CN102151563B - Gadolinium-yttrium-antimony based composite magnetic particle photo catalyst of core-shell structure, preparation and application thereof - Google Patents
Gadolinium-yttrium-antimony based composite magnetic particle photo catalyst of core-shell structure, preparation and application thereof Download PDFInfo
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- 239000006249 magnetic particle Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 37
- 239000002131 composite material Substances 0.000 title abstract description 20
- 239000011258 core-shell material Substances 0.000 title abstract 4
- 239000011941 photocatalyst Substances 0.000 title description 7
- PXGPPRDLWWPVCX-UHFFFAOYSA-N [Sb].[Y].[Gd] Chemical compound [Sb].[Y].[Gd] PXGPPRDLWWPVCX-UHFFFAOYSA-N 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 125
- 239000002245 particle Substances 0.000 claims abstract description 97
- 239000000463 material Substances 0.000 claims abstract description 86
- 238000000151 deposition Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 61
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 60
- 239000007789 gas Substances 0.000 claims description 51
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 229910001566 austenite Inorganic materials 0.000 claims description 43
- 230000005303 antiferromagnetism Effects 0.000 claims description 34
- 230000005298 paramagnetic effect Effects 0.000 claims description 33
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- 229910052786 argon Inorganic materials 0.000 claims description 32
- 238000006555 catalytic reaction Methods 0.000 claims description 31
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 238000009413 insulation Methods 0.000 claims description 27
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- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 238000000427 thin-film deposition Methods 0.000 claims description 7
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- ZDINGUUTWDGGFF-UHFFFAOYSA-N antimony(5+) Chemical compound [Sb+5] ZDINGUUTWDGGFF-UHFFFAOYSA-N 0.000 claims description 4
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- HGGPVCKBWYYOBU-UHFFFAOYSA-L dibromo(trimethyl)-$l^{5}-stibane Chemical compound C[Sb](C)(C)(Br)Br HGGPVCKBWYYOBU-UHFFFAOYSA-L 0.000 description 2
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- LDWZIXQSZWFRGT-UHFFFAOYSA-N gadolinium(3+);trinitrate;hydrate Chemical compound O.[Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LDWZIXQSZWFRGT-UHFFFAOYSA-N 0.000 description 2
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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
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- Catalysts (AREA)
Abstract
The invention discloses a catalytic material of a core-shell structure: gamma-Fe2O3-Y3-xGdxSbO7 (x is not less than 0.5 and not more than 1), SiO2-Y3-xGdxSbO7 (x is not less than 0.5 and not more than 1), MnO-Y3-xGdxSbO7 (x is not less than 0.5 and not more than 1), and application of the catalytic material of the core-shell structure ; wherein particle diameters of the gamma-Fe2O3, the SiO2 and the MnO are 0.06-2 microns, the particle diameter of the Y3- xGdxSbO7 (x is not less than 0.5 and not more than 1) wrapped with a core is 0.08-1.2 microns; organic pollutants in waste water, such as pentachlorphenol, atrazine, diuron, dye rhodamin B and the like are degraded by a reaction system consisting of a magnetic field device and the catalytic material of the core-shell structure; the magnetic field device is an intensity-adjustable alternating magnetic field generator; a light source is a xenon lamp or a high pressure mercury lamp; a volume percent of the three magnetic composite photo catalytic materials occupies one third of a volume ratio respectively; the materials are uniformly distributed in a water solution and are aerated by oxygenizing; and the overall light reaction is performed under a closed and light-tight environment. A novel catalyst is loaded on the magnetic particle core by adopting a multi-target magnetron sputtering deposition method, a pulse laser sputtering deposition method or a metal organic chemical vapor deposition method.
Description
Technical field
The present invention relates to a kind of novel photocatalysis agent, preparation and application, especially powder catalytic material Y
3-xGd
xSbO
7γ-the Fe of (0.5≤x≤1) and " magnetic-particle nuclear-photochemical catalyst shell " structure
2O
3-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2-Y
3-xGd
xSbO
7(0.5≤x≤1), MnO-Y
3-xGd
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 that photochemical catalyzing is produced hydrogen.
Background technology
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 technology 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 the poor removal effect or the basic non-processor effect of this type material.And then the developmental research that causes the organic novel advanced oxidation treatment technology of refractory organics in the water becomes the focus and the advanced subject in present international environment engineering field.In addition, the energy hydrogen that adopts less cost to prepare novel clean also is present hot subject, and based on this, development can utilize solar energy and have a corresponding novel photocatalysis material of visible light also extremely urgent.
Novel semi-conductor catalysis material and photocatalytic advanced oxidation technology be in various countries' scientists processing water of generally acknowledging the refractory organics organic matter the most effectively, the catalysis material and the technical matters of market prospects arranged most; Utilize novel semi-conductor catalysis material and the photocatalytic advanced oxidation technology refractory organics organic pollution in the water body of can degrading expeditiously; The photocatalytic advanced oxidation technology has tangible advantage at the aspects such as mineralising decomposition of difficult for biological degradation organic matter than electro-catalysis, catalytic wet oxidation technology, and 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 the not industrialization as yet of hydrogen aspect with decomposition water aspect the organic pollution in removing water body; Mainly have following two problems: (1) suspension system photocatalysis system photocatalysis efficiency is high; There is catalyst post processing problem; If photochemical catalyst is fixed on the Separation and Recovery problem that can solve photochemical catalyst on the materials such as glass, but its photocatalysis efficiency is starkly lower than suspension system; (2) titanium dioxide only can absorbing ultraviolet light; In not response of visible-range; Utilization rate to sunshine low (4%), and solar spectrum medium ultraviolet light part only accounts for less than 5%, wavelength is that the visible light of 400-750nm then accounts for 43% of solar spectrum; If can ultraviolet light wave band and the visible light wave range in the sunshine be fully utilized simultaneously, photo-quantum efficiency will be greatly improved.Therefore, the recovery that under the prerequisite that guarantees higher photocatalysis efficiency, solves photochemical catalyst has become organic pollution and photochemical catalyzing in the photocatalysis removal water body to produce the key of hydrogen industrial applications with the quantum efficiency problem.
