CN115043422B - Method for controllably preparing CuO nano material by ultrasonic chemistry and annealing assistance and application - Google Patents
Method for controllably preparing CuO nano material by ultrasonic chemistry and annealing assistance and application Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000000137 annealing Methods 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 26
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 25
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 19
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 19
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical group [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012467 final product Substances 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 40
- 239000005751 Copper oxide Substances 0.000 abstract description 17
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 17
- 230000015556 catabolic process Effects 0.000 abstract description 14
- 238000006731 degradation reaction Methods 0.000 abstract description 14
- 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 13
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 13
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [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 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- 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
- B01J23/72—Copper
-
- B01J35/39—
-
- B01J35/50—
-
- B01J35/51—
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/16—Reducing
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a method for controllably preparing CuO nano material by ultrasonic chemistry and annealing assistance and application thereof, comprising the following preparation steps: firstly, pouring an ascorbic acid solution into a soluble metal copper source solution, uniformly stirring and mixing the mixed solution, then adding hydrogen peroxide, carrying out ultrasonic treatment, centrifuging, washing and drying to obtain precursor powder; finally, the precursor powder was annealed at 400 ℃ for 2 hours to obtain black CuO powder. The reactants and the system adopted by the invention have no pollution to the environment, and no harmful pollutant is generated in the preparation process. Meanwhile, cuO with different morphologies (cubic block shape, pillow shape and sphere shape) is prepared by regulating and controlling the proportion of reaction precursors, and the prepared product has a degradation effect on methylene blue, so that the cubic copper oxide has optimal photocatalytic performance and can be completely degraded within 120 min.
Description
Technical Field
The invention relates to the technical field of synthesis of photocatalytic materials, in particular to a method for controllably preparing a CuO nano material by ultrasonic chemistry and annealing assistance, and further relates to application of the CuO nano material prepared by the method in degradation of organic dye methylene blue.
Background
Copper oxide (CuO) is an important transition metal oxide, and its crystal structure is a monoclinic structure, belonging to a narrow bandgap semiconductor (1.2 eV-1.9 eV), and is a typical P-type semiconductor. The nano-sized copper oxide material has certain changes in properties and the like under the actions of surface effect, quantum size effect, macroscopic quantum tunneling effect, and further endows the nano-sized copper oxide with unique physical and chemical properties, and the nano-sized copper oxide material is widely applied to the fields of electrode materials, photocatalytic materials, gas sensors, biological sensors, semiconductor materials, magnetic storage media and the like. The property that the resistance value can be obviously changed when the copper oxide nano material contacts with alcohols, aldehydes, ketones, benzene organic volatile gases or hydrogen sulfide and other gases is utilized to detect the concentration and the like of the gas-sensitive material of the gases; the copper oxide nano material is used as a lithium ion battery anode material with good performance by utilizing the advantages of low cost, easy storage, high theoretical capacity, high energy density and the like; the copper oxide nano material is made into a good pseudo capacitor electrode material by utilizing the characteristics of good chemical stability, multiple active sites and the like, and can be used for forming a super capacitor; in addition, most of industrial production can produce organic dye waste, so that serious pollution can be caused to surface water, and the copper oxide nano material can produce photo-generated electron-hole pairs under the illumination condition and can generate oxidation-reduction reaction with adsorbates on the surface of the material, so that the copper oxide nano material also has important application in the aspect of catalyzing degradation of organic pollutants under the illumination condition as a photocatalytic material. The properties of nanomaterials are largely dependent on their size, morphology and composition, and so far researchers have produced a large number of different sizes and morphologies of nano-copper oxide by various methods. Zhang Yan et al used a post-electrospinning calcination process to prepare CuO fibers, which were treated with H 2 O 2 Has good photocatalytic degradation effect on methyl orange with the assistance of the catalyst; mohaptra et al synthesized nano sheets with mulberry pore structures by a hydrothermal method, and have good performance in the aspect of serving as a lithium ion battery anode material; li Xiangyu et al uses NaOH and K 2 S 2 O 8 The copper mesh is etched successfully to prepare a grid coated by CuO nano rods, which can effectively catalyze the degradation of Congo red under visible light; liu jin et al prepared and discussed the photocatalytic decomposition of rhodamine B (RhB) as a pollutant in water by using PEG200 as a structure directing agent and by using CuO nanostructures with different morphologies (nanoneedle, nanoribbon, nanoleaf and nanoflower); cui Remei copper oxide having a particle size of 50 to 75 nm was prepared in a microemulsion using DBS-toluene-water or the like as a reaction system. The methods have various problems such as low yield, side reactions, difficult product morphology, size and crystal form regulation, certain toxicity of the used reaction system, environmental pollution and the like. In order not to increase environmental burden, researchers have in recent years sought environmentally friendly preparation methods, such as using non-toxic or soluble reagents instead of the reagents originally having toxicity.