Platinum-ruthenium catalyst for irreversible hydrogen elimination, hydrogen absorption composite material thereof and application

Abstract

The application provides a platinum-ruthenium catalyst for irreversible elimination of hydrogen, and a hydrogen absorption composite material and application thereof. The platinum-ruthenium catalyst for irreversible elimination of hydrogen comprises a modified porous carrier and a platinum-ruthenium bimetallic active center loaded on the modified porous carrier; the platinum and ruthenium exist in the form of an atomic-scale alloy phase or independent nanoparticles adjacent to each other, generating an electronic and geometric synergistic effect. The hydrogen absorption composite material comprises the platinum-ruthenium catalyst, an unsaturated organic compound and a polymer; the platinum-ruthenium catalyst is used to catalyze an irreversible hydrogenation reaction of hydrogen and the unsaturated organic compound at room temperature and normal pressure. The platinum-ruthenium catalyst of the application can efficiently catalyze an irreversible hydrogenation reaction of 1,4-di(phenylethynyl)benzene and hydrogen at room temperature and normal pressure, so as to realize fast, safe and permanent chemical fixation of hydrogen.

Description

Technical Field

[0001] This invention relates to the fields of hydrogen safety technology and functional catalytic materials, specifically to a platinum-ruthenium catalyst for irreversible hydrogen removal, its hydrogen-absorbing composite material, and its applications. Background Technology

[0002] Hydrogen is increasingly widely used in energy, chemical, electronics, and aerospace fields due to its clean and efficient properties. However, hydrogen is the lightest and least dense gas in nature, with extremely high permeability and diffusivity, a wide explosive limit range (4% to 75% by volume in air), and extremely low ignition energy. These characteristics make it highly susceptible to leakage and accumulation during the production, storage, transportation, and use of hydrogen, forming gas clouds with serious explosive hazards, posing a significant threat to life and property. Furthermore, leaked atomic hydrogen can penetrate into metallic materials, causing hydrogen embrittlement, leading to a significant decrease in the mechanical properties of equipment components (such as hydrogen storage tanks, pipelines, and valves), and creating a potential risk of catastrophic failure.

[0003] Therefore, developing efficient and reliable active hydrogen removal technologies is crucial for ensuring the safety of hydrogen-related activities. Currently, the main hydrogen treatment methods include ventilation dilution, catalytic combustion, physical adsorption, and chemical capture. Among these, The ventilation dilution method uses forced ventilation to dilute the leaked hydrogen concentration below the lower explosive limit. However, this method has limited effectiveness in confined spaces and requires continuous energy consumption, potentially failing in the absence of external power or in emergencies. The catalytic combustion method uses a precious metal catalyst to oxidize hydrogen with oxygen in the air at room temperature, producing water. However, the effectiveness of this method is highly dependent on the oxygen concentration in the environment and cannot work in oxygen-deficient environments. Furthermore, the reaction is exothermic; when the hydrogen concentration is high, it may cause localized overheating of the catalyst bed, even becoming an ignition source, thus posing a danger. The physical adsorption method uses porous materials such as activated carbon and zeolite molecular sieves to adsorb hydrogen through physical forces. However, its adsorption capacity is limited, and the adsorption forces are weak, making hydrogen desorption easy and causing secondary release. It cannot achieve permanent hydrogen fixation and its reliability is insufficient.

[0004] Compared to the methods mentioned above, chemical capture (or irreversible chemical hydrogen capture) exhibits unique advantages. This method utilizes the addition reaction between unsaturated organic compounds and hydrogen to irreversibly convert gaseous hydrogen (H2) into solid or liquid hydrogenated organic compounds, thereby achieving permanent hydrogen fixation. This process is oxygen-free, flameless, mild, and extremely safe, making it an ideal way to address the hydrogen hazards in confined spaces. In the past, hydrogenation catalysts represented by Pd / C have been widely studied and applied in this field. Researchers have used the typical unsaturated organic compound 1,4-bis(phenylethynyl)benzene (DEB) as a hydrogen capture substrate, explored different catalyst supports such as graphene and molecular sieves for Pd metal, and made many contributions to the integrated molding of Pd-based catalysts, such as aerogels with hydrogen capture capacity almost equivalent to hydrogen absorber powder and flexible hydrogen absorber films. On the other hand, a high-entropy alloy catalyst has been developed in recent years that can add large π bonds of benzene rings at room temperature and atmospheric pressure, changing the situation where Pd-based catalysts only added alkenyne bonds in the past. This greatly improves the hydrogen absorption capacity of hydrogen absorption composite materials and significantly increases the saturated hydrogen absorption capacity.

[0005] Among numerous unsaturated organic compounds used as hydrogen absorbers, 1,4-bis(phenylethynyl)benzene (DEB) is considered a promising solid-state hydrogen absorber due to its high theoretical hydrogen absorption capacity and stable product with minimal volume change after hydrogenation, caused by the presence of multiple unsaturated bonds (acetylene bonds and benzene rings) in its molecule. However, the stable structure of DEB results in an extremely slow reaction with hydrogen at room temperature and atmospheric pressure without a catalyst, failing to meet the rate requirements for emergency hydrogen removal. Therefore, developing a highly active catalyst is crucial for the practical application of DEB-based chemical hydrogen removal technology.

[0006] While existing technologies contain various catalysts for the hydrogenation of unsaturated compounds (for example, Chinese patent CN116173983 A discloses a core-shell structured multi-component nanoalloy catalyst), these catalysts are primarily designed for chemical synthesis and have the following limitations, making them difficult to apply directly to the field of hydrogen safety: Complex composition: It usually uses a variety of precious metals, resulting in high material costs and making it unsuitable for large-scale deployment in security systems.

