CN106552674A - Aerogel carried nickel-phosphorus alloy catalysis material of a kind of nanofiber and preparation method thereof - Google Patents

Abstract

The invention discloses aerogel carried nickel-phosphorus alloy catalysis material of a kind of nanofiber and preparation method thereof, belongs to nano-functional material field.The catalysis material that the present invention is provided is made up of the nickel-phosphorus alloy nano-particle that Nanofiber Network skeleton and bag are attached to Nanofiber Network skeleton surface, and Nanofiber Network skeleton is made up of with the binding agent for being attached to nanofiber surface nanofiber.The preparation method of the present invention includes, it is separated initially with melt blending, disperses suspension modified and cryodesiccated method to prepare thermoplastic polymer nanofiber's fiber aeroge, then with thermoplastic polymer nanofiber's fiber aeroge as carrier, by the method for chemical deposition by nickel phosphorus nanoparticle deposition in the fiber surface of constitutionally stable aerogel material, the aerogel carried nickel-phosphorus alloy catalysis material of nanofiber is prepared.The preparation method process of the present invention is simple, it is easy to accomplish large-scale production, and the catalysis material for preparing has high specific surface area, porosity and preferable catalytic effect.

Description

A nanofiber airgel-supported nickel-phosphorus alloy catalytic material and its preparation method

technical field

The invention belongs to the field of nanometer functional materials, in particular to a nanofiber airgel-loaded nickel-phosphorus alloy catalytic material and a preparation method thereof.

Background technique

At present, industrial sewage has become an important factor restricting social and economic development. Pollutants Nitrobenzene compounds are a class of important chemical raw materials or intermediates and one of the main organic pollutants in the environment, but the reduced form of p-nitrophenol, p-aminophenol, is a common pharmaceutical, chemical It is of great significance to realize the transformation of waste into treasure. Nickel alloy is a cheap and widely used catalyst, which has obvious catalytic effect on pollutants such as p-nitrophenol. Catalysts include non-supported catalysts, and the other is supported catalysts. The carriers used are mainly natural minerals, adsorbents, ceramics and organics. Nanofiber is a kind of ultrafine fiber with large specific surface area and large aspect ratio. After forming a film, it has small pore size and large porosity. Especially after it is prepared into aerogel, the overall specific surface area and The porosity will be significantly improved, and the prepared supported catalyst will show high catalytic activity based on the carrier.

Chinese invention patent application (application publication number: CN105148996A, application publication date: 2015-12-16) discloses a nickel nanofiber membrane for membrane catalysis and a preparation method thereof. In the method, a thermoplastic polymer nanofiber membrane material is prepared by a dispersion coating method, and then a nickel alloy material is deposited on the inner and outer surfaces of the membrane material by an electroless plating method to prepare a nickel nanofiber membrane material for catalytic decomposition of pollutants. The advantage is that the method is simple and efficient, and it is easy to mass produce. The catalytic material inherits the high specific surface area of the nanofiber membrane material, has excellent catalytic performance, is flexible and easy to process, and is easy to separate and reuse during application. The disadvantage is that the prepared thermoplastic polymer nanofiber membrane has limited specific surface area and porosity, and the catalytic performance of the supported nickel-based catalytic material needs to be further improved.

Contents of the invention

In order to solve the above technical problems, the present invention provides a nanofiber airgel-supported nickel-phosphorus alloy catalytic material and a preparation method thereof. The present invention uses thermoplastic polymer nanofiber airgel as a carrier, and deposits nickel nanoparticles on the fiber surface of the airgel material with stable structure by chemical deposition. The carrier has a very high specific surface area and porosity, which improves the catalyst catalytic effect.

In order to achieve the above purpose, the present invention discloses a nanofiber airgel-supported nickel-phosphorus alloy catalytic material, the catalytic material is composed of a nanofiber network skeleton and nickel-phosphorus alloy nanoparticles wrapped on the surface of the nanofiber network skeleton, the nanofiber The fiber network skeleton is composed of nanofibers and a binder attached to the surface of the nanofibers, and the nanofibers are composed of thermoplastic polymers.

Further, the mass percentage of the nanofiber network skeleton and the nickel-phosphorus alloy nanoparticles is: 50-75%: 25-50%, the mass percentage of the nanofibers and the binder is: 50-80%: 20-50% 50%.

Still further, the atomic number percentages of nickel and phosphorus in the nickel-phosphorus alloy nanoparticles are: 50-80%: 20-50%, and the particle diameter of the nickel-phosphorus alloy nanoparticles is 1-50nm.

