CN109126814B - Method for in-situ growth of copper molybdate with micro-nano structure - Google Patents
Method for in-situ growth of copper molybdate with micro-nano structure Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 26
- IKUPISAYGBGQDT-UHFFFAOYSA-N copper;dioxido(dioxo)molybdenum Chemical compound [Cu+2].[O-][Mo]([O-])(=O)=O IKUPISAYGBGQDT-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910004619 Na2MoO4 Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 5
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
-
- 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
-
- B01J35/23—
-
- B01J35/393—
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
Abstract
An in-situ growth method of copper molybdate with a micro-nano structure, which can be used for quickly, simply and conveniently synthesizing Cu3Mo2O9. With Na2MoO4·2H2O is taken as a raw material, and is subjected to anodic oxidation on a copper net to grow CuMoO with a micro-nano spherical structure in situ4Then the mixture is dried in a vacuum drying oven and calcined in a tube furnace to finally obtain the micro-nano spherical Cu with stable performance3Mo2O9. The method is simple and convenient, has low cost, can be used for industrial production in a large scale, has small catalyst particles (the particle size is only 860nm), high catalytic activity, can be regenerated and recycled, does not generate toxic and harmful substances in the process, and has extremely high economic benefit and social benefit.
Description
Technical Field
The invention belongs to the field of inorganic micro-nano semiconductor material synthesis, and relates to a method for in-situ growth of micro-nano structured copper molybdate3Mo2O9And placing the oxidized material in a tubular furnace for high-temperature calcination. The invention can obtain materials with stable performance, and can be applied to the fields of intumescent fire-retardant coatings, electrode materials and the like.
Background
Due to the specific structure, electrical property and catalytic property, the metal molybdate nano material is widely concerned. Researches show that the metal molybdate nano material not only has good application value in the fields of photocatalytic degradation of wastewater, electrode materials, seawater corrosion, pigments, negative thermal expansion materials and the like, but also has excellent application potential in the fields of optics, fluorophors, humidity induction and antibiosis. Therefore, the development of the novel molybdate nano material has very important significance.
The metal molybdate has excellent properties of high specific surface, surface energy, multiple active sites, high selectivity and the like, and is concerned by a plurality of scholars. Several methods for synthesizing molybdate are also disclosed in China. Chinese patent CN 201510096407.3 discloses a method for preparing micron spherical basic copper molybdate (Cu)3(OH)2(MO4)2) The diameter of the produced micro-sphere is 20 mu m, although the method can synthesize high-purity micro-sphere basic copper molybdate (Cu)3(OH)2(MO4)2) However, this method has high requirements on the pH of the solution. In addition, the Chinese invention patent CN201110347508.5 discloses a method for preparing radial copper molybdate micron sphere structure (Cu) by microwave reaction3Mo2O9) The method is novel, but the particle size of the synthesized particles is larger, and the reaction conditions need microwaves, so that the method is not the optimal method for synthesizing the basic copper molybdate. To solve the above problems of the prior art, the present invention provides an active Cu3Mo2O9A method for preparing a micro-nano spherical structure. The method has the advantages of short reaction time and mild reaction conditions, and the prepared material has good appearance and good stability. In addition, the synthetic material particles consist of micro-nano spheres, and the particle size is only 860nm, so that a large specific surface area and more reactive active sites are provided for the material to degrade organic pollutants.
Disclosure of Invention
Aiming at the problems in the prior art, the applicant provides a micro-nano spherical structure Cu with stable electrochemical synthesis3Mo2O9The method of (1). The method is simple and convenient, has low cost, can be used for industrial production in a large scale, has small catalyst particles (the particle size is only 860nm), high catalytic activity, can be regenerated and recycled, does not generate toxic and harmful substances in the process, and has extremely high economic benefit and social benefit.
The technical scheme of the invention is as follows: a method for in-situ growth of copper molybdate with a micro-nano structure comprises the following steps of passing a 2cm x 4cm copper net through ethanol and 0.1mol/L H2SO4And after washing pretreatment by deionized water, placing the mixture in a vacuum drying oven for drying, and then carrying out high-temperature calcination. Obtaining the final product: the method comprises the following specific steps:
(1) pretreatment: with ethanol, 0.1mol/L H2SO4Sequentially ultrasonically cleaning copper with deionized water for 30min and the size of 2cm multiplied by 4cmAnd (5) drying the slices in a vacuum drying oven.
(2) Anodic oxidation: and (2) taking the copper sheet cleaned in the step (1) as an anode, taking a Pt sheet as a cathode, and taking a sodium molybdate solution containing 5% as an electrolyte to carry out anodic oxidation. The anodic oxidation voltage was 3V, time was 5min, temperature was 25 ℃. After the reaction is finished, taking out the copper net from the reaction system, washing the copper net for 3 times by using deionized water to remove the solution on the surface of the material, and obtaining the copper-based Cu with the yellowish green micro-nano spherical structure3Mo2O9。
(3) And (3) post-treatment: and (3) placing the oxidized material obtained in the step (2) in the air for natural drying.
(4) And (3) calcining: the copper-based Cu with yellow green color obtained in the step (3)3Mo2O9And (3) placing the material with the micro-nano spherical structure into a tubular furnace for calcination treatment. The temperature is 450 ℃ and the time is 2 h.
In the step (1), the material may be a copper mesh or a copper sheet. The drying method comprises the following steps: freeze drying, air drying, and vacuum drying. The material was placed in a tube furnace in an air atmosphere during the calcination treatment.
The solution preparation method involved in the step (2) can be as follows: stirring with a glass rod, ultrasonic treatment, and magnetic stirring. The solvent used was deionized water.
