in the contaminated water body purification process.And utilize the degrade rarely seen report of research of organic pollution in the water body of oxide semiconductor film catalysis material.In recent years, scientists has obtained a lot of achievements aspect the research of novel visible catalysis material: 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 of can degrading; Adopt Bi
2GaTaO
7Can the degradation of methylene blue dyestuff; Adopt Fe
0.9Ni
0.1TaO
4With visible light can the decomposition water hydrogen making.The LaFeO of Fu Xixian preparation
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 effectively degradation water and airborne formaldehyde, acetaldehyde, methylene blue and H
2The 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.Luan Jing flies seminar and has successfully prepared first Ga
2BiTaO
7Powder photocatalytic degradation water body Methylene Blue dyestuff, methylene blue is by degradable after 140 minutes.Therefore, the photoresponse scope of expansion catalysis material is to improve effective ways of photocatalysis quantum efficiency.In addition; adopting novel visible responsive photocatalytic material, can take full advantage of in the solar spectrum 43% visible light, is hydrogen and oxygen with water decomposition; and then obtain hydrogen energy source clean, non-secondary pollution, alleviate oil and natural gas and be about to the exhausted energy crisis of bringing.Utilize these above-mentioned hydrogen energy source can prepare the energy source and power that fuel cell is used for the vehicles such as electric automobile and electric bicycle.Mostly the visible-light photocatalysis material of reporting at present is powdered, good photocatalytic activity is arranged in suspension system, 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.
In sum, adopt novel catalysis material, under radiation of visible light, the organic pollution in the water body of not only can degrading can also prepare clean hydrogen energy source, has both solved to a certain extent problem of environmental pollution, has also solved energy crisis.Therefore, so organic pollution or decomposition water hydrogen making that the development of new catalysis material is removed in the water body 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 Gd
3-xEr
xSbO
7(0.5≤x≤1) and 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)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Gd
3-xEr
xSbO
7(photochemical catalyst shell) preparation technology, performance characterization and application.Especially adopt the oxide material of rare earth Er to have better effect.
Technical scheme of the present invention is: the powder catalytic material, and such as following structural formula: Gd
3-xEr
xSbO
7(0.5≤x≤1), the particle diameter of powder are the 0.04-0.32 micron.
Catalysis material γ-the Fe of nucleocapsid structure
2O
3(ferromagnetic particle nuclear)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).γ-Fe
2O
3, SiO
2With the particle diameter of MnO be the 0.06-1 micron, Gd
3-xEr
xSbO
7Particle diameter is the 0.09-1.30 micron behind (0.5≤x≤1) parcel nuclear.
Gd is passed through in the application of powder catalytic material or nucleocapsid structure catalysis material
3-xEr
xSbO
7(0.5≤x≤1) powder is catalyst, or difference supporting Pt, NiO or RuO
2(lower-cost scheme is cocatalyst: the NiO or the RuO that add the 20-30% mass ratio
2Particle or powder and Gd
3-xEr
xSbO
7Evenly mixed), light source is xenon lamp or high-pressure sodium lamp, carries out decomposition water hydrogen making or degrading waste water in the airtight glass piping interior lighting reactor by a plurality of valve controls.
The application of the catalysis material of nucleocapsid structure is by the organic pollution titan yellow (C in the reaction system degrading waste water of magnetic field device and nucleocapsid structure catalysis material formation
28H
19N
5Na
2O
6S
4), aniline blue (C
32H
25N
3Na
2O
9S
3), the green B (C of diaminourea
34H
22N
8Na
2O
10S
2), nuclear fast red (C
14H
8NNaO
7S), Ponceau S (C
22H
12N
4Na
4O
13S
4), methylene blue (C
16H
18ClN
3S) etc., 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 the catalysis material γ-Fe of nucleocapsid structure
2O
3(ferromagnetic particle nuclear)-Gd
3-xEr
xSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
3-xEr
xSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
3-xEr
xSbO
7(photochemical catalyst shell) as catalyst, (cost scheme lower and better effects if is above-mentioned three kinds of magnetic coupling catalysis materials: the NiO or the RuO that add the 20-30% mass ratio
2Particle or powder and Gd
3-xEr
xSbO
7Even mixing) percent by volume respectively accounts for volume ratio and is 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.
