CN109012699A - Symmetrical anti-Z-type photochemical catalyst and its preparation method and application - Google Patents
Symmetrical anti-Z-type photochemical catalyst and its preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910003122 ZnTiO3 Inorganic materials 0.000 claims abstract description 73
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical group [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 claims description 16
- 230000015556 catabolic process Effects 0.000 claims description 16
- 238000006731 degradation reaction Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- DTWCOCYXNRTSIA-UHFFFAOYSA-N C(C)O.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] Chemical compound C(C)O.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] DTWCOCYXNRTSIA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims 2
- 239000010936 titanium Substances 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 238000005286 illumination Methods 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000009977 dual effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 230000001699 photocatalysis Effects 0.000 description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- LMDAGMAWWYVRJZ-UHFFFAOYSA-N ethanol;zinc Chemical compound [Zn].CCO LMDAGMAWWYVRJZ-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
-
- 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
Abstract
The present invention relates to symmetrical anti-Z-type photochemical catalysts and its preparation method and application.The scheme route of use is as follows: synthesizing ZnIn with hydro-thermal method2S4And CaIn2S4, sol-gal process synthesis ZnTiO3And Er3+:Y3Al5O12.By certain mass ratio, by Er3+:Y3Al5O12It is added to ZnTiO3In colloidal sol, Er is finally prepared3+:Y3Al5O12@ZnTiO3Compound.There is this characteristic of different isoelectric points using material, PH is transferred to a certain range, using calcining, prepares ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4Photochemical catalyst.Symmetrical anti-Z-type photochemical catalyst ZnIn provided by the invention2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4, simultaneously hydrogen can be prepared simultaneously by degradable organic pollutant under simulated solar irradiation irradiation, be that pollutant is considered as to a kind of available energy resources, realize Environment control and produce the dual purpose of clean energy resource.
Description
Technical field
The invention belongs to photocatalysis fields, and in particular to compound photocatalytic system ZnIn2S4/Er3+:Y3Al5O12@
ZnTiO3/CaIn2S4Preparation and photocatalysis degradation organic contaminant and answering in hydrogen manufacturing simultaneously under simulated solar irradiation irradiation
With.
Background technique
Environmental pollution and energy crisis have become two large problems urgently to be resolved in current social development.In particular, close
Nian Lai, waste water from dyestuff pollution are particularly acute.Mostly contain azo dyes in this kind of sewage, due to their stable structure, high poison
Property, electron-withdrawing group is had, degradation is hardly resulted in.Therefore, this kind of organic pollutant long-term existence is in environment, to ecological environment
Great harm is brought with human health.However, the organic pollutant in sewage is also energy resources abundant, only to this kind of
It is also a kind of waste that organic pollutant, which is degraded without utilizing,.So should propose that the method for an economical rationality is useless to realize
Water warfare and synchronous energy are converted.This provides a kind of promising resolution policy to solve environmental pollution and energy crisis.So far
Until the present, there are many methods to be used to degradation of contaminant, such as bioanalysis, physical and chemical method, flocculence and absorption method.But it is raw
For object method due to needing long time cultivation microorganism, the period is longer, and other methods only only reside within how degradation of contaminant
In level, a kind of green high-efficient is not formed, the contaminant degradation system of environment is conducive to.Under comparing, photocatalysis skill
In art, photochemical catalyst is stablized with chemical property, and oxidation-reduction quality is strong, long service life, utilizes cheap solar energy abundant
Occur redox reaction, realize to persistent organic pollutants degrade while generate high fuel value and combustion product be water and
The Hydrogen Energy of non-environmental-pollution not only degrades pollutant while also creating hydrogen, and production is clear while realizing environmental improvement
The purpose of the clean energy.
Summary of the invention
In order to solve the above-mentioned technical problem, the object of the present invention is to provide a kind of symmetrical anti-Z-type photochemical catalyst ZnIn2S4/
Er3+:Y3Al5O12@ZnTiO3/CaIn2S4, under simulated solar irradiation irradiation, hydrogen manufacturing while realizing organic pollutant degradation.
The present invention is achieved through the following technical solutions, and symmetrical anti-Z-type photochemical catalyst, the symmetrical anti-Z-type light is urged
Agent is ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4。
Preferably, above-mentioned symmetrical anti-Z-type photochemical catalyst, in mass ratio, (ZnIn2S4):(Er3+:Y3Al5O12@
ZnTiO3):(CaIn2S4)=1:1:1；(Er3+:Y3Al5O12):(ZnTiO3)=7:3.