At present, the light utilization efficiency of raising photochemical catalyst mainly contains both direction.The one, TiO 2 visible lightization partly replaces the oxygen element in the titanium dioxide like 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 a lot of achievements: 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.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 degradation water and airborne formaldehyde, acetaldehyde, methylene blue and H effectively
2Nuisances such as S.Zhu Yongfa, Zhao Jincai etc. utilize homemade new material (like 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 Ga first
2BiTaO
7Methylene blue dye in the powder photocatalytic degradation water body, methylene blue is by degraded fully after 140 minutes.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-xGd
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)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell) preparation technology, performance characterization and application.
Technical scheme of the present invention is: powder catalytic material, following structural formula: Y
3-xGd
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)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), MnO (anti-ferromagnetism granular core)-Y
3-xGd
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-xGd
xSbO
7(0.5≤x≤1) parcel nuclear back particle diameter is the 0.08-1.2 micron.
The application of powder catalytic material is through Y
3-xGd
xSbO
7(0.5≤x≤1) powder is a catalyst, or supporting Pt respectively,, NiO and RuO
2Cocatalyst, light source are xenon lamp or high-pressure sodium lamp, in the airtight glass piping interior lighting reactor by a plurality of valve controls, carry out decomposition water and produce hydrogen.
The application of the catalysis material of nucleocapsid structure; Reaction system degrading organic contaminant in wastewater pentachlorophenol, Atrazine, diuron and dyestuff rhodamine B etc. through magnetic field device and nucleocapsid structure catalysis material formation; Magnetic field device is the adjustable alternating magnetic field generator of intensity; 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)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell) is as catalyst; The percent by volume of above-mentioned three kinds of magnetic composite photocatalyst materials respectively accounts for volume ratio and is 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, and 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 catalysis material magnetic-particle nuclear-Y of nucleocapsid structure
3-xGd
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-xGd
xSbO
7(0.5≤x≤1) target, the target diameter is 10mm, thickness is 2mm;
B. choose substrate: the ferromagnetic particle γ-Fe that selects above-mentioned size 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, the distance of target to substrate is 3～7 centimetres, substrate temperature is 300～700 ℃, sputter Y
3-xGd
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 particle 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 1320 ± 10 ℃ of temperature, make it crystallization and obtain required magnetic compound catalyze material γ-Fe
2O
3-Y
3-xGd
xSbO
7(0.5≤x≤1), SiO
2-Y
3-xGd
xSbO
7(0.5≤x≤1) or MnO-Y
3-xGd
xSbO
7(0.5≤x≤1).
The catalysis material magnetic-particle nuclear-Y of nucleocapsid structure
3-xGd
xSbO
7The preparation method of (0.5≤x≤1): the method that it is characterized in that adopting the multi-target magnetic control sputtering deposition:
A. target preparation: prepare simple metal Gd, 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: with metal Y, Gd and Sb is target, and 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, the distance of target to substrate is 4～15 centimetres, and substrate temperature is 0～400 ℃, and film deposition rate is 1～2nm/min;
Cosputtering simple metal Gd, Y 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-xGd
xSbO
7(0.5≤x≤1) rete is handled 120 ± 10min at 1320 ± 10 ℃ with above-mentioned three kinds of retes in nitrogen or argon gas; Make it crystallization and obtain required γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1) or MnO (anti-ferromagnetism granular core)-Y
3-xGd
xSbO
7(0.5≤x≤1).
The catalysis material magnetic-particle nuclear-Y of nucleocapsid structure
3-xGd
xSbO
7The preparation method of (0.5≤x≤1): the method that it is characterized in that adopting metal-organic chemical vapor deposition equipment (MOCVD):
MOCVD equipment mainly is made up of source supply system, reative cell, heating system, gas transport and flow control system, vacuum and low voltage control part, gas extraction system, operation control system and safety system.System adopts vertical stainless steel reaction chamber, and the substrate pallet diameter 52mm that high purity graphite is coated is rotatable, resistance heated, temperature range 200-900 ℃.Adopt Britain's Continental Europe 808 temperature controller temperature controls, precision ± 1 ℃, reacting gas and source steam entering reative cell are controlled the even distribution of substrate surface gas flow through the distance fine regulation between nozzle and the pallet.The solid metal-organic compound source is contained in the bubbler, and temperature is by HA8800 type semiconductor heat trap control, temperature-controlled precision ± 0.1 ℃.Be carried to reative cell to the source steam by the highly purified argon carrier bubbler of flowing through during growth.The pipeline of institute's active power flow warp all adopts the heating tape insulation, is higher than 5～10 ℃ of metallo-organic compound source operating temperatures, avoids the source steam in pipeline, to deposit.Reacting gas is high-purity O
2, for fear of pre-reaction takes place, metallo-organic compound source capsule road and reaction gas pipeline are mixed after getting into reative cell respectively again.The low pressure of catalyst film in growth course, the nothing dried pump of oil (DVT-300) that is produced by Japan provides, and system's stable operation under the low pressure condition is regulated pressure precision less than 1%.
