CN113355716B - Preparation of mesoporous MoO by electrochemical anodic oxidation method 2 Method (2) - Google Patents
Preparation of mesoporous MoO by electrochemical anodic oxidation method 2 Method (2) Download PDFInfo
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- CN113355716B CN113355716B CN202110659798.0A CN202110659798A CN113355716B CN 113355716 B CN113355716 B CN 113355716B CN 202110659798 A CN202110659798 A CN 202110659798A CN 113355716 B CN113355716 B CN 113355716B
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Abstract
The invention discloses a method for preparing mesoporous MoO by an electrochemical anodic oxidation method 2 The method comprises the steps of preparing a mixed solution of phosphoric acid and ammonium fluoride with a certain molar concentration as an electrolyte for anodic oxidation, taking a high-purity molybdenum foil as an anode and a platinum sheet as a cathode, and obtaining a product under a certain current condition. The method can obviously reduce the preparation of mesoporous MoO 2 The complexity of the nano material process can prepare the mesoporous MoO by one step at normal temperature through an electrochemical anodic oxidation method 2 Nano material and obviously shortened synthesis time. The method of the invention can obtain the MoO of the nanopore layer 2 Compared with MoO prepared by other methods 2 The surface area is larger, the active sites of the reaction are increased, and the storage of various cations can be realized.
Description
Technical Field
The invention belongs to MoO 2 The field of preparation methods, in particular to a method for preparing mesoporous MoO by an electrochemical anodic oxidation method 2 The method of (1).
Background
With the excessive consumption of non-renewable energy sources such as petroleum, the realization of optimal management and large-scale storage of energy sources is very important. Secondary batteries are widely considered as powerful competitors of large-scale energy storage technologies, and aqueous batteries are considered as one of the most promising large-scale energy storage technologies due to their advantages of low cost, high safety, environmental friendliness, and the like. The performance of the battery is related to the electrode material, the electrolyte and the separator used by the electrolyte, and the electrode material is the most important factor, and the performance of the electrode material directly influences the performance of the battery. The molybdenum element has the semi-filled electronic structure, so that Mo can change from 0 valence to +6 valence, has high theoretical capacity, can embody good physical and chemical properties, and is a suitable electrochemical energy storage material. However, no quick and effective method for preparing mesoporous MoO capable of realizing storage of various cations exists so far 2 . Therefore, the method for preparing the mesoporous MoO is simple, feasible and low in cost 2 The method for realizing storage of various cations is of great significance.
Disclosure of Invention
The invention aims to solve the problem of the existing MoO 2 MoO is present in the preparation method 2 Long synthesis time, high synthesis temperature, complex operation steps and the like, and aims to provide an electrochemical anodePreparation of mesoporous MoO by oxidation method 2 The method of (1).
The invention is realized by the following technical scheme:
mesoporous MoO prepared by electrochemical anodic oxidation method 2 The method comprises the following steps:
preparing an anode
Cutting a high-purity molybdenum foil, cleaning the high-purity molybdenum foil, and drying after cleaning to obtain an anode;
(ii) preparing an electrolyte
Preparing a mixed aqueous solution of phosphoric acid and ammonium fluoride as an electrolyte for anodic oxidation in proportion;
(iii) assembling the electrolytic cell
Adding the anode and the cathode in the step (i) into the electrolyte prepared in the step (ii), and connecting a stabilized voltage power supply to form an electrolytic cell;
(iv) electrochemical anodic oxidation reaction
Under the condition of temperature, the anode is taken out after the direct current voltage is switched on for a certain time;
(v) obtaining of the product
And (iv) cleaning the anode taken out in the step (iv), and drying after cleaning to obtain the mesoporous MoO 2 。
In the technical scheme, the purity of the high-purity molybdenum is more than or equal to 99.5%.
In the above technical solution, the cleaning treatment specifically comprises: and ultrasonically cleaning the high-purity molybdenum foil by using ethanol and deionized water respectively.
In the above technical scheme, the drying is performed in N 2 Is carried out in (1).
In the technical scheme, the molar ratio of phosphoric acid to ammonium fluoride is 50 to 10.
In the technical scheme, the concentration of the ammonium fluoride is less than 0.5mol/L.
In the technical scheme, the concentration of phosphoric acid in the electrolyte is 1 mol/L.
In the above technical scheme, the cathode is a platinum sheet.
In the technical schemeIn (iv), the temperature condition in said step (iv) is 40 o C; the direct current voltage is 0.1V to 0.5V; the electrifying time is 0.5 to 24 hours.
In the above technical solution, the washing in the step (v) is washed with ethanol, and dried in N 2 Is carried out in an atmosphere.