The preparation method of symmetrical anti-Z-type photochemical catalyst is prepared by the property and calcination method of isoelectric point, including walked as follows
It is rapid: with dilute HNO3Deionized water is transferred to PH=5, is stirred evenly, ZnIn is then sequentially added2S4、CaIn2S4And Er3+:
Y3Al5O12@ZnTiO3, after being uniformly mixed, 80 DEG C of baking oven drying are put into, the mixture of drying is transferred in Muffle furnace,
500 DEG C, 2.0h is calcined, is cooled to room temperature, is washed with deionized, dry again, obtain symmetrically anti-Z-type photochemical catalyst ZnIn2S4/
Er3+:Y3Al5O12@ZnTiO3/CaIn2S4。
Further, ZnIn is synthesized by hydro-thermal method2S4, preparation method includes the following steps: ZnCl2With In (NO3)3It is molten
Solution in deionized water, adds thioacetamide (C2H5NS), 1.0h is stirred on magnetic ion blender form clear solution,
Then clear solution is transferred in polytetrafluoroethyllining lining stainless steel cauldron, the heat treatment of 6.0h is carried out at 160 DEG C, it will
Obtained product is cooled to room temperature, and is then cleaned with deionized water and ethyl alcohol, is dried 6.0h at 80 DEG C, is obtained ZnIn2S4。
Further, CaIn is synthesized by hydro-thermal method2S4, preparation method includes the following steps: Ca (NO3)2·4H2O and
In(NO3)3It is dissolved in deionized water, adds thioacetamide (C2H5It NS), will be upper after magnet suspension stirrer stirring 1.0h
State solution to be transferred in polytetrafluoroethyllining lining stainless steel cauldron, be heated to 120 DEG C and keep 24.0h, with deionized water and
Dehydrated alcohol washing, centrifugation, 60 DEG C of dry 12.0h obtain CaIn2S4。
Further, Er is synthesized by sol-gel method3+:Y3Al5O12@ZnTiO3, preparation method includes the following steps:
Zinc nitrate and butyl titanate are first dissolved in dehydrated alcohol by Zn: Ti=1: 1 meter feedstock in molar ratio respectively, then by nitre
Sour zinc ethanol solution is added dropwise in butyl titanate ethanol solution, and glacial acetic acid is added dropwise, and controls the pH value of solution in 2-3
Range form ZnTiO after heating stirring 3.0h at 60 DEG C3Colloidal sol, in mass ratio, Er3+:Y3Al5O12:ZnTiO3=7:3,
By ground Er3+:Y3Al5O12Powder is added in colloidal sol, continuously stirs until colloidal sol is transformed into gel；By resulting gel in
Dry at 80 DEG C, then grinding, gel powder is placed in Muffle furnace, calcines 3.0h at 600 DEG C, be cooled to room temperature, and is ground,
Then at 800 DEG C of calcining 3.0h, Er is obtained3+:Y3Al5O12@ZnTiO3。
Symmetrical anti-Z-type photochemical catalyst ZnIn of the invention2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4In photocatalytic degradation
Application in organic pollutant.Method is as follows: by above-mentioned symmetrical anti-Z-type photochemical catalyst ZnIn2S4/Er3+:Y3Al5O12@
ZnTiO3/CaIn2S4It is added in the solution containing organic pollutant, light application time 1.0-6.0h.
Further, above-mentioned application, the organic pollutant are Acid Orange IIs.
Further, above-mentioned application, using Acid Orange II as sacrifice agent under conditions of, carry out photocatalytic degradation and simultaneously
Hydrogen manufacturing.
The beneficial effects of the present invention are:
1, usually alternative wide band gap semiconducter catalyst material is considerably less, and since wide band gap needs very
High energy excites.Therefore, present invention selection has the semiconductor of strong oxidizing property and strong reducing property, constructs Z-type photocatalysis body
System, can preferably achieve the object of the present invention.In order to generate more hydrogen, by two catalyst and tool with more negative conduction band
There is the catalyst of calibration valence band to carry out compound, obtain the photocatalytic system of one strong reduction-oxidation, realizes that photocatalytic degradation is same
When hydrogen manufacturing.ZnTiO3As broadband semiconductor, there are two defects: first is that wider band gap (Ebg=3.65eV), forbidden bandwidth compared with
Greatly, make ZnTiO3The visible light part in sunlight cannot be efficiently used, light utilization efficiency is low.The present invention utilizes up-conversion luminescence material
Expect Er3+:Y3Al5O12It can will be seen that light is converted into this feature of ultraviolet light, widen ZnTiO3Optical response range.The other is
ZnTiO3The lower unsuitable hydrogen manufacturing of reducing power, the present invention is by the semiconductor material ZnIn with strong reducing power thus2S4With
CaIn2S4It carries out compound, is constructed comprising ZnIn therewith2S4, CaIn2S4And ZnTiO3Compound symmetrical anti-Z-type photochemical catalyst, can
Realize photocatalytic degradation hydrogen manufacturing simultaneously.
