Foamed nickel-based bionic nanoneedle catalyst as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of photocatalytic functional materials, and discloses a foamed nickel-based bionic nanoneedle catalyst as well as a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: self-assembling bionic nanoneedles on the surface of foamed nickel in situ, removing stains on the surface of the foamed nickel, then carrying out ultrasonic cleaning in hydrochloric acid to remove surface oxides, and carrying out vacuum drying to obtain surface-activated foamed nickel; soaking the surface-activated foamed nickel into a mixed solution of dimethylglyoxime, an organic solvent and hydrochloric acid, carrying out ultrasonic treatment, carrying out self-assembly reaction at 25-80 DEG C, and then sequentially cooling, washing and drying to obtain the nickel-based composite material. The bionic nanoneedle catalyst is synthesized on the surface of the foamed nickel through in-situ self-assembly, catalytic sites are exposed abundantly by adjusting the aspect ratio and sharpness of the nanoneedle structure, and the bionic nanoneedle catalyst shows excellent activity and stability in the aspects of dynamic capture and photocatalytic killing of biological aerosol particles.

Description

Technical Field

[0001] The present invention belongs to the technical field of photocatalytic air purification, and more specifically, relates to a foam nickel-based bionic nanoneedle catalyst and a preparation method and application thereof. Background Art

[0002] Bioaerosol particles contain a variety of complex pathogens, which can lead to the rapid spread of respiratory infectious diseases (such as influenza and asthma), posing a serious threat to human health and life. Chemical disinfectants and physical filtration purification methods can remove bioaerosol particles to a certain extent, but these technologies inherently suffer from incomplete disinfection and / or secondary contamination. Photocatalytic killing technology can physically capture bioaerosol particles while simultaneously inactivating these enriched microbial pathogens in situ. It can be considered an environmentally friendly air purification technology with excellent removal efficiency, economical efficiency, and no secondary contamination risk. Currently, three-dimensional nickel foam, a low-cost, mechanically stable, and uniquely structured catalyst substrate, is widely used for the adsorption and degradation of various gaseous pollutants, such as formaldehyde and volatile organic compounds. However, a growing number of studies have found that light cannot penetrate the porous structure of the three-dimensional nickel foam, resulting in insufficient activation of the photocatalyst loaded within the foam, severely affecting the generation of free radicals in the reaction system and leading to low inactivation efficiency. Therefore, there is an urgent need to develop a new photocatalytic control technology that can effectively and thoroughly kill bioaerosol particles.

[0003] The wings of insects like cicadas and dragonflies, with their sharp nanostructures, can physically damage cell membranes and even kill bacteria. Manipulating the nanostructure of nickel foam surface catalysts can enhance their physical capture and cleavage of bioaerosol particles, improving purification efficiency. In situ design of nickel foam surfaces through in situ self-assembly to achieve the directional growth of nickel foam-based biomimetic nanoneedle catalysts is considered a very effective means of manipulating nanomaterial morphology. However, no such biomimetic nanoneedle catalyst technology has yet been applied to the photocatalytic inactivation of bioaerosol particles. Summary of the Invention

[0004] To address the shortcomings and deficiencies of the prior art, the present invention primarily aims to provide a nickel foam-based biomimetic nanoneedle catalyst. This catalyst exhibits a large specific surface area and atomic exposure. By manipulating the aspect ratio of the nickel foam-based biomimetic nanoneedle catalyst, it achieves efficient and stable photocatalytic bioaerosol particle capture, addressing the low capture efficiency of conventional catalysts.

[0005] Another object of the present invention is to provide a preparation method for the above-mentioned nickel foam-based biomimetic nano needle catalyst. The method utilizes the principle of dilute hydrochloric acid induction and dimethylglyoxime coordination assembly, and nickel foam-based biomimetic nano needles are uniformly grown on the three-dimensional nickel foam surface by surface etching of nickel foam, and the aspect ratio and sharpness of the nickel foam-based biomimetic nano needles are controlled by adjusting dimethylglyoxime coordination concentration and rate, providing more capture sites and effectively improving physical capture and irreversible killing efficiency, reducing the secondary pollution caused by microbial resurrection. And by in situ self-assembly method, overcome the drawbacks of traditional catalysts prepared by bonding mode that are easy to fall off and have poor stability.

[0006] Another object of the present invention is to provide an application of a foam nickel-based bionic nanoneedle catalyst in the field of photocatalytic killing of bioaerosol particles.