Further, the binder is one of polyvinyl alcohol, chitosan or polydopamine; the thermoplastic polymer is polyvinyl alcohol-ethylene copolymer, polypropylene, polyamide, polyethylene terephthalic acid One of ethylene glycol ester, polytrimethylene terephthalate, polybutylene terephthalate or polyurethane.

The present invention also provides a method for preparing a nanofiber airgel-loaded nickel-phosphorus alloy catalytic material, comprising the following steps:

1) Prepare composite fiber: uniformly mix thermoplastic polymer and cellulose acetate butyrate, extrude and granulate through twin-screw extruder to prepare thermoplastic polymer/cellulose acetate butyrate composite material, continue to mix thermoplastic polymer/cellulose acetate The cellulose acetate butyrate composite material is drawn and spun by a melt spinning machine to obtain composite fibers;

2) Preparation of nanofiber suspension: put the composite fiber prepared in step 1) into acetone to reflux, extract cellulose acetate butyrate and dry at room temperature to prepare thermoplastic polymer nanofibers, and then the thermoplastic polymer Nanofibers are dispersed in a mixed solution of organic solvent and water at a concentration of 1-10g/L to prepare a uniformly dispersed nanofiber suspension;

3) Preparation of adhesive solution: adhesive solution is one of polyvinyl alcohol solution, chitosan solution or dopamine solution, and the polyvinyl alcohol solution is prepared by dissolving polyvinyl alcohol in water; the shell The polysaccharide solution is prepared by dispersing chitosan powder in water; the dopamine solution is prepared by dispersing dopamine hydrochloride powder in a buffer solution of trishydroxymethylaminomethane hydrochloride;

4) Preparation of nanofiber airgel: mix the binder solution prepared in step 3) with the nanofiber suspension prepared in step 2) to prepare a mixed suspension of nanofibers, and mix the suspension of nanofibers placed in a container template, and then placed in a freeze dryer to freeze-dry to prepare nanofiber airgel;

5) Configure nickel nanofiber membrane sensitization solution, activation solution and nickel bath;

6) Preparation of nanofiber airgel-supported nickel-phosphorus alloy catalytic material: immerse the nanofiber airgel prepared in step 4) into the nickel nanofiber membrane sensitization solution prepared in step 5) to obtain sensitized Nanofiber airgel, continue to immerse the sensitized nanofiber airgel in the activation solution prepared in step 5), vibrate and absorb to obtain activated nanofiber airgel, and immerse the activated nanofiber airgel in a nickel bath Shake reaction in medium, rinse with deionized water and ethanol, and then dry to prepare nanofiber airgel-loaded nickel-phosphorus alloy catalytic material.

Further, in the step 5),

Configure nickel nanofiber membrane sensitization solution: take 10g of stannous chloride, 30ml of hydrochloric acid solution with a mass concentration of 38%, and add it to 1L of deionized water;

Configure the activation solution: take 0.25g of palladium chloride, 20ml of hydrochloric acid solution with a mass concentration of 38%, and add it to 1L of deionized water;

Configure nickel bath: the molar concentration of divalent nickel ions in the nickel bath is 0.07～0.12mol/L, the mass concentration of sodium hypophosphite is 16～40g/L, and the mass concentration of sodium acetate is 15～20g/L. The mass concentration of Laton X-100 is 5-10mg/L or the mass concentration of Tween 80 is 5-10mg/L, the mass concentration of sodium citrate is 8-10g/L, and the mass concentration of lactic acid is 10-12g/L L, the pH of the nickel bath is pH=4.5-5.0.

Further, in the step 6), the nanofiber aerogel prepared in the step 4) is immersed in the nanofiber membrane sensitization solution prepared in the step 5), ensuring that the bath ratio is 30:1, and at 15 Take it out after oscillating and adsorbing for 1-5 minutes at ~25°C to obtain the sensitized nanofiber airgel, and continue to immerse the sensitized nanofiber aerogel in the activation solution prepared in step 5) to ensure that the bath ratio is 30: 1. Then wash with deionized water, shake and absorb at 15-25°C for 1-5 minutes, then take it out to obtain activated nanofiber aerogel; immerse the activated nanofiber aerogel in a nickel bath for reaction, and ensure that the bath ratio is 10:1, then oscillating at constant temperature for 10-20 minutes, then take it out, rinse it with deionized water and ethanol three times, and finally dry it at 50°C to prepare the nanofiber airgel-supported nickel-phosphorus alloy catalytic material.

