CN110681384B - TiO2Preparation method of-samarium cuprate nano photocatalytic and electrocatalytic powder - Google Patents
TiO2Preparation method of-samarium cuprate nano photocatalytic and electrocatalytic powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 70
- 229910052772 Samarium Inorganic materials 0.000 title claims abstract description 53
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title abstract description 16
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims abstract description 20
- 229940107698 malachite green Drugs 0.000 claims abstract description 20
- 238000007146 photocatalysis Methods 0.000 claims abstract description 9
- 239000011941 photocatalyst Substances 0.000 claims abstract description 4
- 239000002351 wastewater Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 11
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 9
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- JPDBEEUPLFWHAJ-UHFFFAOYSA-K samarium(3+);triacetate Chemical compound [Sm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JPDBEEUPLFWHAJ-UHFFFAOYSA-K 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical group Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000011858 nanopowder Substances 0.000 description 10
- 229910052761 rare earth metal Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 150000002910 rare earth metals Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
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- 241001465754 Metazoa Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
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- FSEUPUDHEBLWJY-UHFFFAOYSA-N diacetylmonoxime Chemical compound CC(=O)C(C)=NO FSEUPUDHEBLWJY-UHFFFAOYSA-N 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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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
- B01J23/70—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
- B01J23/83—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 rare earths or actinides
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- B01J35/23—
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- B01J35/33—
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- B01J35/39—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- 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
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- 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
- C02F2305/08—Nanoparticles or nanotubes
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- 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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- 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 invention belongs to the technical field of photocatalysis and electrocatalysis, and particularly relates to TiO2A method for preparing samarium cuprate nano photocatalysis and electrocatalysis powder. The powder prepared by the method has stronger catalytic effect in a visible light region and an ultraviolet light region, the powder has high purity, uniform granularity, good controllability and excellent performance, and the prepared samarium cuprate nano photocatalytic powder can be used as a photocatalyst and applied to industries containing malachite green and the treatment of dye wastewater.
Description
Technical Field
The invention belongs to the technical field of photocatalysis and electrocatalysis, and particularly relates to TiO2A method for preparing samarium cuprate nano photocatalysis and electrocatalysis powder.
Background
Rare earth is an important strategic resource, and rare earth elements are the name of industrial vitamins. The rare earth elements not only have wide application in the traditional industries of petroleum, steel, metallurgy, agriculture and the like, but also have great significance in high and new technical fields of energy, environment, biology, new materials and the like. Compared with the existing noble metal catalyst with mature preparation technology and practical application, the rare earth catalytic material has outstanding advantages in many aspects. Firstly, the resource distribution of the prepared rare earth catalytic material is wider, the production cost is lower, the stock quantity of the rare earth which is proved in China already exceeds 13000 ten thousand tons, and the recoverable reserve quantity of the rare earth far exceeds 5600 ten thousand tons of noble metal. Secondly, the preparation process of the rare earth catalytic material is simpler, the requirement on equipment conditions is lower, and industrialization is easier to realize. Finally, the rare earth catalytic material has higher stability and has obvious advantages in catalytic efficiency and development space.
Malachite Green (MG) is also called aniline Green, alkaline Green, basic block Green or Chinese Green, belongs to triphenylmethane dyes, is easy to dissolve in solvents such as water, methanol, ethanol and the like, and the solution is blue-Green, can be used as dyes for textile industry, leather industry, ceramic industry and cell dyeing, and can also be used as insect repellents and bactericides for aquaculture industry, so that the Malachite Green is used for preventing saprolegniasis, fish egg disease and the like of aquaculture animals in China and other countries. However, with the gradual and deep toxicological research of malachite green at home and abroad in recent years, a great deal of research shows that the malachite green and the metabolite colorless malachite green thereof have great side effects on organisms and environment. Because triphenylmethane, a functional group of triphenylmethane, has high toxicity, high residue, three causes (carcinogenesis, teratogenesis, mutagenesis) and other toxic and side effects, malachite green has been banned from being used in aquaculture industry in many countries and organizations such as the United states, Japan, European Union and the like, and is listed in 'animal medicine banned for edible animals and compound list' in 5 months in 2002 in China.