[0007] The purpose of the present invention is achieved through the following technical solutions:

[0008] A nickel foam-based bionic nanoneedle catalyst is prepared by in-situ self-assembling bionic nanoneedles on the surface of nickel foam. Surface stains on the nickel foam are first removed, and then surface oxides are removed by ultrasonic cleaning in hydrochloric acid. Surface-activated nickel foam is obtained by vacuum drying. The surface-activated nickel foam is immersed in a mixture of dimethylglyoxime, an organic solvent, and hydrochloric acid, and ultrasonically treated. A self-assembly reaction is carried out at 25 to 80° C., and the catalyst is then cooled, washed, and dried in sequence to obtain the catalyst.

[0009] Preferably, the concentration of the hydrochloric acid is 0.1-3 mol / L.

[0010] Preferably, the molar ratio of dimethylglyoxime, organic solvent and dilute hydrochloric acid in the mixed solution is (1-5):10:(1-10).

[0011] Preferably, the organic solvent is ethanol, ether, acetone or pyridine.

[0012] Preferably, the ultrasonication time is 1 to 30 minutes, the self-assembly reaction time is 0.5 to 3 minutes, and the drying temperature is 30 to 150°C.

[0013] The preparation method of the foamed nickel-based bionic nanoneedle catalyst comprises the following steps:

[0014] S1. The nickel foam was sequentially placed in acetone and ethanol to remove surface stains, and then ultrasonically cleaned in dilute hydrochloric acid to remove surface oxides, and finally rinsed with deionized water and dried in vacuo to obtain a surface-activated nickel foam;

[0015] S2. The surface-activated nickel foam was immersed in a mixture of dimethylglyoxime, an organic solvent, and dilute hydrochloric acid and ultrasonically treated;

[0016] S3. The mixture obtained in step S2 is subjected to a self-assembly reaction at 25-80° C., and then cooled and dried in sequence to obtain a foamed nickel-based bionic nanoneedle catalyst.

[0017] The application of the foam nickel-based bionic nanoneedle catalyst in the field of preparing bioaerosol particles for catalytic purification.

[0018] Preferably, the bioaerosol particles are viral aerosols, bacterial aerosols or fungal aerosols.

[0019] The present invention uses nickel foam with unique three-dimensional holes as a substrate and a nickel source precursor. By a simple chlorine corrosion method, a dense and uniform nickel foam-based biomimetic nano needle catalyst is grown in situ on the nickel foam surface, and a nickel foam-based biomimetic nano needle catalyst is successfully prepared. Thanks to the unique biomimetic structure and super-hydrophilicity, the nickel foam-based biomimetic nano needle catalyst has a large specific surface area and abundant atomic exposed active sites. At the same time, by regulating the aspect ratio of the nickel foam-based biomimetic nano needle catalyst, efficient and stable photocatalytic bioaerosol particle killing performance is achieved, solving the problem that the traditional catalyst killing efficiency is not high. In addition, by the in situ self-assembly method, the drawbacks of the traditional catalyst prepared by the bonding method that is easy to fall off and has poor stability are overcome. The nickel foam-based biomimetic nano needle catalyst prepared by the present invention can efficiently capture bioaerosol particles suspended in the air, and under the synergistic effect of the unique biomimetic nano needle structure and the nickel foam three-dimensional structure, it promotes the rapid generation and migration of reactants, electrons and reactive oxygen species. The in situ self-assembly method applied simultaneously enhances the stability of the catalyst.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] 1. The nickel foam-based bionic nanoneedle catalyst of the present invention has the performance of efficiently capturing and inactivating airborne pathogenic microorganisms and also exhibits good catalytic stability.

[0022] 2. This invention uses nickel foam as both a substrate and a nickel source precursor, leveraging the rapid self-assembly of diacetyl and nickel ions to controllably form biomimetic nanoneedle catalysts on the surface of the nickel foam. This overcomes the complex preparation process and harsh conditions associated with traditional methods for modifying three-dimensional nickel foam. It also avoids the use of conventional insulating polymer binders, facilitates rapid electron transport, and improves catalyst stability.

[0023] 3. The nickel foam-based biomimetic nanoneedle catalyst prepared by this invention exhibits a unique hierarchical structure. Its three-dimensional macroscopic multi-level pore channels and biomimetic nanoneedle catalyst enable efficient capture of bioaerosol particles. The uniformly grown biomimetic nanoneedles on the nickel foam surface exhibit highly exposed active sites. Their excellent mass transfer capacity and stability ensure the efficient transport of electrons and reactive oxygen species, addressing the limited air purification and disinfection performance of conventional catalysts. This research also provides guidance for the direct growth of composite catalysts on three-dimensional porous metal foam substrates.