Further, in the step 4), the binder solution prepared in the step 3) is mixed with the nanofiber suspension prepared in the step 2) according to a volume ratio of 2 to 5:10, and the The mixed suspension of nanofibers was prepared under the action of an emulsifier. The mixed suspension of nanofibers was placed in a container template, and then placed in a freeze dryer to freeze-dry. The freezing temperature was -80°C to -20°C, and the freezing time was 4 ～6h, and the drying time is 24～72h, and the nanofiber airgel is prepared.

Further, in the step 3),

The preparation process of the polyvinyl alcohol solution is as follows: dissolving the polyvinyl alcohol in water and fully stirring to obtain a polyvinyl alcohol adhesive solution with a mass concentration of 1.0-2.0%;

The preparation process of the chitosan solution is as follows: the mass percentage is 50%: 50% chitosan powder is mixed with acetic acid, then added to the water whose quality is 25 to 50 times that of the chitosan powder, dispersed evenly, A chitosan solution with a mass concentration of 1.0 to 2.0% is prepared;

The preparation process of the dopamine solution is as follows: disperse the dopamine hydrochloride powder in the buffer solution of tris hydrochloride with pH=8.5, stir well, and prepare the dopamine solution with a mass concentration of 0.2-2.0%.

Further, in the step 1), the mass percentage of the thermoplastic polymer and cellulose acetate butyrate is 5-40%: 60-95%; in the step 2), the diameter of the thermoplastic polymer nanofiber is 50 ~350 nm, the organic solvent is one of tert-butanol, tert-amyl alcohol or sec-amyl alcohol, and the volume ratio of the organic solvent to water is 1-3:1.

Beneficial effects of the present invention:

1. The thermoplastic polymer nanofiber airgel in the present invention adopts the method of melt-blending phase separation, dispersion suspension modification and freeze-drying, the process is simple, energy-saving and environmentally friendly, and is easy to realize large-scale production; on the other hand, the obtained gas The thermoplastic nanofibers in the gel material are resistant to solvents and have a stable structure after the adhesive is cross-linked, so that the airgel material obtained by this method has excellent physical and chemical structure stability compared with other methods, and is more widely used.

2. The supported nickel-phosphorus catalyst of the present invention takes thermoplastic polymer nanofiber airgel as a carrier, and nickel-phosphorus nanoparticles are deposited on the fiber surface of the structurally stable airgel material by chemical deposition, and the carrier has a very high The specific surface area and porosity make the catalyst have a high catalytic effect, which not only solves the separation problem of the catalyst, reactants and products caused by the non-supported nickel-phosphorus catalyst produced by the traditional method, but also avoids the separation of the catalyst and the reactant and product in the sewage treatment. The secondary pollution that comes, and has greatly improved the problem that the catalytic efficiency of supported nickel-phosphorous catalyst (membrane catalyst) made by existing method is difficult to improve.

3. The nickel nanofibrous film of the present invention adopts the method of whole liquid phase synthesis, is easy to control the growth of nickel layer, changes the thickness of nano-nickel coating, the size of coating particle and the compactness of coating; The concentration optimizes the phosphorus content in the coating, optimizes the electronic structure of the nickel alloy, and further improves the catalytic performance of the nickel nanofiber membrane.

detailed description

In order to better explain the present invention, the main content of the present invention is further clarified below in conjunction with specific examples, but the content of the present invention is not limited to the following examples.

Example 1

This implementation discloses a method for preparing a nanofiber airgel-supported nickel-phosphorus alloy catalytic material, which includes the following steps:

1) Preparation of composite fibers: 1 kg of polyvinyl alcohol-ethylene copolymer (PVA-co-PE) and 4 kg of cellulose acetate butyrate (CAB) are uniformly mixed, and processed in a twin-screw extruder with a processing temperature of 170 ° C Extrude and granulate to obtain PVA-co-PE/CAB composite material;

2) Preparation of nanofiber suspension: draw and spin the PVA-co-PE/CAB composite material through a melt spinning machine to obtain composite fibers; reflux the composite fibers in acetone at 60°C for 72 hours to extract acetate butyrate fibers The composite fibers after extracting cellulose acetate butyrate were dried at room temperature to prepare PVA-co-PE nanofibers with an average diameter of 200nm; 0.5g of PVA-co-PE nanofibers were dispersed in 20ml of water and 30ml of tertiary In the mixed solution of butanol, fully stir and disperse to obtain nanofiber suspension;

