CN108273565A - A kind of perovskite composite photo-catalyst of degradation of dye waste water - Google Patents
A kind of perovskite composite photo-catalyst of degradation of dye waste water Download PDFInfo
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- CN108273565A CN108273565A CN201810225842.5A CN201810225842A CN108273565A CN 108273565 A CN108273565 A CN 108273565A CN 201810225842 A CN201810225842 A CN 201810225842A CN 108273565 A CN108273565 A CN 108273565A
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- perovskite
- aqueous solution
- houghite
- catalyst
- ionic liquid
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims description 12
- 230000015556 catabolic process Effects 0.000 title abstract description 10
- 238000006731 degradation reaction Methods 0.000 title abstract description 10
- 239000010919 dye waste Substances 0.000 title abstract description 6
- 239000011941 photocatalyst Substances 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000002608 ionic liquid Substances 0.000 claims abstract description 32
- 239000000975 dye Substances 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 17
- -1 3 aminopropyl hexafluorophosphate Chemical compound 0.000 claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 229910003112 MgO-Al2O3 Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229960005439 propantheline bromide Drugs 0.000 claims description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 claims description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims 1
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 claims 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 235000012222 talc Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 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 6
- 230000003197 catalytic effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002254 LaCoO3 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- LGZQSRCLLIPAEE-UHFFFAOYSA-M sodium 1-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C(S([O-])(=O)=O)C2=C1 LGZQSRCLLIPAEE-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
-
- B01J35/39—
-
- B01J35/50—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention proposes a kind for the treatment of process of photocatalytic degradation of dye waste water, and the visible light catalyst used wraps up houghite photochemical catalyst for the perovskite of Ionic Liquid Modified.The catalyst wraps up houghite as substrate using the perovskite with photocatalytic activity, and modification can improve substrate to visible light utilization efficiency and can improve the ionic liquid of its photocatalytic activity, and the ionic liquid is 1 methyl, 3 aminopropyl hexafluorophosphate.The present invention solves the problems, such as that dye wastewater degradation efficiency is low in the prior art, the organic dyestuff suitable for pollution degradation water body.
Description
Technical field
The present invention relates to a kind for the treatment of process of photocatalytic degradation of dye waste water, using the perovskite packet of Ionic Liquid Modified
Houghite photochemical catalyst is wrapped up in, which has many advantages, such as that easy to operate, of low cost, degradation efficiency is high.
Background technology
Industrial development be unable to do without the use of dyestuff, and dyestuff is widely used in weaving, papermaking, printing, food, pharmacy, answers
Many fields such as print and printing.There are about 100,000 kinds for whole world industrial dye, and there are about 1,000,000 tons of yield every year.It is generated by dyestuff
Industrial wastewater be one of main pollution of current water body, the whole world is every year with about 60,000 tons of the dyestuff in discharge of wastewater to environment.
China is DYE PRODUCTION and big export country, and output, export volume account for the first in the world.In DYE PRODUCTION and fabrics printing and dyeing process
In, the discharge of industrial dye changes the property and component of natural water, makes water body by physiology, physics, chemistry, biological dirt
Dye, not only causes harm, it is often more important that jeopardize the health of human body to environment and production.
The problem of water is the most important component part of human lives, water will directly affect the development of national economy and society,
Various harm based on waste water from dyestuff, it is imperative to the processing of waste water from dyestuff.Waste water from dyestuff has complicated composition, water and water
The features such as qualitative changeization is big, high chroma, high salinity, poor biodegradability, is one of intractable industrial wastewater.Traditional processing side
Satisfied removal effect is often not achieved in method, in recent years Ozonation, deep oxidation under high temperature method, photocatalytic oxidation, ultrasound
The materializations technology such as wave edman degradation Edman continuously emerges, and the use of especially photocatalysis oxidation technique is concerned.Use is most universal at present
Photochemical catalyst be TiO2, but it is not high to solar energy utilization ratio.Therefore, it develops and the novel light of solar energy utilization ratio can be improved urges
Agent becomes new focus.
