CN107930633A - A kind of new SrTiO3/Cu2O ties the preparation method and application of composite nano materials - Google Patents
A kind of new SrTiO3/Cu2O ties the preparation method and application of composite nano materials Download PDFInfo
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- CN107930633A CN107930633A CN201711180113.4A CN201711180113A CN107930633A CN 107930633 A CN107930633 A CN 107930633A CN 201711180113 A CN201711180113 A CN 201711180113A CN 107930633 A CN107930633 A CN 107930633A
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- 229910002370 SrTiO3 Inorganic materials 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910002367 SrTiO Inorganic materials 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000009413 insulation Methods 0.000 claims abstract description 8
- -1 isopropyl ester Chemical class 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- AMGRXJSJSONEEG-UHFFFAOYSA-L strontium dichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Sr]Cl AMGRXJSJSONEEG-UHFFFAOYSA-L 0.000 claims abstract description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 6
- 239000008103 glucose Substances 0.000 claims abstract description 6
- 230000036571 hydration Effects 0.000 claims abstract description 5
- 238000006703 hydration reaction Methods 0.000 claims abstract description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000975 dye Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 16
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 3
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000010919 dye waste Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000021332 multicellular organism growth Effects 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous 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
- C02F2101/308—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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
A kind of new SrTiO3/Cu2O ties the preparation method of composite nano materials, comprises the following steps：By metatitanic acid (four) isopropyl ester and Strontium dichloride hexahydrate respectively with after acid dissolving, it is 3~4 that pH is adjusted after mixing, is heated to 90 DEG C, when insulation 3 is small；It is then heated to 400~500 DEG C, when insulation 4~6 is small；Obtain SrTiO3Catalyst；At 35 DEG C, two hydration copper acetate stirrings are dissolved in glycol methyl ether, are stirred, and be ultrasonically treated 60 minutes, then add SrTiO3Catalyst, stirring, adds sodium hydroxide solution, adjusts pH value and is stirred 10 minutes for 10~14,50 DEG C；Enough glucose solutions are added, when reaction 1~1.5 is small；Be cooled to room temperature, be centrifugally separating to obtain precipitation solid, to obtain the final product.The SrTiO of the present invention3/Cu2SrTiO in O Heterogeneous Composite catalyst3And Cu2O forms hetero-junctions, is conducive to the application divided in electronics and hole, degrading organic dye waste water, the photocatalytic degradation efficiency of particularly methylene blue organic solution reach 92% to the hetero-junctions catalyst under visible light.
Description
Technical field
The invention belongs to field of photocatalytic material, is specially a kind of new smooth SrTiO3/Cu2O ties the system of composite nano materials
Standby and application.
Background technology
In recent years, the dye industry in China is fast-developing, and according to incompletely statistics, various dye wastewaters discharge about daily in China
Ten thousand tons of 90-100, waste water from dyestuff become one of environment major polluting sources.Dye industry is various in style, complex process, its waste water
In contain substantial amounts of organic matter, there is high CODCr, the features such as color and luster is deep, and acid-base property is strong, is always the problem in wastewater treatment.
Then new material for water treatment and novel process are developed, control toxic organic pollutant has become environmental area pass urgently to be resolved hurrily
One of key problem.Find to utilize ZnO, TiO by the extensively and profoundly research of decades2Photocatalysis, which can occur, Deng semiconductor makes to have
CO is resolved into organic pollutants conversion completely2、H2The inorganic molecules material such as O, and reaction condition is gentle, energy consumption is low, safe and non-toxic,
It is easy to operate, it is considered as a kind of preferably efficient, low consumption green environment Treatment process and is paid close attention to be subject to environmentalist.
SrTiO3Be one kind with TiO2Based on the semi-conducting material developed, led in photodissociation aquatic products hydrogen and mineralization of organic material
Domain has a wide range of applications (Yan Jian Hui, J.A.Com., 472 (2009) 429-433).SrTiO3Energy gap be
3.4eV, mainly absorbs ultraviolet light, still, in solar spectrum ultraviolet light (below 420nm) less than 5%, and wavelength for 420~
The visible ray of 750nm accounts for 43%, therefore, in order to efficiently use sunlight, studies and is urged under ultraviolet-visible light with efficiency light
The catalysis material of change activity is very significant, and it will be that light is urged to seek ultraviolet-visible light catalysis material cheap, with high performance
Change development and go further to practical inexorable trend.Previous report is mostly to be directed to SrTiO3The research of monomer, Chang etc.
(Chia-Hao Chang, Materials Letters, 60 (1)：129-132) using the method for Cr doping, there is SrTiO3
It is visible light-responded, the degradation capability of methylenum careuleum is greatly improved, good thinking is provided to expand its light abstraction width.