The complex method is a method of reacting a metal cation with an organic solvent to combine the metal ion and a ligand in the form of a coordinate bond, thereby forming a complex ion having a certain composition or spatial configuration. The formed coordination ions react with a precipitator to generate an insoluble coordination compound, and the insoluble coordination compound is filtered, dried or calcined at high temperature to synthesize the composite powder with special performance.
Samarium cuprate Sm2CuO4Has good superconductivity, gas sensitivity and photocatalysis characteristics, and is one of copper-based rare earth materials with better performance. But samarium cuprate Sm2CuO4The existing preparation method is not satisfactory, and has the problems of complex preparation process, difficult popularization, poor performance of the obtained product and the like. The preparation method provided by the invention can solve the problems, and the improved Sm is coated with the TiO2 nano powder2CuO4On the nano powder, the prepared powder has stronger catalytic effect in a visible light region and an ultraviolet light region, and the preparation methodThe obtained powder has high purity, uniform granularity, good controllability and excellent performance, and reports on malachite green are not found at present. In addition, the nano powder prepared by the method has potential application space in the aspects of hydrogen production and oxygen production through electrocatalysis hydrolysis.
Disclosure of Invention
To solve the above technical problems, the present invention provides TiO2A method for preparing samarium cuprate nano photocatalysis and electrocatalysis powder. The powder prepared by the method has stronger catalytic effect in a visible light region and an ultraviolet light region, the powder has high purity, uniform granularity, good controllability and excellent performance, and the prepared samarium cuprate nano photocatalytic powder can be used as a photocatalyst and applied to industries containing malachite green and the treatment of dye wastewater.
The specific technical scheme is as follows:
TiO2the preparation method of the-samarium cuprate nano photocatalytic and electrocatalytic powder comprises the following steps:
(1) according to samarium Sm cuprate2CuO4Weighing soluble salt of Cu and soluble salt of Sm according to the stoichiometric ratio of Cu to Sm, dissolving the soluble salts of Cu and Sm in deionized water, and uniformly mixing to obtain solution A;
(2) adding a certain amount of acetonitrile and a certain amount of dimethylglyoxime into the solution A, heating the solution at 60-90 ℃ and stirring for 2-3 h to obtain a solution B;
(3) adding 5-10mL of 1mol/L alkali liquor into the solution B by using a liquid transfer gun, and stirring until the alkali liquor is dissolved to prepare a solution C;
(4) putting the solution C into an oven, reacting for 3-6 hours at a constant temperature of 120-150 ℃, and cooling to room temperature in the air; after the solution system is stable, filtering the obtained mixed solution, washing the obtained solid with water for 2-4 times to obtain flaky crystals, putting the obtained crystals into liquid nitrogen for pulverization, and taking out powder D;
(5) mixing the powder D with a certain amount of nano TiO2Putting the powder into deionized water, performing spray granulation by a sprayer, and drying for 1-2h in an oven at the temperature of 60-90 ℃ to prepare TiO2-samarium cuprate nano photocatalytic and electrocatalytic powder.
The soluble salt of copper in the step (1) can be copper chloride, copper nitrate or copper acetate, and the soluble salt of samarium can be samarium chloride, samarium nitrate or samarium acetate.
The volume usage amount of the deionized water in the step (1) is 4-6 times of the total molar amount of the soluble salt of copper and the soluble salt of samarium.
The stirring condition in the step (2) is mechanical stirring or magnetic stirring, and the rotation number of a rotor is 500-1000 r/min.
In the step (2), the dosage of the acetonitrile is 3-4 times of the molar weight of the copper salt, and the dosage of the dimethylglyoxime is 1-2 times of the molar weight of the copper salt.
And (3) the solute of the alkali liquor is triethylamine, and the solvent is ethanol.
Nano TiO in the step (5)2The dosage of the soluble salt is 1-2 times of the total molar weight of the soluble salt of copper and the soluble salt of samarium.