Perovskite composite oxide（ABO3）Light is had become with the crystal structure of its stabilization with good catalytic activity to urge
One of the hot spot in change field.After A and B ions metal ion similar in radius replace, catalytic activity can be improved by introducing
Point defect, and radical change does not occur for crystal form, but improve the catalytic activity of this type oxide.In recent years to ABO3And its
The research report of doping type compound photocatalytic degradation of dye waste water is more and more.
Hydrotalcite（LDHs）It is a kind of anion type laminated compound, main body is generally by the hydroxide structure of two kinds of metals
At, therefore also known as layered di-hydroxyl composite metal oxidate.The composition of hydrotalcite can be by different modes come modulation, interlayer
Anion can also be replaced by many other anion, the size of interlamellar spacing depend on interlayer anion and layer with it is cloudy from
The state of electrostatic interaction between son, modified hydrotalcite are commonly referred to as hydrotalcite-like materials.It is with hydrotalcite and houghite
The catalyst of carrier or Component Vectors has many researchs.
Ionic liquid refers to the liquid containing ion.They are liquid salt, need not be dissolved in solvent.In general, when one
Kind of salt is in the presence of being in liquid form for 100 DEG C or less, just referred to as ionic liquid.Alkyl imidazole, pyridine, ammonium and phosphonium ion are
Typical cation.The size and symmetry of ion can prevent from forming stronger crystal lattices, that is to say, that only only small amounts of
Thermal energy can overcome lattice energy, and can destroy its solid crystal structure.Existing ionic liquid can enhance catalyst at present
The active research of photolysis water hydrogen, but by ionic liquid loaded in being used to prepare with excellent photocatalytic degradation on suitable carrier
The catalyst of waste water from dyestuff is then rarely reported.
Invention content
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of catalysis of degradation of dye waste water
Agent, preparation method and its treatment process, dyestuff therein of being degraded by the way of visible light catalytic, the photochemical catalyst used for
The perovskite of Ionic Liquid Modified wraps up houghite photochemical catalyst.
The treatment process of the Visible Light Induced Photocatalytic waste water from dyestuff, includes the following steps：
A certain amount of waste water from dyestuff is taken, particulate matter therein, wherein a concentration of 5mg/L~20mg/ of dyestuff are removed by flocculation
L is added the perovskite package houghite photochemical catalyst of a certain amount of Ionic Liquid Modified, ultrasound point is carried out under half-light thereto
Dissipate 30min so that Catalyst Adsorption is complete, and room temperature visible light is then carried out under the xenon source of 400-600W filtering ultraviolet light
The amount ratio of catalysis reaction 0.5-3h, the photochemical catalyst and waste water from dyestuff is 20~40g：100L, xenon lamp are useless with the dyestuff
The liquid level distance of water is 18cm~22cm, completes the degradation to dyestuff.
The dyestuff is one or more in Congo red, acid red A or Acid Red G.
The perovskite of the Ionic Liquid Modified wraps up houghite catalyst with the perovskite packet with photocatalytic activity
It is substrate to wrap up in houghite, and modification can improve substrate to visible light utilization efficiency and can improve the ion of its photocatalytic activity
Liquid, the ionic liquid are -3 aminopropyl hexafluorophosphate of 1- methyl.
Perovskite wraps up the preparation of houghite substrate, first synthesis hydrotalcite-like material base composite oxidate, such as MgO-Al2O3；
Secondly, the key component of perovskite oxide is introduced on it using " the reconstruct effect " of houghite base composite oxidate；Again
It is secondary gained sample is calcined after formed with nucleocapsid perovskite package houghite base oxide.Specifically include as
Lower step：
A, Mg (NO are prepared3)2With Al (NO3)3Mixed aqueous solution, the molar ratio of wherein Mg and Al are 1-4, wherein mixing water-soluble
A concentration of 0.2-2mol/L of liquid；
B, under the conditions of intensively stirred, to Na2CO3The mixed aqueous solution that a dropping step a is prepared in aqueous solution, waits being added dropwise
Use Na again afterwards2CO3System pH is transferred to 8.5-11 by aqueous solution, and maintains aging 1-24h at 40-80 DEG C, and preferably 6-20 is small
When；
The wherein described strong stirring condition is 150-300 rpm/min, preferably 180-240 rpm/min, the Na2CO3It is water-soluble
A concentration of 0.2-2mol/L of liquid, during dropwise addition, Na2CO3The volume ratio for the mixed aqueous solution that aqueous solution and step a are prepared
For (2-8):(8-32) during entire dropwise addition, controls rate of addition so that the mixed aqueous solution of step a preparations is in 0.5-3h
It is added dropwise.
