A nickel-based catalytic material

Abstract

The present application relates to the technical field of catalytic materials, in particular to a novel nickel-based catalytic material, which is prepared from a precursor synthesized by nickel nitrate, hexamino triphenyl four carboxylic acid, distilled water and N, N-dimethylformamide. To solve the problems of high cost, poor stability, catalyst poisoning and difficult recovery in the existing catalyst in the catalytic reaction of nitrophenol. The novel nickel-based catalytic material can maintain high catalytic activity and good stability under harsh conditions such as high temperature and high pressure by using low-cost, environmentally friendly and efficient catalytic material. At the same time, the nickel-based catalytic material has strong anti-poisoning ability, which can effectively improve the selectivity and conversion rate of the reaction, and has excellent recovery and regeneration performance, which can reduce production cost, reduce resource consumption and environmental pollution, and meet the demand of large-scale industrial application.

Description

Technical Field

[0001] The present invention relates to the technical field of catalytic materials, and in particular to a nickel-based catalytic material. Background Art

[0002] Nitroaniline is an important organic chemical raw material, widely used in dyes, rubber, plastics, pesticides, pharmaceuticals, and polymer materials. In the dye industry, aniline is used to synthesize indigo and azo dyes, which are widely used in textile and leather dyeing. In the rubber industry, it serves as a vulcanization accelerator, improving rubber properties. In pharmaceutical synthesis, aniline is a precursor for the preparation of drugs such as acetaminophen. Furthermore, aniline is used in the production of polymer materials such as phenolic resins and polyurethanes, and even plays a key role in the production of certain pesticides and fungicides.

[0003] Industrially, the primary method for preparing nitroaniline is through catalytic hydrogenation (catalytic reduction), where p-nitrophenol is reduced to p-nitroaniline in the presence of hydrogen and a catalyst. Currently, precious metals (such as platinum and palladium) are commonly used catalysts, but their high cost and demanding operating conditions limit their widespread application. In recent years, novel catalysts such as nanomaterials and metal-organic frameworks (MOFs) have demonstrated excellent catalytic performance due to their large surface area and unique structure.

[0004] However, catalyst recyclability, resistance to poisoning, and environmental sustainability remain key research priorities. With increasing environmental protection requirements and the advancement of sustainable development, the development of green, efficient catalysts has become a key development direction in this field. Therefore, there is an urgent need for new catalytic materials that are low-cost, environmentally friendly, and highly efficient. Summary of the Invention

[0005] To solve the above problems, the present invention provides a nickel-based catalytic material for reducing the production cost of nitroaniline, reducing resource consumption and environmental pollution, and meeting the needs of large-scale industrial applications.

[0006] In order to achieve the above object, the technical solution of the present invention is as follows: a nickel-based catalytic material is prepared from a precursor synthesized from nickel nitrate, hexamidotriphenyltetracarboxylic acid, distilled water and N,N-dimethylformamide.

[0007] Furthermore, the raw material preparation for precursor synthesis includes:

[0008] Take 0.03 g of experimental grade nickel nitrate, 0.010 g of hexamethylenetriphenyltetracarboxylic acid, 0.5 mL of distilled water, and 2 mL of N,N-dimethylformamide;

[0009] Add the above reagents into a glass vial and stir until all components are completely dissolved or evenly dispersed.

[0010] Furthermore, the reaction conditions for precursor synthesis include:

[0011] The glass vial was sealed and placed in an oven at 358 K for 72 h;

[0012] The glass vial was then cooled to room temperature, the mother liquor was precipitated, and green crystals were obtained.

[0013] Further, the crystal purification of the precursor synthesis includes:

[0014] The green crystals were washed several times with N,N-dimethylformamide solvent to remove excess reactants and solvent;

[0015] The washed green crystals were placed in a vacuum drying oven and dried under vacuum to obtain a pure precursor.

[0016] Furthermore, the preparation steps of the nickel-based catalytic material include:

[0017] 0.2 g of the precursor was taken and ground to make the particles uniform;

[0018] Place the ground precursor into a vacuum tube furnace, introduce high-purity argon gas, exhaust the air in the tube, and keep the argon gas to protect the environment;

[0019] The vacuum tube furnace is heated to 800°C by a programmed temperature rising method and maintained for 1 hour to convert the precursor into a nickel-based composite material; the vacuum tube furnace is then cooled to below 50°C by a programmed temperature falling method;

[0020] The nickel-based composite material is cleaned with dilute hydrochloric acid to remove impurities and then rinsed with distilled water until it becomes neutral;

[0021] The nickel-based composite material washed to neutrality is then placed in a vacuum drying oven and dried under vacuum conditions for 3 hours to obtain a nickel-based catalytic material.

[0022] Furthermore, the duration of introducing high-purity argon gas is greater than or equal to 30 minutes.