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for controllably preparing CuO nanomaterial with the assistance of sonochemistry and annealing; the second purpose of the invention is to provide the application of the CuO nano material prepared by the method in degrading the organic dye methylene blue. The invention provides a research thought of the project and carries out corresponding experimental research on the basis of deep understanding of the current situation of research and relevant research progress at home and abroad. From the green and environment-friendly preparation method, deionized water is used as a reaction system, ultrasonic chemical synthesis is based, and a high-temperature annealing process is combined to synthesize the nano-scale CuO material. In a mild and controllable liquid phase system, a green and environment-friendly nano material preparation process is explored. On the basis, the proportion of reactants is regulated and controlled, and the relation between the morphology of the material and the photocatalytic performance is explored.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. a method for controllably preparing CuO nano-materials with the assistance of sonochemistry and annealing comprises the following preparation steps:
(1) Weighing a soluble metal copper source and ascorbic acid, respectively adding the soluble metal copper source and the ascorbic acid into water, stirring and dissolving, rapidly pouring an ascorbic acid solution into the soluble metal copper source solution, and uniformly stirring and mixing the mixed solution;
(2) Adding hydrogen peroxide into the mixed solution obtained in the step (1), performing ultrasonic treatment, and then centrifuging, washing and drying to obtain precursor powder;
(3) And (3) sintering the precursor powder prepared in the step (2) at 400 ℃ for 2 hours, and then annealing to obtain black powder which is the final product CuO.
In the step (1), the soluble metal copper source is copper acetate, the concentration of the prepared copper acetate solution is 50mmol/L, and the concentration of the ascorbic acid solution is 33-100 mmol/L; the mole ratio of the soluble metallic copper source to the ascorbic acid in the mixed solution is 2: 2-9.
In a preferred embodiment of the present invention, in the step (2), the H 2 O 2 The mass fraction of the catalyst is 20-30%, H 2 O 2 The volume ratio of the mixed solution is 1:10.
in the preferred embodiment of the present invention, in the step (2), the ultrasonic treatment is performed at a power of 200-400W and a temperature of 25 ℃ for 30 min.
In the step (2), the centrifugal speed is 8000-10000 r/min for 3 min.
In the preferred embodiment of the present invention, in the step (2), the drying is performed at 60 ℃ for 2 hours.
Preferably, the method further comprises grinding the precursor powder in the step (2) before the annealing treatment.
Preferably, the annealing temperature reduction rate is 5 ℃ min -1 。
2. The CuO nano material prepared by the method is applied to degradation of organic dye.
Preferably, the organic dye is methylene blue.
The invention has the beneficial effects that: the invention discloses a method for controllably preparing CuO nano material by ultrasonic chemistry and annealing assistance and application thereof. Meanwhile, cuO with different morphologies (cube, pillow shape and sphere shape) is prepared by regulating and controlling the proportion of copper acetate and ascorbic acid, and the prepared products have degradation effects on methylene blue. The experimental result shows that the cubic copper oxide nano material has optimal photocatalytic performance and can completely degrade rhodamine within 120 minutes (the degradation rate is 99.8%). The preparation method is green and environment-friendly, and the adopted reactants and the system have no pollution to the environment, and no harmful pollutants are generated in the preparation process. The preparation method can be popularized and applied to the preparation of other indissolvable oxalates and metal oxides, and can realize mass production of photocatalytic materials and put into environmental treatment.
Drawings
In order to make the objects, technical solutions and advantageous effects of the present invention more clear, the present invention provides the following drawings for description:
FIG. 1 shows XRD patterns of CuO prepared under different reaction ratio conditions;
FIG. 2 is a SEM image of low power (a, c, e) and high power (b, d, f) of CuO prepared under different reaction ratio conditions;
FIG. 3 is a graph showing the comparison of the catalytic degradation performance of methylene blue by CuO nano-materials prepared under different reaction proportion conditions;
fig. 4 is a UV-Vis spectrum during catalytic degradation of CuO nanomaterial prepared under different reaction ratios.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to limit the invention, so that those skilled in the art may better understand the invention and practice it.