C, the precipitation for preparing gained by step b is filtered, after washing is dry, 4-10h is calcined in 400-800 DEG C, then
By gained pressed by powder at particle.
Specifically, by being filtered by the precipitation obtained by step b, deionized water fully washs and in vacuum or air atmosphere
In in 80-120 DEG C of dry 6-24h, obtain houghite presoma；Houghite presoma after drying is at 400-800 DEG C
In air or Ar or N24-10h is calcined in atmosphere, 0.5-20 DEG C of heating rate/min, calcines gained powder by preferably 1-10 DEG C/min
Body is pressed into particle, i.e. MgO-Al2O3Particle.
D, by gained MgO-Al2O3Particle is soaked in mixing Co (NO3)3With La (NO3)3Mixed aqueous solution in carry out weight
The molar ratio of structure, wherein Co and La is 1-2.
Reconstruct in the step d, it is main in upper introducing perovskite using " the reconstruct effect " of houghite base oxide
Component La and Co.Reconstruction condition directly affects the thickness for the shell structure to be formed, and may be selected to impregnate at least at 20-80 DEG C of room temperature
0.5 hour, preferably 0.5-3 hours.
E, by after the drying of product filtering and washing that step d is reconstructed, after being calcined 3-12 hours at 700-1200 DEG C, preferably
4-8h is calcined at 800-1000 DEG C wraps up houghite substrate to get to perovskite.
The preparation of ionic liquid includes the following steps：3- propantheline bromide hydrobromides are dissolved in anhydrous acetonitrile, 1- methyl is added
Imidazoles is warming up to 45-75 DEG C of reaction, and it is for 24 hours, solvent to be removed, with volume ratio 1 to begin to warm to the time that reaction terminates:1 first
Residue after rotary evaporation removes methanol and ether, is dissolved in methanol, saturation NaOH first is added dropwise by alcohol and the washing of ether mixed solution
For alcoholic solution to the pH value of solution to 8-9, rotary evaporation removes methanol, centrifuges and reacts 1h with ammonium hexafluorophosphate after inorganic salts,
- 3 aminopropyl limidazolium hexafluorophosphate ionic liquid of Chinese red 1- methyl is detached to obtain with silica gel column chromatography, 4 DEG C save backup.
Wherein, 3- propantheline bromide hydrobromides, 1- methylimidazoles, ammonium hexafluorophosphate addition molar ratio be (2-8):1:
(1-5)。
The method of Ionic Liquid Modified includes the following steps：
F, under ice bath, nitrogen atmosphere, -3 aminopropyl limidazolium hexafluorophosphate ionic liquid of a certain amount of Chinese red 1- methyl is taken
Then methanol solution is added perovskite and wraps up houghite substrate, is stirred to react 2h thereto.Reaction product rotary evaporation removes
Solvent obtains buff powder, and the as perovskite of Ionic Liquid Modified wraps up houghite catalyst.
The wherein matter of -3 aminopropyl limidazolium hexafluorophosphate ionic liquid of 1- methyl and perovskite package houghite substrate
Amount is than being 1：（20-30）.
