NICKEL-BASED MOF FILM PHOTOCATALYST GROWN IN-SITU ON FOAMED NICKEL SURFACE, PREPARATION METHOD THEREFOR, AND APPLICATION THEREOF

Abstract

A nickel-based MOF film photocatalyst grown in-situ on a foamed nickel surface, a preparation method therefor, and an application thereof. The nickel-based MOF film photocatalyst grown in-situ on a foamed nickel surface is prepared by first immersing foamed nickel in a diluted acid and performing ultrasonic processing, then cleaning the foamed nickel with deionized water, and drying the foamed nickel to obtain surface-activated foamed nickel; immersing the surface-activated nickel foam in a mixture of an imidazole compound, sodium formate, and a solvent and reacting at 100° C. to 180° C. to obtain an unactivated nickel-based MOFs film on the surface of the foamed nickel, and after cooling to room temperature, removing same and soaking in an organic solvent to activate, and then drying the obtained product. The film photocatalyst synthesized in-situ on the foamed nickel can increase the specific surface area of the material to facilitate the adsorption and diffusion of VOCs, and can expose more catalytic sites, so that the VOCs can be effectively degraded under the action of sunlight.

Claims

1. A nickel-based MOF film photocatalyst grown in-situ on a foamed nickel surface, characterized in that, the nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface is prepared by first immersing the foamed nickel in a diluted acid and performing ultrasonic processing, then cleaning the foamed nickel with deionized water, and drying the foamed nickel to obtain a surface-activated foamed nickel; immersing the surface-activated foamed nickel in a mixed solution of imidazole compounds, sodium formate and a solvent, reacting at 100 to 180° C. to give rise to a coordination effect of the imidazole compounds with nickel ions released by etching the surface of the foamed nickel, so as to obtain an unactivated nickel-based MOF film on the surface of the foamed nickel, and after cooling to room temperature, taking out the unactivated nickel-based MOF film and immersing it in an organic solvent for activating, and drying the obtained product.

2. The nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface according to claim 1, characterized in that, the imidazole compounds are one or more of 2-methyl imidazole, imidazole, benzoimidazole or 2-ethyl imidazole.

3. The nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface according to claim 1, characterized in that, the dilute acid is nitric acid, hydrochloric acid or sulfuric acid; and a concentration of the dilute acid is 0.5 to 6 mol/L.

4. The nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface according to claim 1, characterized in that, a molar ratio of the imidazole compounds, sodium formate and the solvent is (1 to 10):1:(100 to 200).

5. The nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface according to claim 1, characterized in that, the solvent is one or any two of methanol, water or DMF, and the organic solvent is methanol or ethanol.

6. The nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface according to claim 1, characterized in that, a time for the ultrasonic processing is 5 to 60 min; a time for the reaction is 4 to 18 h; and a time for the activating is 12 to 48 h.

7. A preparation method for the nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface according to claim 1, characterized in that, the method includes the following steps: S1. immersing the foamed nickel in a diluted acid and performing ultrasonic processing, then cleaning the foamed nickel with deionized water, and drying the foamed nickel to obtain a surface-activated foamed nickel; S2. immersing the surface-activated foamed nickel obtained in the step S1 in a mixed solution of imidazole compounds, sodium formate and a solvent, and reacting at 100 to 180° C. to give rise to a coordination effect of the imidazole compounds with nickel ions released by etching the surface of the foamed nickel, so as to obtain an unactivated nickel-based MOF film on the surface of the foamed nickel; and S3. after cooling the obtained unactivated nickel-based MOF film on the surface of the foamed nickel to room temperature, taking out the unactivated nickel-based MOF film and immersing it in an organic solvent for activating, and drying to obtain the nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface.

8. An application of the nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface specified in claim 1 in degrading a volatile organic matter in air under driving of sunlight.

9. The application of the nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface in degrading the volatile organic matter in air under driving of sunlight according to claim 8, characterized in that, the volatile organic matter is VOC discharged in paint spraying industry.

10. The application of the nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface in degrading the volatile organic matter in air under driving of sunlight according to claim 9, characterized in that, the VOC discharged in paint spraying industry is ethyl acetate.

