CN107930633B - Preparation method and application of SrTiO3/Cu2O heterojunction composite nano material - Google Patents
Preparation method and application of SrTiO3/Cu2O heterojunction composite nano material Download PDFInfo
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- 229910002370 SrTiO3 Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title description 27
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 229910002367 SrTiO Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229940047908 strontium chloride hexahydrate Drugs 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
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 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
- NQFNBCXYXGZSPI-UHFFFAOYSA-L copper;diacetate;dihydrate Chemical compound O.O.[Cu+2].CC([O-])=O.CC([O-])=O NQFNBCXYXGZSPI-UHFFFAOYSA-L 0.000 claims abstract description 6
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- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 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 5
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract 1
- 229940112669 cuprous oxide Drugs 0.000 description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- 229910021389 graphene Inorganic materials 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033558 biomineral tissue development 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
- 239000000969 carrier 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
- 238000000975 co-precipitation 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
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- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 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
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 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
- 238000004626 scanning electron microscopy Methods 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
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- 238000003980 solgel method Methods 0.000 description 1
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Images
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
-
- B01J35/39—
-
- 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
Abstract
Novel SrTiO3/Cu2The preparation method of the O-junction composite nano material comprises the following steps: dissolving (tetra) isopropyl titanate and strontium chloride hexahydrate in acid respectively, mixing, adjusting the pH value to 3-4, heating to 90 ℃, and preserving heat for 3 hours; then heating to 400-500 ℃, and preserving heat for 4-6 hours; obtaining SrTiO3A catalyst; stirring and dissolving copper acetate dihydrate in glycol monomethyl ether at 35 ℃, stirring, performing ultrasonic treatment for 60 minutes, and then adding SrTiO3Stirring a catalyst, adding a sodium hydroxide solution, adjusting the pH value to 10-14, and stirring for 10 minutes at 50 ℃; adding sufficient glucose solution, and reacting for 1-1.5 hours; cooling to room temperature, and performing centrifugal separation to obtain a precipitate solid. SrTiO of the invention3/Cu2SrTiO in O heterogeneous composite catalyst3And Cu2The heterojunction is formed by O, the application of the electron and the hole is facilitated, the heterojunction catalyst degrades organic dye wastewater under visible light, and particularly the photocatalytic degradation efficiency of methylene blue organic solution reaches 92%.
Description
Technical Field
The invention belongs to the field of photocatalytic materials, and particularly relates to a preparation method and application of a SrTiO3/Cu2O heterojunction composite nano material.
Background
In recent years, the dye industry in China is rapidly developed, according to incomplete statistics, about 90-100 million tons of various dye sewage are discharged every day in China, and dye wastewater becomes one of the environmental important pollution sources. The dye industry has various varieties and complex processes, and the waste water contains a large amount of organic matters, has the characteristics of high CODCr, dark color, strong acid-base property and the like, and is always a difficult problem in waste water treatment. Therefore, the development of novel water treatment materials and novel processes, and the control of toxic organic pollutants become one of the key problems to be solved urgently in the environmental field. Extensive and intensive research for decades shows that organic pollutants can be completely converted and decomposed into inorganic small molecular substances such as CO2, H2O and the like by utilizing the photocatalysis of semiconductors such as ZnO, TiO2 and the like, and the method has the advantages of mild reaction conditions, low energy consumption, safety, no toxicity and simple and convenient operation, and is regarded as an ideal high-efficiency and low-consumption green environment treatment technology and is paid attention by environmental experts.