Compared with prior art, the present invention has the following advantages：
1, compared with prior art, processing method of the invention is easy to operate, easy control of reaction conditions, of low cost, purification
It is efficient, there is potential industrial applications foreground；
2, photochemical catalyst of the invention combines two major classes metal composite oxide, i.e. perofskite type oxide and houghite oxygen
Compound is introduced on the surface of stratiform houghite oxide with photocatalytic activity using " the reconstruct effect " of houghite
La, Co based perovskite type oxide, the nucleocapsid thus constituted improve conduction of the light induced electron in substrate, are conducive to photoproduction
Electrons and holes efficiently separate, and the structure additionally aids mass transfer and heat transfer efficiency in Photocatalytic Degradation Process, improve
The activity of photochemical catalyst；
3, the modification of -3 aminopropyl hexafluorophosphate of ionic liquid 1- methyl, has widened response range of the perovskite to visible light,
Utilization rate of the catalyst for visible light is improved, catalyst is greatly improved and lives for the photocatalytic degradation of waste water from dyestuff
Property.
Specific implementation mode
With reference to specific embodiment the present invention is further elaborated the solution of the present invention.
1 perovskite of embodiment wraps up the preparation of houghite substrate
Specifically comprise the following steps：
A, Mg (NO are prepared3)2With Al (NO3)3Mixed aqueous solution, the molar ratio of wherein Mg and Al is:3, wherein mixed aqueous solution
A concentration of 0.4mol/L；
B, under 150-300 rpm/min stirring conditions, to Na2CO3The mixed aqueous solution that a dropping step a is prepared in aqueous solution,
1h is dripped off, during dropwise addition, Na2CO3The volume ratio for the mixed aqueous solution that aqueous solution and step a are prepared is 1:4, it waits being added dropwise
Use Na again afterwards2CO3System pH is transferred to 10 by aqueous solution, and maintains aging 12h at 80 DEG C；
C, the precipitation that gained is prepared by step b is filtered, deionized water washing, then after 100 DEG C of dry 6h, at 800 DEG C
6h is calcined in air atmosphere, then by gained pressed by powder at MgO-Al2O3Particle.
D, by gained MgO-Al at 40 DEG C2O3Particle is soaked in Co (NO3)3With La (NO3)3Mixed aqueous solution in carry out weight
The molar ratio of structure 2h, wherein Co and La are 2.
E, by after the drying of product filtering and washing that step d is reconstructed, to get to perovskite after being calcined 6 hours at 800 DEG C
Wrap up houghite substrate.
The preparation of 2 ionic liquid of embodiment
3- propantheline bromide hydrobromides are dissolved in anhydrous acetonitrile, 1- methylimidazoles are added, are warming up to 55 DEG C of reactions, are begun to warm to anti-
The time that should terminate is for 24 hours, solvent to be removed, with volume ratio 1:1 methanol and ether mixed solution washing, rotary evaporation remove first
After alcohol and ether, residue is dissolved in methanol, saturation NaOH methanol solutions are added dropwise to the pH value of solution to 8.5, rotary evaporation moves
Except methanol, 1h is reacted with ammonium hexafluorophosphate after centrifugation inorganic salts, -3 ammonia of Chinese red 1- methyl is detached to obtain with silica gel column chromatography
Propyl imidazole hexafluorophosphoric acid ionic liquid, 4 DEG C save backup.Wherein, 3- propantheline bromide hydrobromides, 1- methylimidazoles, hexafluoro
The molar ratio of ammonium phosphate addition is 4:1:3.
The perovskite of 3 Ionic Liquid Modified of embodiment wraps up houghite photochemical catalyst
F, under ice bath, nitrogen atmosphere, -3 aminopropyl limidazolium hexafluorophosphate ionic liquid of a certain amount of Chinese red 1- methyl is taken
Then methanol solution is added perovskite and wraps up houghite substrate, is stirred to react 2h thereto.Reaction product rotary evaporation removes
Solvent obtains buff powder, and the as perovskite of Ionic Liquid Modified wraps up houghite catalyst.Wherein -3 ammonia third of 1- methyl
Base limidazolium hexafluorophosphate ionic liquid and the mass ratio of perovskite package houghite substrate are 1：25.
Comparative example 1 prepares LaCoO using stearic acid gel method3Perovskite oxide
A certain amount of stearic acid is taken to heat, it is in molten condition to make it, sequentially adds cobalt nitrate and lanthanum nitrate, and constant temperature stirring has waited for
After fully dissolved, itself and benzene azeotropic are distilled, remove the water in colloidal sol, cooling at room temperature obtains gel, obtains composite oxides
Presoma.It after being fully ground, places it in Muffle furnace, 800 DEG C of calcining 6h obtain LaCoO3Perovskite oxide.