2, the present invention devises a novel symmetrical anti-Z-type photochemical catalyst ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/
CaIn2S4, and prepared by isoelectric point method and calcination method.It is degraded under simulated solar irradiation irradiation using obtained catalyst
Acid Orange II hydrogen manufacturing simultaneously.Er3+:Y3Al5O12As up-conversion luminescence agent by the visible light transformation of absorption be ultraviolet light, thus swash
Send out ZnTiO3Generate photo-generate electron-hole pairs.Under simulated solar irradiation irradiation, ZnIn2S4And CaIn2S4It can be excited and generate photoproduction
Electron hole pair.Therefore, ZnTiO3Electrons and ZnIn on conduction band2S4And CaIn2S4Hole progress in valence band is compound, leaves
ZnIn2S4And CaIn2S4With the electronics of strong reducing property on conduction band, by H+It restores and generates H2, and it is accumulated in ZnTiO3In valence band
Oxidation reaction, oxidising acid orange II occur for the hole of strong oxidizing property.The novel double Z shaped photocatalytic system that the present invention designs has
Strong oxidation-reduction quality, generates hydrogen while using photocatalysis technology by contaminant degradation, both reached the mesh of purification sewage
, and pollutant is considered as a kind of resource reutilization production clean energy resource, it is provided for following environmental improvement and clean manufacturing
One promising strategy.
Detailed description of the invention
Fig. 1 is ZnIn2S4/ZnTiO3X-ray diffractogram.
Fig. 2 is CaIn2S4/ZnTiO3X-ray diffractogram.
Fig. 3 is ZnIn2S4/ZnTiO3/CaIn2S4X-ray diffractogram.
Fig. 4 is ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4X-ray diffractogram.
Specific embodiment
The symmetrical anti-Z-type photochemical catalyst ZnIn of embodiment 12S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4
The preparation method is as follows:
1、ZnIn2S4Preparation:
By ZnCl2(0.68g) and In (NO3)3(3.0g) is dissolved in 80mL deionized water, adds thioacetamide
(2.3g) stirs 1.0h on magnetic ion blender and forms clear solution.Then the clear solution of formation is transferred to polytetrafluoro
In ethylene inner liner stainless steel reaction kettle, 6.0h heat treatment is carried out at 160 DEG C.Obtained product is cooled to room temperature, is then used
Deionized water and ethyl alcohol are cleaned.Obtained product is finally put into baking oven, 6.0h is dried at 80 DEG C, is ground.
2、CaIn2S4Preparation:
By Ca (NO3)2·4H2O (1.2g), In (NO3)3(3.0g) is dissolved in 80mL deionized water, uses magnetic at room temperature
Power is stirred to being completely dissolved, and thioacetamide (3.0g) then is added into mixed solution again, and magnet suspension stirrer stirs 1.0h,
Then acquired solution is transferred in the stainless steel autoclave of teflon lining of 100mL, is heated to 120 DEG C and keeps 24.0h.
It is washed with deionized water and dehydrated alcohol, CaIn is obtained after centrifugation2S4Powder, 60 DEG C of dry 12.0h.
3、Er3+:Y3Al5O12Preparation:
By Er2O3(0.0128g) and Y2O3(2.2715g) powder is dissolved in magnetic agitation and at heating 60 DEG C of holding
It is in 50mL concentrated nitric acid until colorless and transparent, obtain mixed rare-earth oxide solution.Then by Al (NO3)3·9H2O (12.6208g) and
Solid citric acid (molar ratio of 33.9351g, citric acid and rare earth ion is 3:1) is dissolved in secondary distilled water, and is slowly added
Into above-mentioned manufactured mixed rare-earth oxide solution.Stirring is until solution is in sticky foaming colloidal solution at 50-60 DEG C.So
After be placed into baking oven and maintain 36.0h at 80 DEG C, obtain gel.Obtained gel is first to heat to 500 DEG C in Muffle furnace, and
50min is maintained, continues thereafter with and is heated to 1100 DEG C, and continue 2.0h.Cooling, grinding obtains Er3+:Y3Al5O12Nano particle.
