Production of a hybrid structure composed of ruthenium nanoparticles and amine-functionalized network co-polymer support material

Abstract

This invention relates to the production of a hybrid structure composed of ruthenium nanoparticles and an amine-functionalized network-interwoven co-polymer support material, which can be used in nanomaterials, catalysis, and energy storage systems, and its application in hydrogen energy production. Its characteristic feature is that 400 mg of amine-functionalized copolymer polystyrene is transferred to a two-necked round bottom flask, a solution is prepared by adding 10 ml of pure water, a ruthenium precursor salt is added to the solution, the mixture is stirred on a magnetic stirrer at 600 rpm at room temperature for 3 hours, 1.0 ml of aqueous 46.74 mg (1.23 mmol) NaBH4 solution is added to the solution for the reduction process, ruthenium(III) ions are reduced to metallic ruthenium(O) nanoparticles by NaBH4, the mixture is centrifuged at 6000 rpm for 10 minutes to separate the solid and liquid phases, the obtained solid product is washed three times with 20 ml of ethanol to remove remaining chemical residues, the purified hybrid catalyst is dried at 423 K under 0.1 bar vacuum for 12 hours, and the ruthenium / amine-functionalized copolymer PS catalyst is obtained and made ready for use, comprising these process steps.

Description

[0001] PRODUCTION OF A HYBRID STRUCTURE COMPOSED OF RUTHENIUM NANOP ARTICEES AND AMINE-FUNCTIONALIZED NETWORK COPOLYMER SUPPORT MATERIAL

[0002] Technological Field:

[0003] This invention relates to the production of a hybrid structure composed of ruthenium nanoparticles and amine -functionalized network co-polymer support material, which can be used in nanomaterials, catalysis, and energy storage systems, as well as its application in hydrogen energy production.

[0004] State of the Art:

[0005] Currently, energy production methods based on the use of fossil fuels pose serious problems in terms of environmental sustainability. Factors such as global warming, increased carbon emissions, and the limited availability of energy resources are increasing the need for new and renewable energy sources every day. In particular, production methods for alternative fuels such as hydrogen, which is clean and has high energy density, are of great importance. However, existing hydrogen production techniques generally have various limitations such as high energy requirements, low efficiency, and byproduct control. Therefore, the demand for low -cost, environmentally friendly, and efficient hydrogen production methods continues to grow.

[0006] Patent application W02007086970A2 describes the "Base Metal Dehydrogenation of Amine-Boranes." The invention presents a method for dehydrogenating an amine-boran with the formula R1H2N-BH2R2 using a base metal catalyst. The method produces hydrogen and at least one oligomer of [RlHN-BHR2]m or [RlN-BR2]n. The dehydrogenation of amine-boranes can be used to ,but not limited to, generate H2 for portable power sources, including fuel cells.Although the invention described above offers an important approach in terms of hydrogen production, it has some disadvantages such as byproduct formation and catalyst stability. In this method, the formation of [RlHN-BHR2]m and [RlN-BR2]n oligomers in addition to hydrogen production requires continuous cleaning of the system and management of byproducts. The accumulation of oligomers on the catalyst surface over time can reduce the reaction rate and reduce the effectiveness of the catalyst by blocking its active sites. In addition, the long-term durability of base metal catalysts is generally low, and activity loss can occur when they are reused, which is a factor limiting the sustainability of the process.

[0007] Patent application US4758543A describes a "Dehydrogenation catalyst." The invention relates to improved catalysts for the dehydrogenation of hydrocarbons to the corresponding more unsaturated hydrocarbons, and more particularly to the production of vinyl aromatic hydrocarbons from alkyl aromatic hydrocarbons and the production of olefins from the corresponding more saturated aliphatic hydrocarbons.

[0008] The invention described above focuses on the process of converting hydrocarbons to more unsaturated hydrocarbons, and this method is generally applied to the petrochemical industry. The fact that this system is not directly optimized for hydrogen production reduces the efficiency of the process and increases energy consumption due to the high temperature requirement. In addition, problems such as coking (carbon deposition) of the catalysts over time create a disadvantage in terms of long-term efficiency. While modem methods developed for hydrogen production offer high yields at low temperatures, the catalyst systems in this patent are disadvantageous, especially in terms of energy efficiency and environmental sustainability.

