Preparation method and application of novel hydrophobic porous cobalt-nickel nano composite material
By constructing a hydrophobic porous cobalt-nickel nanocomposite material, the problem of the active sites of traditional cobalt-nickel catalysts being blocked in high humidity environments was solved, achieving high activity and long-term stable catalytic degradation performance, which is suitable for industrial waste gas treatment.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-15
- Publication Date
- 2026-03-13
AI Technical Summary
Traditional hydrophilic cobalt-nickel catalysts are easily adsorbed by water molecules in high-humidity industrial waste gas environments, which leads to the masking of active sites, hindered mass transfer of reactants, reduced catalytic efficiency and shortened lifespan, making it difficult to maintain high efficiency and stability in complex industrial environments.
A hydrophobic porous cobalt-nickel nanocomposite material was constructed. By loading a hydrophobic layer, the hydrophobicity of the material was enhanced, ensuring the accessibility of active sites in humid environments and maintaining chemical stability in acidic or alkaline waste gas components.
It achieves high activity and long-term stability of cobalt-nickel catalysts under high humidity conditions, improves the degradation performance and stability of catalysts in industrial waste gas treatment, and is suitable for the purification and treatment of organic waste gas under harsh humidity conditions.
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Figure CN121648920A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of functional materials technology, and in particular to a method for preparing a hydrophobic porous cobalt-nickel nanocomposite material. Background Technology
[0002] In the field of functional materials technology, with increasingly stringent environmental standards, the efficient treatment of industrial organic waste gas has become a critical issue that urgently needs to be addressed. Volatile organic compounds (VOCs), as one of the major pollutants, rely on catalysts with high activity, high stability, and adaptability to complex industrial environments for catalytic degradation technology. Cobalt-nickel based nanomaterials have been extensively studied in this field due to their diverse valence states, excellent redox capabilities, and activation potential for various VOC molecules.
[0003] However, in actual industrial waste gases, high humidity or water vapor condensation environments are often present. Traditional hydrophilic cobalt-nickel catalysts are easily adsorbed or covered by water molecules, leading to the obscuring of active sites and hindered mass transfer of reactants, resulting in a significant decrease in catalytic efficiency and a shortened lifespan. This bottleneck severely restricts the application performance of existing materials under real-world conditions. To address this problem, constructing hydrophobic catalysts is considered a promising modification strategy. By endowing the catalyst surface with hydrophobic properties, the competitive adsorption of water molecules on its surface can be effectively prevented, ensuring the accessibility of active sites to VOC molecules in humid environments, while simultaneously enhancing the chemical stability of the material in acidic or alkaline waste gas components.
[0004] Therefore, combining cobalt-nickel nanomaterials with hydrophobic components to construct a novel hydrophobic porous cobalt-nickel nanocomposite material is expected to simultaneously achieve a synergistic improvement in its intrinsic catalytic activity and interfacial water resistance. This material aims to solve the core problem of activity decay of traditional catalysts in high-humidity industrial waste gas environments, providing a new material basis for developing adaptable and stable organic waste gas catalytic degradation technologies. In view of this, this invention proposes a method for preparing a novel hydrophobic cobalt-nickel nanocomposite material for industrial organic waste gas catalytic degradation and its application. Summary of the Invention
[0005] To address the shortcomings of existing technologies, this invention provides a novel method for preparing hydrophobic porous cobalt-nickel nanocomposites and their applications. This method overcomes the limitations of single cobalt-nickel oxides in catalytic reaction processes. By comprehensively considering factors such as how to construct porous structures and achieve hydrophobic coating loading, the catalytic activity of the novel hydrophobic cobalt-nickel nanocomposites can effectively degrade organic pollutants and play an important role in environmental governance, energy conversion, and other fields.
[0006] The objective of this invention is achieved as follows: a method for preparing a novel hydrophobic porous cobalt-nickel nanocomposite material, comprising the following steps: S1. Preparation of cobalt nanowire precursor: A quantitative amount of cobalt inorganic solution and aspartic acid were added to a mixture of a quantitative amount of deionized water and a quantitative amount of ethylene glycol. The mixture was stirred to obtain a uniform pink solution A. At the same time, a sodium hydroxide solution B of a set concentration was prepared. During the stirring of solution A, solution B was slowly added to solution A to obtain a final mixed solution. The final mixed solution was placed in a hydrothermal synthesis reactor, and cobalt nanowire precursor material was prepared by hydrothermal method. After filtration and separation, a light pink product was obtained. The product was washed three times with water and ethanol, and then placed in a drying oven at 60±5℃ for drying. S2, cobalt nanotubes were prepared by calcining the cobalt nanowire precursor from S1 in a tubular furnace to obtain particles; S3, preparation of cobalt-nickel composite material: Take the particles obtained from S2, dissolve them in a set amount of anhydrous ethanol, add a set amount of nickel inorganic solution, urea and PVP, stir and reflux, wash and dry, and calcine to obtain cobalt-nickel composite material. S4, hydrophobic layer loading: S4 cobalt-nickel composite material was mixed with the solution and dried to obtain the target product. Furthermore, in S1, the hydrothermal temperature is 100~120℃ and the hydrothermal time is 10~14h.