3) Preparation of adhesive solution: take 0.1 g of polyvinyl alcohol, stir and fully dissolve it in 10 ml of water at 80° C., and prepare a polyvinyl alcohol adhesive solution with a mass concentration of 1%;

4) Preparation of nanofiber airgel: add the polyvinyl alcohol binder solution prepared in step 3) to the nanofiber suspension prepared in step 2), mix evenly, place in a container template, and place in- Freeze at 30°C for 6 hours and dry for 36 hours to obtain PVA-co-PE nanofiber airgel;

5) Prepare sensitizing solution: take 10 g of stannous chloride (SnCl ₂ ), 30 ml of hydrochloric acid solution with a mass concentration of 38%, and add it to 1 L of deionized water;

Configure the activation solution: take 0.25g of palladium chloride (PdCl ₂ ), 20ml of hydrochloric acid solution with a mass concentration of 38%, and add it to 1L of deionized water;

Configure nickel bath: the concentration of divalent nickel ion (Ni ²⁺ ) in the nickel bath is 0.07mol/L, the concentration of sodium hypophosphite (NaH ₂ PO ₂ ) is 16g/L, the concentration of sodium acetate (CH ₃ COONa) The concentration is 18g/L, the concentration of Triton X-100 is 10mg/L, the concentration of sodium citrate is 8g/L, the concentration of lactic acid is 10g/L, and the pH of the nickel bath is pH=4.6;

6) Preparation of nanofiber airgel-loaded nickel-phosphorus alloy catalytic material: immerse the PVA-co-PE nanofiber airgel prepared in step 4) into the sensitizing solution configured in step 5), ensuring that the bath ratio is 30:1, oscillating and adsorbing at 20°C for 3 minutes and then taking it out to obtain sensitized nanofiber aerogel, then immerse the sensitized nanofiber aerogel in the activation solution prepared in step 5) to ensure the bath ratio 30:1, and then washed with deionized water, shaken and adsorbed at 20°C for 2 minutes and then taken out to obtain activated nanofiber airgel; finally, the activated nanofiber airgel was immersed in the step 5 at 50°C ) in a nickel bath to ensure that the bath ratio is 10:1, then take it out after oscillating for 15 minutes at a constant temperature, rinse it with deionized water and ethanol for 3 times, and finally dry it at 50°C to obtain PVA-co- PE nanofiber airgel supports Ni ₂ P catalytic material.

The performance parameters of the PVA-co-PE nanofiber airgel loaded Ni ₂ P catalytic material in this example are shown in Table 1.

Example 2

This implementation discloses a method for preparing a nanofiber airgel-supported nickel-phosphorus alloy catalytic material, which includes the following steps:

1) Preparation of composite fiber: Take 2kg of polyamide (PA) and 3kg of cellulose acetate butyrate (CAB) to uniformly mix, extrude and pelletize in a twin-screw extruder with a processing temperature of 170°C to obtain PA/CAB composite materials;

2) Preparation of nanofiber suspension: the PA/CAB composite material is drawn and spun by a melt spinning machine to obtain a composite fiber; the composite fiber is refluxed in acetone at 60° C. for 72 hours to extract cellulose acetate butyrate, and After extracting cellulose acetate butyrate, the composite fiber was dried at room temperature to prepare PA nanofibers with an average diameter of 200nm; take 0.5g of PA nanofibers and disperse them in a mixed solution of 25ml of water and 25ml of tert-amyl alcohol, stir and disperse Obtain nanofiber suspension;

3) Preparation of binder solution: take 0.4g chitosan powder, stir and fully dissolve 0.4g acetic acid in 20ml of water at room temperature, and prepare a chitosan binder solution with a mass concentration of 2%;

4) Preparation of nanofiber airgel: adding the chitosan adhesive solution prepared in step 3) to the nanofiber suspension prepared in step 2), mixing evenly, placing it in a container template, and placing it in the - Freeze at 50°C for 4 hours and dry for 24 hours to obtain PA nanofiber airgel;

5) Prepare sensitizing solution: take 10 g of stannous chloride (SnCl ₂ ), 30 ml of hydrochloric acid solution with a mass concentration of 38%, and add it to 1 L of deionized water;

Configure the activation solution: take 0.25g of palladium chloride (PdCl ₂ ), 20ml of hydrochloric acid solution with a mass concentration of 38%, and add it to 1L of deionized water;

