Alpha-phase ferrous molybdate catalyst as well as preparation method and application thereof

Abstract

The invention relates to an alpha-phase ferrous molybdate catalyst as well as a preparation method and application thereof. The preparation method of the alpha-phase ferrous molybdate catalyst comprises the following steps: dissolving 2-4 mmol of a molybdenum source in 12-24 mL of water to obtain a solution I, dissolving 2-4 mmol of an iron source in 12-24 mL of water to obtain a solution II, adding the solution II into the solution I to obtain a reaction mixed solution, fully stirring the reaction mixed solution, carrying out a hydrothermal reaction, cooling, centrifuging and washing after the reaction is finished, and drying to obtain the alpha-phase ferrous molybdate catalyst. And drying to obtain the product. The alpha-phase ferrous molybdate catalyst is prepared by adopting a hydrothermal method, the reaction route is simple, the reaction condition is mild, the equipment requirement is low, the cost is low, and the method has obvious market competitive advantages.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and in particular relates to an alpha-phase ferrous molybdate catalyst and a preparation method and application thereof. Background Art

[0002] Ferrous molybdate (FeMoO4) is an important bimetallic oxide with excellent catalytic activity and thermoelectric properties. It is widely used in the fields of rechargeable battery cathode materials, magnetic materials, catalysts, etc. At present, the most commonly used method for preparing ferrous molybdate is the hydrothermal method. The prepared ferrous molybdate has nanocube structure, spherical structure, rod structure, and hollow microsphere structure.

[0003] The invention patent with application publication number CN118237034A discloses a method for preparing a rod-shaped ferrous molybdate catalyst material. The method for preparing a rod-shaped ferrous molybdate catalyst material comprises the following steps: (1) fully dissolving sodium molybdate dihydrate in deionized water to form a solution; (2) fully dissolving ferrous sulfate heptahydrate in deionized water to form a solution, and adding the solution obtained in the above step (1) to obtain a reaction mixture; (3) using a magnetic stirrer to fully stir the reaction mixture; (4) charging the reaction mixture obtained in the above step (3) into a polytetrafluoroethylene liner, placing the polytetrafluoroethylene liner into a hydrothermal reaction kettle, and performing a hydrothermal reaction in an electric constant temperature blast drying oven; (5) cooling after the hydrothermal reaction is completed, centrifugally collecting the cooled product, and washing it with deionized water for multiple cycles; (6) transferring the centrifugation washing product obtained in the above step (5) into a vacuum drying oven for drying; (7) taking out the dried product obtained in the above step (6), grinding it with an agate mortar, and obtaining a rod-shaped ferrous molybdate material. The preparation method of the rod-shaped ferrous molybdate catalytic material obtains a mixture of α-phase ferrous molybdate and β-phase ferrous molybdate, and cannot prepare a single α-phase ferrous molybdate. Summary of the invention

[0004] The first object of the present invention is to provide a method for preparing an α-phase ferrous molybdate catalyst to solve the technical problem that a single α-phase ferrous molybdate cannot be obtained by a hydrothermal method in the prior art.

[0005] The second object of the present invention is to provide an α-phase ferrous molybdate catalyst.

[0006] The third object of the present invention is to provide an application of an α-phase ferrous molybdate catalyst.

[0007] In order to achieve the above purpose, the technical solution adopted by the present invention is:

[0008] A preparation method of an alpha-phase ferrous molybdate catalyst comprises the following steps: dissolving 2-4 mmol of a molybdenum source in 12-24 mL of water to obtain a first solution, dissolving 2-4 mmol of an iron source in 12-24 mL of water to obtain a second solution, adding the second solution into the first solution to obtain a reaction mixture, fully stirring the reaction mixture and then performing a hydrothermal reaction, cooling after the reaction is completed, centrifuging, washing and drying to obtain the catalyst.

[0009] Furthermore, the temperature of the hydrothermal reaction is 180° C., and the time of the hydrothermal reaction is 12 h.