[0009] In the article titled "Synthesis, Characterization and Investigation of Catalytic Activity in Hydrolysis Reaction of Methylamine-Borane of Ru-Fe Nanoclusters Stabilized with Poly(N-vinyl-2-pyrrolidone)", Ru-Fe nanoparticles (RuFe@PVP) stabilized with poly(N-vinyl-2-pyrrolidone) (PVP) were synthesized by a widely used alcohol reduction technique. The synthesized nanoparticles were characterized by SEM, SEM / EDX, UV / Vis techniques. The prepared nanoparticles were used as a catalyst inthe production of hydrogen from the hydrolysis reaction of methylamine-borane, an important boron-nitrogen (B-N) derivative that stores hydrogen in the solid state. The bimetallic nanoparticles, with a TOF value (38.4 1 / min) and activation energy (87.7 kJ / mol), were evaluated as an efficient catalytic system with these properties. As a result of investigating the effects of catalyst and substrate concentrations on the catalytic reaction, it was determined that the rate expression of the reaction proceeds from the O.5th order with respect to the catalyst concentration and from the 1.7th order with respect to the substrate concentration.

[0010] Although the article described above presents the catalyst system developed for hydrogen production from the hydrolysis of methylamine-borane as an efficient alternative, it contains some limitations. First of all, the TOF (38.4 1 / min) and activation energy (87.7 kJ / mol) values of the Ru-Fe nanoparticles used show a relatively lower efficiency compared to modem catalyst systems. In addition, special methods such as alcohol reduction techniques are required for the synthesis of such nanoparticles, and the production process is complex and costly. Furthermore, the dependence of the catalytic reaction on the substrate concentration makes it difficult to control the reaction rate, creating a restrictive factor in terms of the scalability of the system. All these disadvantages pose significant challenges in providing a long-term and sustainable hydrogen production process in industrial applications.

[0011] Description of the Invention:

[0012] This invention enables high-yield hydrogen production using a minimal amount of catalyst and materials. Traditional methods require the use of large quantities of metalbased catalysts, which increases costs. However, thanks to a hybrid product functionalized with ruthenium nanoparticles, more hydrogen production is achieved using less material. This offers a method that reduces costs and uses resources more efficiently.

[0013] The invention is formed by placing ruthenium nanoparticles on an amine -functionalized polymer support material. This hybrid structure provides a system that is reusable andpossesses high catalytic activity. A common problem with traditional catalysts is that they lose activity over time. However, this system ensures the catalyst's longevity and reusability, thereby significantly reducing costs.

[0014] Hydrogen production from compounds such as methylamine borane typically requires high temperatures, which increases energy consumption. However, thanks to this invention, hydrogen production can be carried out at lower temperatures. This saves energy while making the process more efficient.

[0015] In hydrogen production processes, the formation of boron-based byproducts is a significant problem. In traditional methods, these byproducts accumulate in the reaction environment, reducing the system's efficiency and potentially causing environmental problems. This invention improves the management of byproducts, making the system more durable and sustainable. It also minimizes harmful gas emissions during hydrogen production, thereby reducing environmental damage.

[0016] One of the greatest advantages of the invention is that the ruthenium nanoparticles deployed on the support material can remain active for a long time and can be repeatedly used in hydrogen production. While traditional systems require frequent catalyst renewal due to rapid deactivation, this hybrid system extends the catalyst's lifespan, offering a more economical solution.

[0017] The invention increases hydrogen efficiency, enabling the production of more hydrogen gas. Compared to traditional methods, more hydrogen production is achieved with the same amount of material. This is a major advantage for the development of the hydrogen economy and offers a promising solution for portable hydrogen storage systems.

[0018] The invention increases hydrogen efficiency, enabling the production of more hydrogen gas. Compared to traditional methods, more hydrogen production is achieved with the same amount of material. This is a major advantage for the development of thehydrogen economy and offers a promising solution for portable hydrogen storage systems.

[0019] Given the environmental problems and global warming caused by fossil fuels, hydrogen has great potential for clean energy production. This invention supports carbon-free energy production, offering an eco-friendly solution. When combined with hydrogen fuel cells, zero-emission energy production becomes possible.