The catalysis material magnetic-particle nuclear-Gd of nucleocapsid structure
3-xEr
xSbO
7The preparation method of (0.5≤x≤1): adopt the method for electrostatic interaction to prepare hud typed complex microsphere: by the Gd of lotus positive electricity ethylene-acrylic rubber AEM modification
3-xEr
xSbO
7Ferromagnetic particle γ-the Fe of (0.5≤x≤1) and bear electricity
2O
3, paramagnetic particle SiO
2Or anti-ferromagnetism particle MnO interacts; Adopt micron-sized powder photocatalytic material Gd
3-xEr
xSbO
7(0.5≤x≤1), AEM (ethylene-acrylic rubber), Nanoscale Iron magnetic-particle γ-Fe
2O
3, paramagnetic particle SiO
2Or anti-ferromagnetism particle MnO; To be powder photocatalytic material Gd
3-xEr
xSbO
7Quality 2-5 times nanometer γ-Fe
2O
3, SiO
2Or MnO places respectively the water of 500-1000 part quality to stir, and adds weak aqua ammonia 1-8 part, makes nanometer γ-Fe
2O
3, SiO
2Or MnO bear electricity, add weak aqua ammonia, make oxide surface absorption OH
-And with negative electrical charge.For subsequent use; Get 0.1g powder photocatalytic material Gd
3-xEr
xSbO
7(0.5≤x≤1), the ethanolic solution dipping stirring with AEM concentration 2-9%w/w makes Gd
3-xEr
xSbO
7(0.5≤x≤1) lotus positive electricity is used the nanometer γ of above-mentioned configuration-Fe again
2O
3, SiO
2Or the mixed swelling that stirs of MnO ammoniacal liquor mixed solution, make electronegative nanometer γ-Fe
2O
3, SiO
2Or MnO is by the Gd of the AEM modification of electrostatic interaction and lotus positive electricity
3-xEr
xSbO
7(0.5≤x≤1) is at Gd
3-xEr
xSbO
7(0.5≤x≤1) surface forms shell structure, and the thickness of shell can be according to the nanometer γ that adds-Fe
2O
3, SiO
2Or the amount of MnO decides, and then use absolute ethyl alcohol successively, the deionized water cyclic washing, remove unnecessary AEM ethanolic solution and ammonia spirit, room temperature is dried, and namely gets the catalysis material magnetic-particle nuclear-Gd with nucleocapsid structure
3-xEr
xSbO
7(0.5≤x≤1).
The invention has the beneficial effects as follows: prepare hud typed complex microsphere by the method that adopts electrostatic interaction and successfully prepare powder catalytic material Gd
3-xEr
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)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
3-xEr
xSbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).And it a series of signs have been carried out, study the above-mentioned novel photocatalysis material contaminated Organic Pollutants In Water of under visible light or UV-irradiation, degrading and (comprised titan yellow, aniline blue, the green B of diaminourea, the nuclear fast red, Ponceau S, methylene blue) efficient and mechanism of degradation, 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.The present invention especially adopts the oxide material of rare earth Er to have better effect: final beneficial effect is to make the clearance of above-mentioned organic pollution reach NiO or the RuO that 99.9%(assists the 20-30% mass ratio
2), above-mentioned organic pollution total organic Carbon removal reaches 99.5%.
Description of drawings
Fig. 1 is Gd of the present invention
2ErSbO
7The transmission electron microscope collection of illustrative plates.
Fig. 2 is Gd of the present invention
2ErSbO
7Actual measurement XRD collection of illustrative plates.
Fig. 3 is Gd of the present invention
2ErSbO
7Band structure.
The specific embodiment
Preparation powder catalytic material Gd
3-xEr
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)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
3-xEr
xSbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).
(1) preparation can be at the novel photocatalyst Gd of visible light wave range or the response of ultraviolet light wave band
3-xEr
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)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
3-xEr
xSbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Gd
3-xEr
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.
(1-1) powder catalytic material Gd
3-xEr
xSbO
7The preparation of (0.5≤x≤1): adopt the method for high temperature solid-phase sintering to prepare Gd
3-xEr
xSbO
7(0.5≤x≤1) photocatalytic powder material; Take the Er of purity as 99.99%
2O
3, Gd
2O
3And Sb
2O
5Be raw material, with Er, Gd and the Sb Er with the atomic ratio of described molecular formula
2O
3, Gd
2O
3And Sb
2O
5Fully mix, then in grinding in ball grinder, the particle diameter of powder reaches the 1.3-1.7 micron, and 200 ± 30 ℃ of oven dry 3 ± 1 hours, compacting was put into high temperature sintering furnace and fired in flakes.Furnace temperature is risen to 700 ± 30 ℃, be incubated and cool off with stove after 7 ± 2 hours, 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, puts into the high temperature sintering furnace sintering, the highest furnace temperature is 750 ± 20 ℃, be incubated after 7 ± 1 hours and cool off with stove, it is the 1.2-1.4 micron that the pressed powder taking-up is crushed to particle diameter, again that these powder compaction are in blocks, put into the high temperature sintering furnace sintering, 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 60 ± 10min; C. be warming up to 780 ℃ by 400 ℃, the heating-up time is 60 ± 10min; D. at 780 ℃ of insulation 440-820min; E. be warming up to 1320 ± 10 ℃ by 780 ℃, the heating-up time is 50 ± 10min; F. at 1320 ± 10 ℃ of insulation 4000 ± 200min, stove is cold.
With the stove cooling, it is the 0.04-0.32 micron that the taking-up pressed powder is crushed to particle diameter to pressed powder, finally is successfully prepared pure Gd behind 1320 ± 10 ℃ of insulations of maximum temperature, 4000 ± 200min
3-xEr
xSbO
7(0.5≤x≤1) powder photocatalytic material.