The beneficial effects of the invention are:
the invention provides a method for preparing mesoporous MoO by an electrochemical anodic oxidation method 2 Of the prepared MoO 2 Has a nano-porous layer structure, and can realize various cation storages. The method can obviously reduce the preparation of mesoporous MoO 2 The complexity of the nano material process can prepare the mesoporous MoO by one step at normal temperature through an electrochemical anodic oxidation method 2 Nano material and obviously shortened synthesis time. The method of the invention can obtain the MoO of the nanopore layer 2 Compared with MoO prepared by other methods 2 The surface area is larger, the active sites of the reaction are increased, and the storage of various cations can be realized.
Drawings
FIG. 1 is a scanning electron microscope image of MoO2 prepared in example 1 of the method for preparing mesoporous MoO2 by electrochemical anodization of the present invention;
FIG. 2 is a scanning electron microscope (sectional photograph) of MoO2 prepared in example 1 of the method for preparing mesoporous MoO2 by electrochemical anodization of the present invention;
FIG. 3 shows that the electrochemical anodic oxidation method of the invention prepares mesoporous MoO 2 Method of (3) CV curves of MoO2 prepared in example 1 at different sweep rates;
FIG. 4 shows that the electrochemical anodic oxidation method of the invention prepares mesoporous MoO 2 Method example 1 different cation intercalation mass specific capacities of MoO2 prepared.
Detailed Description
In order to make the technical scheme of the invention better understood by those skilled in the art, the technical scheme of the invention is further explained by the specific embodiments in the accompanying drawings of the specification.
Mesoporous MoO prepared by electrochemical anodic oxidation method 2 Method (2)The method comprises the following steps:
preparing an anode
Cutting high-purity molybdenum foil with purity of more than or equal to 99.5% into proper size, ultrasonic cleaning the high-purity molybdenum foil with ethanol and deionized water respectively, removing oil stains and impurities on the surface, and then removing the impurities in N 2 Drying to obtain the anode;
(ii) preparing an electrolyte
Preparing a mixed aqueous solution of phosphoric acid and ammonium fluoride as an anodic oxidation electrolyte according to a molar ratio of 50 to 10, wherein the concentration of the ammonium fluoride is less than 0.5 mol/L;
(iii) assembling the electrolytic cell
Adding the high-purity molybdenum foil treated in the step (i) as an anode and a platinum sheet as a cathode into the electrolyte prepared in the step (ii), and connecting a stabilized voltage power supply to form an electrolytic cell;
(iv) electrochemical anodic oxidation reaction
Electrifying under the condition of 40 ℃ and direct current voltage of 0.1V to 0.5V, keeping for 0.5 to 2.0h, and taking out the anode;
(v) product acquisition
Washing the anode taken out in the step (iv) with ethanol and then washing the anode with N 2 Drying in the atmosphere to obtain the mesoporous MoO 2 。
Example 1
A phosphoric acid solution having a concentration of 1mol/L was prepared in a 100mL volumetric flask, 0.185g of ammonium fluoride was weighed, and the phosphoric acid solution was added thereto and stirred until uniform, to obtain an electrolyte solution for the experiment. Pouring 20mL of electrolyte into an electrolytic cell, taking a high-purity molybdenum foil as a working electrode and a Pt sheet as a counter electrode sheet, enabling the two electrodes to be in full contact with the electrolyte at a distance of 1.5 to 2cm, and applying 0.3V voltage for 1 hour by using a constant voltage power supply. And testing and characterizing after drying treatment. The high-purity molybdenum foil has a thickness of 0.1mm, a length of 1cm and a width of 1cm.
MoO prepared in example 1 2 Testing and characterizing the material:
the SEM test results are shown in FIGS. 1 and 2, FIG. 1 is a scanning electron micrograph magnified 20000 times, and FIG. 1 shows that the anodized molybdenum surface is treated by anodizationMoO to form nanoporous layer structures 2 . FIG. 2 is a photograph of a cross section under a scanning electron microscope at 20000 times, showing the MoO produced 2 The film has a thickness of 2 to 3 μm.
To MoO 2 Electrochemical testing of the material:
Na 2 SO 4 CV test curves in solution, as shown in FIG. 3, at 1mol/L of Na 2 SO 4 In the solution, a working electrode adopts a molybdenum sheet, a counter electrode adopts a Pt electrode, and a reference electrode adopts a saturated calomel electrode. As a result, it can be seen that the CV curve is rectangular even at high scan speeds, indicating its good capacitance.
CV tests are carried out in different solutions, the obtained specific capacity of mass is shown in figure 4, a molybdenum sheet is used as a working electrode, a Pt electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. As a result, it can be seen that the sample prepared by us can store a variety of ions.