[0020] This invention represents a technology that can be applied not only in the laboratory but also on an industrial scale. With great potential in hydrogen production-related sectors, this technology can be used in various fields such as renewable energy, fuel cells, transportation, and industry. Furthermore, the low-cost production process offers a commercially viable solution.

[0021] Explanation of the Figures:

[0022] The invention will be described with reference to the accompanying figures, so that the features of the invention will be more clearly understood and appreciated, but this is not intended to limit the invention to these specific arrangements. On the contrary, it is intended to cover all alternatives, modifications, and equivalents that may be included within the scope of the invention as defined by the appended claims. It should be understood that the details shown are presented for the purpose of describing only the preferred arrangements of the present invention, and for providing the most useful and readily understood description of both the shaping of the methods and the principles and conceptual features of the invention. In these drawings:

[0023] Figure 1 A graph showing the EDX spectrum.

[0024] Figure 2 A graph showing H2 gas production as a function of temperature.

[0025] Figure 3 A graph showing H2 gas production after repeated use.

[0026] Figures that will help in understanding this invention are numbered as indicated in the attached drawing and are given below with their names.Detailed Description of the Invention:

[0027] The invention involves the synthesis and preparation of a ruthenium / amine- functionalized copolymer polystyrene (Ru / PS) hybrid catalyst developed for hydrogen production. The process begins with transferring 400 mg of amine-functionalized copolymer polystyrene (PS) into a two-necked round-bottom flask to provide the reaction environment. Subsequently, 10 mb of pure water is added to prepare a solution, ensuring the prepared copolymer support is homogeneously dispersed in the solvent medium and suitable for the reaction conditions. This step is followed by the careful addition of a ruthenium salt solution, which serves as the precursor to the ruthenium nanoparticles that will act as the catalyst in hydrogen production. To maximize the interaction between the components of the mixture and to ensure the adhesion of the nanoparticles to the surface, the solution is continuously stirred at room temperature at a speed of 600 rpm for a full 3 hours using a magnetic stirrer. To reduce the ruthenium ions to their metallic form and bind them to the polymer surface, 1.0 mb of aqueous 46.74 mg (1.23 mmol) NaBH4 solution is added to the solution as a reducing agent. Upon the addition of the NaBH4 solution, ruthenium (III) ions are reduced to metallic ruthenium (0) nanoparticles through a chemical reaction, binding to the amine- functionalized copolymer PS surface. After the reaction is complete, the solution is centrifuged at 6000 rpm for 10 minutes to separate the solid and liquid phases within the mixture, thereby isolating the catalyst. The solid product obtained after centrifugation is purified by washing three times with 20 mb of ethanol to completely remove any residual reaction by-products and solvent residues. Finally, to ensure the chemical stability of the hybrid catalyst and make it suitable for use, it is carefully dried in a specialized vacuum oven at a temperature of 423 K and under a vacuum of 0.1 bar for 12 hours. As a result of all these steps, a ruthenium / amine-functionalized copolymer PS catalyst with high stability and catalytic activity is successfully obtained, making it ready for use in catalytic applications such as hydrogen production.

[0028]

[0029] COPOLYMER-PS COPOLYMER-PS Functionalized with Amine Groups

[0030]

Claims

CLAIMS1- An invention is the production of a hybrid structure consisting of a ruthenium nanoparticle and amine-functionalized network-linked co-polymer support material, characterized by:— Transferring 400 mg of amine-functionalized copolymer polystyrene into a twonecked round bottom flask,— Preparing a solution by adding 10 ml of pure water,— Adding the ruthenium precursor salt to the solution,— Stirring the mixture on a magnetic stirrer at 600 rpm at room temperature for 3 hours,— Adding 1.0 ml of aqueous 46.74 mg (1.23mmol) NaBH4 solution to the solution for the reduction process,— Reducing ruthenium(III) ions to metallic ruthenium(O) nanoparticles by means of NaBH4,— Centrifuging the mixture at 6000 rpm for 10 minutes to separate the solid and liquid phases,— Washing the obtained solid product three times with 20 ml of ethanol to remove remaining chemical residues,— Drying the purified hybrid catalyst at 423 K under 0.1 bar vacuum for 12 hours, and — Obtaining the ruthenium / amine-functionalized copolymer PS catalyst and making it ready for use, comprising the process steps.

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