Organic hydride dehydrogenation catalysts, preparation methods, integrated processes and equipment

Abstract

This invention belongs to the field of catalyst technology, and discloses an organic hydride dehydrogenation catalyst, its preparation method, integrated process, and equipment. The organic hydride dehydrogenation catalyst comprises Pt nanoparticles and MnO. x And oxide carrier (MO) powder, wherein the Pt nanoparticles are supported on MnO x Pt-MnO was obtained from / MO powder. x The Pt / MO catalyst contains 0.5–1.5 wt.% Pt, and the MO support is Al₂O₃ or MgAl₂O₄. This invention introduces manganese oxide into the oxide support to further regulate the electronic structure of the Pt nanoparticles in the catalyst. With minimal impact on the dispersion of Pt nanoparticles in the catalyst, the introduction of Mn₂O₃ optimizes the positive charge state of the Pt nanoparticles, thus balancing reactant adsorption and product desorption. The Pt-Mn₂O₃ / MO catalyst exhibits the highest dehydrogenation activity for organic hydrides at different temperatures.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, and particularly relates to organic hydride dehydrogenation catalysts, preparation methods, integrated processes and equipment. Background Technology

[0002] Traditional fossil fuels such as coal, oil, and natural gas have provided humanity with a vast energy supply, offering convenience and comfort alongside industrialization. However, with the accelerating pace of modern civilization and ever-increasing energy demands, the gradual depletion and non-renewable nature of traditional fossil fuels are placing immense pressure on future energy supply systems. Simultaneously, the extensive use of traditional fossil fuels also generates numerous problems. For instance, their widespread application increases carbon emissions, posing challenges to the global climate; the combustion of fossil fuels produces harmful gases that pollute the environment; and over-exploitation of fossil fuels causes environmental damage. These issues compel the continuous exploration of alternative energy sources to replace traditional fossil fuels and drive a shift in the world's energy supply towards cleaner, low-carbon alternatives to meet energy demands and protect the environment upon which humanity depends.

[0003] Hydrogen energy is a clean energy source. The combustion product of hydrogen is water, and the combustion process does not produce any pollutants. Furthermore, the calorific value of hydrogen is 1.4 × 10⁻⁶. 8 With a calorific value of J / kg, hydrogen is approximately three times that of gasoline and 4.7 times that of coal under the same conditions. The cleanliness and high calorific value of hydrogen make it an ideal alternative to fossil fuels, attracting widespread analysis from scholars. The industrial chain of hydrogen energy mainly includes hydrogen production, storage, and utilization. Hydrogen production includes industrial hydrogen production, biological hydrogen production, and water electrolysis; hydrogen storage and transportation include physical and chemical hydrogen storage; and hydrogen applications include combustion heat generation and hydrogen fuel cells.

[0004] However, the key technological bottleneck currently hindering the widespread adoption of hydrogen energy technology lies in its storage and transportation. Existing hydrogen storage and transportation technologies primarily rely on high-pressure tank storage and liquid hydrogen. The advantage of H2 as a high-pressure gas lies in its rapid filling and release rates, while the large space requirements and safety concerns are its main drawbacks. Liquefying hydrogen for storage can achieve higher energy density per unit volume, but this also results in higher energy consumption. Organic liquid hydrogen storage technology is an emerging approach. This technology utilizes the reversible hydrogenation / dehydrogenation cycle of unsaturated hydrocarbon organic compounds to achieve hydrogen storage and release. Organic hydrides, as hydrogen storage media, offer advantages such as stability, low cost, easy availability, and high hydrogen storage density.

[0005] Decahydronaphthalene, cyclohexane, and methylcyclohexane, as liquid organic hydrides, possess considerable hydrogen storage density and relatively low dehydrogenation temperatures, making them promising hydrogen storage media. However, this organic liquid hydrogen storage technology still faces certain challenges, particularly in the dehydrogenation process. For example, the dehydronaphthalene dehydrogenation reaction is endothermic, resulting in low conversion rates and slow hydrogen release at low temperatures, and poor catalyst stability at high temperatures. Pt group metals, due to their strong CH bond activation ability, have become the main active components in organic hydrocarbon dehydrogenation catalysts. However, Pt-based catalysts are prone to coking and deactivation during dehydrogenation reactions, failing to meet long-term application requirements. Furthermore, Pt group metals are typically expensive, leading to high costs for organic hydride dehydrogenation catalysts. Therefore, the design and development of organic hydride dehydrogenation catalysts are crucial for the widespread adoption of organic liquid hydrogen storage technologies such as decahydronaphthalene.