[0024] 4. The present invention synthesizes nickel-based biomimetic nanoneedle catalysts by in situ self-assembly on the surface of nickel foam. The preparation method is simple, the catalytic sites are abundantly exposed, and it exhibits excellent activity and stability in the dynamic capture of pathogenic microorganisms on bioaerosol particles and photocatalytic in situ killing. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a scanning electron microscope image of the foam nickel-based bionic nanoneedle catalyst obtained in Example 1.

[0026] Figure 2 This is a graph showing the capture efficiency of bioaerosol particles by the nickel foam-based bionic nanoneedle catalyst obtained in Example 1.

[0027] Figure 3 This is a diagram showing the photocatalytic killing efficiency of the nickel foam-based bionic nanoneedle catalyst obtained in Example 1 on bioaerosol particles. DETAILED DESCRIPTION

[0028] The present invention will be further described below in conjunction with specific examples, but should not be construed as limiting the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0029] Example 1

[0030] 1. First, cut the nickel foam into 3×3 cm pieces, immerse them in acetone and anhydrous ethanol in turn to remove surface stains, then use 0.5 mol / L hydrochloric acid ultrasonic cleaning to remove surface oxides, and finally rinse with deionized water. Then, quickly dry the cleaned nickel foam in a vacuum drying oven at 60°C for 12 hours to obtain surface-activated nickel foam.

[0031] 2. The surface-activated nickel foam was immersed in a mixed aqueous solution of dimethylglyoxime, anhydrous ethanol and 1 mol / L hydrochloric acid (the molar ratio of dimethylglyoxime, anhydrous ethanol and hydrochloric acid was 1:1:1) for ultrasonic treatment, and then transferred to a reactor and maintained at 30°C for 6 hours for self-assembly reaction. After the reaction was completed, it was cooled to room temperature and then placed in a drying oven at 80°C for 24 hours to obtain a nickel foam-based bionic nanoneedle catalyst.

[0032] Figure 1 This is a scanning electron microscope image of the nickel foam-based biomimetic nanoneedle catalyst obtained in Example 1. Figure 1 It can be seen that the bionic nanoneedle catalyst is evenly distributed on the surface of nickel foam, indicating that the in situ modification of nickel foam bionic nanoneedle catalyst can be achieved quickly and easily through in situ self-assembly method. Figure 2-3 The capture efficiency and killing efficiency of the nickel-based biomimetic nanoneedle catalyst obtained in Example 1 are shown in FIG. Figure 2 It can be seen that the nickel foam-based biomimetic nanoneedle catalyst shows a high efficiency of capturing bioaerosol particles with an efficiency of more than 90%. Figure 3 The photocatalytic killing efficiency of captured bioaerosols reached over 99.99%. The results demonstrate that the nickel foam-based biomimetic nanoneedle catalyst has highly effective photocatalytic air sterilization activity and has great potential as a functional material for purifying air pollutants such as bioaerosol particles.

[0033] Example 2

[0034] 1. First, place the nickel foam with a size of 10×5cm in acetone and ethanol in turn to remove surface stains, then use 3mol / L hydrochloric acid ultrasonic cleaning to remove surface oxides, and finally rinse it with deionized water. Then, quickly place the washed nickel foam in a vacuum drying oven at 60℃ to obtain surface-activated nickel foam.

[0035] 2. The surface-activated nickel foam was immersed in a mixed aqueous solution of dimethylglyoxime, anhydrous ethanol and 1 mol / L hydrochloric acid (the molar ratio of dimethylglyoxime, anhydrous ethanol and hydrochloric acid was 3:1:1) for ultrasonic treatment, and then transferred to a reactor and maintained at 30°C for 6 hours for self-assembly reaction. After the reaction was completed, the temperature was cooled to room temperature and then placed in a drying oven at 80°C for 24 hours to obtain a nickel foam-based bionic nanoneedle catalyst.

[0036] Example 3

[0037] 1. First, place the nickel foam with a size of 2.5×2.5cm in acetone and ethanol in turn to remove surface stains, then use 0.5mol / L hydrochloric acid ultrasonic cleaning to remove surface oxides, and finally rinse it with deionized water. Then, quickly place the washed nickel foam in a vacuum drying oven at 60℃ to obtain surface-activated nickel foam.