TiO2Application of-samarium cuprate nano photocatalytic and electro-catalytic powder, and TiO2The-samarium cuprate nano photocatalytic powder can be used as a photocatalyst in a visible light region and an ultraviolet light region, is applied to the industries containing malachite green and the treatment of dye wastewater, and can also be used for electrolyzing water to produce hydrogen and oxygen.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) the invention adopts a coordination synthesis method, has simple preparation process and good metal atom matching property, does not cause metal waste, pollutes the environment, saves the cost and is suitable for large-scale production;
(2) in the process of preparing the original simple solution, the acetonitrile and the dimethylglyoxime are added, so that copper ions and samarium ions are effectively dispersed, the prepared powder is finer, the nanocrystallization is facilitated, the dimethylglyoxime and the copper ions are effectively coordinated, the copper and the samarium can be fully dissolved in the acetonitrile solution, and the experimental effect required by the patent can be hardly achieved by using other dispersing agents.
(3) The powder prepared by the method has stronger catalytic effect in a visible light region and an ultraviolet light region, and the prepared powder has high purity, uniform granularity, good controllability and excellent performance, and reports on malachite green are not available at present. In addition, the method has potential application space in the aspects of hydrogen production and oxygen production by electrocatalysis hydrolysis, and develops new performance.
Drawings
FIG. 1 preparation of TiO according to comparative example 1 of the invention2-scanning electron microscopy of samarium cuprate nano photocatalytic, electrocatalytic powder;
FIG. 2 shows TiO prepared in comparative example 2 of the present invention2-scanning electron microscopy of samarium cuprate nano photocatalytic, electrocatalytic powder;
FIG. 3 shows TiO prepared in example 1 of the present invention2-scanning electron microscopy of samarium cuprate nano photocatalytic, electrocatalytic powder;
FIG. 4 shows TiO prepared in example 2 of the present invention2-degradation curve of samarium cuprate nano-photocatalytic and electro-catalytic powder to malachite green.
FIG. 5 shows TiO prepared in example 3 of the present invention2-hydrogen evolution curve of samarium cuprate nano photocatalytic and electrocatalytic powder.
FIG. 6 shows TiO prepared in example 3 of the present invention2-oxygen evolution curve of samarium cuprate nano photocatalytic and electrocatalytic powder.
Detailed Description
The present invention will be described in detail with reference to the following embodiments and drawings, but the scope of the present invention is not limited by the embodiments and drawings.
In the examples, the trade name P25 is nano TiO2。
Example 1
(1) According to samarium Sm cuprate2CuO4Weighing 1mmol of copper acetate and 2mmol of samarium acetate according to the stoichiometric ratio of Cu to Sm, dissolving the copper acetate and the samarium acetate in deionized water, wherein the volume consumption of the deionized water is 6 times of the total molar mass of the copper acetate and the samarium acetate, and uniformly mixing to obtain a solution A;
(2) adding 3mmol of acetonitrile into the solution A, adding 2mmol of dimethylglyoxime, heating at 60 ℃, and stirring for 2 hours to obtain a solution B;
(3) adding 5ml of 1mol/L alkali liquor (the solute is triethylamine and the solvent is ethanol) into the solution B by using a liquid transfer gun, and stirring to dissolve the solution B to prepare a solution C.
(4) Putting the solution C into an oven, reacting for 3 hours at a constant temperature of 120 ℃, and cooling to room temperature in the air; and after the solution system is stable, filtering the obtained mixed solution, washing the obtained solid for 2 times by using water, putting the obtained crystal into liquid nitrogen for pulverization, and taking out the powder D.
(5) Mixing the powder D with 3mmol TiO2Putting the powder into deionized water, wherein the using amount of the deionized water is 10 times of the molar weight of TiO2, carrying out spray granulation by a sprayer, and drying for 1h in an oven at the temperature of 90 ℃ to prepare the nano powder required by the patent.
FIG. 1 preparation of TiO according to comparative example 1 of the invention2A scanning electron microscope image of the samarium cuprate nano photocatalytic and electrocatalytic powder as shown in figure 1, wherein the prepared powder has the particle morphology, the size is 30-50nm, the particles are uniform, the dispersibility is good, the specific surface area is large, and the catalytic reaction is favorably carried out.