Configure a nickel bath: the concentration of divalent nickel ions (Ni ²⁺ ) in the nickel bath is 0.12mol/L, the concentration of sodium hypophosphite (NaH ₂ PO ₂ ) is 40g/L, and the concentration of sodium acetate (CH ₃ COONa) The concentration is 20g/L, the concentration of Tween 80 is 8mg/L, the concentration of sodium citrate is 8g/L, the concentration of lactic acid is 12g/L, and the pH of the nickel bath is pH=4.5;

6) Preparation of nanofiber airgel-loaded nickel-phosphorus alloy catalytic material: immerse the PA nanofiber airgel prepared in step 4) into the sensitizing solution configured in step 5), ensuring that the bath ratio is 30:1, Take it out after oscillating and adsorbing for 3 minutes at 20°C to obtain a sensitized nanofiber airgel, and then immerse the sensitized nanofiber aerogel in the activation solution prepared in step 5) to ensure a bath ratio of 30:1 , and then washed with deionized water, taken out after oscillating and adsorbing for 2 minutes at 20°C to obtain activated nanofiber aerogel; finally immersing the activated nanofiber aerogel into the nickel bath of step 5) at 50°C Medium reaction, to ensure that the bath ratio is 10:1, then shake the reaction at constant temperature for 15 minutes, take it out, rinse with deionized water and ethanol for 3 times, and finally dry at 50 ° C to obtain PA nanofiber airgel loaded Ni _3P catalytic material.

The performance parameters of the PA nanofiber airgel-loaded Ni ₃ P catalytic material in this example are shown in Table 1.

Example 3

This implementation discloses a method for preparing a nanofiber airgel-supported nickel-phosphorus alloy catalytic material, which includes the following steps:

1) Preparation of composite fibers: Take 1kg of polyethylene terephthalate (PET) and 5kg of cellulose acetate butyrate (CAB) to mix evenly, and carry out the process in a twin-screw extruder with a processing temperature of 170°C. Extrude and granulate to obtain PA/CAB composite material;

2) Preparation of nanofiber suspension: the PA/CAB composite material is drawn and spun by a melt spinning machine to obtain a composite fiber; the composite fiber is refluxed in acetone at 60° C. for 72 hours to extract cellulose acetate butyrate, and The composite fiber after extracting cellulose acetate butyrate was dried at room temperature to prepare PET nanofibers with an average diameter of 100nm; take 0.5g of PET nanofibers and disperse them in a mixed solution of 15ml of water and 35ml of sec-amyl alcohol, fully stir and disperse Obtain nanofiber suspension;

3) Preparation of adhesive solution: take 0.1 g of dopamine hydrochloride powder and stir it at room temperature and dissolve it fully in 10 ml of tris hydrochloride to prepare a dopamine adhesive solution with a mass concentration of 1%.

4) Preparation of nanofiber airgel: Add the dopamine binder solution prepared in step 3) to the nanofiber suspension prepared in step 2), mix evenly, place in a container template, and store at -20°C Freeze for 6 hours and dry for 72 hours to obtain PET nanofiber airgel;

5) Prepare sensitizing solution: take 10 g of stannous chloride (SnCl ₂ ), 30 ml of hydrochloric acid solution with a mass concentration of 38%, and add it to 1 L of deionized water;

Configure the activation solution: take 0.25g of palladium chloride (PdCl ₂ ), 20ml of hydrochloric acid solution with a mass concentration of 38%, and add it to 1L of deionized water;

Configure nickel bath: the concentration of divalent nickel ion (Ni ²⁺ ) in the nickel bath is 0.10mol/L, the concentration of sodium hypophosphite (NaH ₂ PO ₂ ) is 30g/L, the concentration of sodium acetate (CH ₃ COONa) The concentration is 18g/L, the concentration of Tween 80 is 7mg/L, the concentration of sodium citrate is 8g/L, the concentration of lactic acid is 11g/L, and the pH of the nickel bath is pH=4.7;

6) Preparation of nanofiber airgel-loaded nickel-phosphorus alloy catalytic material: immerse the PA nanofiber airgel prepared in step 4) into the sensitizing solution configured in step 5), ensuring that the bath ratio is 30:1, Take it out after oscillating and adsorbing for 3 minutes at 20°C to obtain a sensitized nanofiber airgel, and then immerse the sensitized nanofiber aerogel in the activation solution prepared in step 5) to ensure a bath ratio of 30:1 , and then washed with deionized water, taken out after oscillating and adsorbing for 2 minutes at 20°C to obtain activated nanofiber aerogel; finally immersing the activated nanofiber aerogel into the nickel bath of step 5) at 50°C Medium reaction, to ensure that the bath ratio is 10:1, then shake the reaction at constant temperature for 15 minutes, take it out, rinse with deionized water and ethanol for 3 times, and finally dry at 50 ° C to obtain PA nanofiber airgel loaded Ni ₂ P ₅ catalytic material.