[0007] The preparation process is complex and difficult to scale up: the synthesis steps are cumbersome and the yield per batch is low (milligram level), which cannot meet the requirements of hydrogen safety equipment for catalysts in the kilogram or even ton level.

[0008] Insufficient environmental considerations: The preparation process may use toxic reagents, which does not meet the environmentally friendly requirements of safety equipment.

[0009] In summary, there is an urgent need in this field for a novel catalyst specifically designed for hydrogen safety. This catalyst should possess high catalytic activity, high stability, be environmentally friendly, cost-effective, and scalable for production, driving the widespread application of highly efficient hydrogen absorbers in practical engineering and filling the gaps in existing hydrogen treatment technologies. However, commonly used Pd / C catalysts can only catalyze the addition of hydrogen to the ene-yne ​​bonds of unsaturated organic compounds, resulting in a very limited hydrogen absorption capacity. While newly developed high-entropy alloy catalysts can catalyze the hydrogenation of ene-yne ​​bonds and benzene rings, their preparation systems use acetone as a solvent, posing safety risks. Therefore, further research and improvement based on existing catalysts are urgently needed to obtain novel catalysts that meet application requirements, respond to environmental protection calls, and maintain good hydrogenation capabilities. Summary of the Invention

[0010] This invention overcomes the shortcomings of existing hydrogen removal technologies in terms of environmental friendliness, yield, and safety, and provides a platinum-ruthenium catalyst for irreversible hydrogen removal, its preparation method, hydrogen-absorbing composite materials, and applications. This catalyst can efficiently catalyze the irreversible hydrogenation reaction of unsaturated aromatic compounds such as 1,4-bis(phenylethynyl)benzene (DEB) with hydrogen at room temperature and atmospheric pressure, thereby achieving rapid, safe, and permanent chemical fixation of hydrogen. The preparation method is green and environmentally friendly, simple and controllable, and has good potential for large-scale scalability, meeting the large-scale demand for catalysts in the field of hydrogen safety. The application of this catalyst in constructing efficient, passive hydrogen safety control systems provides a novel technical solution to address the risk of hydrogen accumulation in confined or semi-confined spaces.

[0011] The technical method of the present invention is as follows: A platinum-ruthenium catalyst for irreversible hydrogen removal comprises a modified porous support and platinum and ruthenium bimetallic active centers supported on the modified porous support; wherein the platinum and ruthenium exist in the form of an atomic-scale alloy phase or adjacent independent nanoparticles, generating an electronic and geometric synergistic effect.

[0012] Optionally, the platinum and ruthenium form a uniform or non-uniform alloy phase at the atomic scale; or the platinum and ruthenium are distributed adjacent to each other in the form of independent nanoparticles on the modified porous support to form a physically mixed structure.

[0013] Optionally, the platinum-ruthenium catalyst is prepared using a green, environmentally friendly, and scalable process; the process uses low-toxicity, renewable mixed alcohols as solvents and reducing agents, and the catalyst yield of a single reactor can reach the gram to kilogram level.

[0014] The present invention provides a hydrogen absorption mixture comprising the above-mentioned platinum-ruthenium catalyst and an unsaturated organic compound, wherein the platinum-ruthenium catalyst is used to catalyze an irreversible hydrogenation reaction between hydrogen and the unsaturated organic compound at room temperature and atmospheric pressure.

[0015] This invention provides a hydrogen-absorbing composite material, comprising the aforementioned platinum-ruthenium catalyst, unsaturated organic compound, and polymer; the platinum-ruthenium catalyst is used to catalyze an irreversible hydrogenation reaction between hydrogen and the unsaturated organic compound at room temperature and atmospheric pressure; the polymer serves as a substrate for composite material molding.

[0016] Optionally, the unsaturated organic compound contains one or more unsaturated bonds such as double bonds, triple bonds, carbonyl groups, aldehyde groups, and / or benzene rings.

[0017] Optionally, the unsaturated organic compound is preferably 1,4-bis(phenylethynyl)benzene.

[0018] Optionally, the mass ratio of the unsaturated organic compound to the platinum-ruthenium catalyst is 1 to 10:1.

[0019] Optionally, the polymer is any one of styrene-butadiene rubber, hydroxyl cellulose, polyethersulfone, polyamide, and silicone rubber.

[0020] Optionally, the mass ratio of the mixture of platinum ruthenium catalyst and unsaturated organic compound to polymer is (30~98):(70~2).

[0021] Optionally, the hydrogen-absorbing composite material can be prepared in one or more of the following structures: granular, thin film, foam, or array.

[0022] The present invention also provides an application of a hydrogen-absorbing composite material in absorbing hydrogen and its isotope gases.

[0023] The beneficial effects of this invention are: 1) Intrinsically safe and highly reliable: This invention is based on the principle of irreversible chemical hydrogenation. The reaction process does not rely on oxygen, does not produce open flames, and does not release heat violently. It fundamentally avoids the risk of combustion and explosion that may be caused by catalytic combustion methods. It is particularly suitable for oxygen-deficient or confined environments, and the safety level is significantly improved.

[0024] 2) Excellent catalytic activity and rapid response: Through the alloying effect of Pt and Ru, significant electronic and geometric synergistic effects are generated, which greatly enhances the dissociation activation ability of hydrogen molecules and the hydrogenation catalytic efficiency of DEB, enabling rapid capture of hydrogen at room temperature and atmospheric pressure.