Reaction system precursor material acetylacetone,2,4-pentanedione yttrium [Y (CH
3COCHCOCH
3)
3], acetylacetone,2,4-pentanedione gadolinium [Gd (CH
3COCHCOCH
3)
3], trimethyl bromize antimony (V) [Trimethylantimony (V) bromide, Sb (CH
3)
3Br
2] or SbCl
5Deng steam by carrier gas Ar or N
2Dilution is transported to reative cell (or being transported to reacting furnace); In reative cell, utilize laser or UV-irradiation to make above-mentioned raw materials steam generation photochemical reaction; The acceleration presoma decomposes, and each presoma fully mixes in gas phase, controls the component of film through the flow of controlling each vapor phase metal source.Substrate base is by γ-Fe
2O
3(ferromagnetic particle nuclear), SiO
2(paramagnetic particle nuclear), MnO (anti-ferromagnetism granular core) constitute.This experiment MOCVD deposition process relates to multiple gaseous reactant, accomplishes through chemosynthesis reaction and oxidation reaction.As carrier gas, oxidant is an oxygen with argon gas or nitrogen.Adjust various parameters, reacting gas acetylacetone,2,4-pentanedione yttrium, acetylacetone,2,4-pentanedione gadolinium and trimethyl bromize antimony (or SbCl
5) mol ratio be (3-x): x: 1 (0.5≤x≤1); Underlayer temperature is 650 ± 200 ℃; The film growth temperature is 600 ± 250 ℃; The reative cell internal pressure is 133～1596Pa; Oxygen partial pressure power is 25～798Pa in the reative cell; The flow rate in carrier gas and gaseous state metallo-organic compound source is 10～500cm
3/ min; The flow rate of oxygen is 5～300cm
3/ min; Depositing of thin film speed is 0.5～10 μ m/h; The thin film deposition time is 10～100min.Successfully on substrate, deposit formation Y according to above-mentioned technology
3-xGd
xSbO
7(0.5≤x≤1) rete is handled 200 ± 10min at 1320 ± 10 ℃ with above-mentioned three kinds of retes in nitrogen or argon gas; Make it crystallization and obtain required γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1) or MnO (anti-ferromagnetism granular core)-Y
3-xGd
xSbO
7(0.5≤x≤1).
2, powder catalytic material Y
3-xGd
xSbO
7The preparation method of (0.5≤x≤1): it is characterized in that:
(1) powder catalytic material Y
3-xGd
xSbO
7The preparation of (0.5≤x≤1): adopt the method for high temperature solid-phase sintering to prepare Y
3-xGd
xSbO
7(0.5≤x≤1) photocatalytic powder material; With purity 99.99% Y
2O
3, Gd
2O
3And Sb
2O
5Be raw material, with Y, Gd and Sb Y with the atomic ratio of said molecular formula
2O
3, Gd
2O
3And Sb
2O
5Fully mix, then in grinding in ball grinder, the particle diameter of powder reaches the 1.4-1.8 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 after 8 ± 2 hours and cool off with stove, 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, put 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 following:
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 1320 ± 10 ℃ by 800 ℃, the heating-up time is 50 ± 10min; F. at 1320 ± 10 ℃ of insulation 3900 ± 200min, 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 1320 ± 10 ℃ of insulations of maximum temperature, 3900 ± 200min, finally prepares successfully pure Y
3-xGd
xSbO
7(0.5≤x≤1) powder photocatalytic material.
(2) adopt sol-gel process to prepare powder photocatalytic material Y
3-xGd
xSbO
7(0.5≤x≤1): utilize improved Sol-Gel method, adopt organometallic precursor, preparation Y
3-xGd
xSbO
7(0.5≤x≤1).Presoma gadolinium acetate [Gd (CH
3CO
2)
3], yttrium acetate hydrate [Y (CH
3CO
2)
34H
2O] and antimony chloride (SbCl
5) be dissolved in the isopropyl alcohol, and, utilize above-mentioned presoma according to the segmented process for preparing sol-gel with Y, Gd and Sb atomic ratio with said molecular formula; 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 following: 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 1220 ± 30 ℃ by 750 ℃, the heating-up time is 40 ± 10min; F. at 1220 ± 30 ℃ of insulation 2200 ± 400min, stove is cold.With the stove cooling, it is the 0.04-0.20 micron that the taking-up pressed powder is crushed to particle diameter to pressed powder behind 1220 ± 30 ℃ of insulations of maximum temperature, 2200 ± 400min, finally prepares successfully pure Y
3-xGd
xSbO
7(0.5≤x≤1) powder photocatalytic material.
(3) adopt hydrothermal synthesis method to prepare powder photocatalytic material Y
3-xGd
xSbO
7(0.5≤x≤1): utilize precursor material gadolinium nitrate hydrate [Gd (NO
3)
36H
2O], yttrium nitrate hydrate [Y (NO
3)
36H
2O], antimony chloride (SbCl
5) and nitric acid (HNO
3), with Y, Gd and Sb Y (NO with the atomic ratio of said molecular formula
3)
3, Gd (NO
3)
3And SbCl
5Fully mix, promptly the mol ratio of Y, Gd and Sb is (3-x): x: 1 (0.5≤x≤1), then above-mentioned precursor material is changed in the reaction vessel autoclave, and adopt the aqueous solution as reaction medium, polyethylene glycol or ethylene glycol are as dispersant.Liquor capacity accounts for 60% of autoclave volume.The reaction vessel autoclave is put into high temperature sintering furnace heat, heating-up temperature is 200 ± 40 ℃, and pressure is 120MPa ± 30MPa in the autoclave; Insulation 1800 ± 120min; Be cooled to room temperature at last,, handle through the washing of acetone, deionized water and straight alcohol again through centrifugal filtration; In the room temperature dried in vacuum, prepare Y then through the high temperature and high pressure reaction environment
3-xGd
xSbO
7(0.5≤x≤1) powder.Put into the high temperature sintering furnace sintering after at last above-mentioned mixture of powders being pressed into thin slice, the intensification condition is following: a. is warming up to 400 ℃ by 20 ℃, and the heating-up time is 40 ± 10min; B. at 400 ℃ of insulation 40 ± 10min; C. be warming up to 750 ℃ by 400 ℃, the heating-up time is 30 ± 10min; D. at 750 ℃ of insulation 480～600min; E. be warming up to 1150 ± 10 ℃ by 750 ℃, the heating-up time is 50 ± 10min; F. at 1150 ± 10 ℃ of insulation 600 ± 100min, stove is cold.It is the 0.04-0.26 micron that the taking-up pressed powder is crushed to particle diameter, finally prepares successfully pure Y
3-xGd
xSbO
7(0.5≤x≤1) powder photocatalytic material.