4、Er3+:Y3Al5O12@ZnTiO3Preparation:
Zinc nitrate (1.8g) and butyl titanate (2.0g) are first dissolved in by Zn: Ti=1: 1 meter feedstock in molar ratio respectively
In 30mL dehydrated alcohol, then zinc nitrate ethanol solution is added dropwise in butyl titanate ethanol solution, and ice is added dropwise
Acetic acid controls the pH value of solution in 2-3 range, obtains presoma.Precursor solution is formed after 60 DEG C, heating stirring 3.0h light
Yellow transparent colloidal sol.By ground Er3+:Y3Al5O12(2.3g) powder is added in above-mentioned pale yellow transparent colloidal sol, is continuously stirred
It mixes until colloidal sol is transformed into gel；By resulting gel in 80 DEG C of dryings, grinding.Then, gel powder is placed in Muffle furnace,
3.0h is calcined at 600 DEG C, is cooled to room temperature, grinds, then calcine 3.0h at 800 DEG C, obtains Er3+:Y3Al5O12With ZnTiO3Quality
Than the Er for 7:33+:Y3Al5O12@ZnTiO3。
Light conversion agent Er is added without in preparation process3+:Y3Al5O12As ZnTiO3Preparation method.
5、ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4Preparation:
With dilute HNO3Deionized water is transferred to PH=5, is stirred evenly, in mass ratio, (ZnIn2S4):(Er3+:Y3Al5O12@
ZnTiO3):(CaIn2S4)=1:1:1, sequentially adds ZnIn2S4、CaIn2S4And Er3+:Y3Al5O12@ZnTiO3, it is stirred
After even, it is put into 80 DEG C of baking oven drying.The mixture of drying is transferred to 500 DEG C of high-temperature calcination 2.0h in Muffle furnace, is cooled to
It is taken out after room temperature, is repeatedly washed with deionized water, then dry again, obtain ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/
CaIn2S4, it is fully ground spare.
6, comparative example: according to the method for step 5, photochemical catalyst ZnIn is prepared respectively2S4/ZnTiO3, CaIn2S4/ZnTiO3
And ZnIn2S4/ZnTiO3/CaIn2S4, solution pH value is all 5.
In Fig. 1, ZnIn can be clearly observed2S4And ZnTiO3Characteristic diffraction peak be present in binary complex
ZnIn2S4/ZnTiO3XRD diagram in.Also, belong to ZnIn positioned at 21.59 °2S4The position of characteristic peak, has and slightly moves back,
35.22 ° belonging to ZnTiO3Diffraction maximum near region become larger.This shows ZnIn2S4With ZnTiO3It may be compound.Similarly, exist
In Fig. 2, also it can be clearly seen that CaIn2S4, ZnTiO3Characteristic peak, the position at peak and peak area also have significant change, this
It can prove CaIn2S4/ZnTiO3Formation.In Fig. 3, for ZnIn2S4/ZnTiO3/CaIn2S4, it can be seen that CaIn2S4,
ZnIn2S4And ZnTiO3Diffractive features peak.Wherein, CaIn2S4, ZnIn2S4And ZnTiO3Diffraction spike show they have height
Crystallinity.In addition, the common trait peak value at 36.25 ° also has offset slightly.By analyzing above, can be inferred that
ZnIn2S4/ZnTiO3/CaIn2S4Composite material is synthesized.Fig. 4 is ZnIn2S4/ZnTiO3@Er3+: Y3Al5O12/CaIn2S4Spy
Peak is levied, in addition to ZnIn2S4, ZnTiO3And CaIn2S4Characteristic peak outside, can also detect Er3+: Y3Al5O12Characteristic peak.This table
The Er of bright part3+: Y3Al5O12By ZnTiO3Cladding.ZnIn2S4、Er3+: Y3Al5O12@ZnTiO3And CaIn2S4Characteristic peak position
It is equipped with apparent movement.Therefore, the above results can confirm Successful construct ternary ZnIn2S4/Er3+: Y3Al5O12@ZnTiO3/
CaIn2S4Compound.