(Takeshi Toshima, Cryst.Growth Des., 2008,8 (7) such as Takeshi：2066-2069) pass through special crystalline substance
Body growth control method, is prepared for the Ca-Ti ore type SrTiO of more rib stereochemical structures3, produced in terms of extinction characteristic, crystal structure
New characteristic.(RS Yuan, ACSCatal., 2011,1 (3) such as Yuan：It 200-206) have studied the TiO of surface chlorine modification2
And some titanium matrix composites, it was demonstrated that it is obviously improved in terms of photocatalytic degradation.According to the literature, cuprous oxide
(Cu2O P-type semiconductor) is belonged to, energy gap is about 2.2ev, and absorbing wavelength 563.nm, can absorb visible ray, can will too
Sunlight is converted into electric energy or chemical energy, therefore under sunlight irradiation light-catalyzed reaction can occur for cuprous oxide, be a kind of pole
Has the photochemical catalyst of potential.Herein will be using nano heterojunction theory as thinking, with reference to SrTiO3With Cu2The energy band matching characteristic of O,
Build SrTiO3/Cu2Hetero-junctions compound material.
The Chinese invention patent of Publication No. CN102698787A discloses a kind of new solid phase method and prepares high activity, big ratio
The method of surface area photochemical catalyst, it is related to CN/SrTiO3The method of composite photo-catalyst, the preparation method of catalyst are as follows：
By butyl titanate, Sr (NO3)3, citric acid be dissolved in ethylene glycol, mix to obtain solution；By solution is sonicated and microwave treatment after
Colloidal sol is obtained, molten middle dehydration is formed into gel, gel is burnt till into powder, after powder mull, at a temperature of 600~1000 DEG C
8~15h is roasted, obtains SrTiO3Predecessor；By SrTiO3Predecessor and urea, after mixing and grinding, roasting obtains crude product,
Crude product is washed, is dried to obtain composite photo-catalyst.Product good dispersion obtained by the invention, need not acid bar during use
Part, in 50min in can be degradable by rhodamine B, for hydrogen production by water decomposition and light degradation organic matter etc..
The patent of invention of Publication No. CN103949200A discloses a kind of NiFe2O4/Cu2The preparation side of O magnetic composites
Method, the compound of acquisition reach 61.18% for the photocatalytic degradation efficiency of nitrophenol solution.But in existing document
In all preparation processes it is more complicated, expend longer time, the catalyst granules of preparation is larger, and specific surface area is smaller, photocatalysis
The some shortcomings such as degradation efficiency is low.
The number of opening is that the Chinese invention patent of CN103464133A discloses a kind of new SrTiO3/TiO2Composite photocatalyst material
The preparation method and applications of material.The catalyst uses Co deposited synthesis SrTiO3, recycle sol-gal process to be mixed
To TiO2In it is last recycle infusion process to carry out surface chlorination modification, that is, obtain NEW TYPE OF COMPOSITE photochemical catalyst.The tool of preparation method
Body operating procedure is as follows：In mass ratio 18%, by SrTiO3Powder is added in 150ml titanium glue, is vigorously stirred 24h, and microwave dries
It is dry；400-500 DEG C of sintering 3-5h of Muffle furnace, that is, obtain SrTiO3/TiO2Composite photocatalyst material；1g compounds are taken to be immersed in 2ml
In concentrated hydrochloric acid, in dark place sealing and standing 24h, then placed in fume hood split shed, until hydrochloric acid is evaporated completely entirely, finally substantially
50-60 DEG C of drying.The composite catalyst has the characteristics that catalytic activity is high, applicability is wide and stability is good.Ultraviolet
Under the conditions of, the gas-phase photocatalysis performance of new material compares pure TiO2It is greatly improved, in air contaminant treatment, water process
Etc. possess huge potentiality
The Chinese invention patent of Publication No. CN10106964338A discloses a kind of new WO3/SrTiO3Composite photocatalyst
The preparation method and applications of material.The Chinese invention patent of Publication No. CN105817217A discloses SrTiO3/ graphene
Composite catalyst and preparation method and application.Research shows, graphene with catalysis material is compound to be used as electron transmission to be situated between
Matter improves the migration rate of light induced electron in semiconductor, and the compound youngster for reducing carrier leads, and improves the photocatalysis of semi-conducting material
Quantum efficiency.
Recent study personnel surround SrTiO3Substantial amounts of research work is carried out, but relevant patent and technology are all deposited
It is low in catalytic efficiency, up to the present, also without SrTiO3/Cu2The report of O Heterogeneous Composite catalyst.