(1-2) carry out the catalysis material magnetic-particle nuclear-Gd of nucleocapsid structure according to above-mentioned powder catalytic material
3-xEr
xSbO
7The preparation of (0.5≤x≤1): adopt the method for electrostatic interaction to prepare hud typed complex microsphere: by the Gd of lotus positive electricity ethylene-acrylic rubber AEM modification
3-xEr
xSbO
7Ferromagnetic particle γ-the Fe of (0.5≤x≤1) and bear electricity
2O
3, paramagnetic particle SiO
2Or anti-ferromagnetism particle MnO interaction, make the catalysis material magnetic-particle nuclear-Gd with nucleocapsid structure
3-xEr
xSbO
7(0.5≤x≤1).
Material: sol-gel process prepares powder photocatalytic material Gd
3-xEr
xSbO
7(0.5≤x≤1), AEM (ethylene-acrylic rubber), Nanoscale Iron magnetic-particle γ-Fe
2O
3, paramagnetic particle SiO
2Or anti-ferromagnetism particle MnO.
(thickness of the shell that quality can be produced as requested adds, and generally is powder photocatalytic material Gd with a certain amount of
3-xEr
xSbO
72 or 5 times) nanometer γ-Fe
2O
3, SiO
2Or MnO places 100ml water to stir, and adds weak aqua ammonia 2 or 8ml, makes nanometer γ-Fe
2O
3, SiO
2Or MnO bear electricity, for subsequent use; Get 0.1g powder photocatalytic material Gd
3-xEr
xSbO
7(0.5≤x≤1), the AEM ethanolic solution dipping stirring with finite concentration (2%w/w or 9%w/w) makes Gd
3-xEr
xSbO
7(0.5≤x≤1) lotus positive electricity is used the nanometer γ of above-mentioned configuration-Fe again
2O
3, SiO
2Or the mixed swelling that stirs of MnO ammoniacal liquor mixed solution, make electronegative nanometer γ-Fe
2O
3, SiO
2Or MnO is by the Gd of the AEM modification of electrostatic interaction and lotus positive electricity
3-xEr
xSbO
7(0.5≤x≤1) is at Gd
3-xEr
xSbO
7(0.5≤x≤1) surface forms shell structure, and the thickness of shell can be according to the nanometer γ that adds-Fe
2O
3, SiO
2Or the amount of MnO decides, and then use absolute ethyl alcohol successively, the deionized water cyclic washing, remove unnecessary AEM ethanolic solution and ammonia spirit, room temperature is dried, and namely gets the catalysis material magnetic-particle nuclear-Gd with nucleocapsid structure
3-xEr
xSbO
7(0.5≤x≤1).
(1-3) 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 0.3～5T (tesla), and light source is xenon lamp or high-pressure sodium lamp; Adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell) is as catalyst, the 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 0.05～5T (tesla).Light source is 300W xenon lamp and 400W high-pressure sodium lamp.Select typical hardly degraded organic substance titan yellow in the water, aniline blue, the green B of diaminourea, nuclear fast red, Ponceau S, methylene blue as the target degradation product.
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 space 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 Gd
2ErSbO
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.Scheme is preferably: 20% or 30% mass ratio of interpolation is (with Gd
3-xEr
xSbO
7Catalyst granules) NiO or RuO
2Particle or powder and Gd
3-xEr
xSbO
7Evenly mixed.
(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 microstructure of novel photocatalyst to the rule that affects of photocatalysis degradation organic contaminant efficient.
Titan yellow in the degraded water body under visible light (or ultraviolet light) irradiation, aniline blue, the green B of diaminourea, the nuclear fast red, Ponceau S, in the process of the persistent organic pollutants such as methylene blue, 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 titan yellow in the water body under visible light (or ultraviolet light) irradiation, aniline blue, the green B of diaminourea, the nuclear fast red, Ponceau S, the degradation mechanism of the organic pollutions such as methylene blue.
Adopt titan yellow in single wavelength visible light (or ultraviolet light) irradiation water body, aniline blue, the green B of diaminourea, the nuclear fast red, Ponceau S, the organic pollutions such as methylene blue, 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 titan yellow in the water body of under single wavelength visible light (or ultraviolet light) effect, degrading, aniline blue, the green B of diaminourea, the nuclear fast red, Ponceau S, the photo-quantum efficiency of the organic pollutions such as methylene blue.
Table 1Gd
2ErSbO
7Atomic Structure Parameters
Table 2Gd
2FeSbO
7The XPS collection of illustrative plates in each essential element in conjunction with can peak value (eV)
(3) .Gd
2ErSbO
7Performance characterization
Learn Gd by XRD, XPS result
2ErSbO
7For single-phase, and experiment original material height is pure, without any impurity phase.