The symmetrical anti-Z-type photochemical catalyst of embodiment 2 is to Acid Orange II photocatalytic degradation
Simulated solar irradiation photocatalytic degradation: the Acid Orange II solution of 25mL 10mg/L is measured in 100mL conical flask, such as
The catalyst 25mg of the present invention and comparative example prepared by embodiment 1 is added in table 1, irradiates 6.0h under simulated solar irradiation.Filtering,
200-800nm measures its ultraviolet spectra.It takes the absorbance at 485nm to calculate the degradation rate of Acid Orange II, the results are shown in Table 1.
Degradation rate (%)=(C0–C)/C0× 100% (wherein C0: the concentration of stoste；C: the concentration of sample)
(1) influence of the light application time to degradation rate
1 ZnIn of table2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4Simulated solar irradiation photocatalytic degradation Acid Orange II
As shown in table 1, as 4 kinds of catalyst of the extension of light application time gradually increase the degradation rate of Acid Orange II.Wherein,
ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4, when light application time is 6.0h, degradation rate 82.3%.
(2) change the access times of catalyst system to the photodegradative influence of Acid Orange II
Choose ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4, 6.0h is irradiated with simulated solar irradiation, other conditions are not
Become, only changes the access times of catalyst.It the results are shown in Table 2.
Influence of 2 cycle-index of table to light degradation Acid Orange II
From Table 2, it can be seen that the degradation rate of Acid Orange II does not significantly decrease, still keep stable.This is indicated five
In secondary continuous cyclic test, photocatalytic system ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4Good light is presented to urge
Change degrading activity.Therefore when removing water pollutant, the catalyst system is with good stability.
The symmetrical anti-Z-type photochemical catalyst of embodiment 3 is using Acid Orange II as sacrifice agent Photocatalyzed Hydrogen Production
Method: measuring the Acid Orange II solution of 500mL 50mg/L in Photocatalyzed Hydrogen Production reactor, as table 1 is added
The catalyst of the present invention and comparative example prepared by 500mg embodiment 1, it is seen that light irradiates 6.0h.Reaction is measured with gas-chromatography
In generated hydrogen amount.It the results are shown in Table 3.
(1) influence of the light application time to hydrogen output
The symmetrical anti-Z-type photochemical catalyst simulated solar irradiation Photocatalyzed Hydrogen Production of table 3
As shown in table 3, as time increases with the hydrogen output of 4 kinds of catalyst of the extension of light application time, hydrogen output is in
The trend now increased.Wherein, when light application time is 6.0h, ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4Hydrogen output
Highest, hydrogen output are 358.2 μm of olg-1。
(2) influence of the access times to hydrogen output
Change ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4The access times of catalyst, other conditions are constant.Knot
Fruit is shown in Table 4.
Table 4 changes influence of the access times to simulated solar irradiation hydrogen manufacturing
As can be seen from Table 4, Photocatalyzed Hydrogen Production amount keeps stablizing, and does not significantly decrease.This is indicated continuous five
In secondary loop test, photochemical catalyst ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4Present good photocatalytic activity.
Therefore in Photocatalyzed Hydrogen Production reaction, the photochemical catalyst is with good stability.
Claims (10)
1. symmetrical anti-Z-type photochemical catalyst, which is characterized in that the symmetrical anti-Z-type photochemical catalyst is ZnIn2S4/Er3+:
Y3Al5O12@ZnTiO3/CaIn2S4。
2. symmetrical anti-Z-type photochemical catalyst according to claim 1, which is characterized in that in mass ratio, (ZnIn2S4):(Er3+:
Y3Al5O12@ZnTiO3):(CaIn2S4)=1:1:1；(Er3+:Y3Al5O12):(ZnTiO3)=7:3.