Example 4

This implementation discloses a method for preparing a nanofiber airgel-supported nickel-phosphorus alloy catalytic material, which includes the following steps:

1) Preparation of composite fiber: Take 1kg of polyvinyl alcohol-ethylene copolymer (PVA-co-PE) and 4.5kg of cellulose acetate butyrate (CAB) to mix evenly, and extrude it at a processing temperature of 170°C with a twin-screw Extrude and granulate in the machine to obtain PVA-co-PE/CAB composite material;

2) Preparation of nanofiber suspension: the PA/CAB composite material is drawn and spun by a melt spinning machine to obtain a composite fiber; the composite fiber is refluxed in acetone at 60° C. for 72 hours to extract cellulose acetate butyrate, and The composite fibers after extracting cellulose acetate butyrate were dried at room temperature to prepare PVA-co-PE nanofibers with an average diameter of 100nm; take 0.5g of PVA-co-PE nanofibers and disperse them in 20ml of water and 30ml of tert-butyl In the mixed solution of alcohol, fully stir and disperse to obtain nanofiber suspension;

3) Preparation of adhesive solution: take 0.2 g of polyvinyl alcohol, stir and fully dissolve it in 10 ml of water at 80° C., and prepare a polyvinyl alcohol adhesive solution with a mass concentration of 2%;

4) Preparation of nanofiber airgel: add the polyvinyl alcohol binder solution prepared in step 3) to the nanofiber suspension prepared in step 2), mix evenly, place in a container template, and place in- Freeze at 80°C for 7 hours and dry for 36 hours to obtain PVA-co-PE nanofiber airgel;

5) Prepare sensitizing solution: take 10 g of stannous chloride (SnCl ₂ ), 30 ml of hydrochloric acid solution with a mass concentration of 38%, and add it to 1 L of deionized water;

Configure the activation solution: take 0.25g of palladium chloride (PdCl ₂ ), 20ml of hydrochloric acid solution with a mass concentration of 38%, and add it to 1L of deionized water;

Configure nickel bath: the concentration of divalent nickel ion (Ni ²⁺ ) in the nickel bath is 0.12mol/L, the concentration of sodium hypophosphite (NaH ₂ PO ₂ ) is 30g/L, the concentration of sodium acetate (CH ₃ COONa) Concentration is 19g/L, and the concentration of Triton X is 100.8mg/L, and the concentration of sodium citrate is 10g/L, and the concentration of lactic acid is 11g/L, and the pH value of described nickel bath is pH=5.0;

6) Preparation of nanofiber airgel-loaded nickel-phosphorus alloy catalytic material: immerse the PA nanofiber airgel prepared in step 4) into the sensitizing solution configured in step 5), ensuring that the bath ratio is 30:1, Take it out after oscillating and adsorbing for 3 minutes at 20°C to obtain a sensitized nanofiber airgel, and then immerse the sensitized nanofiber aerogel in the activation solution prepared in step 5) to ensure a bath ratio of 30:1 , and then washed with deionized water, taken out after oscillating and adsorbing for 2 minutes at 20°C to obtain activated nanofiber aerogel; finally immersing the activated nanofiber aerogel into the nickel bath of step 5) at 50°C Medium reaction, to ensure that the bath ratio is 10:1, then shake the reaction at a constant temperature for 15 minutes, take it out, rinse with deionized water and ethanol for 3 times, and finally dry it at 50 ° C to obtain PVA-co-PE nanofiber gas Gel supported Ni ₃ P catalytic material.

The performance parameters of the PVA-co-PE nanofiber airgel loaded Ni ₃ P catalytic material in this example are shown in Table 1.

In order to illustrate that the nanofiber airgel-loaded nickel-phosphorus alloy catalytic material prepared by the present invention has better performance, further explanations will be given below in conjunction with relevant comparative examples.