Measure Gd by Xray fluorescence spectrometer
2ErSbO
7The average atom molar percentage be Gd:Er:Sb:O=2.00:1.01:0.99:6.98.With Rietveld software to Gd
2ErSbO
7XRD result carry out structure refinement, the structure refinement factor R
PValue is R
P=11.30%.Gd
2ErSbO
7Space group be Fd-3m, structure is cubic system, pyrochlore constitution, cell parameter a is
Gd
2ErSbO
7The indices of crystallographic plane such as (222) of each diffraction maximum, (400), (440), (622), (444), (800), (662), (840), (844) are demarcated.Gd
2ErSbO
7In the space atom site parameter of each atom be determined (seeing Table 1).Adopt the UV-vis DRS spectrometer to Gd
2ErSbO
7The characteristic absorption limit that produces under the irradiation of light is measured, and obtains Gd
2ErSbO
7Band gap width be 2.53eV, obtain Gd
2ErSbO
7Band structure, conduction band is made of the 4d track of Er, the 5d track of Gd and the 5p track of Sb, valence band is made of the 2p track of O.Under radiation of visible light, with Gd
2ErSbO
7Be catalyst, crystal violet (C
25H
30ClN
3) initial concentration be 0.0293mM, initial soln 300mL, radiation of visible light are after 200 minutes, the clearance of crystal violet is 97.39%, the degraded crystal violet photo-quantum efficiency be 0.04996%; Behind the radiation of visible light 240 minutes, the clearance of crystal violet is 100%.Behind the radiation of visible light 200 minutes, crystal violet concentration changes with time dynamics Changshu K
CBe 0.0151min
-1Crystal violet total organic carbon concentration changes with time dynamics Changshu K
TOCBe 0.0131min
-1Behind the radiation of visible light 200 minutes, CO
2Spill-out be 0.2102mmol, the clearance of total organic carbon is 96.30%.
Application example
1. adopt Gd
2ErSbO
7Titan yellow (C in the powder degrading waste water
28H
19N
5Na
2O
6S
4)
With Gd
2ErSbO
7Powder 0.8g puts into the 300mL titan yellow aqueous solution and forms suspension system, and the initial concentration of the titan yellow aqueous solution is 0.03mmol L
-1, original ph is 7.Choose the xenon lamp irradiation titan yellow solution of 300W, mix edge filter (λ〉420nm).The incident light intensity of illumination is 4.76 * 10
-6Einstein L
-1s
-1In 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.With Gd
2ErSbO
7Powder is catalyst, under radiation of visible light, along with the prolongation of irradiation time, the concentration of titan yellow reduces gradually, and total organic carbon (TOC) concentration also reduced gradually, through 320 minutes, the clearance of titan yellow is 100%, and the clearance of total organic carbon TOC (mineralization rate) reaches 99.52%, CO
2Productive rate be 0.25012mmol, first order kinetics Changshu K of titan yellow concentration and time
cBe 0.02182min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.01324min
-1Detailed data see Table 3.
Table 3 is with Gd
2ErSbO
7Powder is the related data that the catalyst degradation titan yellow obtains
2. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
7Titan yellow (C in (photochemical catalyst shell) degrading waste water
28H
19N
5Na
2O
6S
4)
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)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
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 titan yellow of typical difficult degradation in the water as the target degradation product.When magnetic field intensity is 2.5～3.2 tesla, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in containing the aqueous solution of titan yellow, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Select the 900mL titan yellow aqueous solution this moment, simultaneously the Gd of all magnetic-particle surface coatings
2ErSbO
7Weight is near 2.4g, and the initial concentration of the titan yellow aqueous solution is 0.03mmol L
-1, original ph is 7.Choose the xenon lamp irradiation titan yellow solution of 300W, mix edge filter (λ〉420nm).The incident light intensity of illumination is 4.76 * 10
-6Einstein L
-1s
-1In 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.The result shows with γ-Fe
2O
3(magnetic-particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, prolongation along with irradiation time, the concentration of titan yellow reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 300 minutes, the clearance of titan yellow reaches 100%, and the clearance of total organic carbon TOC (mineralization rate) reaches 99.55%, CO
2Productive rate be 0.24867mmol, first order kinetics Changshu K of titan yellow concentration and time
cBe 0.02592min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.01469min
-1Detailed data see Table 4.
Table 4 adopts γ-Fe
2O
3-Gd
2ErSbO
7, SiO
2-Gd
2ErSbO
7And MnO-Gd
2ErSbO
7The related data that obtains for the catalyst degradation titan yellow
3. adopt Gd
2ErSbO
7Aniline blue (C in the powder degrading waste water
32H
25N
3Na
2O
9S
3)
With Gd
2ErSbO
7Powder 0.8g puts into the 300mL aniline blue aqueous solution and forms suspension system, and the initial concentration of the aniline blue aqueous solution is 0.03mmol L
-1, original ph is 7.Choose the xenon lamp irradiation aniline blue solution of 300W, mix edge filter (λ〉420nm).The incident light intensity of illumination is 4.76 * 10
-6Einstein L
-1s
-1In 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.With Gd
2ErSbO
7Powder is catalyst, under radiation of visible light, along with the prolongation of irradiation time, the concentration of aniline blue reduces gradually, and total organic carbon (TOC) concentration also reduced gradually, through 370 minutes, the clearance of aniline blue is 100%, and the clearance of total organic carbon TOC (mineralization rate) reaches 99.54%, CO
2Productive rate be 0.28467mmol, first order kinetics Changshu K of aniline blue concentration and time
cBe 0.01572min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.00938min
-1Detailed data see Table 5.