3. the preparation method of symmetrical anti-Z-type photochemical catalyst of any of claims 1 or 2, which comprises the steps of:
With dilute HNO3Deionized water is transferred to pH=5, is stirred evenly, ZnIn is then sequentially added2S4、CaIn2S4And Er3+:Y3Al5O12@
ZnTiO3, after being uniformly mixed, 80 DEG C of baking oven drying are put into, the mixture of drying is transferred in Muffle furnace, 500 DEG C, is forged
2.0h is burnt, is cooled to room temperature, is washed with deionized, dry again, obtain symmetrically anti-Z-type photochemical catalyst ZnIn2S4/Er3+:
Y3Al5O12@ZnTiO3/CaIn2S4。
4. the preparation method of symmetrical anti-Z-type photochemical catalyst according to claim 3, which is characterized in that the ZnIn2S4's
Preparation method includes the following steps: ZnCl2With In (NO3)3Dissolution in deionized water, add thioacetamide, magnetic from
1.0h is stirred on sub- blender and forms clear solution, and clear solution is then transferred to polytetrafluoroethyllining lining stainless steel cauldron
In, the heat treatment of 6.0h is carried out at 160 DEG C, and obtained product is cooled to room temperature, is then carried out with deionized water and ethyl alcohol
It cleans, dries 6.0h at 80 DEG C, obtain ZnIn2S4。
5. the preparation method of symmetrical anti-Z-type photochemical catalyst according to claim 3, which is characterized in that the CaIn2S4's
Preparation method includes the following steps: Ca (NO3)2·4H2O and In (NO3)3It is dissolved in deionized water, adds thioacetyl
Amine transfers the solution into polytetrafluoroethyllining lining stainless steel cauldron after magnet suspension stirrer stirs 1.0h, is heated to 120
DEG C and keep 24.0h, washed, be centrifuged, 60 DEG C of dry 12.0h obtain CaIn with deionized water and dehydrated alcohol2S4。
6. the preparation method of symmetrical anti-Z-type photochemical catalyst according to claim 3, which is characterized in that the Er3+:
Y3Al5O12@ZnTiO3Preparation method include the following steps: Zn: Ti=1: 1 meter feedstock in molar ratio, first by zinc nitrate and titanium
Sour four butyl esters are dissolved in dehydrated alcohol respectively, and then zinc nitrate ethanol solution is added dropwise in butyl titanate ethanol solution,
And glacial acetic acid is added dropwise, the pH value of solution is controlled in 2-3 range, at 60 DEG C, is formed colloidal sol after heating stirring 3.0h, will be ground
The Er of milled3+:Y3Al5O12Powder is added in colloidal sol, continuously stirs until colloidal sol is transformed into gel；By resulting gel in 80 DEG C
It is dry, grinding；Then, gel powder is placed in Muffle furnace, calcines 3.0h at 600 DEG C, is cooled to room temperature, ground, then at 800
DEG C calcining 3.0h, obtain Er3+:Y3Al5O12@ZnTiO3。
7. symmetrical anti-Z-type photochemical catalyst ZnIn of any of claims 1 or 22S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4In light
Application in catalytic degradation organic pollutant.
8. application according to claim 7, which is characterized in that method is as follows: by symmetrical anti-Z of any of claims 1 or 2
Type photochemical catalyst ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4It is added in the solution containing organic pollutant, when illumination
Between be 1.0-6.0h.
9. application according to claim 8, which is characterized in that the organic pollutant is Acid Orange II.
10. application according to claim 9, which is characterized in that under conditions of using Acid Orange II as sacrifice agent, carry out light
Catalytic degradation and hydrogen manufacturing simultaneously.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102895965A (en) * | 2012-10-31 | 2013-01-30 | 辽宁大学 | Er<3+>: Y3Al5O12/TiO2 composite membrane and application thereof in catalytic degradation of organic dye |
| CN105964275A (en) * | 2016-05-05 | 2016-09-28 | 齐齐哈尔大学 | Microwave-assistant one-step synthesis method of CuS/CdIn2S4/ZnIn2S4 composite photocatalyst |
| CN107597142A (en) * | 2017-09-20 | 2018-01-19 | 辽宁大学 | A kind of new Z-type sound catalyst for antibiotic waste water of degrading and its preparation method and application |
| CN108057452A (en) * | 2018-02-02 | 2018-05-22 | 辽宁大学 | Sunlight photocatalysis agent of electronics and its preparation method and application is efficiently shifted in a kind of self assembly |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102895965A (en) * | 2012-10-31 | 2013-01-30 | 辽宁大学 | Er<3+>: Y3Al5O12/TiO2 composite membrane and application thereof in catalytic degradation of organic dye |
| CN105964275A (en) * | 2016-05-05 | 2016-09-28 | 齐齐哈尔大学 | Microwave-assistant one-step synthesis method of CuS/CdIn2S4/ZnIn2S4 composite photocatalyst |
| CN107597142A (en) * | 2017-09-20 | 2018-01-19 | 辽宁大学 | A kind of new Z-type sound catalyst for antibiotic waste water of degrading and its preparation method and application |
| CN108057452A (en) * | 2018-02-02 | 2018-05-22 | 辽宁大学 | Sunlight photocatalysis agent of electronics and its preparation method and application is efficiently shifted in a kind of self assembly |
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