4 photocatalytic degradation of dye of embodiment（With Congo red for dyestuff Model Molecule）Waste water
The Congo red solution 100mL of three parts of 10mg/L is prepared as reaction contaminant, 0.03g comparative examples 1 are added thereto respectively
LaCoO obtained3Ionic liquid made from perovskite package houghite made from perovskite oxide, embodiment 1 and embodiment 3
The perovskite of body modification wraps up houghite photochemical catalyst.Ultrasonic disperse 30min under half-light, then in 400W filtering ultraviolet light
Room temperature visible light catalytic is carried out under xenon source reacts 2.5h, it is 20cm to keep the liquid level of xenon lamp and waste water from dyestuff distance, every
Congo red concentration in 30min sampling analysis sample liquids, to investigate the degrading activity of different time catalyst, specific data referring to
The following table 1：
The photocatalytic activity test of the different samples of table 1.
By the data analysis in table 1 it is found that preparing LaCoO compared to stearic acid gel method3Perovskite oxide, in class neatly
After introducing La, Co formation perovskite core-shell material on graphite/oxide, Congo red efficiency of degrading has no small promotion, this is
Since the stroke of nucleocapsid enhances the separation in light induced electron and hole, while also enhancing the mass transfer and biography of base material
Heat improves photocatalytic activity；And again after modified ion liquid, due to ionic liquid widening for visible light-responded range,
Catalyst has Congo red degradation efficiency the promotion of bigger, it can be seen that, perovskite complex light prepared by the present invention is urged
Agent has excellent dye wastewater degradation effect.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of perovskite composite catalyst of Visible Light Induced Photocatalytic waste water from dyestuff, which is characterized in that with photocatalytic activity
It is substrate that perovskite, which wraps up houghite, and -3 aminopropyl hexafluorophosphonate of modified ion liquid 1- methyl is prepared and specifically included
Following steps：
A, Mg (NO are prepared3)2With Al (NO3)3Mixed aqueous solution, the molar ratio of wherein Mg and Al are 1-4, wherein mixed aqueous solution
A concentration of 0.2-2mol/L；
B, under the conditions of intensively stirred, to Na2CO3The mixed aqueous solution that a dropping step a is prepared in aqueous solution, waits being added dropwise
Use Na again afterwards2CO3System pH is transferred to 8.5-11 by aqueous solution, and maintains aging 1-24h at 40-80 DEG C；
C, the precipitation that gained will be prepared by step b filters, and after washing is dry, calcines 4-10h in 400-800 DEG C, then by institute
Pressed by powder is obtained into particle；
D, by gained MgO-Al2O3Particle is soaked in mixing Co (NO3)3With La (NO3)3Mixed aqueous solution in be reconstructed,
The molar ratio of middle Co and La is 1-2；
E, by after the product filtering and washing drying that step d is reconstructed, after being calcined 3-12 hours at 700-1200 DEG C, preferably exist
800-1000 DEG C of calcining 4-8h wraps up houghite substrate to get to perovskite.
2. perovskite composite catalyst as described in claim 1, which is characterized in that the ageing time of step b is 6-20h.
3. perovskite composite catalyst as claimed in claim 1 or 2, which is characterized in that strong stirring condition described in step b
For 150-300 rpm/min, preferably 180-240 rpm/min, the Na2CO3A concentration of 0.2-2mol/L of aqueous solution, is dripping
During adding, Na2CO3The volume ratio for the mixed aqueous solution that aqueous solution and step a are prepared is (2-8):(8-32), was entirely added dropwise
Cheng Zhong, control rate of addition is so that the mixed aqueous solution that step a is prepared is added dropwise in 0.5-3h.