[0025] 3) Environmental friendliness and cost advantage: The preparation process uses low-toxicity, renewable mixed alcohols as solvents and reducing agents, avoiding the use of toxic reagents in traditional methods, which is in line with the principles of green chemistry.

[0026] 4) Scalable and highly practical: The hydrothermal synthesis method used in this invention is simple and the parameters are easy to control. It has excellent scale-up adaptability and can achieve stable production from gram-level in the laboratory to kilogram-level in industrial production. It solves the bottleneck problem of the difficulty in scaling existing high-activity catalysts and lays the material foundation for large-scale application in hydrogen safety engineering.

[0027] 5) Simple application and good stability: The catalyst and DEB form a solid composite hydrogen scavenger, which is easy to store, transport and fill into various safety devices. It has stable performance and long service life. It does not require a complicated external energy input or control system and can achieve passive, all-weather hydrogen safety protection. Attached Figure Description

[0028] Figure 1 The images shown are transmission electron microscope (TEM) images and EDS spectra of PtRu / CNFs from Example 1; where a and b are TEM images, and c, d, and e are EDS spectra. Figure 2 The images shown are spherical aberration electron microscope (SEM) images and corresponding EDS spectra of PtRu / CNFs from Example 1; where a, b, and c are SEM images, and d, e, f, and g are EDS spectra. Figure 3 The graph shows the hydrogen absorption kinetics of ball-milled PtRu / CNFs in Example 1. Figure 4 This is a graph showing the hydrogen absorption kinetics of PtRu / aminosilicon spheres in Example 2. Figure 5 The hydrogen absorption kinetics curve for the preparation of PtRu / CNFs-DEB at a 50-fold increase in dosage in Example 4; Figure 6 This is a graph showing the hydrogen absorption kinetics of the platinum-ruthenium bimetallic catalyst in Example 5. Figure 7 The NMR spectra of catalysts prepared in different alcohol solution ratios in Example 6 after reacting with DEB at 1 bar for 4 h. Figure 8 The hydrogen absorption kinetics curve of the PtRu / CNFs-DEB@styrene-butadiene rubber (SBR) composite material in Example 7 is shown. Figure 9 The hydrogen absorption kinetics curve of the PtRu / CNFs-DEB@hydroxycellulose (HPC) composite material in Example 8 is shown. Figure 10 The hydrogen absorption kinetics curve of Pt / CNFs-DEB in Comparative Example 1 is shown. Figure 11 The hydrogen absorption kinetics curve and NMR spectrum of the reaction product of Pd / C-DEB in Comparative Example 2 are shown; where a is the hydrogen absorption kinetics curve and b is the NMR spectrum of the reaction product. Figure 12 Hydrogen absorption kinetics curves of PdPtRuCuNi / CNFs high-entropy alloy catalyst and DEB composite hydrogen absorber prepared in large-scale manner for comparative example 3.

[0029] Figure 13 The hydrogen absorption kinetics curve of the Pd / C-DEB@SBR composite material in Comparative Example 6 is shown. Figure 14 The hydrogen absorption kinetics curve is shown for the Pd / C-DEB@HPC composite material of Comparative Example 7. Detailed Implementation

[0030] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, 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.

[0031] In a first aspect, the present invention provides a platinum-ruthenium catalyst for irreversible hydrogen removal, comprising a modified porous support and platinum and ruthenium bimetallic active centers supported on the modified porous support; wherein the platinum and ruthenium exist in the form of an atomic-scale alloy phase or mutually adjacent independent nanoparticles, generating an electronic and geometric synergistic effect.

[0032] In this invention, platinum and ruthenium form a uniform or non-uniform alloy phase at the atomic scale, or platinum and ruthenium are distributed adjacent to each other in the form of independent nanoparticles on the modified porous support, forming a physically mixed structure. The average particle size of the platinum nanoparticles and the ruthenium nanoparticles is independently controlled within 1~15 nm, preferably 1~5 nm.

[0033] In this invention, based on the total mass of the catalyst, the mass fraction of platinum is 0.1% to 40%, preferably 1% to 20%; the mass fraction of ruthenium is 0.1% to 20%, preferably 1% to 10%; and the molar ratio of platinum to ruthenium is 20:1 to 1:3, preferably 5:1 to 1:1.

[0034] In this invention, the porous support comprises one or more of carbon materials, oxides, and organic framework materials; the carbon material comprises one or more of carbon nanofibers, activated carbon, and graphene; the oxide comprises one or more of alumina, titanium dioxide, zirconium dioxide, and porous silicon spheres. Preferably, the porous support can be a modified porous support. The modified porous support is obtained by pretreating the porous support, thereby enhancing metal anchoring or altering electronic effects. Pretreatment includes oxidation or amination.

[0035] In this invention, the platinum-ruthenium catalyst is prepared using a green, environmentally friendly, and scalable process. This process uses a low-toxicity, renewable mixed alcohol as both a solvent and a reducing agent, and the catalyst yield per reactor can reach gram to kilogram levels. The low-toxicity, renewable mixed alcohol includes at least two of ethylene glycol, ethanol, and isopropanol.

[0036] In this invention, the platinum-ruthenium catalyst can also be prepared by sodium borohydride reduction or carbothermal shock method.

[0037] This invention provides a method for preparing a platinum-ruthenium catalyst. When preparing an alloy phase catalyst, the method includes the following steps: S1. Pre-treat the porous support to obtain a modified porous support.