[0010] Furthermore, the molybdenum source is a hexavalent molybdenum salt, and the iron salt is a ferrous salt.

[0011] Furthermore, the molybdenum source is hydrated sodium molybdate, and the iron salt is ferrous sulfate heptahydrate.

[0012] Furthermore, the hydrothermal reaction is carried out in an electric constant temperature blast drying oven, and the power consumption of the electric constant temperature blast drying oven is ≤950W.

[0013] Furthermore, the washing method is to wash with water in a circulating manner for 3 to 5 times.

[0014] Furthermore, the drying method is to dry in a vacuum drying oven at a temperature of 60 to 80° C. for 12 to 24 hours, and the power consumption of the vacuum drying oven is less than 350W.

[0015] Furthermore, the stirring time is 10 to 20 minutes.

[0016] An alpha-phase ferrous molybdate catalyst is prepared by adopting the preparation method of the alpha-phase ferrous molybdate catalyst.

[0017] The invention discloses an alpha-phase ferrous molybdate catalyst used as a catalyst for activating persulfate in catalytic degradation of tetracycline hydrochloride in water.

[0018] Beneficial effects of the present invention:

[0019] The invention adopts a hydrothermal method to prepare an alpha-phase ferrous molybdate catalyst, has a simple reaction route, mild reaction conditions, low equipment requirements, economical cost, and has obvious market competitive advantages.

[0020] The α-phase ferrous molybdate catalyst of the present invention exhibits efficient catalytic performance and excellent stability in the degradation of tetracycline hydrochloride in water. The α-phase ferrous molybdate catalyst of the present invention is applied to photocatalytic degradation of tetracycline hydrochloride in water. After adding sodium persulfate and irradiating with light for 30 minutes, the removal rate of tetracycline is as high as 99.5%. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1This is a product diagram of the α-phase ferrous molybdate catalyst in Example 1;

[0022] Figure 2 is the XRD pattern of the α-phase ferrous molybdate catalyst in Example 1;

[0023] Figure 3 This is the SEM image of the α-phase ferrous molybdate catalyst in Example 1. DETAILED DESCRIPTION

[0024] The present invention will be further described below in conjunction with the embodiments of the present invention and the accompanying drawings.

[0025] Example 1

[0026] The preparation method of the α-phase ferrous molybdate catalyst of Example 1 comprises the following steps: dissolving 0.605 g of sodium molybdate dihydrate in 15 mL of deionized water to obtain solution 1, dissolving 0.695 g of ferrous sulfate heptahydrate in 15 mL of deionized water to obtain solution 2, adding solution 2 to solution 1 to obtain a reaction mixture, stirring the reaction mixture for 10 min and transferring it to a hydrothermal reactor, and performing a hydrothermal reaction in an electric constant temperature blast drying oven with a power consumption of 950 W, cooling after the reaction is completed, and collecting the cooled product by centrifugation, washing the collected product with deionized water for 3 times, then drying it in a vacuum drying oven, and grinding it to obtain an α-phase ferrous molybdate catalyst, from Figure 3 It can be seen that the prepared α-phase ferrous molybdate catalyst has a spherical structure. The temperature of the hydrothermal reaction is 180°C, and the time of the hydrothermal reaction is 12h. The temperature of the vacuum drying is 60°C, the time of the vacuum drying is 12h, and the power consumption of the vacuum drying oven is 250W.

[0027] Example 2

[0028] The preparation method of the α-phase ferrous molybdate catalyst of embodiment 2 comprises the following steps: 0.484g of sodium molybdate dihydrate is dissolved in 18mL of deionized water to obtain solution one, 0.556g of ferrous sulfate heptahydrate is dissolved in 18mL of deionized water to obtain solution two, solution two is added to solution one to obtain a reaction mixture, the reaction mixture is stirred for 15min and then transferred to a hydrothermal reactor, and hydrothermally reacted in an electric constant temperature blast drying oven with a power consumption of 900W, after the reaction is cooled and centrifuged to collect the cooled product, the collected product is washed 4 times with deionized water circulation, then dried in a vacuum drying oven, and the α-phase ferrous molybdate catalyst is obtained after grinding. The temperature of the hydrothermal reaction is 180°C, and the time of the hydrothermal reaction is 12h. The temperature of vacuum drying is 60°C, the time of vacuum drying is 20h, and the power consumption of the vacuum drying oven is 300W.