[0038] 2. The surface-activated nickel foam was immersed in a mixed aqueous solution of dimethylglyoxime, anhydrous ethanol and 1 mol / L hydrochloric acid (the molar ratio of dimethylglyoxime, anhydrous ethanol and hydrochloric acid was 1:1:1) for ultrasonic treatment, and then transferred to a reactor and maintained at 30°C for 6 hours for self-assembly reaction. After the reaction was completed, the temperature was cooled to room temperature and then placed in a drying oven at 80°C for 24 hours to obtain a nickel foam-based bionic nanoneedle catalyst.

[0039] Example 4

[0040] 1. First, place the nickel foam with a size of 10×5cm in acetone and ethanol in turn to remove surface stains, then use 3mol / L hydrochloric acid ultrasonic cleaning to remove surface oxides, and finally rinse it with deionized water. Then, quickly place the washed nickel foam in a vacuum drying oven at 60℃ to obtain surface-activated nickel foam.

[0041] 2. The surface-activated nickel foam was immersed in a mixed aqueous solution of dimethylglyoxime, anhydrous ethanol and 1 mol / L hydrochloric acid (the molar ratio of dimethylglyoxime, anhydrous ethanol and hydrochloric acid was 1:1:1) for ultrasonic treatment, and then transferred to a reactor and maintained at 30°C for 6 hours for self-assembly reaction. After the reaction was completed, the temperature was cooled to room temperature and then placed in a drying oven at 80°C for 24 hours to obtain a nickel foam-based bionic nanoneedle catalyst.

[0042] The foam nickel-based biomimetic nanoneedle catalyst prepared in Examples 1-4 was modularly assembled in a flow-type ultraviolet photocatalytic air purification efficiency evaluation device (application number 202122196768.9), and the concentration of 10 5 ~10 9 cfu / ml bacterial aerosol was introduced into the air, and the concentration of aerosol in the air before and after killing was compared, and the killing efficiency was found to be above 90%.

[0043] The above embodiments are preferred implementations of the present invention, but the implementations of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A foam nickel-based bionic nanoneedle catalyst, characterized in that: The catalyst is prepared by in-situ self-assembling bionic nanoneedles on the surface of nickel foam. Surface stains of the nickel foam are first removed, and then surface oxides are removed by ultrasonic cleaning in hydrochloric acid, followed by vacuum drying to obtain surface-activated nickel foam. The surface-activated nickel foam is then immersed in a mixed solution of dimethylglyoxime, an organic solvent, and hydrochloric acid for ultrasonic treatment, followed by self-assembly reaction at 25-80° C., and then sequentially cooled, washed, and dried to obtain the catalyst.

2. The foam nickel-based biomimetic nanoneedle catalyst according to claim 1, characterized in that The concentration of the hydrochloric acid is 0.1-3 mol / L.

3. The foamed nickel-based biomimetic nanoneedle catalyst according to claim 1, characterized in that The molar ratio of dimethylglyoxime, organic solvent and dilute hydrochloric acid in the mixed solution is (1-5):10:(1-10).

4. The foamed nickel-based biomimetic nanoneedle catalyst according to claim 1, characterized in that The organic solvent is ethanol, ether, acetone or pyridine.

5. The foamed nickel-based biomimetic nanoneedle catalyst according to claim 1, characterized in that: The ultrasonic treatment time is 1 to 30 minutes, the self-assembly reaction time is 0.5 to 3 minutes, and the drying temperature is 30 to 150°C.

6. The method for preparing the foamed nickel-based bionic nanoneedle catalyst according to any one of claims 1 to 5, characterized in that: The steps include: S1. The nickel foam was sequentially placed in acetone and ethanol to remove surface stains, and then ultrasonically cleaned in dilute hydrochloric acid to remove surface oxides, and finally rinsed with deionized water and dried in vacuo to obtain a surface-activated nickel foam; S2. The surface-activated nickel foam was immersed in a mixture of dimethylglyoxime, an organic solvent, and dilute hydrochloric acid and ultrasonically treated; S3. The mixture obtained in step S2 is subjected to a self-assembly reaction at 25-80° C., and then cooled and dried in sequence to obtain a foamed nickel-based bionic nanoneedle catalyst.

7. Use of the foamed nickel-based biomimetic nanoneedle catalyst according to any one of claims 1 to 5 in the field of catalytic purification of bioaerosol particles.

8. The use of the foamed nickel-based biomimetic nanoneedle catalyst in the field of bioaerosol particle purification according to claim 7, characterized in that: The bioaerosol particles are viral aerosols, bacterial aerosols or fungal aerosols.

Images