[0038] In this invention, the pretreatment includes oxidation or amination. For example, the oxidation treatment uses a nitric acid solution, the treatment temperature is 90-110 °C, and the reflux time is 2-6 hours.

[0039] S2. Dissolve or disperse a platinum source and a ruthenium source simultaneously in a solvent to obtain a precursor solution, wherein the platinum source and the ruthenium source are each independently selected from soluble metal salts; the solvent is preferably a low-toxicity, renewable mixed alcohol.

[0040] In this invention, the platinum source includes chloroplatinic acid or platinum acetylacetonate, and the ruthenium source includes ruthenium trichloride or ruthenium acetylacetonate; the low-toxicity, renewable mixed alcohol includes at least two of ethylene glycol, ethanol, and isopropanol. Preferably, it is a mixed solution of ethanol and isopropanol, or ethanol and ethylene glycol, with a preferred mixing volume ratio of 1:1 to 1:3.

[0041] S3. The modified porous support is added to the precursor solution, stirred, and then subjected to hydrothermal reduction under inert gas protection to alloy platinum and ruthenium at the atomic scale and load them onto the support to obtain a platinum-ruthenium alloy phase catalyst.

[0042] In this invention, the hydrothermal reduction temperature is 160~240 °C, and the time is 2~6 hours. Preferably, the hydrothermal reduction temperature is 180~220 °C, and the hydrothermal reduction time is 3~5 hours. More preferably, the hydrothermal reduction is carried out under the protection of an inert gas, which is helium or argon.

[0043] In this invention, the stirring is carried out at room temperature for 6 to 12 hours and at a speed of 800 to 1500 rpm.

[0044] In this invention, the preparation method further includes post-treatment. The post-treatment steps include: after the hydrothermal reduction reaction is completed, cooling, separation, washing, and drying to obtain the final catalyst product. Preferably, the drying is vacuum drying at a temperature of 60-80°C for 6-12 hours.

[0045] This invention also provides a method for preparing a platinum-ruthenium catalyst. When preparing a physically mixed structure catalyst, the method includes the following steps: A1. The porous carrier is pretreated to obtain the modified porous carrier.

[0046] In this invention, the pretreatment includes oxidation or amination. For example, the oxidation treatment uses a nitric acid solution, the treatment temperature is 90-110 °C, and the reflux time is 2-6 hours.

[0047] A2. Dissolve or disperse a platinum source in a solvent to obtain a platinum precursor solution, and dissolve or disperse a ruthenium source in a solvent to obtain a ruthenium precursor solution, wherein the platinum source and the ruthenium source are each independently selected from soluble metal salts; the solvent contains a low-toxicity, renewable mixed alcohol.

[0048] In this invention, the platinum source includes chloroplatinic acid or platinum acetylacetonate, and the ruthenium source includes ruthenium trichloride or ruthenium acetylacetonate; the low-toxicity, renewable mixed alcohol includes at least two of ethylene glycol, ethanol, and isopropanol. Preferably, it is a mixed solution of ethanol and isopropanol, or ethanol and ethylene glycol, with a preferred mixing volume ratio of 1:1 to 1:3.

[0049] A3. The platinum precursor solution is mixed with the modified porous support and reacted at 160~240 °C for 2~6 h to obtain a platinum-loaded intermediate; the ruthenium precursor solution is mixed with the modified porous support and reacted at 160~240 °C for 2~6 h to obtain a ruthenium-loaded intermediate.

[0050] In this invention, the mixing in step A3 can be achieved through methods such as ultrasound or stirring.

[0051] A4. The intermediate supported on platinum and the intermediate supported on ruthenium are physically mixed to obtain a physically mixed platinum-ruthenium catalyst in which platinum and ruthenium nanoparticles are adjacent to each other.

[0052] In this invention, the physical method includes one of ball milling, grinding, and high-speed stirring. Preferably, the ball milling time is 0.5 to 10 hours.

[0053] Secondly, the present invention provides a hydrogen absorption mixture comprising the aforementioned platinum-ruthenium catalyst and an unsaturated organic compound, wherein the platinum-ruthenium catalyst is used to catalyze an irreversible hydrogenation reaction between hydrogen and the unsaturated organic compound at room temperature and atmospheric pressure.

[0054] In this embodiment, the mass ratio of the unsaturated organic compound to the platinum-ruthenium catalyst is 1 to 10:1. For example, the mass ratio can be 3:1, 5:1, or 7:1.

[0055] The present invention also provides a method for preparing a hydrogen-absorbing mixture, comprising: mixing a platinum-ruthenium catalyst with an unsaturated organic compound to obtain a hydrogen-absorbing mixture.

[0056] In this embodiment, the mixing method includes one or more of ball milling, grinding, and dissolving. For example, ball milling can be used for mixing, with a rotation speed of 100-400 rpm and a milling time of 10-200 min.

[0057] Thirdly, the present invention also provides a hydrogen absorption (also known as hydrogen elimination) composite material, comprising the above-mentioned platinum-ruthenium catalyst, unsaturated organic compound and polymer; the platinum-ruthenium catalyst is used to catalyze the irreversible hydrogenation reaction between hydrogen and the unsaturated organic compound at room temperature and atmospheric pressure; the polymer serves as a substrate for molding the composite material.

[0058] In this embodiment, the unsaturated organic compound contains one or more unsaturated bonds such as double bonds, triple bonds, carbonyl groups, aldehyde groups, and / or benzene rings. Preferably, the unsaturated organic compound is 1,4-bis(phenylethynyl)benzene.