SrTiO3 is a semiconductor material developed on the basis of TiO2, and has wide application in the fields of photolysis of water to produce hydrogen and mineralization of organic substances (Yan Jian Hui, j.a. com., 472(2009) 429-433). Although SrTiO3 has a forbidden band width of 3.4eV and mainly absorbs ultraviolet light, it is significant to study a catalytic material having high photocatalytic activity under ultraviolet-visible light in order to effectively utilize sunlight, since ultraviolet light (below 420 nm) is less than 5% and visible light having a wavelength of 420 to 750nm accounts for 43% in the solar spectrum, and it is a necessary trend for photocatalytic development to be further put into practical use to find an inexpensive and high-performance ultraviolet-visible photocatalytic material. The previous reports mostly aim at the research of SrTiO3 monomer, and the Cr doping method is utilized by Chang et al (Chia-Hao Chang, Materials Letters, 60 (1): 129-132), so that SrTiO3 has visible light response, the degradation capability of methylene blue is greatly improved, and a good idea is provided for expanding the light absorption range of the SrTiO 3. Takeshi et al (Takeshi Toshima, Crystal.growth Des., 2008, 8 (7): 2066-2069) prepare perovskite type with multi-edge three-dimensional structure by a special crystal growth control method
SrTiO3 has new characteristics in light absorption characteristics and crystal structure. Yuan et al (RS Yuan, ACCcatal., 2011, 1 (3): 200-206) studied TiO2 with chlorine modified surface and some titanium-based composites, and proved that the photocatalytic degradation is remarkably improved. The document reports that cuprous oxide (Cu2O) belongs to a P-type semiconductor, the forbidden band width is about 2.2ev, the absorption wavelength is 563.nm, visible light can be absorbed, sunlight can be converted into electric energy or chemical energy, and therefore the cuprous oxide can generate a photocatalytic reaction under the irradiation of sunlight and is a photocatalyst with extremely high potential. The SrTiO3/Cu2 heterojunction composite material is constructed by taking a nano heterojunction theory as an idea and combining the energy band matching characteristics of SrTiO3 and Cu 2O.
The Chinese patent with publication number CN102698787A discloses a method for preparing a photocatalyst with high activity and large specific surface area by a novel solid phase method, which relates to a method for preparing a CN/SrTiO3 composite photocatalyst, and the preparation method of the catalyst is as follows: dissolving butyl titanate, Sr (NO3)3 and citric acid in ethylene glycol, and mixing to obtain a solution; carrying out ultrasonic treatment and microwave treatment on the solution to obtain sol, dehydrating the sol to form gel, firing the gel into powder, grinding the powder, and roasting at the temperature of 600-1000 ℃ for 8-15 h to obtain a SrTiO3 precursor; mixing and grinding the SrTiO3 precursor and urea, roasting to obtain a crude product, washing the crude product, and drying to obtain the composite photocatalyst. The product obtained by the method has good dispersibility, does not need acidic conditions when in use, can completely degrade rhodamine B within 50min, and is used for decomposing water to produce hydrogen, photodegrading organic matters and the like.
The invention patent with the publication number of CN103949200A discloses a preparation method of a NiFe2O4/Cu2O magnetic compound, and the photocatalytic degradation efficiency of the obtained compound on nitrophenol solution reaches 61.18%. However, in the existing documents, the preparation process is complex, takes a long time, and the prepared catalyst has the defects of large particles, small specific surface area, low photocatalytic degradation efficiency and the like.
Chinese patent with the patent number CN103464133A discloses a preparation method and application of a novel SrTiO3/TiO2 composite photocatalytic material. The catalyst is prepared by synthesizing SrTiO3 by adopting a coprecipitation method, doping the SrTiO3 into TiO2 by utilizing a sol-gel method, and finally performing surface chlorination modification by utilizing an impregnation method to obtain the novel composite photocatalyst. The preparation method comprises the following specific operation steps: adding SrTiO3 powder into 150ml of titanium glue according to the mass ratio of 18%, violently stirring for 24 hours, and drying by microwave; sintering the mixture for 3 to 5 hours in a muffle furnace at the temperature of between 400 and 500 ℃ to obtain the SrTiO3/TiO2 composite photocatalytic material; soaking 1g of the compound in 2ml of concentrated hydrochloric acid, sealing and standing in dark for 24h, then placing in a fume hood with an opening until the hydrochloric acid is completely volatilized, and finally drying at 50-60 ℃. The composite catalyst has the characteristics of high catalytic activity, wide applicability and good stability. Under the ultraviolet condition, the gas phase photocatalysis performance of the novel material is greatly improved compared with that of pure TiO2, and the novel material has great potential in the aspects of atmospheric pollution treatment, water treatment and the like
The Chinese patent with the publication number of CN10106964338A discloses a preparation method and application of a novel WO3/SrTiO3 composite photocatalytic material. The Chinese patent with the publication number of CN105817217A discloses a SrTiO 3/graphene composite catalyst, and a preparation method and application thereof. Researches show that the graphene and the photocatalytic material can be compounded to be used as an electron transfer medium to improve the migration rate of photo-generated electrons in a semiconductor, reduce the recombination rate of current carriers and improve the photocatalytic quantum efficiency of the semiconductor material.
In recent years, researchers have conducted a great deal of research work around SrTiO3, but related patents and technologies have low catalytic efficiency, and no SrTiO3/Cu2O heterogeneous composite catalyst has been reported so far.