[0023] Furthermore, the heating and cooling rates of the vacuum tube furnace were both 5°C·min -1 .

[0024] Beneficial effects of the present invention:

[0025] 1. Improved catalytic activity and selectivity: The use of this new catalyst significantly enhances the catalytic activity of the reaction. With a higher specific surface area and more active sites, the catalyst can effectively enhance the speed and selectivity of the catalytic reaction, especially in the fields of environmental protection and energy conversion. It can more accurately control the reaction process and reduce the formation of by-products.

[0026] 2. Enhanced stability and resistance to poisoning: The catalyst maintains high stability under harsh conditions such as high temperature and high pressure. Compared with traditional catalysts, it has stronger resistance to poisoning and can effectively inhibit the poisoning effect of harmful substances on the catalyst during the reaction. This allows the catalyst to maintain high activity and selectivity during long-term use, thereby extending the service life of the catalyst and reducing the need for replacement and regeneration.

[0027] 3. Efficient recovery and regeneration performance: Compared with traditional noble metal catalysts, the catalyst can remove impurities in the reaction through a simple cleaning process and restore its catalytic activity, making it suitable for multiple uses and reducing catalyst waste and resource consumption, thereby significantly reducing production costs.

[0028] 4. Environmentally friendly and low cost: The catalyst replaces traditional noble metal catalysts and has lower production costs. Since nickel is a relatively abundant resource, its raw material cost is lower than that of platinum and palladium noble metal catalysts. In addition, the preparation process of the catalyst has less environmental impact, which helps to achieve green production and meets the needs of modern sustainable development.

[0029] 5. Lower price than noble metal catalysts: The catalyst has a clear advantage in cost. Compared with traditional noble metal catalysts (such as platinum and palladium), the production cost of the catalyst is lower, mainly because nickel resources are relatively abundant and the price is relatively low. This makes the catalyst more economical in large-scale industrial applications, reducing overall production costs and making it more competitive in cost-sensitive applications.

[0030] Additional aspects and advantages of the present application will be partially given in the following description, partially will become apparent from the following description, or will be learned by practice of the present application. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 X-ray powder diffraction pattern of the nickel-based catalytic material embodiment of the present application;

[0032] Figure 2 Raman spectrum of the nickel-based catalytic material of the nickel-based catalytic material embodiment of the present application;

[0033] Figure 3 PXRD spectrum of the nickel-based catalytic material of the nickel-based catalytic material embodiment of the present application;

[0034] Figure 4 Catalytic effect diagram of the p-nitrophenol reduction reaction of the nickel-based catalytic material embodiment of the present application. DETAILED DESCRIPTION

[0035] The technical solutions of the present application will be described clearly and completely in connection with the drawings. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0036] The specific embodiments are further described in detail as follows:

[0037] A nickel-based catalytic material is prepared from a precursor synthesized by nickel nitrate, hexamino triphenyl four carboxylic acid, distilled water and N, N-dimethylformamide. The nickel-based catalytic material has high catalytic activity, excellent stability, good anti-poisoning ability and strong recyclability, and can exhibit good performance in the catalytic reduction reaction of nitrophenol.

[0038] The precursor synthesis steps of the nickel-based catalytic material in the embodiment are as follows:

[0039] Raw material preparation:

[0040] 1. Take 0.03 g of experimental grade nickel nitrate, 0.010 g of hexamino triphenyl four carboxylic acid (0.016 mmol), 0.5 mL of distilled water and 2 mL of DMF (N, N-dimethylformamide).

[0041] 2. Add the above reagents to a 5 mL glass vial and stir with a magnetic stirrer for 30 minutes to ensure complete dissolution or uniform dispersion of the components.

[0042] Reaction conditions:

[0043] 1. Place the sealed glass vial in an oven at 358 K and react for 72 hours. At this time, the precursor will form green crystals through self-assembly reaction.

[0044] 2. After the reaction is completed, cool the vial to room temperature, and the mother liquor is separated to obtain green crystals.

[0045] Crystal purification:

[0046] 1. Wash the green crystals several times with DMF solvent to remove excess reactants and solvents.

[0047] 2. Place the washed green crystals in a vacuum drying oven and dry them in a vacuum environment to obtain pure precursors.

[0048] The synthesis steps of the nickel-based catalytic material in the embodiment are as follows:

[0049] 1. Take 0.2 g of the precursor and put it into an agate mortar for grinding to make the particles more uniform.

[0050] 2. Put the milled precursor into a vacuum tube furnace.

[0051] 3. Introduce high purity argon gas (preferably for 30 minutes) to expel the air inside the tube and maintain an argon protective environment.

[0052] 4. Under argon atmosphere, heat the temperature to 800℃ at a rate of 5℃·min -1 using programmed temperature method. Keep the temperature for 1 hour to convert the precursor into nickel-based composite material with high catalytic performance.