The invention has the beneficial effects as follows: successfully prepared powder catalytic material Y through physical method, sol-gel process or hydrothermal synthesis method
3-xGd
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-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).And it a series of signs have been carried out; Above-mentioned novel photocatalysis material under visible light or UV-irradiation, the degrade efficient and the mechanism of degradation of organic pollution (comprising pentachlorophenol, Atrazine and diuron) in the contaminated water body have been studied; Research decomposition water under visible light or UV-irradiation is produced the efficient and the optical activity of hydrogen; Through magnetic field-light-catalyzed reaction system, promoted the Gradient distribution of composite magnetic catalysis material in organic wastewater, also promoted the even distribution of magnetic composite photocatalyst material simultaneously; 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
2GdSbO
7The transmission electron microscope collection of illustrative plates
Fig. 2 .Y
2GdSbO
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
2GdSbO
7Photo-quantum efficiency and the lambda1-wavelength of degraded rhodamine B concern collection of illustrative plates (last figure among Fig. 3) under visible light; Y
2GdSbO
7Diffuse reflection absorb collection of illustrative plates (figure below among Fig. 3).
Fig. 4. to Y
2GdSbO
7(α hv)
2Concern collection of illustrative plates with hv.
Fig. 5. under the radiation of visible light, with Y
2GdSbO
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
2GdSbO
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
2GdSbO
7Deng the first order kinetics curve that is obtained for the catalyst degradation rhodamine B.
Fig. 8. under the radiation of visible light, with Y
2GdSbO
7The CO that is obtained for the catalyst degradation rhodamine B
2Productive rate.
Fig. 9. under the radiation of visible light, with Y
2GdSbO
7During for the catalyst degradation rhodamine B, total organic carbon TOC and incident light irradiation time chart spectrum.
Figure 10 .Y
2GdSbO
7Band structure.
The specific embodiment
Preparation powder catalytic material Y
3-xGd
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-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Y
3-xGd
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-xGd
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-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1), MnO (anti-ferromagnetism granular core)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).Adopt ultraviolet-visible spectrophotometer and the ultraviolet-visible spectrometer that diffuses 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 characteristic on above-mentioned new catalyst surface and the transport mechanism in electronics and hole in the catalyst crystal under the effect of magnetic field; 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 combine ESEM power spectrum (SEM-EDS) and x-ray photoelectron power spectrum (XPS) measured they become to be grouped into, disclosed the electron structure characteristic of catalyst surface.Profound level has disclosed the influence rule of the microstructure of novel photocatalysis agent to photocatalysis degradation organic contaminant efficient.
In the process of the persistent organic pollutants such as water body inner dye, Atrazine, diuron or pentachlorophenol of under visible light (or ultraviolet light) irradiation, degrading; Through 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 water body is degraded in visible light (or ultraviolet light) irradiation has down disclosed the degradation mechanism of organic pollutions such as water body inner dye, Atrazine, diuron or pentachlorophenol.
Adopt organic pollutions such as single wavelength visible light (or ultraviolet light) irradiation water body inner dye, Atrazine, diuron or pentachlorophenol; Successfully derive photogenerated charge (light induced electron or the photohole) quantity of participating in the photocatalytic degradation reaction through experimental study result and Theoretical Calculation; And then derive visible light (or ultraviolet light) number of photons of participating in reaction; In conjunction with the total number of photons of the incident light that calculates, finally draw the photo-quantum efficiency of organic pollutions such as dyestuff, Atrazine, diuron or pentachlorophenol in the water body of under single wavelength visible light (or ultraviolet light) effect, degrading.
Table 1Y
2GdSbO
7The atomic structure parameter
Table 2Y
2GdSbO
7The XPS collection of illustrative plates in the binding energy peak value (eV) of each essential element
The specific embodiment
1. powder catalytic material Y
3-xGd
xSbO
7The preparation were established of (0.5≤x≤1) is following:
(1) powder catalytic material Y
3-xGd
xSbO
7The preparation of (0.5≤x≤1): adopt the method for high temperature solid-phase sintering to prepare Y
3-xGd
xSbO
7(0.5≤x≤1) photocatalytic powder material; With purity 99.99% Y
2O
3, Gd
2O
3And Sb
2O
5Be raw material, with Y, Gd and Sb Y with the atomic ratio of said molecular formula
2O
3, Gd
2O
3And Sb
2O
5Fully mix, then in grinding in ball grinder, the particle diameter of powder reaches the 1.4-1.8 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 after 8 ± 2 hours and cool off with stove, 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, put 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 following:
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 1320 ± 10 ℃ by 800 ℃, the heating-up time is 50 ± 10min; F. at 1320 ± 10 ℃ of insulation 3900 ± 200min, 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 1320 ± 10 ℃ of insulations of maximum temperature, 3900 ± 200min, finally prepares successfully pure Y
3-xGd
xSbO
7(0.5≤x≤1) powder photocatalytic material;
(2) adopt sol-gel process to prepare Y
3-xGd
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-xGd
xSbO
7(0.5≤x≤1).Presoma gadolinium acetate [Gd (CH
3CO
2)
3], yttrium acetate hydrate [Y (CH
3CO
2)
34H
2O] and antimony chloride (SbCl
5) be dissolved in the isopropyl alcohol, and, utilize above-mentioned presoma according to the segmented process for preparing sol-gel with Y, Gd and Sb atomic ratio with said molecular formula; 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 following: 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 1220 ± 30 ℃ by 750 ℃, the heating-up time is 40 ± 10min; F. at 1220 ± 30 ℃ of insulation 2200 ± 400min, stove is cold.With the stove cooling, it is the 0.04-0.20 micron that the taking-up pressed powder is crushed to particle diameter to pressed powder behind 1220 ± 30 ℃ of insulations of maximum temperature, 2200 ± 400min, finally prepares successfully pure Y
3-xGd
xSbO
7(0.5≤x≤1) powder photocatalytic material.