[0059] In this embodiment, the mass ratio of the unsaturated organic compound to the platinum-ruthenium catalyst is 1 to 10:1. For example, the mass ratio can be 3:1, 5:1, or 7:1.

[0060] In this embodiment, the polymer is any one of styrene-butadiene rubber, hydroxyl cellulose, polyethersulfone, polyamide, and silicone rubber.

[0061] In this embodiment, the mass ratio of the mixture of platinum-ruthenium catalyst and unsaturated organic compound to polymer is (30~98):(70~2).

[0062] Hydrogen-absorbing composite materials can be prepared in one or more of the following forms: granular, thin film, foam, and array.

[0063] This invention also provides an application of a hydrogen-absorbing composite material in the absorption of hydrogen and its isotope gases. A platinum-ruthenium catalyst is mixed with an unsaturated organic compound, and an irreversible hydrogenation reaction is catalyzed between hydrogen and the unsaturated organic compound at room temperature and atmospheric pressure, achieving the chemical fixation and elimination of hydrogen. This application is oxygen-free, requires no open flame, and produces no violent exothermic reactions, exhibiting intrinsic safety characteristics.

[0064] In this invention, unless otherwise specified, all raw materials used in the preparation are commercially available products well known to those skilled in the art.

[0065] The present invention will be described in detail below through embodiments and experimental examples. However, these are merely examples and do not limit the present invention in any way.

[0066] Example 1 0.0528 g of chloroplatinic acid hexahydrate and 0.0146 g of ruthenium acetylacetonate metal salt were dissolved in 40 mL of deionized water and 40 mL of ethanol / ethylene glycol mixed solution, respectively. The solutions were combined and sonicated at 100 W for 30 min to obtain a metal salt precursor solution. 40 mg of oxidized modified carbon nanofibers were added to this solution, and the mixture was stirred at 1200 rpm at room temperature for 10 h to form a homogeneous carbon nanofiber / metal precursor suspension. The suspension was poured into a 200 mL three-necked flask and heated to 160 °C at 500 rpm for 6 h. After cooling to room temperature, the product was collected by centrifugation at 8000 rpm for 10 min and repeatedly washed with deionized water and anhydrous ethanol. The washed product was then vacuum dried at 100 °C for 8 h to obtain 76 mg of PtRu / CNFs catalyst. The PtRu / CNFs catalyst and DEB were ball-milled in a 50 mL ball mill jar at a mass ratio of 1:3. The milling speed was set to 250 rpm, the milling time to 30 min, and the ball-to-material ratio to be 1:1, yielding 45 mg of PtRu / CNFs-DEB hydrogen absorber. The saturated hydrogen absorption capacity was measured to be 748 mL / g using a hydrogen absorption analyzer. Figure 1 Transmission electron microscope images and EDS spectra of PtRu / CNFs; Figure 2 The images show spherical aberration electron microscopy images and corresponding EDS spectra of PtRu / CNFs. Figure 3 The graph shows the hydrogen absorption kinetics of ball-milled PtRu / CNFs in Example 1.

[0067] Example 2 A 150 mL solution of platinum and ruthenium precursors was prepared according to the metal molar ratio in Example 1. Aminosilicone spheres were vacuum-dried at 50 °C for 8 h, and 50 mg were weighed and stirred for 12 h to uniformly disperse the aminosilicone spheres in the precursor solution. The homogeneous solution was poured into a 250 mL hydrothermal reactor and placed in a high-temperature oven. The reaction temperature was set to 190 °C, and the reaction was carried out for 5 h. After the reaction, circulating water was introduced for rapid cooling. After cooling to room temperature, the product was collected by centrifugation at 6000 rpm for 15 min, washed repeatedly with ethanol and deionized water, and vacuum-dried at 50 °C for 12 h to obtain the PtRu / aminosilicone sphere catalyst. This catalyst was ball-milled with DEB at a mass ratio of 1:4 at 100 rpm for 60 min, with a ball-to-material ratio of 1:1, yielding 48 mg of PtRu / aminosilicone sphere-DEB hydrogen absorber. The irreversible hydrogen elimination capacity was tested using a constructed hydrogen absorption tester, and its hydrogen absorption capacity reached 815 mL / g. Figure 4 This is a graph showing the hydrogen absorption kinetics of PtRu / aminosilicon spheres in Example 2.

[0068] Example 3 The feed amounts from Example 1 were scaled up eightfold: 0.3895 g of chloroplatinic acid hexahydrate and 0.1017 g of ruthenium acetylacetonate were dissolved in 165 mL of deionized water and 165 mL of a mixed ethanol / ethylene glycol solution, respectively. The solutions were combined, and 280 mg of oxidized carbon fiber support was added. The mixture was sonicated at 100 W for 24 h and stirred at 600 rpm for 24 h to prepare a suspension in which carbon fibers were uniformly dispersed. This suspension was poured into a 1 L hydrothermal reactor, and the temperature was set to 200 °C. After heating, the reaction was carried out for 4 h. After the reaction was completed, circulating water was introduced for rapid cooling. The mixture was repeatedly centrifuged and washed several times, and the product was collected. It was then dried in a vacuum oven at 60 °C for 24 h to obtain 0.0408 g of PtRu / CNFs catalyst. Using a 300 mL ball mill jar, the obtained catalyst and DEB were ball milled and mixed under the same reaction conditions as in Example 1, ultimately yielding 0.16 g of PtRu / CNFs-DEB hydrogen absorber product in a single step. The hydrogen absorbance of this product was tested in a hydrogen absorption analyzer and found to be 747 mL / g.