Disclosure of Invention
In order to solve the defect that the catalytic efficiency of the composite catalyst of SrTiO3 is low and still low in the prior art, the invention provides a SrTiO3/Cu2O heterogeneous composite catalyst.
A preparation method of SrTiO3/Cu2O heterojunction composite nano-materials comprises the following steps:
1) respectively dissolving (tetra) isopropyl titanate and strontium chloride hexahydrate in acetic acid and citric acid, and stirring for 10-20 minutes;
2) mixing a (tetra) isopropyl titanate solution and a strontium chloride hexahydrate solution, uniformly stirring, adjusting the pH value to 3-4, heating to 90 ℃, preserving heat for 3 hours, and transferring to a reaction kettle;
3) heating the reaction kettle to 400-500 ℃, and preserving heat for 4-6 hours; separating, washing and drying the obtained powder solid to obtain SrTiO3 catalyst;
4) stirring and dissolving copper acetate dihydrate into glycol monomethyl ether at 35 ℃, stirring for 10-20 minutes, and carrying out ultrasonic treatment for 60 minutes to obtain a copper acetate solution;
5) adding the SrTiO3 catalyst obtained in the step 3) into the solution 4), stirring for 10-20 minutes, adding a sodium hydroxide solution, adjusting the pH value to 10-14, and stirring for 10 minutes at 50 ℃;
6) adding sufficient glucose solution, and reacting for 1-1.5 hours; cooling to room temperature, and performing centrifugal separation to obtain a precipitate solid;
7) and washing the precipitated solid obtained in the step 6) with clear water, drying and drying to obtain the SrTiO3/Cu2O heterojunction composite nano material.
Furthermore, the molar ratio of the added SrTiO3 catalyst in the step (5) to the copper acetate in the solution is 3: 2-1: 4. Preferably, the molar ratio of the SrTiO3 catalyst to the copper acetate in the solution is 2-1.
Further, the molar ratio of the added glucose in the step (6) to the copper acetate in the solution is 1:1-1: 1.5.
Further, the molar ratio of the titanium atoms to the strontium atoms in the step (1) is 1:1.
Further, the concentration of the copper acetate dihydrate solution in the step (4) is 0.1 mol per liter.
Further, the concentration of acetic acid in the step (1) is 2 mol per liter, and the concentration of citric acid is 4mol per liter.
Has the advantages that: in the SrTiO3/Cu2O heterogeneous composite catalyst, SrTiO3 and Cu2O form a heterojunction, so that the application of electrons and holes is facilitated, the heterojunction catalyst degrades organic dye wastewater under visible light, and particularly the photocatalytic degradation efficiency of a methylene blue organic solution reaches 92%.
Drawings
FIG. 1 is a spectrum of XRD of SrTiO3/Cu2O
FIG. 2 is an SEM picture of SrTiO3/Cu2O composite nanoparticles
FIG. 3 is a Uv-Vis spectrum of SrTiO3/Cu 2O.
FIG. 4 shows the degradation effect of SrTiO3/Cu2O heterojunction composite nano-material on methylene blue solution.
Detailed Description
Examples
A preparation method of SrTiO3/Cu2O heterojunction composite nano-materials comprises the following steps:
1) 2.8422g of (tetra) isopropyl titanate is weighed and dissolved in 24mL of acetic acid solution, the solution is continuously stirred for 10 to 20 minutes, and 20mL of deionized water is added at the same time;
weighing 2.6662g of strontium chloride hexahydrate, respectively dissolving in 4mol/l of citric acid, and stirring for 10-20 minutes;
2) mixing a (tetra) isopropyl titanate solution and a strontium chloride hexahydrate solution, uniformly stirring, adjusting the pH value to 3.5, heating to 90 ℃, preserving heat for 3 hours, and then transferring to a reaction kettle;
3) heating the reaction kettle to 400-500 ℃, and preserving heat for 5 hours; separating, washing and drying the obtained powder solid to obtain SrTiO3 catalyst;
4) 1.9965g of copper acetate dihydrate is stirred and dissolved in 100mL of glycol methyl ether at 35 ℃, stirred for 15 minutes and ultrasonically treated for 60 minutes to obtain 0.1 mol of copper acetate solution per liter;
5) adding 0.9173g of SrTiO3 catalyst obtained in the step 3) into the solution 4), stirring the mixture for 15 minutes, adding 24mL of 0.04g/mL sodium hydroxide solution, adjusting the pH value to 10, and stirring the mixture for 10 minutes at 50 ℃;
6) adding 24mL of 0.05g/mL glucose solution, and reacting for 1 hour; cooling to room temperature, and performing centrifugal separation to obtain a precipitate solid;
7) and washing the precipitated solid obtained in the step 6) with clear water, and drying in a vacuum oven at the temperature of 80 ℃ for 8 hours to obtain the SrTiO3/Cu2O heterojunction composite nano-material.