Example 2
(1) According to samarium Sm cuprate2CuO4Weighing 1mmol of copper nitrate and 2mmol of samarium nitrate according to the stoichiometric ratio of Cu to Sm, dissolving the copper nitrate and the samarium nitrate into deionized water, wherein the volume consumption of the deionized water is 6 times of the total molar mass of the copper nitrate and the samarium nitrate, and uniformly mixing to obtain a solution A;
(2) adding 4mmol of acetonitrile into the solution A, adding 2mmol of dimethylglyoxime, heating at 80 ℃, and stirring for 2.5 hours to obtain a solution B;
(3) adding 5ml of 1mol/L alkali liquor (the solute is triethylamine and the solvent is ethanol) into the solution B by using a liquid transfer gun, and stirring until the solution B is dissolved to prepare a solution C.
(4) Putting the solution C into an oven, reacting for 4 hours at a constant temperature of 150 ℃, and cooling to room temperature in the air; and after the solution system is stable, filtering the obtained mixed solution, washing the obtained solid for 3 times by using water, putting the obtained crystal into liquid nitrogen for pulverization, and taking out the powder D.
(5) Mixing powder D and 4.5mmol TiO2Putting the powder into deionized water, wherein the dosage of the deionized water is 1 molar weight of TiO25 times, spraying and granulating by a sprayer, and drying for 2 hours in an oven at the temperature of 60 ℃ to prepare the nano powder required by the patent.
Accurately weighing 0.5g of malachite green, putting the malachite green into a 100ml volumetric flask, and keeping the constant volume at 5g/L, and then stirring for 1h to fully dissolve the malachite green; taking 4ml of malachite green solution with the concentration of 5g/L by using a liquid transfer gun, accurately measuring 96ml of deionized water by using a measuring cylinder, then adding the deionized water into a photocatalytic reactor, and fully stirring to prepare the model degradation liquid.
Accurately weighing 0.05g of TiO 2-samarium cuprate nano photocatalytic and electrocatalytic powder sample, slowly pouring the powder sample into a 100ml reaction glass tube filled with a malachite green standard solution, and taking care not to stick Sm2CuO4 powder to the wall in the pouring process so as to avoid unnecessary experimental errors; the reaction glass tube was placed in an ultrasonic cleaner under dark conditions and ultrasonically oscillated for 30 min.
FIG. 2 shows TiO prepared in comparative example 2 of the present invention2A scanning electron microscope image of the samarium cuprate nano photocatalytic and electrocatalytic powder, as shown in figure 2, the degradation speed is fast in 30min, and the degradation is complete in 60 min.
Example 3
(1) According to samarium Sm cuprate2CuO4Weighing 1mmol of copper chloride and 2mmol of samarium chloride according to the stoichiometric ratio of Cu to Sm, dissolving the copper chloride and the samarium chloride in deionized water, wherein the volume consumption of the deionized water is 5 times of the total molar mass of the copper chloride and the samarium chloride, and uniformly mixing to obtain a solution A;
(2) adding 9mmol of acetonitrile into the solution A, adding 3mmol of dimethylglyoxime, heating at 80 ℃, and stirring for 2 hours to obtain a solution B;
(3) adding 5ml of 1mol/L alkali liquor (the solute is triethylamine and the solvent is ethanol) into the solution B by using a liquid transfer gun, and stirring until the solution B is dissolved to prepare a solution C.
(4) Putting the solution C into an oven, reacting for 6 hours at a constant temperature of 130 ℃, and cooling to room temperature in the air; and after the solution system is stable, filtering the obtained mixed solution, washing the obtained solid for 4 times by using water, putting the obtained crystal into liquid nitrogen for pulverization, and taking out the powder D.
(5) Mixing powder D with 6mmol TiO2Putting the powder into deionized water, wherein the using amount of the deionized water is 20 times of the molar weight of TiO2, carrying out spray granulation by a sprayer, and drying for 1.52h in an oven at the temperature of 80 ℃ to prepare the nano powder required by the patent.
The method comprises the following steps of testing the electro-catalytic hydrogen evolution and oxygen evolution performance of a TiO 2-samarium cuprate nano photocatalytic and electro-catalytic material by adopting a three-electrode system, taking a Pt sheet as a counter electrode, a Saturated Calomel Electrode (SCE) as a reference electrode, and taking an ITO electrode of which the surface is dropwise coated with the samarium cuprate photocatalytic and electro-catalytic material; the testing instrument is a PARSTAT 2273 electrochemical workstation; the test solution was 1mol/L KOH.