[0006] Over the past two decades, researchers both domestically and internationally have conducted extensive analyses focusing on improving the dehydrogenation performance of organic hydrides in catalysts and reducing the amount of Pt used. These analyses primarily involve two approaches: one is to form alloys of Pt with other metals (the second metal being Ru, Re, Ir, Pd, Ni, Mo, and W, etc.), and the other is to develop non-noble metal catalysts. Analytical results show that even carefully designed non-noble metal alloys (such as Ni-Cu) exhibit significantly lower catalytic activity (93.84 mmol H2 / gmetal / min) compared to Pt catalysts (460 mmol H2 / gmetal / min) under the same reaction conditions, while the introduction of even a small amount of Pt can significantly improve the activity of non-noble metal catalysts.

[0007] Based on the above analysis, the problems and shortcomings of the existing technology are as follows:

[0008] (1) In the existing technology, the hydrogen production rate per unit Pt is slow, the preparation method is complicated and difficult to control.

[0009] (2) Existing technologies cannot perform integrated catalyst design for strongly endothermic reactions, resulting in poor mass and heat transfer performance. Summary of the Invention

[0010] To overcome the problems existing in related technologies, the present invention discloses an organic hydride dehydrogenation catalyst, preparation method, integrated process and equipment.

[0011] The technical solution is as follows: an organic hydride dehydrogenation catalyst, comprising Pt element and MnO. x and the oxide support MO, wherein the Pt element is loaded onto MnO x MnO made with oxide support MO x Pt-MnO was obtained from / MO composite powder. x / MO catalyst, X is 1 to 3, Pt element content is 0.5 to 1.5 wt.%.

[0012] In one embodiment, the MO oxide support is Al2O3 or MgAl2O4.

[0013] In one embodiment, the Pt element is Pt 0 Pt 2+ and Pt 4+ It exists in the form of.

[0014] In one embodiment, the elemental content of Mn is 0–5 wt.%.

[0015] Another object of the present invention is to provide a method for preparing the aforementioned organic hydride dehydrogenation catalyst, comprising:

[0016] Preparation of MnO x / MO powder, wherein MO is an oxide carrier;

[0017] Pt element loaded on MnO x Pt-MnO was obtained from / MO powder. x / MO catalyst, X is 1 to 3, Pt element content is 0.5 to 1.5 wt.%.

[0018] In one embodiment, Pt-MnO x The preparation methods of / MO catalysts include:

[0019] Preparation of S1,γ-Al2O3: Materials with a specific surface area ≥250m² 2 / g of pseudoboehmite was placed in a muffle furnace and heated to 600-800℃ at a certain heating rate. Then, it was kept at a constant temperature for 4-12h and cooled to room temperature to obtain γ-Al2O3.

[0020] Preparation of S2,MgAl2O4: Magnesium acetate as magnesium source and aluminum isopropoxide as aluminum source were mixed in anhydrous ethanol and placed in a micro high-pressure reactor; the mixture was continuously stirred and heated to 120℃ and held for 10 h, then heated to 160℃ and held for 10 h; after cooling to room temperature, the precipitate was washed several times with deionized water and ethanol, dried at 100℃, and finally calcined in a muffle furnace at 700℃;

[0021] S3, using γ-Al2O3 or MgAl2O4 as a support, introduces at least one manganese oxide onto an alumina support to prepare MnO. x / MO, MnO x / MO includes: MnO / MO, Mn2O3 / MO and MnO2 / MO;

[0022] S4, loading Pt elements onto MnO xPt-MnO was prepared on / MO. x / MO catalyst; X is 1 to 3, Pt content is 0.5 to 1.5 wt.%, and MO oxide support is Al2O3 or MgAl2O4.

[0023] In one embodiment, the Pt-MnO is obtained x / MO catalyst, further steps are needed:

[0024] Testing Pt-MnO x / MO catalysts exhibited dehydrogenation activity of organic hydrides at different reaction temperatures (230℃, 250℃, and 270℃), and the Pt-MnO4 catalyst at 250℃ was also tested. x The cyclic catalytic performance of the / MO catalyst; and the further evaluation of Pt-MnO x The Pt-MnO catalyst was comprehensively characterized and analyzed. x Structure-activity relationship of / MO catalysts.