Table 5 is with Gd
2ErSbO
7Powder is the related data that the catalyst degradation aniline blue obtains
4. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
7Aniline blue (C in (photochemical catalyst shell) degrading waste water
32H
25N
3Na
2O
9S
3)
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)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
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 aniline blue of typical difficult degradation in the water as the target degradation product.When magnetic field intensity is 2.5～3.2 tesla, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in containing the aqueous solution of aniline blue, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Select the 900mL aniline blue aqueous solution this moment, simultaneously the Gd of all magnetic-particle surface coatings
2ErSbO
7Weight is near 2.4g, and the initial concentration of the aniline blue aqueous solution is 0.03mmol L
-1, original ph is 7.Choose the xenon lamp irradiation aniline blue solution of 300W, mix edge filter (λ〉420nm).The incident light intensity of illumination is 4.76 * 10
-6Einstein L
-1s
-1In 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.The result shows with γ-Fe
2O
3(magnetic-particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, prolongation along with irradiation time, the concentration of aniline blue reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 350 minutes, the clearance of aniline blue reaches 100%, and the clearance of total organic carbon TOC (mineralization rate) reaches 99.57%, CO
2Productive rate be 0.28497mmol, first order kinetics Changshu K of aniline blue concentration and time
cBe 0.01681min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.01022min
-1Detailed data see Table 6.
Table 6 adopts γ-Fe
2O
3-Gd
2ErSbO
7, SiO
2-Gd
2ErSbO
7And MnO-Gd
2ErSbO
7The related data that obtains for the catalyst degradation aniline blue
5. adopt Gd
2ErSbO
7Methylene blue (C in the powder degrading waste water
16H
18ClN
3S)
With Gd
2ErSbO
7Powder 0.8g puts into the 300mL aqueous solution of methylene blue and forms suspension system, and the initial concentration of aqueous solution of methylene blue is 0.03mmol L
-1, original ph is 7.Choose the xenon lamp irradiation methylene blue solution of 300W, mix edge filter (λ〉420nm).The incident light intensity of illumination is 4.76 * 10
-6Einstein L
-1s
-1In 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.With Gd
2ErSbO
7Powder be catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of methylene blue reduces gradually, total organic carbon (TOC) concentration also reduces gradually, and through 390 minutes, the clearance of methylene blue was 100%, the clearance of total organic carbon TOC (mineralization rate) reaches 99.55%, CO
2Productive rate be 0.14187mmol, first order kinetics Changshu K of methylene blue concentration and time
cBe 0.01544min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.00861min
-1Detailed data see Table 7.
Table 7 is with Gd
2ErSbO
7Powder is the related data that the catalyst degradation methylene blue obtains
6. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
7Methylene blue (C in (photochemical catalyst shell) degrading waste water
16H
18ClN
3S)
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)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
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 methylene blue of typical difficult degradation in the water as the target degradation product.When magnetic field intensity is 1.9～2.6 tesla, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in containing the aqueous solution of methylene blue, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Select the 900mL aqueous solution of methylene blue this moment, simultaneously the Gd of all magnetic-particle surface coatings
2ErSbO
7Weight is near 2.4g, and the initial concentration of aqueous solution of methylene blue is 0.03mmol L
-1, original ph is 7.Choose the xenon lamp irradiation methylene blue solution of 300W, mix edge filter (λ〉420nm).The incident light intensity of illumination is 4.76 * 10
-6Einstein L
-1s
-1In 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, the result shows with γ-Fe
2O
3(magnetic-particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, prolongation along with irradiation time, the concentration of methylene blue reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 360 minutes, the clearance of methylene blue reaches 100%, and the clearance of total organic carbon TOC (mineralization rate) reaches 99.56%, CO
2Productive rate be 0.14302mmol, first order kinetics Changshu K of methylene blue concentration and time
cBe 0.01673min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.00963min
-1Detailed data see Table 8.