(3) adopt hydrothermal synthesis method to prepare powder photocatalytic material Y
3-xGd
xSbO
7(0.5≤x≤1): utilize precursor material gadolinium nitrate hydrate [Gd (NO
3)
36H
2O], yttrium nitrate hydrate [Y (NO
3)
36H
2O], antimony chloride (SbCl
5) and nitric acid (HNO
3), with Y, Gd and Sb Y (NO with the atomic ratio of said molecular formula
3)
3, Gd (NO
3)
3And SbCl
5Fully mix, promptly the mol ratio of Y, Gd and Sb is (3-x): x: 1 (0.5≤x≤1), then above-mentioned precursor material is changed in the reaction vessel autoclave, and adopt the aqueous solution as reaction medium, polyethylene glycol or ethylene glycol are as dispersant.Liquor capacity accounts for 60% of autoclave volume.The reaction vessel autoclave is put into high temperature sintering furnace heat, heating-up temperature is 200 ± 40 ℃, and pressure is 120MPa ± 30MPa in the autoclave; Insulation 1800 ± 120min; Be cooled to room temperature at last,, handle through the washing of acetone, deionized water and straight alcohol again through centrifugal filtration; In the room temperature dried in vacuum, prepare Y then through the high temperature and high pressure reaction environment
3-xGd
xSbO
7(0.5≤x≤1) powder.Put into the high temperature sintering furnace sintering after at last above-mentioned mixture of powders being pressed into thin slice, the intensification condition is following: a. is warming up to 400 ℃ by 20 ℃, and the heating-up time is 40 ± 10min; B. at 400 ℃ of insulation 40 ± 10min; C. be warming up to 750 ℃ by 400 ℃, the heating-up time is 30 ± 10min; D. at 750 ℃ of insulation 480～600min; E. be warming up to 1150 ± 10 ℃ by 750 ℃, the heating-up time is 50 ± 10min; F. at 1150 ± 10 ℃ of insulation 600 ± 100min, stove is cold.It is the 0.04-0.26 micron that the taking-up pressed powder is crushed to particle diameter, finally prepares successfully pure Y
3-xGd
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 following:
(1) γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xGd
xSbO
7The preparation of (0.5≤x≤1) (photochemical catalyst shell):
Adopt the method for pulsed laser deposition deposition:
A. target preparation: the method through the above-mentioned solid phase sintering prepares Y
3-xGd
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, the distance of target to substrate is 3～7 centimetres, substrate γ-Fe
2O
3Temperature be 300～700 ℃, sputter Y
3-xGd
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 respectively at nitrogen or in argon gas under 1320 ± 10 ℃ of temperature, makes it crystallization and obtains required magnetic compound catalyze material γ-Fe
2O
3-Y
3-xGd
xSbO
7(0.5≤x≤1).
Adopt the method for multi-target magnetic control sputtering deposition:
A. target preparation: prepare simple metal Gd, 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 Gd, Y 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-xGd
xSbO
7(0.5≤x≤1) rete is handled 120 ± 10min at 1320 ± 10 ℃ with above-mentioned rete in nitrogen or argon gas; Make it crystallization and obtain required γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell).
(2) SiO
2(paramagnetic particle nuclear)-Y
3-xGd
xSbO
7The preparation of (0.5≤x≤1) (photochemical catalyst shell):
Adopt the method for pulsed laser deposition deposition:
A. target preparation: the method through the above-mentioned solid phase sintering prepares Y
3-xGd
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, the distance of target to substrate is 3～7 centimetres, substrate Si O
2Temperature be 300～700 ℃, sputter Y
3-xGd
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 respectively at nitrogen or in argon gas under 1320 ± 10 ℃ of temperature, makes it crystallization and obtains required magnetic compound catalyze material SiO
2-Y
3-xGd
xSbO
7(0.5≤x≤1).
Adopt the method for multi-target magnetic control sputtering deposition:
A. target preparation: prepare simple metal Gd, 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 Gd, Y and Sb target are to paramagnetic particle SiO in the mist of oxygen and argon gas
2Substrate surface, deposition forms Y on substrate
3-xGd
xSbO
7(0.5≤x≤1) rete is handled 120 ± 10min at 1320 ± 10 ℃ with above-mentioned rete in nitrogen or argon gas; Make it crystallization and obtain required SiO
2(paramagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1).
(3) MnO (anti-ferromagnetism granular core)-Y
3-xGd
xSbO
7The preparation of (0.5≤x≤1) (photochemical catalyst shell):
Adopt the method for pulsed laser deposition deposition:
A. target preparation: the method through the above-mentioned solid phase sintering prepares Y
3-xGd
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, the distance of target to substrate is 3～7 centimetres, the temperature of substrate MnO is 300～700 ℃, sputter Y
3-xGd
xSbO
7(0.5≤x≤1) target 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 respectively at nitrogen or in argon gas under 1320 ± 10 ℃ of temperature, make it crystallization and obtain required magnetic compound catalyze material MnO-Y
3-xGd
xSbO
7(0.5≤x≤1).
Adopt the method for multi-target magnetic control sputtering deposition:
A. target preparation: prepare simple metal Gd, 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 Gd, Y and Sb target to anti-ferromagnetism particle MnO substrate surface in the mist of oxygen and argon gas, deposition forms Y on substrate
3-xGd
xSbO
7(0.5≤x≤1) rete is handled 120 ± 10min at 1320 ± 10 ℃ with above-mentioned rete in nitrogen or argon gas; Make it crystallization and obtain required MnO (anti-ferromagnetism granular core)-Y
3-xGd
xSbO
7(0.5≤x≤1).