[0025] Another object of the present invention is to provide a Pt-MnO x The preparation method of / MO / honeycomb ceramic catalyst includes the following steps:

[0026] (1) Pretreatment of the monolithic catalyst matrix: use hydrochloric acid or acetic acid with a mass fraction of 10% to 30% as a pretreatment agent, treat at 60 to 80°C for 3 hours, wash with water until neutral after acid treatment, dry and weigh for later use.

[0027] (2) Active component Pt-MnO x Preparation of / MO catalyst powder;

[0028] (3) Preparation of binder: Weigh Al2O3 sol and surfactant polyethylene glycol according to the weight of active component powder. The weight ratio of active component powder to binder is 1:1 to 3, and the weight ratio of active component powder to polyethylene glycol is 1:0.1 to 0.3.

[0029] (4) Preparation of coating slurry: Based on the mass of cordierite honeycomb ceramics, the weight ratio of active component and binder is as follows: 9-11 parts by weight of active component, 10-25 parts by weight of binder mixture, and 64-77 parts by weight of water. The active component powder is added to a ball mill and ground for 1 hour. The binder is dissolved in water and mixed to prepare a coating slurry. The solid content of the coating slurry is 20%-50%.

[0030] (5) Coating operation: The cordierite honeycomb ceramic pretreated in step (1) is immersed in the coating slurry prepared in step (4) for 30 minutes. After removal, excess slurry is blown off, dried at 80 degrees Celsius for 2 hours, and calcined at 300 degrees Celsius for 3 hours. The weight is measured and the above operation is repeated until the required weight is achieved on the honeycomb ceramic to obtain Pt-MnO. x / MO / Cellular ceramic catalyst.

[0031] Another objective of this invention is to provide an organic liquid hydrogen storage and release device that uses the organic hydride dehydrogenation catalyst as the core material.

[0032] Combining all the above technical solutions, the advantages and positive effects of this invention are as follows:

[0033] First, addressing the technical problems existing in the prior art and the difficulty in solving them, this paper closely analyzes, in conjunction with the technical solution to be protected by this invention and the results and data obtained during the research and development process, how the technical solution of this invention solves the technical problems, and the inventive technical effects brought about by solving these problems. The specific description is as follows:

[0034] In this invention, a self-made γ-Al₂O₃ catalyst support is used. First, three manganese oxides are introduced onto the support to prepare MnO. x / Al2O3, then load Pt elements onto MnO x Three types of Pt-MnO were prepared on Al2O3. x / Al2O3 catalyst;

[0035] Testing Pt / Al2O3 and Pt-MnO x The dehydronaphthalene dehydrogenation activity (mainly including conversion rate and hydrogen yield) of Pt / Al2O3 catalyst at different reaction temperatures (230, 250 and 270 °C) was tested, and the dehydrogenation activity of Pt / Al2O3 and Pt-MnO3 at 250 °C was also tested. x Cyclic catalytic performance of Pt / Al2O3 catalyst (three cycles); followed by Pt / Al2O3 and Pt-MnO3 catalysts. x A comprehensive characterization analysis was performed on the Pt / Al2O3 catalyst to analyze Pt / Al2O3 and Pt-MnO. x Structure-activity relationship of Al2O3 catalyst.

[0036] In the early stages of research and development, by comparing the catalytic activities of Pt catalysts supported on carbon nanofibers (Pt / CNF) and Pt catalysts supported on magnesium aluminum spinel (Pt / MgAl2O4), combined with structural characterization and theoretical calculations, it was found that Pt in a slightly positive valence state is beneficial to improving the dehydronaphthalene dehydrogenation performance. Based on this, this invention introduces MnO with a diverse and tunable electronic structure. xBy adjusting the positive charge of Pt, the adsorption behavior of key species during the reaction can be optimized, thereby achieving efficient dehydrogenation of organic hydrides.

[0037] Organic liquid hydrogen storage technology is a potential solution for hydrogen energy storage and transportation. Decahydronaphthalene, as a liquid organic hydrogen storage compound, has advantages such as large theoretical hydrogen storage capacity and high hydrogen storage efficiency. However, the current bottleneck in decahydronaphthalene hydrogen storage technology lies in the development of dehydrogenation catalysts. This invention addresses the key scientific problems of low catalytic dehydrogenation activity and poor stability of decahydronaphthalene. It utilizes a transition metal oxide support to regulate the electronic structure of Pt nanoparticles, optimizes the adsorption capacity of reactants and products, and systematically analyzes the structure-activity relationship of the catalyst. This guides the design and development of highly efficient Pt-based catalysts for the dehydrogenation of organic hydrides. The main contents include:

[0038] Excessively positively charged Pt (such as PtO2) can lead to decreased dehydrogenation activity due to weak adsorption of the reactant decahydronaphthalene. Therefore, theoretically, there exists an optimal degree of Pt positive charge to coordinate the activation of decahydronaphthalene and the desorption of the product naphthalene, thereby achieving the best dehydrogenation activity for decahydronaphthalene. Therefore, introducing manganese oxides into the oxide support (Al2O3 or MgAl2O4) further modulates the electronic structure of Pt nanoparticles in the catalyst. The introduction of MnO, Mn2O3, and MnO2 enhances the Pt-MnO... x In the Al2O3 catalyst, the positive charge of Pt gradually decreases. Under the premise of minimal impact on the dispersion of Pt nanoparticles in the catalyst, the introduction of Mn2O3 optimizes the positive charge of Pt nanoparticles. The average valence state of Pt nanoparticles in the Pt-Mn2O3 / Al2O3 catalyst is [value missing]. Avs The value is 0.9, thus taking into account both the adsorption of reactants and the desorption of products. At different temperatures, the Pt-Mn2O3 / Al2O3 catalyst exhibits the highest dehydrogenation activity of decahydronaphthalene.

[0039] Second, considering the technical solution as a whole or from the perspective of the product, the technical effects and advantages of the technical solution to be protected by this invention are specifically described as follows:

[0040] While minimizing the impact on the dispersion of Pt nanoparticles in the catalyst, the introduction of Mn2O3 optimizes the positive charge state of the Pt nanoparticles, thus balancing reactant adsorption and product desorption. The Pt-Mn2O3 / Al2O3 catalyst exhibits the highest dehydrogenation activity for organic hydrides at different temperatures. This invention achieves an internationally leading hydrogen production rate per unit of Pt, with a simple, controllable, and easily scaled-up preparation method. Furthermore, it allows for integrated catalyst design to enhance mass and heat transfer, particularly for strongly endothermic reactions. Organic hydrides include, but are not limited to, decahydronaphthalene, cyclohexane, and methylcyclohexane. Attached Figure Description

[0041] The accompanying drawings, which are incorporated in and form a part of this specification, illustrate embodiments consistent with this disclosure and, together with the description, serve to explain the principles of this disclosure.

[0042] Figure 1 This is a flowchart of the preparation method provided in the embodiments of the present invention;

[0043] Figure 2(a) shows the relationship between hydrogen release amount and time within 30 min in the catalytic performance of Pt-Mn2O3 / Al2O3, Pt / Al2O3, Pt-MnO2 / Al2O3 and Pt-MnO / Al2O3 catalysts in the dehydronaphthalene dehydrogenation reaction at different temperatures provided in the embodiments of the present invention.

[0044] Figure 2(b) shows the relationship between hydrogen release rate and temperature in the catalytic performance of Pt-Mn2O3 / Al2O3, Pt / Al2O3, Pt-MnO2 / Al2O3 and Pt-MnO / Al2O3 catalysts in the dehydronaphthalene dehydrogenation reaction provided in the embodiments of the present invention at different temperatures.

[0045] Figure 2(c) shows the hydrogen yield at 30 min in the catalytic performance of Pt-Mn2O3 / Al2O3, Pt / Al2O3, Pt-MnO2 / Al2O3 and Pt-MnO / Al2O3 catalysts in the dehydronaphthalene dehydrogenation reaction at different temperatures provided in the embodiments of the present invention.

[0046] Figure 3 These are the XRD patterns of the reduced Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3 and Pt-MnO2 / Al2O3 catalysts provided in the embodiments of the present invention;

[0047] Figure 4(a) shows the HAADF-STEM images of the reduced Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3 and Pt-MnO2 / Al2O3 catalysts provided in the embodiments of the present invention.

[0048] Figure 4(b) is an HRTEM image of the reduced Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3 and Pt-MnO2 / Al2O3 catalysts provided in the embodiments of the present invention;

[0049] Figure 5 These are H2-TPR results of the Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3 and Pt-MnO2 / Al2O3 catalysts provided in the embodiments of the present invention;

[0050] Figure 6(a) shows the XPS spectrum of Pt 4d in the catalyst provided by the embodiment of the present invention;

[0051] Figure 6(b) shows the XPS spectrum fitting of Pt 4d in the catalyst provided in the embodiment of the present invention, where the main peak is convolved into three peaks, corresponding to Pt respectively. 0 (~331.1eV), Pt 2+ (~332.3eV) and Pt 4+ (~334.1eV), the content of Pt in each valence state was calculated based on the proportion of peak area;