[0069] Example 4 The feed amounts from Example 1 were scaled up 20 times: 0.8684 g of chloroplatinic acid hexahydrate and 0.2305 g of ruthenium acetylacetonate were dissolved in 165 mL of deionized water and 165 mL of a mixed ethanol / ethylene glycol solution, respectively. The solutions were combined, and 680 mg of oxidized carbon fiber carrier was added. The mixture was sonicated at 150 W for 24 h and stirred at 800 rpm for 36 h to prepare a suspension with uniformly dispersed carbon fibers. This suspension was poured into a 5 L large hydrothermal reactor and heated to 200 °C at 300 rpm for 5 h, during which the temperature fluctuation was controlled to not exceed 10 °C by controlling the circulating water flow rate. After the reaction was completed, the mixture was naturally cooled to 140 °C, and then rapidly cooled with cooling water. The resulting suspension was filtered through a Buchner funnel to remove the supernatant. The solution was then washed several times with ethanol and deionized water. The remaining solid product was poured into a tray and freeze-dried at -60 °C for 48 h to obtain 1.023 g of PtRu / CNFs catalyst. Using a 500 mL ball mill jar, the obtained catalyst was ball-milled with DEB under the same reaction conditions as in Example 1, ultimately producing 1.038 g of PtRu / CNFs-DEB hydrogen absorber product in one step. The hydrogen absorption capacity was measured to be 748 mL / g using a hydrogen absorption analyzer. Figure 5 The hydrogen absorption kinetics curve for PtRu / CNFs-DEB prepared by increasing the dosage by 50 times in Example 4 is shown.

[0070] Example 5 The method used was the same as in Comparative Example 1, except that the Pt / CNFs catalyst and the Ru / CNFs catalyst were ball-milled at a mass ratio of 5:1 for 30 min at 250 rpm, resulting in a platinum-ruthenium bimetallic catalyst with a simple physical mixture of Pt / CNFs and Ru / CNFs catalysts. 30 mg of this physically mixed catalyst was weighed and manually ground with DEB at a mass ratio of 1:3 in a 75 mm mortar for 10 min to prepare a Pt / CNFs-Ru / CNFs-DEB hydrogen absorber. This hydrogen absorber was tested in a hydrogen absorption analyzer and showed a saturated hydrogen absorption capacity of 787 mL / g. Figure 6 This is a graph showing the hydrogen absorption kinetics of the platinum-ruthenium bimetallic catalyst in Example 5.

[0071] Example 6 Using the catalyst from Example 4, hydrogen absorption mixtures with catalyst-to-DEB mass ratios of 1:3, 1:5, 1:8, 1:10, and 1:15 were prepared. These mixtures were placed in small borosilicate glass vials and then placed in a multi-stage series reactor to test their hydrogen absorption capacity. The multi-stage series reactor ensured that the hydrogen absorption mixtures reacted under identical pressure, temperature, and atmosphere. The DEB conversion rates after 2 h, 4 h, and 8 h at 1 bar hydrogen pressure and 25 °C are shown in Table 1. The final results indicate that a catalyst:DEB ratio of 1:3 exhibits a faster reaction rate and the highest final saturated hydrogen absorption capacity, achieving a 92% DEB conversion rate at room temperature and atmospheric pressure after 8 h. Figure 7 The NMR spectra of the catalysts prepared in different alcohol solution ratios in Example 6 after reacting with DEB at 1 bar for 4 h are shown.

[0072] Example 7 Styrene-butadiene rubber (SBR) and cyclohexane were added to a mixing cup and homogenized at 1000 rpm for 25 min to form a homogeneous SBR solution. Then, PtRu / CNFs-DEB hydrogen-absorbing composite slurry was added to the mixing cup, and homogenization was continued at the same speed and time to obtain a homogeneous slurry with a solid content of 50 wt%, wherein the mass ratio of the hydrogen-absorbing mixture to the SBR substrate was 1:1. The hydrogen-absorbing composite slurry was dried in an oven at 60 ℃ for 5 minutes to obtain a hydrogen-absorbing composite material with a thickness of 100 μm. The hydrogen absorption capacity of this composite material was measured using a high-temperature, high-pressure gas adsorption analyzer, showing a hydrogen absorption capacity as high as 401 mL / g. Figure 8 The graph shows the hydrogen absorption kinetics of the PtRu / CNFs-DEB@SBR composite material in Example 7.

[0073] Example 8 A self-made PtRu / CNFs catalyst and DEB were ball-milled at a mass ratio of 1:3 at 200 rpm for 30 min, with a ball-to-material ratio of 1:1, to obtain a PtRu / CNFs-DEB hydrogen-absorbing mixture. Hydroxycellulose was slowly poured into ethanol under magnetic stirring at 800 rpm and stirred at room temperature for 8 h to prepare a viscous, homogeneous solution. The remaining hydrogen-absorbing mixture was added at a mass ratio of 90 wt%:10 wt% to the hydrogen-absorbing mixture and hydroxycellulose. The mixture was homogenized at 1200 rpm in a homogenizer to obtain a hydrogen-absorbing slurry. The slurry was freeze-dried at -140 °C. The freeze-dried powder was then crushed into powder by rolling and grinding. This powder was then filled into a pre-made mold and pressed at 3 MPa for 5 min to obtain the hydrogen-absorbing composite material. The prepared PtRu / CNFs-DEB@HPC hydrogen-absorbing composite material has a saturated hydrogen absorption capacity of 599 mL / g. Figure 9 The graph shows the hydrogen absorption kinetics of the PtRu / CNFs-DEB@HPC composite material in Example 8.