Description

DESCRIPTION OF DRAWINGS

[0027] FIG. 1 is SEM photographs for the Ni-MOF/NF prepared in Example 1; and

[0028] FIG. 2 is a kinetic curve for adsorption and a kinetic curve for photocatalytic degradation of the Ni-MOF/NF film photocatalyst prepared in Example 1 for the gas-phase ethyl acetate.

DETAILED DESCRIPTION OF EMBODIMENTS

[0029] The present invention will be further described below in combination with drawings and specific Examples in specification, which should not be interpreted as limits to the present invention. Unless otherwise specified, technical means in Examples are technical means well known by those skilled in the art. Unless otherwise specified, reagents, methods and apparatuses adopted in the present invention are conventional reagents, methods and apparatuses in this technical field.

Example 1

[0030] 1. Dilute hydrochloric acid (0.5 mol/L) and deionized water are used respectively for immersing and ultrasonically processing a foamed nickel with a dimension of 1 cm.sup.2. Stain, oxidized film and organic matter etc. on the surface of the foamed nickel are washed off to expose the fresh surface of the foamed nickel. Then, the washed foamed nickel is put in a vacuum drying oven at 60° C. and dried to obtain a surface-activated foamed nickel.

[0031] 2. The surface-activated foamed nickel is immersed in a mixed solution of 2-methyl imidazole, methanol and sodium formate with a molar ratio of 1:1:100 within a reaction still with polytetrafluoroethylene. The reaction still is placed in a baking oven with a program set up. The temperature within the baking oven is raised to 120° C. at 1° C./min, and the baking oven is maintained at this temperature for 12 h. After the reaction is completed, the temperature in the baking oven is decreased to room temperature, to obtain an unactivated nickel-based MOF film grown on the surface of the foamed nickel.

[0032] 3. The obtained unactivated nickel-based MOF film grown on the surface of the foamed nickel is first washed alternately with alcohols and deionized water, and then placed in a vacuum drying oven at 120° C. to dry for 24 h to obtain a nickel-based MOF film photocatalyst grown in-situ on the foamed nickel (Ni-MOF/NF).

[0033] FIG. 1 is SEM photographs for the Ni-MOF/NF prepared in Example 1. It can be seen from FIG. 1 that, the nickel-based MOF material is grown in-situ on the foamed nickel and uniformly distributed in a state of pieces. FIG. 2 is a kinetic curve for adsorption and a kinetic curve for photocatalytic degradation of the nickel-based MOF film photocatalyst synthesized in-situ on the surface of the foamed nickel (Ni-MOF/NF) prepared in the present Example for the gas-phase ethyl acetate. It can be seen from FIG. 2 that, the adsorption of Ni-MOF/NF for ethyl acetate reaches the equilibrium of adsorption and desorption within 60 min, and the photocatalytic degradation efficiency of Ni-MOF/NF for the gas-phase ethyl acetate reaches 95% within 60 min. Results show that this nickel-based MOF film photocatalyst has a certain adsorption performance, and has very high photocatalytic activity. The nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface is a novel material having certain adsorption ability for VOC and high photocatalytic activity.

Example 2

[0034] 1. Dilute hydrochloric acid (6 mol/L) and deionized water are respectively used for immersing and ultrasonically processing a foamed nickel with a dimension of 1 cm.sup.2. Stain, oxidized film and organic matter etc. on the surface of the foamed nickel are washed off to expose the fresh surface of the foamed nickel. Then, the washed foamed nickel is put in a vacuum drying oven at 60° C. and dried to obtain a surface-activated foamed nickel.

[0035] 2. The surface-activated foamed nickel is immersed in a mixed solution of 2-methyl imidazole, methanol and sodium formate with a molar ratio of 10: 1: 200, and the same is added in a reaction still with polytetrafluoroethylene. The reaction still is placed in a baking oven with a program set up. The temperature within the baking oven is raised to 100° C. at 5° C./min, and the baking oven is maintained at this temperature for 12 h. After the reaction is completed, the temperature in the baking oven is decreased to room temperature, to obtain an unactivated nickel-based MOF film grown on the surface of the foamed nickel.

[0036] 3. The obtained unactivated nickel-based MOF film grown on the surface of the foamed nickel is first washed alternately with alcohols and deionized water, and then placed in a vacuum drying oven at 120° C. to dry for 24 h to obtain a nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface.