(4) method of employing metal-organic chemical vapor deposition equipment (MOCVD) prepares the catalysis material magnetic-particle nuclear-Y of nucleocapsid structure
3-xGd
xSbO
7(0.5≤x≤1):
MOCVD equipment mainly is made up of source supply system, reative cell, heating system, gas transport and flow control system, vacuum and low voltage control part, gas extraction system, operation control system and safety system.System adopts vertical stainless steel reaction chamber, and the substrate pallet diameter 52mm that high purity graphite is coated is rotatable, resistance heated, temperature range 200-900 ℃.Adopt Britain's Continental Europe 808 temperature controller temperature controls, precision ± 1 ℃, reacting gas and source steam entering reative cell are controlled the even distribution of substrate surface gas flow through the distance fine regulation between nozzle and the pallet.The solid metal-organic compound source is contained in the bubbler, and temperature is by HA8800 type semiconductor heat trap control, temperature-controlled precision ± 0.1 ℃.Be carried to reative cell to the source steam by the highly purified argon carrier bubbler of flowing through during growth.The pipeline of institute's active power flow warp all adopts the heating tape insulation, is higher than 5～10 ℃ of metallo-organic compound source operating temperatures, avoids the source steam in pipeline, to deposit.Reacting gas is high-purity O
2, for fear of pre-reaction takes place, metallo-organic compound source capsule road and reaction gas pipeline are mixed after getting into reative cell respectively again.The low pressure of catalyst film in growth course, the nothing dried pump of oil (DVT-300) that is produced by Japan provides, and system's stable operation under the low pressure condition is regulated pressure precision less than 1%.
Reaction system precursor material acetylacetone,2,4-pentanedione yttrium [Y (CH
3COCHCOCH
3)
3], acetylacetone,2,4-pentanedione gadolinium [Gd (CH
3COCHCOCH
3)
3], trimethyl bromize antimony (V) [Trimethylantimony (V) bromide, Sb (CH
3)
3Br
2] or SbCl
5Deng steam by carrier gas Ar or N
2Dilution is transported to reative cell (or being transported to reacting furnace); In reative cell, utilize laser or UV-irradiation to make above-mentioned raw materials steam generation photochemical reaction; The acceleration presoma decomposes, and each presoma fully mixes in gas phase, controls the component of film through the flow of controlling each vapor phase metal source.Substrate base is by γ-Fe
2O
3(ferromagnetic particle nuclear), SiO
2(paramagnetic particle nuclear), MnO (anti-ferromagnetism granular core) constitute.This experiment MOCVD deposition process relates to multiple gaseous reactant, accomplishes through chemosynthesis reaction and oxidation reaction.As carrier gas, oxidant is an oxygen with argon gas or nitrogen.Adjust various parameters, reacting gas acetylacetone,2,4-pentanedione yttrium, acetylacetone,2,4-pentanedione gadolinium and trimethyl bromize antimony (or SbCl
5) mol ratio be (3-x): x: 1 (0.5≤x≤1); Underlayer temperature is 650 ± 200 ℃; The film growth temperature is 600 ± 250 ℃; The reative cell internal pressure is 133～1596Pa; Oxygen partial pressure power is 25～798Pa in the reative cell; The flow rate in carrier gas and gaseous state metallo-organic compound source is 10～500cm
3/ min; The flow rate of oxygen is 5～300cm
3/ min; Depositing of thin film speed is 0.5～10 μ m/h; The thin film deposition time is 10～100min.Successfully on substrate, deposit formation Y according to above-mentioned technology
3-xGd
xSbO
7(0.5≤x≤1) rete is handled 200 ± 10min at 1320 ± 10 ℃ with above-mentioned three kinds of retes in nitrogen or argon gas; Make it crystallization and obtain required γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1) or MnO (anti-ferromagnetism granular core)-Y
3-xGd
xSbO
7(0.5≤x≤1).
3. the method for building up of magnetic field-light-catalyzed reaction system
The application of the catalysis material of nucleocapsid structure, through 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-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
3-xGd
xSbO
7(0.5≤x≤1) (photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
3-xGd
xSbO
7(0.5≤x≤1) (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, and 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.
Through 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 by degraded expeditiously under visible light (or ultraviolet light) irradiation.
The application of nucleocapsid structure catalysis material also is through Y
3-xGd
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, in the airtight glass piping interior lighting reactor by a plurality of valve controls, carry out decomposition water and produce hydrogen.
4.Y
2GdSbO
7Performance characterization
Learn Y through XRD, XPS result
2GdSbO
7For single-phase, and experiment original material height is pure, does not have any impurity phase.
Measure Y through Xray fluorescence spectrometer
2GdSbO
7The average atom molar percentage be Y: Gd: Sb: O=2.00: 1.01: 0.98: 6.99.With Rietveld software to Y
2GdSbO
7XRD result carry out structure refinement, the structure refinement factor R
PValue is R
P=9.58%.Y
2GdSbO
7Space group be Fd-3m, structure is a cubic system, pyrochlore constitution, cell parameter a does
Y
2GdSbO
7The indices of crystallographic plane such as (222) of each diffraction maximum, (400), (440), (622), (444), (800), (662), (840), (844) are demarcated.Y
2GdSbO
7In each atoms in space atom site parameter be determined (seeing table 1).Adopt UV, visible light to diffuse spectrometer to Y
2GdSbO
7The characteristic absorption limit that under the irradiation of light, produces is measured, and obtains Y
2GdSbO
7Band gap width be 2.437eV, obtain Y
2GdSbO
7Band structure, conduction band is made up of the 4d track of Y, the 5d track of Gd and the 5p track of Sb, valence band is made up of the 2p track of O.Under radiation of visible light, with Y
2GdSbO
7Be catalyst, the initial concentration of rhodamine B is 0.0293mM, and initial soln 300mL, radiation of visible light are after 235 minutes, and the clearance of rhodamine B is 100%; The photo-quantum efficiency of degraded rhodamine B is 0.04946%; Rhodamine B concentration changes with time dynamics Changshu K
CBe 0.017192min
-1Rhodamine B total organic carbon concentration changes with time dynamics Changshu K
TOCBe 0.014578min
-1Behind the radiation of visible light 200 minutes, CO
2Spill-out be 0.22805mmol, the clearance of total organic carbon is 95.08%.