In combination with Table 1, Comparative Example 1 and Comparative Example 2 are respectively Example 1 and Example 4 in the Chinese invention patent application: CN105148996A. The catalytic performance test process of catalytic material in the embodiment 1-4 of the present invention and comparative example is as follows: the catalytic material of 3mg is placed in the quartz cuvette that contains 3mL, the p-nitrophenol (PNP) aqueous solution of 0.5mM adsorption 20min , and then inject 0.3ml, 1M sodium borohydride aqueous solution into this cuvette, test the variation trend of the absorption intensity of the mixed solution to ultraviolet light over time, and calculate the catalytic material p-nitrophenol by comparing the light intensity at different times. The catalytic rate of the reduction reaction. The experimental results of the embodiments of the present invention and comparative examples are shown in Table 1.

The porosity and catalytic performance of table 1 embodiment and comparative example

It can be seen from Table 1 that the nanofiber airgel-loaded nickel-phosphorus alloy catalytic material prepared by the present invention has a higher porosity due to the nanofiber network skeleton structure, while the supported nickel catalyst uses the nanofiber network skeleton as a carrier and is deposited on the structure. The stable fiber surface of the airgel material makes the catalyst have a high catalytic effect.

Claims (10)

1. A nanofiber airgel-loaded nickel-phosphorus alloy catalytic material is characterized in that: the catalytic material is made up of nanofiber network framework and nickel-phosphorus alloy nanoparticles attached to the surface of the nanofiber network framework, and the nanofiber network framework It consists of nanofibers and a binder attached to the surface of the nanofibers, the nanofibers are composed of thermoplastic polymers. 2. The nanofiber airgel-supported nickel-phosphorus alloy catalytic material according to claim 1, characterized in that: the mass percentage of the nanofiber network skeleton and nickel-phosphorus alloy nanoparticles is: 50-75%: 25-50% %, the mass percentages of the nanofibers and the binder are: 50-80%: 20-50%. 3. The nanofiber airgel-supported nickel-phosphorus alloy catalytic material according to claim 1 or 2, characterized in that: the atomic number percentage of nickel and phosphorus in the nickel-phosphorus alloy nanoparticles is: 50-80%: 20-50%, and the particle size of nickel-phosphorus alloy nanoparticles is 1-50nm. 4. nanofiber airgel-loaded nickel-phosphorus alloy catalytic material according to claim 1 or 2, is characterized in that: the binder is one of polyvinyl alcohol, chitosan or polydopamine; The thermoplastic polymer is one of polyvinyl alcohol-ethylene copolymer, polypropylene, polyamide, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate or polyurethane kind. 5. A preparation method of nanofiber airgel loaded nickel-phosphorus alloy catalytic material, characterized in that: comprising the following steps: 1) Prepare composite fiber: uniformly mix thermoplastic polymer and cellulose acetate butyrate, extrude and granulate through twin-screw extruder to prepare thermoplastic polymer/cellulose acetate butyrate composite material, continue to mix thermoplastic polymer/cellulose acetate The cellulose acetate butyrate composite material is drawn and spun by a melt spinning machine to obtain composite fibers; 2) Preparation of nanofiber suspension: put the composite fiber prepared in step 1) into acetone to reflux, extract cellulose acetate butyrate and dry at room temperature to prepare thermoplastic polymer nanofibers, and then the thermoplastic polymer Nanofibers are dispersed in a mixed solution of organic solvent and water at a concentration of 1-10g/L to prepare a uniformly dispersed nanofiber suspension; 3) Preparation of adhesive solution: adhesive solution is one of polyvinyl alcohol solution, chitosan solution or dopamine solution, and the polyvinyl alcohol solution is prepared by dissolving polyvinyl alcohol in water; the shell The polysaccharide solution is prepared by dispersing chitosan powder in water; the dopamine solution is prepared by dispersing dopamine hydrochloride powder in a buffer solution of trishydroxymethylaminomethane hydrochloride; 4) Preparation of nanofiber airgel: mix the binder solution prepared in step 3) with the nanofiber suspension prepared in step 2) to prepare a mixed suspension of nanofibers, and mix the suspension of nanofibers placed in a container template, and then placed in a freeze dryer to freeze-dry to prepare nanofiber airgel; 5) Configure nickel nanofiber membrane sensitization solution, activation solution and nickel bath; 6) Preparation of nanofiber airgel-supported nickel-phosphorus alloy catalytic material: immerse the nanofiber airgel prepared in step 4) into the nickel nanofiber membrane sensitization solution prepared in step 5) to obtain sensitized Nanofiber airgel, continue to immerse the sensitized nanofiber airgel in the activation solution prepared in step 5), vibrate and absorb to obtain activated nanofiber airgel, and immerse the activated nanofiber airgel in a nickel bath Shake reaction in medium, rinse with deionized water and ethanol, and then dry to prepare nanofiber airgel-loaded nickel-phosphorus alloy catalytic material. 