The washing times in the steps (1) and (2) are 3-6 times.
The beneficial effects of the invention are embodied in the following three aspects:
(1) the reaction equipment is simple, the reaction time is short, and the reaction is convenient to operate.
(2) The reaction raw materials are easy to obtain and cheap, and can be used for industrial production on a large scale.
(3) Synthesized Cu3Mo2O9The grape-shaped microspheres have small diameters (860nm), and can provide large specific surfaces and more reactive sites when reacting to degrade organic pollutants.
(4) The whole reaction process does not produce any toxic and harmful substances, and belongs to clean production.
(5) The catalyst regeneration can be realized by cleaning the surface substances of the catalyst with serious loss through ultrasonic cleaning, so that the cost is reduced.
Drawings
FIG. 1 shows a synthesized micro-nano spherical structure Cu3Mo2O9A preparation flow chart.
FIG. 2 shows synthesized Cu3Mo2O9SEM images (the insert in the figure b is a real object image) of the micro-nano spherical structure under different magnifications.
FIG. 3 shows synthesized Cu3Mo2O9Eds spectrum of micro-nano spherical structure.
FIG. 4 shows synthesized Cu3Mo2O9XRD pattern of micro-nano spherical structure.
Detailed Description
The present invention will be described in detail with reference to the accompanying fig. 1 and the embodiments.
Example 1
(1) With ethanol, 0.1mol/L H2SO4And sequentially ultrasonically cleaning a copper sheet with the size of 2cm multiplied by 4cm for 30min by deionized water, and drying in a vacuum drying oven.
(2) And (2) taking the copper sheet cleaned in the step (1) as an anode, taking a Pt sheet as a cathode, and taking a solution containing sodium molybdate as an electrolyte to carry out anodic oxidation. The anodic oxidation voltage was 3V, time was 5min, temperature was 25 ℃. After the reaction is finished, taking out the copper net from the reaction system, washing the copper net for 3-5 times by using deionized water to remove the solution on the surface of the material, and obtaining the copper-based Cu with the yellowish green micro-nano spherical structure3Mo2O9。
(3) And (3) placing the oxidized material obtained in the step (2) in the air for natural drying.
(4) The copper-based Cu with yellow green color obtained in the step (3)3Mo2O9And (3) putting the micro-nano spherical material into a tubular furnace filled with air for calcination treatment. The process of calcination treatment is as follows: heating to 450 deg.C at 1 deg.C/min, maintaining at 450 deg.C for 2h, and cooling to room temperature at 1 deg.C/min.
(5) And (5) performing SEM representation on the material obtained in the step (4), and showing that the synthesized substance is in a micro-nano spherical structure in a figure 2. The obtained material has small catalyst particle (particle size of only 860 nm).
(6) EDS characterization is carried out on the material obtained in the step (4), and FIG. 3 illustrates that the synthesized material contains three elements of O, Cu and Mo. From table 1 it can be seen that the approximate proportions of the elements of the synthesized material can be seen from the schematic diagram.
| Element(s) | Weight％ | Atomic％ |
| O | 30.87 | 68.73 |
| Cu | 29.63 | 16.61 |
| Mo | 39.49 | 14.66 |
| Total | 100 | 100 |
(7) XRD characterization is carried out on the material obtained in the step (4), and as can be seen from figure 4, the substance synthesized by the method is Cu3Mo2O9。
Claims (3)
1. A method for in-situ growth of copper molybdate with a micro-nano structure comprises the following steps:
(1) with ethanol, 0.1mol/L H2SO4Sequentially ultrasonically cleaning a copper sheet with the size of 2cm multiplied by 4cm for 30min by deionized water, and drying the copper sheet in a vacuum drying oven;
(2) taking the dried copper sheet as an anode, taking a Pt sheet as a cathode, and carrying out anodic oxidation by taking a solution containing sodium molybdate as an electrolyte, wherein the voltage of the anodic oxidation is 3V, the time is 5min, the temperature is 25 ℃, after the reaction is finished, taking out the copper mesh from the reaction system, washing the copper mesh for 3 times by using deionized water to remove the solution on the surface of the material, and obtaining the copper-based Cu with the yellowish green micro-nano spherical structure3Mo2O9；
(3) Placing the oxidized material obtained in the step (2) in the air for natural drying;
(4) the copper-based Cu with yellow green color obtained in the step (3)3Mo2O9Placing the micro-nano spherical material in an air pipe type furnace for calcination treatment;
the copper molybdate is applied to degrading organic pollutants.
2. The method for in-situ growth of copper molybdate with a micro-nano structure according to claim 1, wherein the mass fraction of sodium molybdate in the electrolyte in the step (2) is 5%, 2.5g of sodium molybdate is weighed in a 50mL glass beaker during electrolyte preparation, 50mL of deionized water is weighed in the beaker, and a glass rod is used for stirring the electrolyte for 2-5 minutes to obtain a uniformly mixed electrolyte system.
3. The method for in-situ growth of copper molybdate with a micro-nano structure according to claim 1, wherein the calcination treatment in the step (4) comprises the following steps: heating to 450 deg.C at 1 deg.C/min, maintaining at 450 deg.C for 2h, and cooling to room temperature at 1 deg.C/min.
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| CN113061954A (en) * | 2021-03-15 | 2021-07-02 | 深圳大学 | Method for preparing metal molybdate by anodic oxidation method, metal molybdate and application thereof |
| CN113880141A (en) * | 2021-11-01 | 2022-01-04 | 陕西科技大学 | Cu3Mo2O9 nanosheet array and preparation method thereof |
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