The spectrum analysis of XRD of SrTiO3/Cu2O prepared by the method is shown in figure 1. SEM analysis and detection of the SrTiO3/Cu2O prepared by the embodiment shows that the composite nano-particles have the size of about 500-1.5 μm as shown in figure 2. The results of UV-VIS spectroscopy analysis of SrTiO3/Cu2O prepared in this example are shown in FIG. 3.
0.5g of SrTiO3/Cu2O prepared in example was added to 100mL of 20mg/L methylene blue solution, and the solution was placed under a 500W UV-visible lamp to perform a photocatalytic reaction, wherein the distance from the light source to the reaction solution surface was 20 cm. The best degradation rate of 1SrTiO3/1Cu2O after 60 minutes of photocatalysis reaches 92%, as shown in FIG. 4, FIG. 4 shows that the better catalytic effect can be achieved when the molar ratio of SrTiO3 or Cu2O in the SrTiO3/Cu2O heterojunction composite nano-material is greatly influenced than the catalytic performance of the composite nano-material, but the SrTiO3 or Cu2O is not mixed in any ratio, wherein the catalytic performance of the SrTiO3/Cu2O heterojunction composite nano-material is the best when the molar ratio of SrTiO3 to Cu2O is 1:1.
Claims (8)
1. SrTiO3/Cu2The preparation method of the O heterojunction composite nano material is characterized by comprising the following steps of:
1) respectively dissolving (tetra) isopropyl titanate and strontium chloride hexahydrate in acetic acid and citric acid, and stirring for 10-20 minutes;
2) mixing a (tetra) isopropyl titanate solution and a strontium chloride hexahydrate solution, uniformly stirring, adjusting the pH value to 3-4, heating to 90 ℃, preserving heat for 3 hours, and transferring to a reaction kettle;
3) heating the reaction kettle to 400-500 ℃, and preserving heat for 4-6 hours; separating, washing and drying the obtained powder solid to obtain SrTiO3A catalyst;
4) stirring and dissolving copper acetate dihydrate into glycol monomethyl ether at 35 ℃, stirring for 10-20 minutes, and carrying out ultrasonic treatment for 60 minutes to obtain a copper acetate solution;
5) adding 3) the SrTiO to 4)3Stirring the catalyst for 10-20 minutes, adding a sodium hydroxide solution, adjusting the pH value to 10-14, and stirring for 10 minutes at 50 ℃;
6) adding sufficient glucose solution, and reacting for 1-1.5 hours; cooling to room temperature, and performing centrifugal separation to obtain a precipitate solid;
7) washing the precipitated solid obtained in the step 6) with clear water, drying and drying to obtain SrTiO3/Cu2And O heterojunction composite nano-material.
2. SrTiO of claim 13/Cu2The preparation method of the O heterojunction composite nano material is characterized in that the SrTiO in the step (5)3The molar ratio of the addition amount of the catalyst to the copper acetate in the solution is 3: 2-1: 4.
3. SrTiO of claim 13/Cu2The preparation method of the O heterojunction composite nano material is characterized in that the SrTiO in the step (5)3The molar ratio of the addition amount of the catalyst to the copper acetate in the solution is 2-1.
4. SrTiO of claim 13/Cu2The preparation method of the O heterojunction composite nanomaterial is characterized in that the molar ratio of the addition amount of glucose to copper acetate in the solution in the step (6) is 1:1-1: 1.5.
5. SrTiO of claim 13/Cu2The preparation method of the O heterojunction composite nanomaterial is characterized in that the molar ratio of titanium atoms to strontium atoms in the step (1) is 1:1.
6. SrTiO of claim 13/Cu2The preparation method of the O heterojunction composite nano material is characterized in that the concentration of the copper acetate dihydrate solution in the step (4) is 0.1 mol per liter.
7. SrTiO of claim 13/Cu2The preparation method of the O heterojunction composite nanomaterial is characterized in that the concentration of acetic acid in the step (1) is 2 mol per liter, and the concentration of citric acid is 4mol per liter.
8. SrTiO of any one of claims 1 to 73/Cu2SrTiO prepared by preparation method of O heterojunction composite nano material3/Cu2The application of the O heterojunction composite nano material in treating organic pollutants in dye wastewater.
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