4. perovskite composite catalyst as claimed in claim 3, which is characterized in that it will be filtered by the precipitation obtained by step b,
Deionized water is fully washed and in vacuum or air atmosphere in 80-120 DEG C of dry 6-24h, and houghite presoma is obtained；Through
Houghite presoma after drying is at 400-800 DEG C in air or Ar or N24-10h, heating rate 0.5-20 are calcined in atmosphere
DEG C/min, preferably 1-10 DEG C/min, calcining gained pressed by powder is at particle, i.e. MgO-Al2O3Particle.
5. perovskite composite catalyst as claimed in claim 4, which is characterized in that impregnate at least 0.5 at 20-80 DEG C of room temperature
Hour, preferably 0.5-3 hours.
6. perovskite catalyst as described in claim 1, which is characterized in that preparation process further includes：The preparation of ionic liquid
Step：3- propantheline bromide hydrobromides are dissolved in anhydrous acetonitrile, 1- methylimidazoles are added, is warming up to 45-75 DEG C of reaction, starts to warm up
The time terminated to reaction is for 24 hours, solvent to be removed, with volume ratio 1:1 methanol and ether mixed solution washing, rotary evaporation move
After methanol and ether, residue is dissolved in methanol, saturation NaOH methanol solutions are added dropwise to the pH value of solution to 8-9, rotation is steamed
It sends out and removes methanol, react 1h with ammonium hexafluorophosphate after centrifugation inorganic salts, Chinese red 1- methyl-is detached to obtain with silica gel column chromatography
3 aminopropyl limidazolium hexafluorophosphate ionic liquids, 4 DEG C save backup；Wherein, 3- propantheline bromide hydrobromides, 1- methylimidazoles, six
The molar ratio of fluorophosphoric acid ammonium addition is (2-8):1:(1-5).
7. perovskite catalyst as claimed in claim 6, which is characterized in that under ice bath, nitrogen atmosphere, take a certain amount of Exocarpium Citri Rubrum
Then the methanol solution of -3 aminopropyl limidazolium hexafluorophosphate ionic liquid of color 1- methyl is added perovskite and wraps up class water thereto
Talcum substrate, is stirred to react 2h, and reaction product rotary evaporation removes solvent, obtain buff powder, as Ionic Liquid Modified
Perovskite wraps up houghite catalyst, and wherein -3 aminopropyl limidazolium hexafluorophosphate ionic liquid of 1- methyl is wrapped up with perovskite
The mass ratio of houghite substrate is 1：（20-30）.
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| CN110394194A (en) * | 2019-08-07 | 2019-11-01 | 浙江师范大学 | A kind of novel photocatalyst controllable method for preparing based on mineral ligand modification |
| CN116395754A (en) * | 2023-04-14 | 2023-07-07 | 四川大学 | Method for preparing transition metal oxyhydroxide based on perovskite complete structure recombination |
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| CN103111302A (en) * | 2013-01-12 | 2013-05-22 | 天津大学 | Preparation and application of shell-core-type perovskite-wrapping hydrotalcite-like-based oxide reforming hydrogen production catalyst |
| CN103394328A (en) * | 2013-08-20 | 2013-11-20 | 青岛科技大学 | Hydroxyl functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof |
| CN107337644A (en) * | 2017-06-27 | 2017-11-10 | 中南民族大学 | A kind of functionalization perovskite material based on novel ion liquid and its application in solar cell preparation |
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| CN103111302A (en) * | 2013-01-12 | 2013-05-22 | 天津大学 | Preparation and application of shell-core-type perovskite-wrapping hydrotalcite-like-based oxide reforming hydrogen production catalyst |
| CN103394328A (en) * | 2013-08-20 | 2013-11-20 | 青岛科技大学 | Hydroxyl functionalized ionic liquid/hydrotalcite-like compound composite material, and preparation method and application thereof |
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| CN110394194A (en) * | 2019-08-07 | 2019-11-01 | 浙江师范大学 | A kind of novel photocatalyst controllable method for preparing based on mineral ligand modification |
| CN116395754A (en) * | 2023-04-14 | 2023-07-07 | 四川大学 | Method for preparing transition metal oxyhydroxide based on perovskite complete structure recombination |
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