Table 8 adopts γ-Fe
2O
3-Gd
2ErSbO
7, SiO
2-Gd
2ErSbO
7And MnO-Gd
2ErSbO
7The related data that obtains for the catalyst degradation methylene blue
7. adopt Gd
2ErSbO
7Green B (the C of diaminourea in the powder degrading waste water
34H
22N
8Na
2O
10S
2)
With Gd
2ErSbO
7Powder 0.8g puts into the green B aqueous solution of 300mL diaminourea and forms suspension system, and the initial concentration of the green B aqueous solution of diaminourea is 0.03mmol L
-1, original ph is 7.Choose the green B solution of xenon lamp irradiation diaminourea of 300W, mix edge filter (λ〉420nm).The incident light intensity of illumination is 4.76 * 10
-6Einstein L
-1s
-1In 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.With Gd
2ErSbO
7Powder be catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of the green B of diaminourea reduces gradually, total organic carbon (TOC) concentration also reduces gradually, and through 310 minutes, the clearance of the green B of diaminourea was 100%, the clearance of total organic carbon TOC (mineralization rate) reaches 99.58%, CO
2Productive rate be 0.30293mmol, first order kinetics Changshu K of the green B concentration of diaminourea and time
cBe 0.01987min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.01147min
-1Detailed data see Table 9.
Table 9 is with Gd
2ErSbO
7Powder is the related data that the green B of catalyst degradation diaminourea obtains
8. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
7The green B (C of diaminourea in (photochemical catalyst shell) degrading waste water
34H
22N
8Na
2O
10S
2)
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)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
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 green B of diaminourea of typical difficult degradation in the water as the target degradation product.When magnetic field intensity is 1.9～2.6 tesla, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in the aqueous solution that contains the green B of diaminourea, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Select the green B aqueous solution of 900mL diaminourea this moment, simultaneously the Gd of all magnetic-particle surface coatings
2ErSbO
7Weight is near 2.4g, and the initial concentration of the green B aqueous solution of diaminourea is 0.03mmol L
-1, original ph is 7.Choose the green B solution of xenon lamp irradiation diaminourea of 300W, mix edge filter (λ〉420nm).The incident light intensity of illumination is 4.76 * 10
-6Einstein L
-1s
-1In 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, the result shows with γ-Fe
2O
3(magnetic-particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, prolongation along with irradiation time, the concentration of the green B of diaminourea reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 280 minutes, the clearance of the green B of diaminourea reaches 100%, and the clearance of total organic carbon TOC (mineralization rate) reaches 99.65%, CO
2Productive rate be 0.30287mmol, first order kinetics Changshu K of the green B concentration of diaminourea and time
cBe 0.0219min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.01297min
-1Detailed data see Table 10.
Table 10 adopts γ-Fe
2O
3-Gd
2ErSbO
7, SiO
2-Gd
2ErSbO
7And MnO-Gd
2ErSbO
7The related data that obtains for the green B of catalyst degradation diaminourea
9. adopt Gd
2ErSbO
7Nuclear fast red (C in the powder degrading waste water
14H
8NNaO
7S)
With Gd
2ErSbO
7Powder 0.8g puts into the 300mL nuclear fast red aqueous solution and forms suspension system, and the initial concentration of the nuclear fast red aqueous solution is 0.03mmol L
-1, original ph is 7.Choose the xenon lamp irradiation nuclear fast red solution of 300W, mix edge filter (λ〉420nm).The incident light intensity of illumination is 4.76 * 10
-6Einstein L
-1s
-1In 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.With Gd
2ErSbO
7Powder be catalyst under radiation of visible light, along with the prolongation of irradiation time, nuclear fast red concentration reduce gradually, total organic carbon (TOC) concentration also reduces gradually, and through 300 minutes, the clearance of nuclear fast red was 100%, the clearance of total organic carbon TOC (mineralization rate) reaches 99.54%, CO
2Productive rate be 0.12456mmol, nuclear fast red concentration and first order kinetics Changshu K of time
cBe 0.02133min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.01235min
-1Detailed data see Table 11.
Table 11 is with Gd
2ErSbO
7Powder is the related data that catalyst degradation nuclear fast red obtains
10. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
7Nuclear fast red (C in (photochemical catalyst shell) degrading waste water
14H
8NNaO
7S)
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)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
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 nuclear fast red of typical difficult degradation in the water as the target degradation product.When magnetic field intensity is 1.9～2.6 tesla, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in containing the aqueous solution of examining fast red, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Select the 900mL nuclear fast red aqueous solution this moment, simultaneously the Gd of all magnetic-particle surface coatings
2ErSbO
7Weight is near 2.4g, and the initial concentration of the nuclear fast red aqueous solution is 0.03mmol L
-1, original ph is 7.Choose the xenon lamp irradiation nuclear fast red solution of 300W, mix edge filter (λ〉420nm).The incident light intensity of illumination is 4.76 * 10
-6Einstein L
-1s
-1In 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, the result shows with γ-Fe
2O
3(magnetic-particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, prolongation along with irradiation time, the concentration of nuclear fast red reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 280 minutes, the clearance of nuclear fast red reaches 100%, and the clearance of total organic carbon TOC (mineralization rate) reaches 99.65%, CO
2Productive rate be 0.12439mmol, nuclear fast red concentration and first order kinetics Changshu K of time
cBe 0.02359min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.01456min
-1Detailed data see Table 12.