The content of the invention
To solve SrTiO existing in the prior art3Composite catalyst catalytic efficiency it is low still than it is relatively low the defects of, this hair
It is bright that a kind of SrTiO is provided3/Cu2O Heterogeneous Composite catalyst.
A kind of new SrTiO3/Cu2O ties the preparation method of composite nano materials, comprises the following steps：
1), by metatitanic acid (four) isopropyl ester and Strontium dichloride hexahydrate be dissolved separately in acetic acid and citric acid in and stir 10~
20 minutes；
2), metatitanic acid (four) isopropyl ester solution and Strontium dichloride hexahydrate solution are mixed, after stirring evenly, adjust pH for 3~
4,90 DEG C are heated to, when insulation 3 is small, is then transferred in reaction kettle；
3) reaction kettle is heated to 400~500 DEG C, when insulation 4~6 is small；Powder solid separation, washing, drying will be obtained,
Obtain SrTiO3Catalyst；
4), at 35 DEG C, two hydration copper acetate stirrings is dissolved in glycol methyl ether, are stirred 10~20 minutes, and at ultrasound
Reason 60 minutes, obtains acetic acid copper solution；
5), to the SrTiO obtained by 4) middle addition 3)3Catalyst, is stirred 10~20 minutes, adds sodium hydroxide solution, is adjusted
PH value is saved to stir 10 minutes for 10~14,50 DEG C；
6) enough glucose solutions, are added, when reaction 1~1.5 is small；It is cooled to room temperature, is centrifugally separating to obtain precipitation solid；
7), the precipitation solid obtained by 6) is cleaned with clear water, it is dry after drying, SrTiO is made3/Cu2O ties composite Nano material
Material.
Further, the SrTiO in the step (5)3The molar ratio of copper acetate is in the addition and solution of catalyst
3:2~1:4.Preferably, SrTiO3The molar ratio of copper acetate is 2~1 in the addition and solution of catalyst.
Further, the molar ratio of copper acetate is 1 in the addition of glucose and solution in the step (6):1-1:
1.5。
Further, the molar ratio of titanium atom and strontium atom is 1 in the step (1):1.
Further, the concentration of two hydration acetic acid copper solutions is 0.1 mole every liter in the step (4).
Further, the concentration of acetic acid is 2 moles every liter in the step (1), and the concentration of citric acid is 4 moles every liter.
Beneficial effect：The SrTiO of the present invention3/Cu2SrTiO in O Heterogeneous Composite catalyst3And Cu2O forms hetero-junctions, has
Beneficial to electronics and hole point application, the hetero-junctions catalyst degrading organic dye waste water, particularly methylene under visible light
The photocatalytic degradation efficiency of base indigo plant organic solution reaches 92%.
Brief description of the drawings
Fig. 1 is SrTiO3/Cu2The collection of illustrative plates of the XRD of O
Fig. 2 is SrTiO3/Cu2The SEM pictures of O composite nanometer particles
Fig. 3 is SrTiO3/Cu2The collection of illustrative plates of the Uv-Vis of O.
Fig. 4 is SrTiO3/Cu2Degradation effect of the O hetero-junctions composite nano materials to methylene blue solution.
Embodiment
Embodiment
A kind of new SrTiO3/Cu2O ties the preparation method of composite nano materials, comprises the following steps：
1) acetum that metatitanic acid (four) isopropyl ester 2.8422g is dissolved in 24 milliliters, is weighed, and constantly stirs 10~20 points
Clock, while add the deionized water of 20mL；
The citric acid that Strontium dichloride hexahydrate 2.6662g is dissolved separately in 4mol/l is weighed, and is stirred 10~20 minutes；
2), metatitanic acid (four) isopropyl ester solution and Strontium dichloride hexahydrate solution are mixed, after stirring evenly, it is 3.5 to adjust pH,
90 DEG C are heated to, when insulation 3 is small, is then transferred in reaction kettle；
3) reaction kettle is heated to 400~500 DEG C, when insulation 5 is small；Powder solid separation, washing, drying will be obtained, will be obtained
To SrTiO3Catalyst；
4), at 35 DEG C, 1.9965g bis- is hydrated copper acetate stirring and is dissolved in 100mL glycol methyl ethers, is stirred 15 minutes,
And be ultrasonically treated 60 minutes, obtain 0.1 mole every liter of acetic acid copper solution；
5), to the SrTiO obtained by 4) middle addition 3)3Catalyst 0.9173g, is stirred 15 minutes, adds the hydrogen of 0.04g/mL
Sodium hydroxide solution 24mL, adjusts pH value and is stirred 10 minutes for 10,50 DEG C；
6) 0.05g/mL glucose solution 24mL, are added, when reaction 1 is small；It is cooled to room temperature, it is solid is centrifugally separating to obtain precipitation
Body；
7), the precipitation solid obtained by 6) is cleaned with clear water, in 80 DEG C of vacuum drying ovens it is dry 8 it is small when, SrTiO is made3/
Cu2O ties composite nano materials.