6. the preparation method of nanofiber airgel-loaded nickel-phosphorus alloy catalytic material according to claim 5, is characterized in that: in described step 5), Configure nickel nanofiber membrane sensitization solution: take 10g of stannous chloride, 30ml of hydrochloric acid solution with a mass concentration of 38%, and add it to 1L of deionized water; Configure the activation solution: take 0.25g of palladium chloride, 20ml of hydrochloric acid solution with a mass concentration of 38%, and add it to 1L of deionized water; Configure nickel bath: the molar concentration of divalent nickel ions in the nickel bath is 0.07～0.12mol/L, the mass concentration of sodium hypophosphite is 16～40g/L, and the mass concentration of sodium acetate is 15～20g/L. The mass concentration of Laton X-100 is 5-10mg/L or the mass concentration of Tween 80 is 5-10mg/L, the mass concentration of sodium citrate is 8-10g/L, and the mass concentration of lactic acid is 10-12g/L L, the pH of the nickel bath is pH=4.5-5.0. 7. The preparation method of the nanofiber airgel-loaded nickel-phosphorus alloy catalytic material according to claim 5 or 6, characterized in that: in the step 6), the nanofiber airgel prepared in the step 4) is Immerse in the nanofiber membrane sensitization solution prepared in step 5), ensure that the bath ratio is 30:1, take it out after oscillating and adsorbing for 1 to 5 minutes at 15 to 25° C. to obtain a sensitized nanofiber airgel, and continue to The sensitized nanofiber airgel is immersed in the activation solution prepared in step 5) to ensure that the bath ratio is 30:1, then washed with deionized water, and taken out after oscillating and adsorbing for 1 to 5 minutes at 15 to 25°C to obtain Activated nanofiber aerogel; immerse the activated nanofiber aerogel in a nickel bath to ensure that the bath ratio is 10:1, then shake and react at a constant temperature for 10 to 20 minutes, take it out, and rinse with deionized water and ethanol respectively 3 times, and finally dried at 50°C to prepare the nanofiber airgel-supported nickel-phosphorus alloy catalytic material. 8. the preparation method of nanofiber airgel-loaded nickel-phosphorus alloy catalytic material according to claim 5, is characterized in that: in described step 4), the binding agent solution prepared in described step 3) is mixed with described Step 2) The prepared nanofiber suspension is mixed uniformly according to the volume ratio of 2 to 5:10, and the nanofiber mixed suspension is prepared under the action of a shear emulsifier, and the nanofiber mixed suspension is placed in the container template, and then Place in a freeze dryer to freeze-dry, the freezing temperature is -80°C to -20°C, the freezing time is 4-6 hours, and the drying time is 24-72 hours, and the nanofiber airgel is prepared. 9. The preparation method of the nanofiber airgel-loaded nickel-phosphorus alloy catalytic material according to claim 5, characterized in that: in the step 3), The preparation process of the polyvinyl alcohol solution is as follows: dissolving the polyvinyl alcohol in water and fully stirring to obtain a polyvinyl alcohol adhesive solution with a mass concentration of 1.0-2.0%; The preparation process of the chitosan solution is as follows: the mass percentage is 50%: 50% chitosan powder is mixed with acetic acid, then added to the water whose quality is 25 to 50 times that of the chitosan powder, dispersed evenly, A chitosan solution with a mass concentration of 1.0 to 2.0% is prepared; The preparation process of the dopamine solution is as follows: disperse the dopamine hydrochloride powder in the buffer solution of tris hydrochloride with pH=8.5, stir well, and prepare the dopamine solution with a mass concentration of 0.2-2.0%. 10. the preparation method of nanofiber airgel-loaded nickel-phosphorus alloy catalytic material according to claim 5, is characterized in that: in described step 1), the mass percentage of thermoplastic polymer and cellulose acetate butyrate is 5～ 40%: 60-95%; in the step 2), the diameter of the thermoplastic polymer nanofiber is 50-350nm, and the organic solvent is one of tert-butanol, tert-amyl alcohol or sec-amyl alcohol, and organic The volume ratio of solvent and water is 1-3:1.