[0007] Furthermore, the cobalt and nickel in the cobalt-nickel precursor material in S2 are calcined at 400°C for 3-4 hours.
[0008] Furthermore, the S3 cobalt-nickel molar ratio is 1:1, 2:1, and 1:2, the reflux temperature is 80~100 ℃, and the hydrothermal time is 10~12 h.
[0009] Furthermore, the calcination temperature during the preparation of the cobalt-nickel oxide in S3 is 300~400℃, and the calcination time is 3~4h.
[0010] Furthermore, the solution is a mixture of phenyltriethoxysilane and ethanol.
[0011] Furthermore, the specific operation of S4 is as follows: the mixture of phenyltriethoxysilane and ethanol is mixed in an ultrasonic bath for 50-60 minutes, then mixed with the cobalt-nickel nanocomposite material, and then dried.
[0012] An application of a novel hydrophobic porous cobalt-nickel nanocomposite material as a catalyst for the purification and treatment of gaseous pollutants.
[0013] Compared with the prior art, the beneficial effects of the present invention are as follows: The novel hydrophobic cobalt-nickel nanocomposite material involved in this invention has the advantages of strong surface hydrophobicity, high accessibility of active sites, and good stability in humid environments. In particular, it exhibits excellent catalytic degradation performance and long-term stability in the treatment of industrial organic waste gas with high humidity. The preparation method of this composite material is simple, mild, and easy to scale up. The obtained material is particularly suitable as a catalyst for the purification of organic waste gas under harsh humidity conditions, and has significant application potential and market prospects in the fields of industrial waste gas treatment and environmental remediation. Attached Figure Description
[0014] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.
[0015] Figure 1 SEM and TEM images of cobalt nanowires, nanotubes, nickel-cobalt nanocomposites, and hydrophobic nickel-cobalt nanocomposites prepared for embodiments of the present invention.
[0016] Figure 2 The specific surface area and pore size distribution of the hydrophobic nickel-cobalt nanocomposite material prepared in the embodiments of the present invention are shown in the figure.
[0017] Figure 3 This is a diagram showing the water contact angle of an embodiment and a comparative example of the present invention.
[0018] Figure 4 The diagram shows the catalytic effect of the embodiments and comparative examples of the present invention. Detailed Implementation
[0019] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0020] Example 1 Reference Figure 1-3 A novel method for preparing hydrophobic porous cobalt-nickel nanocomposite materials, the specific steps of which are as follows: Step S1: Preparation of cobalt nanowire precursor. Take 3 mmol of cobalt nitrate hexahydrate, 3 mmol of L-aspartic acid, and 3 ml of sodium hydroxide (2M) solution, add them to a mixture of 15 ml of deionized water and 18 ml of ethylene glycol, and stir rapidly until the solution turns pink again. Then, transfer this mixture to a reactor and react at 100 °C for 10 hours. Finally, collect the pink precipitate and wash it several times by centrifugation with deionized water and ethanol. Dry the product under vacuum at 40 °C for 12 hours. A pink solid is finally obtained. SEM images of the product are shown below. Figure 1 As shown in (a).
[0021] Step S2: Preparation of cobalt oxide. The cobalt nanowire precursor from step S1 was calcined in a tube furnace at 400℃ for 3 hours. Slow heating (1℃ / min) to the specific temperature (400℃) removed organic matter from the metal-organic framework, introducing a porous structure into the catalyst. The product was analyzed by SEM and TEM. Figure 1 As shown in (b) and (c).
[0022] Step S3: Preparation of cobalt-nickel composite material. The particles obtained in step S2 were dissolved in 70 ml of anhydrous ethanol. 1 mmol of nickel nitrate, 1 g of urea, and 1 g of PVP were added. The mixture was heated at 80 °C for 10 h. After washing and drying, the mixture was calcined at 400 °C for 3 h to obtain the cobalt-nickel composite material. TEM results of the product are shown below. Figure 1 As shown in (d).
[0023] Step S4, Hydrophobic Layer Loading: Take 100 mg of the product from Step 4 and mix it with a mixed solution, which is a mixture of 0.1 g phenyltriethoxysilane and 1 ml ethanol. Dry the mixture to obtain the target product. Nitrogen adsorption analysis and pore size distribution diagrams are shown below. Figure 2 As shown, the water contact angle in the comparative example is as follows: Figure 3 As shown.