Table 12 adopts γ-Fe
2O
3-Gd
2ErSbO
7, SiO
2-Gd
2ErSbO
7And MnO-Gd
2ErSbO
7For catalyst degradation is examined the related data that fast red obtains
11. adopt Gd
2ErSbO
7Ponceau S (C in the powder degrading waste water
22H
12N
4Na
4O
13S
4)
With Gd
2ErSbO
7Powder 0.8g puts into the 300mL Ponceau S aqueous solution and forms suspension system, and the initial concentration of the Ponceau S aqueous solution is 0.03mmol L
-1, original ph is 7.Choose the xenon lamp irradiation Ponceau S solution of 300W, mix edge filter (λ〉420nm).The incident light intensity of illumination is 4.76 * 10
-6Einstein L
-1s
-1In 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.With Gd
2ErSbO
7Powder be catalyst under radiation of visible light, along with the prolongation of irradiation time, the concentration of Ponceau S reduces gradually, total organic carbon (TOC) concentration also reduces gradually, and through 240 minutes, the clearance of Ponceau S was 100%, the clearance of total organic carbon TOC (mineralization rate) reaches 99.53%, CO
2Productive rate be 0.19582mmol, first order kinetics Changshu K of Ponceau S concentration and time
cBe 0.02750min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.01636min
-1Detailed data see Table 13.
Table 13 is with Gd
2ErSbO
7Powder is the related data that the catalyst degradation Ponceau S obtains
12. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
7Ponceau S (C in (photochemical catalyst shell) degrading waste water
22H
12N
4Na
4O
13S
4)
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)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
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 Ponceau S of typical difficult degradation in the water as the target degradation product.When magnetic field intensity is 1.9～2.6 tesla, above-mentioned three kinds of magnetic coupling catalyst granules distribution gradient in containing the aqueous solution of Ponceau S, and can make it be evenly distributed on upper, middle and lower-ranking in the aqueous solution.Select the 900mL Ponceau S aqueous solution this moment, simultaneously the Gd of all magnetic-particle surface coatings
2ErSbO
7Weight is near 2.4g, and the initial concentration of the Ponceau S aqueous solution is 0.03mmol L
-1, original ph is 7.Choose the xenon lamp irradiation Ponceau S solution of 300W, mix edge filter (λ〉420nm).The incident light intensity of illumination is 4.76 * 10
-6Einstein L
-1s
-1In 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, the result shows with γ-Fe
2O
3(magnetic-particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
2ErSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
2ErSbO
7(photochemical catalyst shell) as catalyst under radiation of visible light, prolongation along with irradiation time, the concentration of Ponceau S reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 210 minutes, the clearance of Ponceau S reaches 100%, and the clearance of total organic carbon TOC (mineralization rate) reaches 99.68%, CO
2Productive rate be 0.19559mmol, first order kinetics Changshu K of Ponceau S concentration and time
cBe 0.03289min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.02060min
-1Detailed data see Table 14.
Table 14 adopts γ-Fe
2O
3-Gd
2ErSbO
7, SiO
2-Gd
2ErSbO
7And MnO-Gd
2ErSbO
7The related data that obtains for the catalyst degradation Ponceau S
13. adopt Gd
2ErSbO
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 4.76 * 10 to the xenon lamp of radiation source employing 300W
-6Einstein L
-1s
-1, the 420nm edge filter) or the 400W(incident flux be 6.01 * 10
-6Einstein L
-1s
-1, the 390nm edge filter) high-pressure sodium lamp, in 300mL (16.65mol) pure water, put into Gd
2ErSbO
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 1673.4 micromoles, and the output of oxygen is 836.2 micromoles; After 24 hours, the output of hydrogen is 2789.8 micromoles under high voltage mercury lamp radiation, and the output of oxygen is 1393.7 micromoles.
With Gd
2ErSbO
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/Gd
2ErSbO
7Be composite catalyst, the output of hydrogen is 5.12mmol after 24 hours; With 1.0wt%-NiO/Gd
2ErSbO
7Be composite catalyst, the output of hydrogen is 3.69mmol after 24 hours; With 1.0wt%-RuO
2/ Gd
2FeSbO
7Be composite catalyst, the output of hydrogen is 2.96mmol after 24 hours, and detailed data see Table 15 and table 16.
Table 15 is with Gd
2ErSbO
7Powder is catalyst, the related data that the decomposition water hydrogen making obtains under UV-irradiation
Table 16 is with Gd
2ErSbO
7Powder is catalyst, the related data that the decomposition water hydrogen making obtains under radiation of visible light
Claims (5)
1. photocatalysis catalysis material, it is characterized in that for as following structural formula: Gd
3-xEr
xSbO
7(0.5≤x≤1), particle diameter are the 0.04-0.32 micron.
2. the catalysis material of nucleocapsid structure according to claim 1 is characterized in that γ-Fe
2O
3Ferromagnetic particle nuclear-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Gd
3-xEr
xSbO
7(0.5≤x≤1) (photochemical catalyst shell); γ-Fe
2O
3, SiO
2With the particle diameter of MnO be the 0.06-1 micron, Gd
3-xEr
xSbO
7Particle diameter is the 0.09-1.30 micron behind (0.5≤x≤1) parcel nuclear.