[0053] 5. Then, reduce the furnace temperature to below 50℃ at a rate of 5℃·min -1 to end the calcination process.

[0054] 6. After taking out the nickel-based composite material, wash it with dilute hydrochloric acid to remove possible impurities in the nickel-based composite material, and rinse it with distilled water until it is neutral.

[0055] 7. Finally, put the nickel-based composite material into a vacuum drying oven and dry it in a vacuum environment for 3 hours to obtain the target catalyst, i.e. nickel-based catalytic material.

[0056] The new nickel-based catalytic material of the present embodiment is further illustrated in combination with the accompanying drawings:

[0057] Figure 1 The figure shows the powder X-ray diffraction pattern, the PXRD spectrum of the prepared precursor is highly consistent with the simulated structure spectrum, the peak position is accurately matched, indicating that the synthesized crystal has high purity and no impurities are detected.

[0058] Figure 2 The figure shows the Raman spectrum of the nickel-based catalytic material, the composite material has characteristic peaks at 1361 cm -1 (D band) and 1696 cm -1 (G band). The D band is related to the defect and edge hybridization vibration of carbon material, and the G band is related to the in-plane stretching vibration of sp² carbon atom. By analyzing the intensity ratio of D band and G band (ID / IG), the defect density information can be obtained. Higher ID / IG ratio indicates higher defect density, which is speculated to have better graphitization degree, which helps to improve the catalytic performance.

[0059] Figure 3 The figure shows the PXRD spectrum of the nickel-based catalytic material, the PXRD spectrum of the material appears two obvious diffraction peaks at 2θ=44.2° and 2θ=51.2° respectively, indicating that there are metal nanoparticles in the catalyst. The diffraction peak has a narrow peak width and a high intensity, which further supports the high crystallinity and large size distribution of the metal nanoparticles.

[0060] Figure 4The figure shows the catalytic effect of the p-nitrophenol reduction reaction. This example evaluates the catalytic performance of the catalyst using sodium borohydride to reduce p-nitrophenol (4-NP). The metal nanoparticles act as electron transfer sites, providing active sites for the reduction process. In the presence of excess sodium borohydride, the reaction follows first-order kinetics, and the reaction progress is monitored by UV-Vis spectroscopy, observing the changes in the intensity of the characteristic peak at 400 nm. Initially, the solution is yellow. As the reduction proceeds, the color gradually fades, eventually becoming colorless. Upon completion of the reaction, control experiments demonstrate that the catalyst in this example catalyzes the reaction quickly and efficiently, while the catalyst alone or the activated carbon alone has no significant catalytic effect.

[0061] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A nickel-based catalytic material for use in catalyzing the reduction of p-nitrophenol with sodium borohydride, characterized in that: The nickel-based catalytic material is prepared from a precursor synthesized from nickel nitrate, hexamidotriphenyltetracarboxylic acid, distilled water and N,N-dimethylformamide; The raw material preparation for precursor synthesis includes: Take 0.03g of experimental grade nickel nitrate, 0.010g of hexamethylenetriphenyltetracarboxylic acid, 0.5mL of distilled water and 2mL of N,N-dimethylformamide; Add the raw materials for precursor synthesis into a glass vial and stir until all components are completely dissolved; The reaction conditions for precursor synthesis include: The glass vial was sealed and placed in an oven at 358 K for 72 h; The glass vial was then cooled to room temperature, the mother liquor was precipitated, and green crystals were obtained; Crystal purification of precursor synthesis includes: The green crystals were washed several times with N,N-dimethylformamide solvent to remove excess reactants and solvent; The washed green crystals were placed in a vacuum drying oven and dried under vacuum to obtain a pure precursor; The steps of preparing the nickel-based catalytic material include: Take 0.2 g of the precursor and grind it to make the particles uniform; Place the ground precursor into a vacuum tube furnace, introduce high-purity argon gas, exhaust the air in the tube, and keep the argon gas to protect the environment; The vacuum tube furnace is heated to 800°C by a programmed temperature rising method and maintained for 1 hour to convert the precursor into a nickel-based composite material; the vacuum tube furnace is then cooled to below 50°C by a programmed temperature falling method; The nickel-based composite material is cleaned with dilute hydrochloric acid to remove impurities and then rinsed with distilled water until it becomes neutral; The nickel-based composite material washed to neutrality is then placed in a vacuum drying oven and dried under vacuum conditions for 3 hours to obtain a nickel-based catalytic material.

2. The nickel-based catalytic material according to claim 1, characterized in that The glass vial had a capacity of 5 ml and was stirred using a magnetic stirrer for 30 min.

3. The nickel-based catalytic material according to claim 1, characterized in that The duration of introducing high-purity argon gas is greater than or equal to 30 minutes.

4. The nickel-based catalytic material according to claim 1, characterized in that The heating and cooling rates of the vacuum tube furnace are both 5℃·min -1 .

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