[0024] Example 2 Step S1: Preparation of cobalt nanowire precursor. Take 3 mmol of cobalt nitrate hexahydrate, 3 mmol of L-aspartic acid, and 3 ml of sodium hydroxide (2M) solution, add them to a mixture of 15 ml of deionized water and 18 ml of ethylene glycol, and stir rapidly until the solution turns pink again. Then, transfer this mixture to a reactor and react at 110 °C for 12 hours. Finally, collect the pink precipitate and wash it several times by centrifugation with deionized water and ethanol. Dry the product under vacuum at 40 °C for 12 hours. A pink solid is finally obtained. SEM images of the product are shown below. Figure 1 As shown in (a).
[0025] Step S2: Preparation of cobalt oxide. The cobalt nanowire precursor from step S1 is calcined in a tube furnace at a temperature of 400℃ for 4 hours. The temperature is slowly increased (1℃ / minute) to a specific temperature (400℃), which can remove organic matter in the metal-organic framework and introduce a porous structure into the catalyst.
[0026] Step S3: Preparation of nickel-cobalt-nickel composite material. Take the particles obtained in step S2, dissolve them in 70 ml of anhydrous ethanol, add 0.5 mmol of nickel nitrate, 1 g of urea and 1 g of PVP, 90 ℃ for 11 h, wash and dry, and calcine at 350 ℃ for 3.5 h to obtain the cobalt-nickel composite material.
[0027] Step S4, hydrophobic layer loading: Take 100 mg of the product from step four and mix it with the mixed solution, which is a mixture of 0.1 g phenyltriethoxysilane and 1 ml ethanol, and dry it to obtain the target product.
[0028] Example 3 Step S1: Preparation of cobalt nanowire precursor. Take 3 mmol of cobalt nitrate hexahydrate, 3 mmol of L-aspartic acid, and 3 ml of sodium hydroxide (2M) solution, add them to a mixture of 15 ml of deionized water and 18 ml of ethylene glycol, and stir rapidly until the solution turns pink again. Then, transfer this mixture to a reactor and react at 120 °C for 14 hours. Finally, collect the pink precipitate and wash it several times by centrifugation with deionized water and ethanol. Dry the product under vacuum at 40 °C for 12 hours.
[0029] Step S2, preparation of cobalt oxide: the cobalt nanowire precursor from step S1 is calcined in a tube furnace at a temperature of 400℃ for 3.5 h. The temperature is slowly increased (1℃ / min) to a specific temperature (400℃), which can remove organic matter in the metal-organic framework and introduce a porous structure into the catalyst.
[0030] Step S3: Preparation of nickel-cobalt-nickel composite material. Take the particles obtained in step S2, dissolve them in 70 ml of anhydrous ethanol, add 2 mmol of nickel nitrate, 1 g of urea and 1 g of PVP, 100 °C for 14 h, wash and dry, and calcine at 300 °C for 4 h to obtain the cobalt-nickel composite material.
[0031] Step S4, hydrophobic layer loading: Take 100 mg of the product from step four and mix it with the mixed solution, which is a mixture of 0.1 g phenyltriethoxysilane and 1 ml ethanol, and dry it to obtain the target product.
[0032] Comparative Example 1 A novel method for preparing hydrophobic porous cobalt nanocomposite materials, the specific steps of which are as follows: Step S1: Preparation of cobalt nanowire precursor. 3 mmol of cobalt nitrate hexahydrate, 3 mmol of L-aspartic acid, and 3 ml of sodium hydroxide (2M) solution were added to a mixture of 15 ml of deionized water and 18 ml of ethylene glycol. The mixture was stirred rapidly until the solution turned pink. Next, this mixture was transferred to an autoclave and reacted under high temperature and pressure for 4 hours. Finally, the pink precipitate was collected and washed several times by centrifugation with deionized water and ethanol. The product was then dried under vacuum at 40°C for 12 hours. A pink solid was finally obtained.
[0033] Step S2: Preparation of cobalt nanotube oxide. The cobalt nanowire precursor from step S1 is calcined in a tube furnace at a temperature of 400℃ for 4 hours. The temperature is slowly increased (1℃ / minute) to a specific temperature (400℃), which can remove organic matter in the metal-organic framework and introduce a porous structure into the catalyst.
[0034] Step S3, hydrophobic layer loading: Take 100 mg of the product from step S2 and mix it with the mixed solution, which is a mixture of 0.1 g phenyltriethoxysilane and 1 ml ethanol, and dry it to obtain the target product.
[0035] The difference between Comparative Example 1 and Example 1 is that step S3 in Example 1 is omitted.