3. the application of powder catalytic material according to claim 2 or nucleocapsid structure catalysis material is characterized in that the catalysis material of nucleocapsid structure or distinguishes supporting Pt, NiO or RuO
2Cocatalyst; Cocatalyst adds mass ratio 20-30%, and light source is xenon lamp or high-pressure sodium lamp, carries out decomposition water hydrogen making or degrading waste water in the airtight glass piping interior lighting reactor by a plurality of valve controls.
4. the application of powder catalytic material according to claim 3 or nucleocapsid structure catalysis material, it is characterized in that the application of the catalysis material of nucleocapsid structure, by the organic pollution titan yellow (C in the reaction system degrading waste water of magnetic field device and nucleocapsid structure catalysis material formation
28H
19N
5Na
2O
6S
4), aniline blue (C
32H
25N
3Na
2O
9S
3), the green B (C of diaminourea
34H
22N
8Na
2O
10S
2), nuclear fast red (C
14H
8NNaO
7S), Ponceau S (C
22H
12N
4Na
4O
13S
4), methylene blue (C
16H
18ClN
3S) etc., 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 the catalysis material γ-Fe of nucleocapsid structure
2O
3(ferromagnetic particle nuclear)-Gd
3-xEr
xSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Gd
3-xEr
xSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Gd
3-xEr
xSbO
7(photochemical catalyst shell) as catalyst, above-mentioned three kinds of magnetic coupling catalysis materials or add NiO or the RuO of 20-30% mass ratio
2Particle or powder and Gd
3-xEr
xSbO
7Evenly mixed percent by volume respectively accounts for volume ratio and is 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.
5. the catalysis material magnetic-particle nuclear-Gd of nucleocapsid structure according to claim 2
3-xEr
xSbO
7The preparation method of (0.5≤x≤1): adopt the method for electrostatic interaction to prepare hud typed complex microsphere: by the Gd of lotus positive electricity ethylene-acrylic rubber AEM modification
3-xEr
xSbO
7Ferromagnetic particle γ-the Fe of (0.5≤x≤1) and bear electricity
2O
3, paramagnetic particle SiO
2Or anti-ferromagnetism particle MnO interacts; Adopt micron-sized powder photocatalytic material Gd
3-xEr
xSbO
7(0.5≤x≤1), AEM (ethylene-acrylic rubber), Nanoscale Iron magnetic-particle γ-Fe
2O
3, paramagnetic particle SiO
2Or anti-ferromagnetism particle MnO; To be powder photocatalytic material Gd
3-xEr
xSbO
7Quality 2-5 times nanometer γ-Fe
2O
3, SiO
2Or MnO places respectively the water of 500-1000 part quality to stir, and adds weak aqua ammonia 1-8 part, makes nanometer γ-Fe
2O
3, SiO
2Or MnO bear electricity, for subsequent use; Get 0.1g powder photocatalytic material Gd
3-xEr
xSbO
7(0.5≤x≤1), the ethanolic solution dipping stirring with AEM concentration 2-9%w/w makes Gd
3-xEr
xSbO
7(0.5≤x≤1) lotus positive electricity is used the nanometer γ of above-mentioned configuration-Fe again
2O
3, SiO
2Or the mixed swelling that stirs of MnO ammoniacal liquor mixed solution, make electronegative nanometer γ-Fe
2O
3, SiO
2Or MnO is by the Gd of the AEM modification of electrostatic interaction and lotus positive electricity
3-xEr
xSbO
7(0.5≤x≤1) is at Gd
3-xEr
xSbO
7(0.5≤x≤1) surface forms shell structure, and the thickness of shell can be according to the nanometer γ that adds-Fe
2O
3, SiO
2Or the amount of MnO decides, and then use absolute ethyl alcohol successively, the deionized water cyclic washing, remove unnecessary AEM ethanolic solution and ammonia spirit, room temperature is dried, and namely gets the catalysis material magnetic-particle nuclear-Gd with nucleocapsid structure
3-xEr
xSbO
7(0.5≤x≤1).
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| CN104645968A (en) * | 2014-12-26 | 2015-05-27 | 南京大学 | Preparation of Tb<3-x>PrxNbO7-zeolite composite porous nanometer catalyst material and application thereof |
| CN107890865A (en) * | 2017-11-09 | 2018-04-10 | 南京大学（苏州）高新技术研究院 | The preparation and application of a kind of powder catalytic material, the compound porous catalysis material of modified coal ash floating bead |
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| CN104645968A (en) * | 2014-12-26 | 2015-05-27 | 南京大学 | Preparation of Tb<3-x>PrxNbO7-zeolite composite porous nanometer catalyst material and application thereof |
| CN107890865A (en) * | 2017-11-09 | 2018-04-10 | 南京大学（苏州）高新技术研究院 | The preparation and application of a kind of powder catalytic material, the compound porous catalysis material of modified coal ash floating bead |
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