Example 1
A method for controllably preparing CuO nano-materials with the assistance of sonochemistry and annealing comprises the following specific operation steps:
(1) 1 mmoL of copper acetate is weighed and stirred at room temperature until the copper acetate is completely dissolved in 20 mL deionized water, and the solution is marked as solution A; then 1 mmoL of ascorbic acid is weighed and dissolved in 30 mL deionized water at room temperature by the same operation, and is marked as solution B; the resulting ascorbic acid solution was quickly poured into copper acetate solution, and 10 mL deionized water was added to the system using a measuring cylinder and stirred for 50s using a magnetic stirrer, at which time the system amounted to 60 mL, designated solution C.
(2) Measuring 5-mL mass percent of hydrogen peroxide with a measuring cylinder, and adding the hydrogen peroxide into the solution C, wherein the pH of the solution is 5-6; transferring the solution into an ultrasonic cleaner, performing ultrasonic treatment for 30 min at the power of 200-400W and the temperature of 25 ℃, and then centrifuging and washing the solution with deionized water and ethanol for multiple times by a refrigerated centrifuge, wherein the centrifuging is performed for 3 min at the rotating speed of 8000-10000 r/min, and the volume ratio of absolute ethanol to deionized water is 0.5-1; finally, 2h was dried in a 60 ℃ forced air oven to give a precursor powder.
(3) Grinding the precursor powder, placing the powder into a ceramic crucible, sintering the powder at 400 ℃ by using a muffle furnace for 2h, and annealing the powder at a cooling rate of 5 ℃ for min -1 The obtained black powder is the final product CuO, named a and to be measured.
Example 2
The procedure of example 2 was followed to the procedure of example 1, except that 1.5 mmoL of ascorbic acid was weighed and dissolved in 30 mL deionized water at room temperature. The product obtained was designated b and tested.
Example 3
The procedure of example 3 was followed to the procedure of example 1, except that 3 mmoL of ascorbic acid was weighed and dissolved in 30 mL deionized water at room temperature. The product obtained was designated as c and tested.
The XRD results of the copper oxide prepared in examples 1-3 are shown in fig. 1, and it can be seen from the figure that the characteristic peaks of the products a, b and c are basically consistent, and the diffraction peaks are compared with the standard PDF card, and the diffraction angle 2θ is 32.53 ° corresponding to crystal plane (110), 35.57 ° corresponding to crystal plane (-111), 38.73 ° corresponding to crystal plane (111), 48.82 ° corresponding to crystal plane (-202), 58.30 ° corresponding to crystal plane (020), 61.60 ° corresponding to crystal plane (202), 65.82 ° corresponding to crystal plane (-113), 66.32 ° corresponding to crystal plane (022), 68.12 ° corresponding to crystal plane (220), 72.43 ° corresponding to crystal plane (311), 75.31 ° corresponding to crystal plane (-222), and the characteristic peaks are sharp to indicate that the sample has good crystallinity and no impurity peaks, and the final product is pure copper oxide without impurities (JCPDS No. 89-5896).
The SEM images of CuO prepared under different reaction ratios shown in fig. 2 show that the ratio of copper acetate to ascorbic acid substance is 2:3, cuO is pillow-shaped with a square front surface, the square edge is about 1 μm, and the central axis is about 300 nm (fig. 2, a, b); when the ratio of the amount of the copper acetate to the amount of the ascorbic acid substance is 2:4.5, the product is in the shape of a cube with uniform distribution and uniform size, has clearer edges and has a side length of about 1 μm (figures 2, c and d); when the ratio of the amount of the copper acetate to the amount of the ascorbic acid substance is 2:9 CuO has a more regular spherical shape with a diameter of about 5 μm (FIGS. 2, e, f).
Example 4
The specific experimental operation of photocatalytic methylene blue using copper oxide nanomaterial is as follows: weighing 50 mg mL to 30mgL -1 Adding 30mg copper oxide nanomaterial into the solution, stirring with a magnetic stirrer, placing the beaker in darkness for 30 min, then placing a 500W power xenon lamp light source above the beaker to simulate visible light, centrifuging every 20min to obtain supernatant 5 mL, measuring the absorption spectrum by using a UV-Vis spectrophotometer, obtaining absorbance by means of the absorption spectrum, and quantitatively analyzing the concentration of the methylene blue solution by using the Lanbert-Beer law.
Fig. 3 shows the uv-vis absorption spectrum of three samples of different morphologies, from the start of the photocatalytic reaction, at intervals of 20min, the test was performed until the end, 3 (a) corresponds to the uv-vis absorption spectrum of sample a, 3 (b) corresponds to the uv-vis absorption spectrum of sample b, and 3 (c) corresponds to sample c. Obviously, the three materials have a strong characteristic absorption peak of methylene blue at 664 nm, and the peak intensity of the characteristic absorption peak gradually decreases with the continuous progress of the reaction, which indicates that the methylene blue in the solution gradually degrades and the concentration thereof continuously decreases. Degradation of rhodamine solutions can be completed in 120 minutes for all three samples.