[0029] Example 3

[0030] The preparation method of the α-phase ferrous molybdate catalyst of Example 3 comprises the following steps: 0.726g of sodium molybdate dihydrate is dissolved in 12mL of deionized water to obtain solution one, 0.834g of ferrous sulfate heptahydrate is dissolved in 12mL of deionized water to obtain solution two, solution two is added to solution one to obtain a reaction mixture, the reaction mixture is stirred for 20min and then transferred to a hydrothermal reactor, and hydrothermally reacted in an electric constant temperature blast drying oven with a power consumption of 850W, after the reaction is completed, the cooled product is collected by centrifugation, the collected product is washed 5 times with deionized water, and then dried in a vacuum drying oven, and the α-phase ferrous molybdate catalyst is obtained after grinding. The temperature of the hydrothermal reaction is 180°C, and the time of the hydrothermal reaction is 12h. The temperature of vacuum drying is 80°C, the time of vacuum drying is 24h, and the power consumption of the vacuum drying oven is 340W.

[0031] The α-phase ferrous molybdate catalyst of Example 1 was added to the pretreated water containing tetracycline hydrochloride and mixed evenly, and then sodium persulfate was added. After irradiation with visible light for 30 minutes, the removal rate of tetracycline hydrochloride in the pretreated water was 99.5%. The concentration of tetracycline hydrochloride in the pretreated water was 10 mg / L.

Claims

1. A method for preparing an α-phase ferrous molybdate catalyst, characterized in that: The method comprises the following steps: dissolving 2-4 mmol of a molybdenum source in 12-24 mL of water to obtain a first solution, dissolving 2-4 mmol of an iron source in 12-24 mL of water to obtain a second solution, adding the second solution into the first solution to obtain a reaction mixture, fully stirring the reaction mixture and then performing a hydrothermal reaction, cooling after the reaction is completed, centrifuging, washing, and drying to obtain the product.

2. The method for preparing an α-phase ferrous molybdate catalyst according to claim 1, wherein The temperature of the hydrothermal reaction is 180° C., and the time of the hydrothermal reaction is 12 h.

3. The preparation method of the α-phase ferrous molybdate catalyst according to claim 1, characterized in that, The molybdenum source is a hexavalent molybdenum salt, and the iron salt is a ferrous salt.

4. The preparation method of the α-phase ferrous molybdate catalyst according to claim 3, characterized in that: The molybdenum source is sodium molybdate dihydrate, and the iron salt is ferrous sulfate heptahydrate.

5. The preparation method of the α-phase ferrous molybdate catalyst according to claim 1, characterized in that: The hydrothermal reaction is carried out in an electric constant temperature blast drying oven, and the power consumption of the electric constant temperature blast drying oven is ≤950W.

6. The method for preparing the α-phase ferrous molybdate catalyst according to claim 1, characterized in that: The washing method is to wash with water in a circulating manner for 3 to 5 times.

7. The method for preparing the α-phase ferrous molybdate catalyst according to claim 1, characterized in that: The drying method comprises drying in a vacuum drying oven at a temperature of 60 to 80° C. for 12 to 24 hours, and the power consumption of the vacuum drying oven is less than 350W.

8. The method for preparing the α-phase ferrous molybdate catalyst according to claim 1, characterized in that: The stirring time is 10 to 20 minutes.

9. An α-phase ferrous molybdate catalyst, characterized in that: The catalyst is prepared by the method for preparing the α-phase ferrous molybdate catalyst described in any one of claims 1 to 8.

10. Use of the α-phase ferrous molybdate catalyst as claimed in claim 9 as a catalyst for activating persulfate in catalytic degradation of tetracycline hydrochloride in water.

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