Application example
1. adopt Y
2GdSbO
7Diuron in the powder degrading waste water
With Y
2GdSbO
7Powder 0.8g puts into the 300mL diuron aqueous solution and forms suspension system, and the initial concentration of the diuron aqueous solution is 0.1mmol L
-1, initial pH value is 7.Choose the xenon lamp irradiation diuron solution of 300W, mix edge filter (λ＞420nm).In the experimentation, 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
2GdSbO
7Powder is a catalyst, under radiation of visible light, along with the prolongation of irradiation time; The concentration of diuron reduced gradually, and total organic carbon (TOC) concentration also reduces gradually, through 400 minutes; The clearance of diuron is 76.90%, and the clearance of total organic carbon TOC (mineralization rate) reaches 75.71%, CO
2Productive rate be 0.20406mmol, first order kinetics Changshu K of diuron concentration and time
cBe 0.0028494min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.0027483min
-1Detailed data are seen table 3.
Table 3 is with Y
2GdSbO
7Powder is the related data that the catalyst degradation diuron is obtained
2. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2GdSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2GdSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2GdSbO
7Diuron in (photochemical catalyst shell) degrading waste water
Utilize homemade magnetic field-light-catalyzed reaction system, through 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
2GdSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2GdSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2GdSbO
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
2GdSbO
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
2GdSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2GdSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2GdSbO
7(photochemical catalyst shell) as 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 reduces gradually; At radiation of visible light after 400 minutes; The clearance of diuron reaches 80.90%, and the clearance of total organic carbon TOC (mineralization rate) reaches 79.72%, CO
2Productive rate be 0.64512mmol, first order kinetics Changshu K of diuron concentration and time
cBe 0.0032894min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.0031706min
-1Detailed data are seen table 4.
Table 4 adopts γ-Fe
2O
3-Y
2GdSbO
7, SiO
2-Y
2GdSbO
7And MnO-Y
2GdSbO
7The related data that is obtained for the catalyst degradation diuron
3. adopt Y
2GdSbO
7Atrazine in the powder degrading waste water
With Y
2GdSbO
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
2GdSbO
7Powder is a catalyst, under radiation of visible light, along with the prolongation of irradiation time; The concentration of Atrazine reduced gradually, and total organic carbon (TOC) concentration also reduces gradually, through 400 minutes; The clearance of Atrazine is 66.50%, and the clearance of total organic carbon TOC (mineralization rate) reaches 64.98%, CO
2Productive rate be 0.15539mmol, first order kinetics Changshu K of Atrazine concentration and time
cBe 0.0021504min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.0020527min
-1Detailed data are seen table 5.
Table 5 is with Y
2GdSbO
7Powder is the related data that the catalyst degradation Atrazine is obtained
4. adopt Y
2GdSbO
7Pentachlorophenol in the powder degrading waste water
With Y
2GdSbO
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
2GdSbO
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 76.80%; The clearance of total organic carbon TOC (mineralization rate) reaches 74.97%, CO
2Productive rate be 0.13428mmol, first order kinetics Changshu K of pentachlorophenol concentration and time
cBe 0.0028822min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.0027121min
-1Detailed data are seen table 6.
Table 6 is with Y
2GdSbO
7Powder is the related data that the catalyst degradation pentachlorophenol is obtained
5. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2GdSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2GdSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2GdSbO
7Atrazine in (photochemical catalyst shell) degrading waste water
Utilize homemade magnetic field-light-catalyzed reaction system, through 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
2GdSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2GdSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2GdSbO
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
2GdSbO
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
2GdSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2GdSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2GdSbO
7(photochemical catalyst shell) as 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 reduces gradually; At radiation of visible light after 400 minutes; The clearance of Atrazine reaches 70.70%, and the clearance of total organic carbon TOC (mineralization rate) reaches 68.64%, CO
2Productive rate be 0.49402mmol, first order kinetics Changshu K of Atrazine concentration and time
cBe 0.0024876min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.0023628min
-1Detailed data are seen table 7.
Table 7 adopts γ-Fe
2O
3-Y
2GdSbO
7, SiO
2-Y
2GdSbO
7And MnO-Y
2GdSbO
7The related data that is obtained for the catalyst degradation Atrazine
6. adopt γ-Fe
2O
3(ferromagnetic particle nuclear)-Y
2GdSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2GdSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2GdSbO
7Pentachlorophenol in (photochemical catalyst shell) degrading waste water
Utilize homemade magnetic field-light-catalyzed reaction system, through 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
2GdSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2GdSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2GdSbO
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 1.9～2.6 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
2GdSbO
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
2GdSbO
7(photochemical catalyst shell), SiO
2(paramagnetic particle nuclear)-Y
2GdSbO
7(photochemical catalyst shell) and MnO (anti-ferromagnetism granular core)-Y
2GdSbO
7(photochemical catalyst shell) under radiation of visible light, along with the prolongation of irradiation time, the concentration of pentachlorophenol reduces gradually as catalyst; Total organic carbon (TOC) concentration also reduces gradually; After 400 minutes, the clearance of pentachlorophenol reaches 81.30% at radiation of visible light, and photo-quantum efficiency is 0.0751%; The clearance of total organic carbon TOC (mineralization rate) reaches 78.03%, CO
2Productive rate be 0.42112mmol, first order kinetics Changshu K of pentachlorophenol concentration and time
cBe 0.0033221min
-1, first order kinetics Changshu K of total organic carbon and time
TOCBe 0.0030746min
-1Detailed data are seen table 8.