FIG. 4 is a graph showing the comparison of methylene blue degradation efficiencies of three samples (a: pillow-shaped, b: cube-shaped, c: sphere), and it is understood that the methylene blue degradation efficiency of the cubic copper oxide nanomaterial is higher than that of both the pillow-shaped and sphere, and the methylene blue degradation efficiency is substantially complete after 120min of the photocatalytic reaction, and the degradation rate is 99.8%.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (8)
1. The method for controllably preparing the CuO nano material with the assistance of ultrasonic chemistry and annealing is characterized by comprising the following preparation steps:
(1) Weighing a soluble metal copper source and ascorbic acid, respectively adding the soluble metal copper source and the ascorbic acid into water, stirring and dissolving, rapidly pouring an ascorbic acid solution into the soluble metal copper source solution, and uniformly stirring and mixing the mixed solution; the mole ratio of the soluble metallic copper source to the ascorbic acid in the mixed solution is 2: 2-9;
(2) Adding hydrogen peroxide into the mixed solution obtained in the step (1), performing ultrasonic treatment, and then centrifuging, washing and drying to obtain precursor powder;
(3) And (3) sintering the precursor powder prepared in the step (2) at 400 ℃ for 2 hours, and then annealing to obtain black powder which is the final product CuO.
2. The method for controllably preparing a CuO nanomaterial with the assistance of ultrasonic chemistry and annealing according to claim 1, wherein in the step (1), the soluble metal copper source is copper acetate, the concentration of the prepared copper acetate solution is 50mmol/L, and the concentration of the ascorbic acid solution is 33-100 mmol/L.
3. The method for controllably producing CuO nanomaterial with the assistance of sonochemistry and annealing as claimed in claim 1, wherein in step (2), the H 2 O 2 The concentration of (C) is 20-30%, H 2 O 2 The volume ratio of the mixed solution is 1:10.
4. The method for controllably preparing a CuO nanomaterial with the assistance of sonochemistry and annealing according to claim 1, wherein in the step (2), the ultrasonic treatment is performed at a power of 200 to 400W and a temperature of 25 ℃ for 30 minutes.
5. The method for controllably preparing a CuO nanomaterial with the assistance of ultrasonic chemistry and annealing according to claim 1, wherein in the step (2), the centrifugation is performed at a rotational speed of 8000-10000 r/min for 3 min.
6. The method for controllably producing CuO nanomaterial with the assistance of sonochemistry and annealing according to claim 1, wherein in step (2), the drying is performed at 60 ℃ for 2 hours.
7. The method for controllably producing CuO nanomaterial according to claim 1, further comprising milling the precursor powder of step (2) prior to the annealing.
8. The method for controllably preparing CuO nanomaterial with the assistance of sonochemistry and annealing as claimed in claim 1, wherein the annealing is performed at a cooling rate of 5 ℃ min -1 。
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| KR20150142755A (en) * | 2014-06-11 | 2015-12-23 | 한국과학기술원 | Method for manufacturing metal or metal oxide having micro-nano sizes using ultra-wave and metal or metal oxide thereby |
| CN105523578A (en) * | 2016-02-04 | 2016-04-27 | 新疆维吾尔自治区分析测试研究院 | Nanometer copper oxide with controllable morphology as well as preparation method and application of nanometer copper oxide |
| CN110436508A (en) * | 2019-08-19 | 2019-11-12 | 甘肃农业大学 | A kind of preparation method and applications of flake nano copper oxide |
| CN111517358A (en) * | 2020-06-16 | 2020-08-11 | 盐城工学院 | Synthetic method and application of flower-shaped copper oxide nanospheres |
| CN111590088A (en) * | 2020-07-13 | 2020-08-28 | 江西省科学院应用物理研究所 | Preparation method of superfine nano copper powder |
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| KR20150142755A (en) * | 2014-06-11 | 2015-12-23 | 한국과학기술원 | Method for manufacturing metal or metal oxide having micro-nano sizes using ultra-wave and metal or metal oxide thereby |
| CN105523578A (en) * | 2016-02-04 | 2016-04-27 | 新疆维吾尔自治区分析测试研究院 | Nanometer copper oxide with controllable morphology as well as preparation method and application of nanometer copper oxide |
| CN110436508A (en) * | 2019-08-19 | 2019-11-12 | 甘肃农业大学 | A kind of preparation method and applications of flake nano copper oxide |
| CN111517358A (en) * | 2020-06-16 | 2020-08-11 | 盐城工学院 | Synthetic method and application of flower-shaped copper oxide nanospheres |
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