Example 3

[0037] 1. Dilute hydrochloric acid (3 mol/L) and deionized water are used respectively for immersing and ultrasonically processing a foamed nickel with a dimension of 1 cm.sup.2. Stain, oxidized film and organic matter etc. on the surface of the foamed nickel are washed off to expose the fresh surface of the foamed nickel. Then, the washed foamed nickel is put in a vacuum drying oven at 60° C. and dried to obtain a surface-activated foamed nickel.

[0038] 2. The surface-activated foamed nickel is immersed in a mixed solution of imidazole, DMF and sodium formate with a molar ratio of 5:1:150, and the same is added in a reaction still with polytetrafluoroethylene. The reaction still is placed in a baking oven with a program set up. The temperature within the baking oven is raised to 180° C. at 10° C./min, and the baking oven is maintained at this temperature for 4 h. After the reaction is completed, the temperature in the baking oven is decreased to room temperature, to obtain an unactivated nickel-based MOF film grown on the surface of the foamed nickel.

[0039] 3. The obtained unactivated nickel-based MOF film grown on the surface of the foamed nickel is first washed alternately with alcohols and deionized water, and then placed in a vacuum drying oven at 120° C. to dry for 24 h to obtain a nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface.

Example 4

[0040] 1. Dilute nitric acid (1 mol/L) and deionized water are used respectively for immersing and ultrasonically processing a foamed nickel with a dimension of 4 cm.sup.2. Stain, oxidized film and organic matter etc. on the surface of the foamed nickel are washed off to expose the fresh surface of the foamed nickel. Then, the washed foamed nickel is put in a vacuum drying oven at 80° C. and dried to obtain a surface-activated foamed nickel.

[0041] 2. The surface-activated foamed nickel is immersed in a mixed solution of benzoimidazole, methanol and sodium formate with a molar ratio of 2: 1: 150, and the same is added in a reaction still with polytetrafluoroethylene. The reaction still is placed in a baking oven with a program set up. The temperature within the baking oven is raised to 140° C. at 3° C./min, and the baking oven is maintained at this temperature for 12 h. After the reaction is completed, the temperature in the baking oven is decreased to room temperature, to obtain an unactivated nickel-based MOF film grown on the surface of the foamed nickel.

[0042] 3. The obtained unactivated nickel-based MOF film grown on the surface of the foamed nickel is first washed alternately with alcohols and deionized water, and then placed in a vacuum drying oven at 120° C. to dry for 48 h to obtain a nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface.

Example 5

[0043] 1. Dilute sulfuric acid (with a concentration of 4 mol/L) and deionized water are used for respectively immersing and ultrasonically processing a foamed nickel with a dimension of 4 cm.sup.2. Stain, oxidized film and organic matter etc. on the surface of the foamed nickel are washed off to expose the fresh surface of the foamed nickel. Then, the washed foamed nickel is put in a vacuum drying oven at 80° C. and dried to obtain a surface-activated foamed nickel.

[0044] 2. The surface-activated foamed nickel is immersed in a mixed solution of 2-ethyl imidazole, water and sodium formate with a molar ratio of 10:1:200, and the same is added in a reaction still with polytetrafluoroethylene. The reaction still is placed in a baking oven with a program set up. The temperature within the baking oven is raised to 140° C. at 0.5° C./min, and the baking oven is maintained at this temperature for 18 h. After the reaction is completed, the temperature in the baking oven is decreased to room temperature, to obtain an unactivated nickel-based MOF film grown on the surface of the foamed nickel.

[0045] 3. The obtained unactivated nickel-based MOF film grown on the surface of the foamed nickel is first washed alternately with alcohols and deionized water, and then placed in a vacuum drying oven at 150° C. to dry for 24 h to obtain a nickel-based MOF film photocatalyst grown in-situ on the foamed nickel surface.

[0046] The above-described Examples are preferred embodiments of the present invention, but embodiments of the present invention are not limited to the above-described Examples, and any other changes, modifications, substitutions, combinations and simplifications made without departing from the spirits and the principle of the present invention should all be equivalent replacing modes, and are all included in the protection scope of the present invention.