Table 8 adopts γ-Fe
2O
3-Y
2GdSbO
7, SiO
2-Y
2GdSbO
7And MnO-Y
2GdSbO
7The related data that is obtained for the catalyst degradation pentachlorophenol
7. adopt Y
2GdSbO
7Decomposition water is produced hydrogen
In the airtight glass piping interior lighting reactor by a plurality of valve controls, carry out decomposition water and produce the hydrogen experiment, (incident flux is 4.513 * 10 to the xenon lamp of radiation source employing 300W
-6Einstein L
-1s
-1, the 420nm edge filter) or 400W (incident flux is 6.013 * 10
-6Einstein L
-1s
-1, the 390nm edge filter) high-pressure sodium lamp, in the 300mL pure water, put into Y
2GdSbO
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 xenon lamp shone following 24 hours, the output of hydrogen was 706.2 micromoles, and the output of oxygen is 352.6 micromoles; After 24 hours, the output of hydrogen is 1928.3 micromoles under high voltage mercury lamp radiation, and the output of oxygen is 963.6 micromoles.
With Y
2GdSbO
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
2GdSbO
7Be composite catalyst, the output of hydrogen is 4.11mmol after 24 hours; With 1.0wt%-NiO/Y
2GdSbO
7Be composite catalyst, the output of hydrogen is 2.84mmol after 24 hours; With 1.0wt%-RuO
2/ Y
2GdSbO
7Be composite catalyst, the output of hydrogen is 2.21mmol after 24 hours, and detailed data are seen table 9 and table 10.
Table 9 is with Y
2GdSbO
7Powder is a catalyst, and decomposition water is produced the related data that hydrogen obtains under UV-irradiation
Table 10 is with Y
2GdSbO
7Powder is a catalyst, and decomposition water is produced the related data that hydrogen obtains under radiation of visible light
Adopt Y
2.5Gd
0.5SbO
7Material obtains extremely similarly result.
Claims (1)
1. the catalysis material magnetic-particle nuclear-Y of nucleocapsid structure
3-xGd
xSbO
7, 0.5≤x≤1, the preparation method, it is characterized in that adopting the method for metal-organic chemical vapor deposition equipment to prepare magnetic-particle nuclear-Y
3-xGd
xSbO
7, 0.5≤x≤1:
Metal-organic chemical vapor deposition equipment MOCVD equipment mainly is made up of source supply system, reative cell, heating system, gas transport and flow control system, vacuum and low voltage control part, gas extraction system, operation control system and safety system, and MOCVD equipment adopts vertical stainless steel reaction chamber, the substrate pallet diameter 52mm that high purity graphite is coated; Rotatable, resistance heated, temperature range 200-900 ℃; Adopt Britain's Continental Europe 808 temperature controller temperature controls; Precision ± 1 ℃, reacting gas and metallo-organic compound source steam get into reative cell, control the even distribution of substrate surface gas flow through the distance fine regulation between nozzle and the substrate pallet; The solid metal-organic compound source is contained in the bubbler; Temperature is by HA8800 type semiconductor heat trap control, and temperature-controlled precision ± 0.1 ℃ is carried to reative cell to metallo-organic compound source steam by the highly purified argon carrier bubbler of flowing through during growth; The pipeline of all metallo-organic compound source and course warps all adopts the heating tape insulation; Be higher than 5～10 ℃ of metallo-organic compound source operating temperatures, avoid metallo-organic compound source steam in pipeline, to deposit, reacting gas is high-purity O
2For fear of pre-reaction takes place, metallo-organic compound source capsule road and reaction gas pipeline are mixed the low pressure of catalyst film in growth course after getting into reative cell respectively again; The dried pump DVT-300 of nothing oil that is produced by Japan provides; The stable operation under the low pressure condition of MOCVD equipment is regulated pressure precision less than 1%
Reaction system precursor material acetylacetone,2,4-pentanedione yttrium, acetylacetone,2,4-pentanedione gadolinium, trimethyl bromize antimony (V) steam are transported to reative cell by carrier gas Ar dilution; In reative cell, utilize laser or UV-irradiation to make above-mentioned raw materials steam generation photochemical reaction; The acceleration presoma decomposes; Each presoma fully mixes in gas phase, controls the component of film through the flow of controlling each vapor phase metal source, and substrate base is ferromagnetic particle nuclear γ-Fe
2O
3, paramagnetic particle nuclear SiO
2Or anti-ferromagnetism granular core MnO; Metal-organic chemical vapor deposition equipment MOCVD deposition process relates to multiple gaseous reactant, accomplish through chemosynthesis reaction and oxidation reaction, with argon gas as carrier gas; Oxidant is an oxygen; Adjust various parameters, the mol ratio of reacting gas acetylacetone,2,4-pentanedione yttrium, acetylacetone,2,4-pentanedione gadolinium and trimethyl bromize antimony (V) is (3-x): x: 1,0.5≤x≤1; Underlayer temperature is 650 ± 200 ℃; The film growth temperature is 600 ± 250 ℃; The reative cell internal pressure is 133～1596Pa; Oxygen partial pressure power is 25～798Pa in the reative cell; The flow rate in carrier gas and gaseous state metallo-organic compound source is 10～500cm
3/ min; The flow rate of oxygen is 5～300cm
3/ min; Depositing of thin film speed is 0.5～10 μ m/h; The thin film deposition time is 10～100min, successfully on substrate base, deposits according to above-mentioned technology and forms Y
3-xGd
xSbO
7Rete, 200 ± 10min handled at 1320 ± 10 ℃ with three kinds of retes in 0.5≤x≤1 in nitrogen or argon gas; Make it crystallization and obtain required ferromagnetic particle nuclear γ-Fe
2O
3-photochemical catalyst shell Y
3-xGd
xSbO
7, 0.5≤x≤1 wherein, paramagnetic particle nuclear SiO
2-Y
3-xGd
xSbO
7, wherein 0.5≤x≤1 or anti-ferromagnetism granular core MnO-Y
3-xGd
xSbO
7, 0.5≤x≤1 wherein.
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