[0036] Comparative Example 2 A novel method for preparing porous cobalt-nickel nanocomposite materials, the specific steps of which are as follows: Step S1: Preparation of cobalt nanowire precursor. Take 3 mmol of cobalt nitrate hexahydrate, 3 mmol of L-aspartic acid, and 3 ml of sodium hydroxide (2M) solution, add them to a mixture of 15 ml of deionized water and 18 ml of ethylene glycol, and stir rapidly until the solution turns pink again. Then, transfer this mixture to a reactor and react under high temperature and pressure for 4-5 hours. Finally, collect the pink precipitate and wash it several times with deionized water and ethanol by centrifugation. Dry the product under vacuum at 40°C for 12 hours. A pink solid is finally obtained.
[0037] Step S2: Preparation of cobalt oxide. The cobalt nanowire precursor from step S1 is calcined in a tube furnace at a temperature of 400℃ for 4 hours. The temperature is slowly increased (1℃ / minute) to a specific temperature (400℃), which can remove organic matter in the metal-organic framework and introduce a porous structure into the catalyst.
[0038] Step S3: Preparation of cobalt-nickel composite material. Take the particles obtained in step S2, dissolve them in 70 ml of anhydrous ethanol, add 1 mmol of nickel nitrate, 1 g of urea and 1 g of PVP, heat at 80 °C for 10-12 h, wash, dry and calcine to obtain cobalt-nickel composite material.
[0039] The difference between Comparative Example 2 and Example 1 is that step S4 in Example 1 is omitted.
[0040] like Figure 3 The results showed that the catalyst product of Example 1 could catalytically degrade toluene gas at 160°C. Compared with Comparative Examples 1 and 2, the catalyst prepared with the complete preparation steps and fillers had high catalytic activity and hydrophobicity, and could effectively degrade pollutants.
[0041] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims
1. A method for preparing a novel hydrophobic porous cobalt-nickel nanocomposite material, characterized in that, Includes the following steps: S1. Preparation of cobalt nanowire precursor: Take a quantitative amount of cobalt inorganic solution and aspartic acid, add them to a mixed liquid of a quantitative amount of deionized water and a quantitative amount of ethylene glycol, stir, and obtain a uniform pink solution A; at the same time, prepare a sodium hydroxide solution B of a set concentration. During the stirring of solution A, solution B is slowly added to solution A to obtain a final mixed solution. The final mixed solution is then placed in a hydrothermal synthesis reactor to prepare cobalt nanowire precursor materials using a hydrothermal method. After filtration and separation, a light pink product is obtained. The product is washed three times with water and ethanol and then placed in a drying oven at 60±5℃ for drying. S2, cobalt nanotubes were prepared by calcining the cobalt nanowire precursor from S1 in a tubular furnace to obtain particles; S3, preparation of cobalt-nickel composite material: Take the particles obtained from S2, dissolve them in a set amount of anhydrous ethanol, add a set amount of nickel inorganic solution, urea and PVP, stir and reflux, wash and dry, and calcine to obtain cobalt-nickel composite material. S4, hydrophobic layer loading: S4 cobalt-nickel composite material is mixed with solution and dried to obtain the target product.
2. The method for preparing a novel hydrophobic porous cobalt-nickel nanocomposite material according to claim 1, characterized in that, The hydrothermal temperature in S1 is 100~120℃, and the hydrothermal time is 10~14h.
3. The method for preparing a novel hydrophobic porous cobalt-nickel nanocomposite material according to claim 1 or 2, characterized in that, The cobalt and nickel in the cobalt-nickel precursor material in S2 are calcined at 400°C for 4 hours.
4. The method for preparing a novel hydrophobic porous cobalt-nickel nanocomposite material according to claim 1 or 2, characterized in that, The S3 cobalt-nickel molar ratio is 1:1, the reflux temperature is 80~100 ℃, and the hydrothermal time is 10~12h.
5. A method for preparing a novel hydrophobic porous cobalt-nickel nanocomposite material according to claim 1 or 2, characterized in that, The cobalt-nickel oxide in S3 is prepared at a calcination temperature of 400℃ and a calcination time of 4h.
6. A method for preparing a novel hydrophobic porous cobalt-nickel nanocomposite material according to claim 1 or 2, characterized in that, The solution is a mixture of phenyltriethoxysilane and ethanol.
7. The method for preparing a novel hydrophobic porous cobalt-nickel nanocomposite material according to claim 6, characterized in that, The specific operation of S4 is as follows: the mixture of phenyltriethoxysilane and ethanol is mixed in an ultrasonic bath for 50-60 minutes, then mixed with cobalt-nickel nanocomposite material, and dried.
8. The application of a novel hydrophobic porous cobalt-nickel nanocomposite material prepared by the preparation method according to any one of claims 1-7, characterized in that, It is used as a catalyst for the purification and treatment of gaseous pollutants.