The working electrode is prepared by adopting a dripping coating method, and the specific process is as follows: 0.04g of TiO was weighed2-samarium cuprate photocatalytic and electrocatalytic material, placing in a small glass bottle, adding 500ml ethanol, 500ml deionized water and 30 mul of perfluorosulfonic acid polymer solution with the mass fraction of 5%, and carrying out ultrasonic treatment on the mixture for more than 20min to form a catalyst solution. When the ITO is used as an electrode, the ITO is required to be washed by sequentially using acetone, ethanol and deionized water, then 20 mu l of the catalyst solution is coated on the ITO conductive surface, and the ITO conductive surface is dried in a drying oven for 1h at 60 ℃ to be tested.
Testing parameters: the scan rate for the LSV test was 5 mV/s.
FIG. 3 shows TiO prepared in example 1 of the present invention2Scanning electron microscope image of samarium cuprate nano photocatalytic and electrocatalytic powder, and FIG. 4 is TiO prepared in example 2 of the present invention2-degradation curve of samarium cuprate nano photocatalytic and electrocatalytic powder to malachite green, as shown in the figure: fig. 3 is a HER curve, the starting point of the curve curving downward represents the starting potential for hydrogen production by reduction, the smaller the better. The slope of the bend represents the reduction rate versus overpotential, with larger being better.
Fig. 4 is an OER curve, and the starting point of the curve curving upward represents the starting potential for hydrogen production by oxidation, the smaller the better. The slope of the bend represents the reduction rate versus overpotential, with larger being better.
COMPARATIVE EXAMPLE 1 (not pulverized in liquid nitrogen)
(1) According to samarium Sm cuprate2CuO4Chemical of medium Cu and SmWeighing 1mmol of copper acetate and 2mmol of samarium acetate according to the metering ratio, dissolving the copper acetate and the samarium acetate in deionized water, wherein the volume usage amount of the deionized water is 4 times of the total molar mass of the copper acetate and the samarium acetate, and uniformly mixing to obtain a solution A;
(2) adding 3mmol of acetonitrile into the solution A, adding 1mmol of dimethylglyoxime, heating at 60 ℃, and stirring for 2 hours to obtain a solution B;
(3) adding 5ml of 1mol/L alkali liquor (the solute is triethylamine and the solvent is ethanol) into the solution B by using a liquid transfer gun, and stirring until the solution B is dissolved to prepare a solution C.
(4) Putting the solution C into an oven, reacting for 3 hours at a constant temperature of 120 ℃, and cooling to room temperature in the air; and after the solution system is stable, filtering the obtained mixed solution, and washing the obtained solid with water for 2 times to obtain a flaky crystal D.
(5) Mixing the powder D with 3mmol TiO2Putting the powder into deionized water, wherein the dosage of the deionized water is TiO2Spraying and granulating by a sprayer with the molar weight being 10 times of that of the nano powder, and drying for 1h in an oven at the temperature of 60 ℃ to prepare the nano powder required by the patent.
FIG. 5 shows TiO prepared in example 3 of the present invention2As shown in fig. 5, the powder is not pulverized in liquid nitrogen, the prepared powder has a particle morphology, a plurality of powders are adhered together, the size is 2um, and although the morphology is consistent, the specific surface area is small, so that the preparation is not beneficial to the photocatalytic and electrocatalytic reactions.
Comparative example 2 (without dimethylglyoxime, powdering in liquid nitrogen)
(1) According to samarium Sm cuprate2CuO4Weighing 1mmol of copper nitrate and 2mmol of samarium nitrate according to the stoichiometric ratio of Cu to Sm, dissolving the copper nitrate and the samarium nitrate into deionized water, wherein the volume consumption of the deionized water is 4 times of the total molar mass of the copper acetate and the samarium acetate, and uniformly mixing to obtain a solution A;
(2) adding 3mmol acetonitrile into the solution A, heating at 60 ℃ and stirring for 2h to obtain a solution B;
(3) adding 5ml of 1mol/L alkali liquor (the solute is triethylamine and the solvent is ethanol) into the solution B by using a liquid transfer gun, and stirring until the solution B is dissolved to prepare a solution C.
(4) Putting the solution C into an oven, reacting for 3 hours at a constant temperature of 130 ℃, and cooling to room temperature in the air; and after the solution system is stable, filtering the obtained mixed solution, and washing the obtained solid with water for 3 times to obtain a flaky crystal D.