[0074] Comparative Example 1 0.0176 g of chloroplatinic acid hexahydrate was dissolved in 40 mL of deionized water, and then 40 mL of a mixed solution of ethanol and ethylene glycol was added. This mixture was sonicated at 100 W for 2 h and magnetically stirred at 500 rpm for 2 h. The solution was then poured into a 100 mL hydrothermal reactor for reaction at 180 °C for 5 h. After natural cooling, the Pt / CNFs catalyst was obtained by centrifugation and washing. 32 mg of this Pt / CNFs catalyst and 96 mg of DEB were weighed and manually ground in a mortar for 10 min to prepare the Pt / CNFs-DEB hydrogen absorber. The hydrogen absorption capacity was tested using an H-sorb 2600 high-temperature and high-pressure gas adsorption device at pressures ranging from 0 to 1 bar. The hydrogen absorption capacity of the absorber was recorded as a function of pressure. Ultimately, the Pt / CNFs-DEB hydrogen absorber exhibited a hydrogen absorption capacity of 367 mL / g. Figure 10 The hydrogen absorption kinetics curves for Pt / CNFs-DEB in Comparative Example 1 are shown.

[0075] Comparative Example 2 Commercially available Pd / C catalyst was purchased and ball-milled with DEB at a mass ratio of 1:3. The ball milling speed was 250 rpm, and the milling time was 30 min, with a ball-to-material ratio of 1:1, to obtain the Pd / C-DEB hydrogen absorber. The hydrogen absorption capacity of this catalyst was tested using a hydrogen absorption analyzer, and it was found to be 196 mL / g. The product after hydrogen absorption was collected, dissolved in deuterated chloroform, and characterized by NMR. The NMR results are shown below. Figure 4As shown, Pd / C can only catalyze the addition of unsaturated alkyne bonds to DEB, while the large π bonds of the benzene ring do not break, thus greatly limiting the hydrogen absorption capacity. Here, Figure 11 The hydrogen absorption kinetics curve and NMR spectrum of the reaction products of Pd / C-DEB in Comparative Example 2 are shown.

[0076] Comparative Example 3 Pd@FAU catalysts were prepared via a hydrothermal method in the presence of MPTS. First, 37.08 g of Na₂SiO₃·9H₂O and 2.97 g of MPTS were dissolved in 90 mL of deionized water at room temperature, denoted as solution A. 0.69 g of Pd(NH₃)₄Cl₂·H₂O was dissolved in 20 mL of deionized water, denoted as solution B. Solution B was added dropwise to solution A, and stirring was continued for 10 min to prepare solution C. Next, 9.33 g of NaAlO₂ was dissolved in 24 mL of deionized water, and the resulting solution was added dropwise to solution C, with vigorous stirring to obtain a homogeneous mixture. Third, 2.42 g of NaOH was dissolved in 20 mL of deionized water, and the resulting solution was added to mixture A to change its composition to 3.25 SiO₂ / 1 Al₂O₃ / 6 Na₂O / 260 H₂O / 0.067 Pd / 0.40 MPTS. The mixture was then stirred at room temperature for 1 h, denoted as mixture B. Fourth, mixture B was transferred to a PTFE-lined stainless steel autoclave and crystallized at 60 °C for 72 h. The crystallized product was washed with deionized water to pH 7-8 and then dried at 80 °C overnight. Subsequently, the resulting product was heated again from room temperature to 350 °C at 5 °C / min and held at this temperature for 2 h to remove the organic fraction, and then cooled to room temperature. Finally, the product was heated to 350 °C at 5 °C / min in a flowing stream of 5 vol% H2 / He and reduced for 2 h to obtain a Pd@FAU catalyst with 1.0 wt% Pd particles and a maximum hydrogen absorption capacity of 257 mL / g. Figure 12 Hydrogen absorption kinetics curves of PdPtRuCuNi / CNFs high-entropy alloy catalyst and DEB composite hydrogen absorber prepared in large-scale manner for comparative example 3.

[0077] Comparative Example 4 Palladium (Pd) nanoparticles with different loadings were prepared on the surface of reduced graphene oxide (rGO / Pd) using a one-step reduction method. 100 mg of graphene oxide (GO) was added to 50 mL of deionized water, and a uniformly dispersed suspension was formed after stirring and ultrasonic dispersion for 2 h. Bottom impurities were then filtered out. Next, Na₂PdCl₄ solution was added dropwise to 50 mL of GO suspension at calculated concentrations of 0.125, 0.25, 0.375, 0.50, 0.625, 1.0, and 3.0 mmol / g GO, and dispersion was continued under ultrasonication for 30 min. Finally, excess NaBH₄ solution was added dropwise to the above solution with continuous stirring, followed by filtration and washing. Then, rGO / Pd catalyst and DEB powder were mixed at a mass ratio of 1:3 to prepare rGO / Pd-DEB composite materials. First, DEB powder was added to dichloromethane (CH₂Cl₂) and ultrasonically dispersed to form a DEB suspension. Then, the rGO / Pd catalyst was immersed in a DEB suspension and sonicated for 30 min to form an rGO / Pd-DEB mixed solution. The mixture was then vacuum-milled and dried at 60 °C for 24 h to obtain the rGO / Pd-DEB composite material. After reacting with hydrogen at 25 °C for about 20 hours, the maximum hydrogen absorption capacity was approximately 182.5 mL / g.