The invention provides a method for preparing mesoporous MoO by an electrochemical anodic oxidation method 2 Of the prepared MoO 2 Has a structure of a nanopore layer, and can realize storage of various cations. The method can obviously reduce the preparation of mesoporous MoO 2 The complexity of the nano material process can prepare the mesoporous MoO by one step at normal temperature through an electrochemical anodic oxidation method 2 Nano material and obviously shortened synthesis time. The method of the invention can obtain the MoO of the nanopore layer 2 Compared with MoO prepared by other methods 2 The surface area is larger, the active sites of the reaction are increased, and the storage of various cations can be realized.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (7)
1. Mesoporous MoO prepared by electrochemical anodic oxidation method 2 The method of (2), characterized by: the method comprises the following steps:
preparing an anode
Cutting a high-purity molybdenum foil, cleaning the high-purity molybdenum foil, and drying to obtain an anode;
(ii) preparing an electrolyte
Preparing a mixed aqueous solution of phosphoric acid and ammonium fluoride as an electrolyte for anodic oxidation in proportion;
(iii) assembling the electrolytic cell
Adding the anode and the cathode in the step (i) into the electrolyte prepared in the step (ii), and connecting a stabilized voltage power supply to form an electrolytic cell;
the molar ratio of the phosphoric acid to the ammonium fluoride is 50-10;
the concentration of phosphoric acid in the electrolyte is 1mol/L;
(iv) electrochemical anodic oxidation reaction
Under the condition of temperature, after the direct current voltage is switched on and kept for a certain time, taking out the anode;
the temperature condition is 40 ℃; the direct current voltage is 0.1V-0.5V; the electrifying time is 0.5-24 h;
(v) obtaining of the product
And (iv) cleaning the anode taken out in the step (iv), and drying after cleaning to obtain the mesoporous MoO 2 。
2. The method of claim 1 for preparing mesoporous MoO by electrochemical anodization 2 The method is characterized in that: the purity of the high-purity molybdenum is more than or equal to 99.5 percent.
3. The electrochemical anodic oxidation method for preparing mesoporous MoO according to claim 1 2 The method of (2), characterized by: the cleaning treatment specifically comprises the following steps: and ultrasonically cleaning the high-purity molybdenum foil by using ethanol and deionized water respectively.
4. The electrochemical anodization of claim 1Method for preparing mesoporous MoO 2 The method of (2), characterized by: said drying is in N 2 Is carried out in (1).
5. The method of claim 1 for preparing mesoporous MoO by electrochemical anodization 2 The method of (2), characterized by: the concentration of the ammonium fluoride is less than 0.5mol/L.
6. The method of claim 1 for preparing mesoporous MoO by electrochemical anodization 2 The method of (2), characterized by: the cathode is a platinum sheet.
7. The electrochemical anodic oxidation method for preparing mesoporous MoO according to claim 1 2 The method is characterized in that: washing in the step (v) by using ethanol, and drying in N 2 Is carried out in an atmosphere.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103556169A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Dandelion-shaped iron phosphate microspheres and preparation method thereof through electrochemical anode oxidation |
| CN104831330A (en) * | 2015-04-24 | 2015-08-12 | 哈尔滨工业大学 | Electrochemical preparation method for one-dimensional self-assembly ordered nanomaterial MoO3 nanopores |
| CN105040069A (en) * | 2015-08-25 | 2015-11-11 | 哈尔滨工业大学 | Method for preparing porous nanometer material Na6Mo7O24 14H2O through electrochemistry anodic oxidation method |
| CN107904645A (en) * | 2017-10-19 | 2018-04-13 | 天津大学 | A kind of anodized surface processing method for improving metal molybdenum foil surface-active |
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| US20100193363A1 (en) * | 2009-01-30 | 2010-08-05 | Shrisudersan Jayaraman | Electrochemical methods of making nanostructures |
| US8911904B2 (en) * | 2012-10-05 | 2014-12-16 | Ut-Battelle, Llc | Mesoporous metal oxide microsphere electrode compositions and their methods of making |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103556169A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Dandelion-shaped iron phosphate microspheres and preparation method thereof through electrochemical anode oxidation |
| CN104831330A (en) * | 2015-04-24 | 2015-08-12 | 哈尔滨工业大学 | Electrochemical preparation method for one-dimensional self-assembly ordered nanomaterial MoO3 nanopores |
| CN105040069A (en) * | 2015-08-25 | 2015-11-11 | 哈尔滨工业大学 | Method for preparing porous nanometer material Na6Mo7O24 14H2O through electrochemistry anodic oxidation method |
| CN107904645A (en) * | 2017-10-19 | 2018-04-13 | 天津大学 | A kind of anodized surface processing method for improving metal molybdenum foil surface-active |
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