(5) Mixing the powder D with 3mmol TiO2Putting the powder into deionized water, wherein the dosage of the deionized water is TiO2Spraying and granulating by a sprayer with the molar weight being 10 times of that of the nano powder, and drying for 1.5 hours in an oven at the temperature of 80 ℃ to prepare the nano powder required by the patent.
FIG. 6 shows TiO prepared in example 3 of the present invention2TiO of-samarium cuprate nano photocatalysis and electrocatalysis powder2-Sm2CuO4As shown in the figure, the oxygen evolution curve of the sample shows that the powder without adding butanedione oxime and without being pulverized in liquid nitrogen is in a large block shape, and the coated TiO2 is also distributed on the surface of the block-shaped powder in a dispersed manner. The prepared powder has large particle morphology, the size is 10-50um, the specific surface area is small, and the catalytic reaction is not favorably carried out.
Claims (7)
1.TiO2The preparation method of the-samarium cuprate nano photocatalytic and electrocatalytic powder is characterized by comprising the following steps of:
(1) according to samarium Sm cuprate2CuO4Weighing soluble salt of Cu and soluble salt of Sm according to the stoichiometric ratio of Cu to Sm, dissolving the soluble salts of Cu and Sm in deionized water, and uniformly mixing to obtain solution A;
(2) adding a certain amount of acetonitrile and a certain amount of dimethylglyoxime into the solution A, heating the solution at 60-90 ℃ and stirring for 2-3 h to obtain a solution B;
(3) adding 5-10mL of 1mol/L alkali liquor into the solution B by using a liquid transfer gun, and stirring until the alkali liquor is dissolved to prepare a solution C;
(4) putting the solution C into an oven, reacting for 3-6 hours at a constant temperature of 120-150 ℃, and cooling to room temperature in the air; after the solution system is stable, filtering the obtained mixed solution, washing the obtained solid with water for 2-4 times to obtain flaky crystals, putting the obtained crystals into liquid nitrogen for pulverization, and taking out powder D;
(5) mixing the powder D with a certain amount of nano TiO2Putting the powder into deionized water, performing spray granulation by a sprayer, and drying for 1-2h in an oven at the temperature of 60-90 ℃ to prepare TiO2-samarium cuprate nano photocatalytic and electrocatalytic powder.
2. The TiO of claim 12The preparation method of the-samarium cuprate nano photocatalytic and electrocatalytic powder is characterized in that the soluble salt of copper in the step (1) is copper chloride, copper nitrate or copper acetate, and the soluble salt of samarium is samarium chloride, samarium nitrate or samarium acetate.
3. The TiO of claim 12The preparation method of the-samarium cuprate nano photocatalytic and electrocatalytic powder is characterized in that the stirring condition in the step (2) is mechanical stirring or magnetic stirring, and the rotating speed of a rotor is 500-1000 r/min.
4. The TiO of claim 12The preparation method of the-samarium cuprate nano photocatalytic and electrocatalytic powder is characterized by comprising the following steps of: in the step (2), the dosage of the acetonitrile is 3-4 times of the molar weight of the copper salt, and the dosage of the dimethylglyoxime is 1-2 times of the molar weight of the copper salt.
5. The TiO of claim 12The preparation method of the-samarium cuprate nano photocatalytic and electrocatalytic powder is characterized by comprising the following steps of: and (3) the solute of the alkali liquor is triethylamine, and the solvent is ethanol.
6. The TiO of claim 12The preparation method of the-samarium cuprate nano photocatalytic and electrocatalytic powder is characterized by comprising the following steps of: nano TiO in the step (5)2The dosage of the soluble salt is 1-2 times of the total molar weight of the soluble salt of copper and the soluble salt of samarium.
7. Root of herbaceous plantTiO produced by the production method according to claim 12The application of samarium cuprate nano photocatalysis and electrocatalysis powder is characterized in that: the TiO is2Samarium cuprate nanometer photocatalysis and electrocatalysis powder is used as photocatalyst in a visible light area and an ultraviolet light area, is applied to industries containing malachite green and the treatment of dye wastewater, or is used for electrolyzing water to produce hydrogen and oxygen.
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