[0078] Comparative Example 5 Commercial palladium-on-carbon catalyst was purchased and mixed with DEB at a mass ratio of 1:3 using ball milling at 200 rpm for 30 min (ball-to-material ratio 1:1) to obtain a Pd / C-DEB hydrogen absorber. This Pd / C-DEB hydrogen absorber was then further mixed with a styrene-butadiene rubber (SBR) substrate at a mass ratio of 1:1 to prepare a hydrogen-absorbing composite membrane via casting. The composite membrane was vacuum-dried before testing its hydrogen absorption capacity. Hydrogen absorption capacity was tested using an H-sorb 2600 high-temperature, high-pressure gas adsorption apparatus at pressures ranging from 0 to 1 bar, and the hydrogen absorption capacity of the composite membrane was recorded as a function of pressure. Ultimately, the PdC-DEB@SBR hydrogen-absorbing composite membrane exhibited a hydrogen absorption capacity of 103 mL / g. Figure 13 The hydrogen absorption kinetics curve is shown for the PdC-DEB@SBR hydrogen absorption composite membrane in Comparative Example 6.

[0079] Comparative Example 6 Commercial palladium-on-carbon catalyst was purchased and mixed with DEB at a mass ratio of 1:3 using ball milling at 200 rpm for 30 min (particle-to-material ratio of 1:1) to obtain a Pd / C-DEB hydrogen absorber. This Pd / C-DEB hydrogen absorber mixture was further mixed with hydroxyl cellulose (HPC) substrate at a mass ratio of 90:10. The powder was filled into a cylindrical mold and pressed under pressure at 3 MPa for 5 min to obtain a hydrogen-absorbing composite material. The composite material was vacuum-dried before testing its hydrogen absorption capacity. Hydrogen absorption capacity was tested using an H-sorb 2600 high-temperature, high-pressure gas adsorption device at pressures ranging from 0 to 1 bar, and the hydrogen absorption amount of the composite material was recorded as a function of pressure. Ultimately, the Pd / C-DEB@HPC hydrogen-absorbing composite material exhibited a hydrogen absorption capacity of 216 mL / g. Figure 14 The hydrogen absorption kinetics curve is shown for the Pd / C-DEB@HPC composite material of Comparative Example 7.

[0080] Table 1 shows the DEB conversion rates after the reaction in Example 6 with different catalysts and DEB mass ratios of 1 bar.

[0081] Table 1 Table 2 is a comparison table of hydrogen removal performance between each embodiment and each comparative example.

[0082] Table 2 Various embodiments of the present invention may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of the invention; therefore, it should be considered that the range description has specifically disclosed all possible subranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the range referred to.

[0083] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A platinum-ruthenium catalyst for irreversible hydrogen removal, characterized in that, It includes a modified porous support and platinum and ruthenium bimetallic active centers loaded on the modified porous support; the platinum and ruthenium exist in the form of atomic-scale alloy phases or adjacent independent nanoparticles, generating electronic and geometric synergistic effects.

2. The platinum-ruthenium catalyst according to claim 1, characterized in that, The platinum and ruthenium form a uniform or non-uniform alloy phase at the atomic scale; or the platinum and ruthenium are distributed adjacent to each other in the form of independent nanoparticles on the modified porous support, forming a physical hybrid structure.

3. The platinum-ruthenium catalyst according to claim 1 or 2, characterized in that, The platinum-ruthenium catalyst is prepared using a green, environmentally friendly, and scalable process. The process uses a low-toxicity, renewable mixed alcohol as a solvent and reducing agent, and the catalyst yield of a single reactor can reach the gram to kilogram level.

4. A hydrogen-absorbing mixture, characterized in that, The invention comprises the platinum-ruthenium catalyst as described in any one of claims 1-3 and the unsaturated organic compound, wherein the platinum-ruthenium catalyst is used to catalyze an irreversible hydrogenation reaction between hydrogen and the unsaturated organic compound at room temperature and atmospheric pressure.

5. A hydrogen-absorbing composite material, characterized in that, The invention comprises a platinum-ruthenium catalyst as described in any one of claims 1-3, an unsaturated organic compound, and a polymer; the platinum-ruthenium catalyst is used to catalyze an irreversible hydrogenation reaction between hydrogen and the unsaturated organic compound at room temperature and atmospheric pressure; the polymer is used as a substrate for composite material molding.

6. The hydrogen-absorbing composite material according to claim 5, characterized in that, The unsaturated organic compound contains one or more unsaturated bonds such as double bonds, triple bonds, carbonyl groups, aldehyde groups, and / or benzene rings.

7. The hydrogen-absorbing composite material according to claim 6, characterized in that, The unsaturated organic compound is preferably 1,4-bis(phenylethynyl)benzene.

8. The hydrogen-absorbing composite material according to claim 5, characterized in that, The mass ratio of the unsaturated organic compound to the platinum-ruthenium catalyst is 1~10:

1.

9. The hydrogen-absorbing composite material according to claim 5, characterized in that, The polymer is any one of styrene-butadiene rubber, hydroxyl cellulose, polyethersulfone, polyamide, and silicone rubber.

10. The hydrogen-absorbing composite material according to claim 5, characterized in that, The mass ratio of the hydrogen-absorbing mixture formed by the platinum-ruthenium catalyst and the unsaturated organic compound to the polymer is (30~98):(70~2).

11. The hydrogen-absorbing composite material according to claim 5, characterized in that, The hydrogen-absorbing composite material can be prepared in one or more of the following forms: granular, thin film, foam, and array.

12. The application of the hydrogen-absorbing composite material according to any one of claims 5 to 11 in the absorption of hydrogen and its isotope gases.

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