SrTiO prepared by this implementation3/Cu2The atlas analysis of the XRD of O is as shown in Figure 1.The SrTiO prepared to this implementation3/
Cu2The sem analysis detection of O, the results are shown in Figure 2, about 500~1.5 μm of the size of composite nanometer particle.It is prepared by this implementation
SrTiO3/Cu2The ultraviolet-visible spectrum analysis of O, the results are shown in Figure 3.
Take the SrTiO prepared in 0.5g embodiments3/Cu2O, adds and extremely arrives 100mL, in the methylene blue solution of 20mg/L, puts
Carry out light-catalyzed reaction under the UV, visible light lamp of 500W, light source is from reaction solution identity distance from for 20cm.Photocatalysis is after sixty minutes
1SrTiO3/1Cu2The best degradation rate of effect of O has reached 92%, as shown in figure 4, Fig. 4 is shown, works as SrTiO3/Cu2O knots are multiple
Close SrTiO in nano material3Or Cu2The molar ratio of O the catalytic performances of composite nano materials is influenced it is very big, not the two with
Arbitrary proportion mixes, and can have preferable catalytic effect, wherein, with SrTiO3With Cu2The molar ratio 1 of O:SrTiO when 13/
Cu2The catalytic performance of O hetero-junctions composite nano materials is optimal.
Claims (8)
- A kind of 1. new SrTiO3/Cu2O ties the preparation method of composite nano materials, it is characterised in that comprises the following steps：1), by metatitanic acid (four) isopropyl ester and Strontium dichloride hexahydrate be dissolved separately in acetic acid and citric acid in and stir 10~20 points Clock；2), metatitanic acid (four) isopropyl ester solution and Strontium dichloride hexahydrate solution are mixed, after stirring evenly, it is 3~4 to adjust pH, is added Heat when insulation 3 is small, is then transferred in reaction kettle to 90 DEG C；3) reaction kettle is heated to 400~500 DEG C, when insulation 4~6 is small；Powder solid separation, washing, drying will be obtained, will be obtained SrTiO3Catalyst；4), at 35 DEG C, two hydration copper acetate stirrings is dissolved in glycol methyl ether, are stirred 10~20 minutes, and be ultrasonically treated 60 Minute, obtain acetic acid copper solution；5), to the SrTiO obtained by 4) middle addition 3)3Catalyst, is stirred 10~20 minutes, adds sodium hydroxide solution, adjusts pH value For 10~14,50 DEG C are stirred 10 minutes；6) enough glucose solutions, are added, when reaction 1~1.5 is small；It is cooled to room temperature, is centrifugally separating to obtain precipitation solid；7), the precipitation solid obtained by 6) is cleaned with clear water, it is dry after drying, SrTiO is made3/Cu2O ties composite nano materials.
- 2. new SrTiO as claimed in claim 13/Cu2O ties the preparation method of composite nano materials, it is characterised in that described SrTiO in step (5)3The molar ratio of copper acetate is 3 in the addition and solution of catalyst:2~1:4.
- 3. new SrTiO as claimed in claim 13/Cu2O ties the preparation method of composite nano materials, it is characterised in that described SrTiO in step (5)3The molar ratio of copper acetate is 2~1 in the addition and solution of catalyst.
- 4. new SrTiO as claimed in claim 13/Cu2O ties the preparation method of composite nano materials, it is characterised in that described The molar ratio of copper acetate is 1 in the addition of glucose and solution in step (6):1-1:1.5.
- 5. new SrTiO as claimed in claim 13/Cu2O ties the preparation method of composite nano materials, it is characterised in that described The molar ratio of titanium atom and strontium atom is 1 in step (1):1.
- 6. new SrTiO as claimed in claim 13/Cu2O ties the preparation method of composite nano materials, it is characterised in that described The concentration of two hydration acetic acid copper solutions is 0.1 mole every liter in step (4).
- 7. new SrTiO as claimed in claim 13/Cu2O ties the preparation method of composite nano materials, it is characterised in that described The concentration of acetic acid is 2 moles every liter in step (1), and the concentration of citric acid is 4 moles every liter.
- 8. the new SrTiO of claim 1-7 any one of them3/Cu2O ties composite nano materials in the processing organic dirt of waste water from dyestuff Contaminate the application in thing.
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