[0052] Figure 6(c) shows the XPS spectrum of Mn 2p in the catalyst analyzed by XPS according to an embodiment of the present invention. The main peak is convolved into three peaks, which correspond to Mn 2p and Mn 2p respectively. 2+ (~653eV), Mn 3+ (~653.5eV) and Mn 4+ (~654eV), the content of Mn in each valence state is calculated based on the proportion of peak area;

[0053] Figure 7 The Pt / Al2O3 and Pt-MnO provided in the embodiments of the present invention x Pt in Al2O3 catalyst Avs Mn Avs value, Pt 0 Percentage content. Detailed Implementation

[0054] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. Many specific details are set forth in the following description to provide a thorough understanding of the present invention. However, the present invention can be practiced in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0055] I. Explanation of the Implementation Example:

[0056] Example 1

[0057] This invention provides an organic hydride dehydrogenation catalyst comprising Pt and MnO. x And oxide support MO, via MnO x MnO was prepared by combining MO with oxide support. x / MO powder, wherein the Pt element is loaded in MnO x Pt-MnO was obtained from / MO powder. x / MO catalyst, X is 1 to 3, Pt element content is 0.5 to 1.5 wt.%.

[0058] In a preferred embodiment, the MO oxide support is Al2O3 or MgAl2O4.

[0059] In a preferred embodiment, the Pt element is Pt 0 Pt 2+ and Pt 4+ It exists in the form of.

[0060] In a preferred embodiment, the elemental content of Mn is 0–5 wt.%, preferably 3 wt.%.

[0061] Example 2

[0062] like Figure 1 As shown, an embodiment of the present invention provides a method for preparing an organic hydride dehydrogenation catalyst, comprising:

[0063] S101, Preparation of MnO x / MO powder, wherein MO is an oxide carrier;

[0064] S102, Pt element loaded in MnO x Pt-MnO was obtained from / MO powder. x / MO catalyst, X is 1 to 3, Pt element content is 0.5 to 1.5 wt.%.

[0065] Specifically,

[0066] This invention provides a method for preparing an organic hydride dehydrogenation catalyst, comprising:

[0067] Preparation of S1,γ-Al2O3: Materials with a specific surface area ≥250m² 2 / g of pseudoboehmite was placed in a muffle furnace and heated to 600-800℃ at a certain heating rate. Then, it was kept at a constant temperature for 4-12h and cooled to room temperature to obtain γ-Al2O3.

[0068] Preparation of S2,MgAl2O4: Magnesium acetate as the magnesium source and aluminum isopropoxide as the aluminum source were mixed in anhydrous ethanol and placed in a micro high-pressure reactor. The mixture was continuously stirred and heated to 120℃ and held for 10 h, then heated to 160℃ and held for 10 h. After cooling to room temperature, the precipitate was washed multiple times with deionized water and ethanol, dried at 100℃, and finally calcined in a muffle furnace at 700℃.

[0069] S3, using γ-Al2O3 or MgAl2O4 as a support, introduces at least one manganese oxide onto an alumina support to prepare MnO. x / MO, MnO x / MO includes: MnO / MO, Mn2O3 / MO, and prepared MnO2 / MO;

[0070] S4, loading Pt elements onto MnO x Pt-MnO was prepared on / MO. x / MO catalyst; X is 1 to 3, Pt content is 0.5 to 1.5 wt.%, and MO oxide support is Al2O3 or MgAl2O4.

[0071] MnO x There are various oxides, and it is proposed to introduce three oxides: MnO, Mn2O3, and MnO2.

[0072] MnO x It can serve as a platform for regulating the electronic structure of Pt, with MnO x MnO is constructed using surface Mn / O atoms as the link. x -Pt nanostructures. Modulating MnO using Mn valence state and crystal structure. x The Mn / O-Pt coordination environment at the Pt interface enables precise control of the Pt electronic structure.

[0073] In a preferred embodiment, step S1, the preparation of the γ-Al2O3 catalyst support includes:

[0074] ≥250m² 2 / g of pseudoboehmite was placed in a muffle furnace, heated to 700℃ at 2℃ / min, then kept at a constant temperature for 9h, and cooled to room temperature to obtain γ-Al2O3.

[0075] In a preferred embodiment, in step S2, MnO is prepared. x The methods for using Al2O3 include:

[0076] Preparation of MnO / Al2O3: Mn(NO3)2 and urea were dissolved in deionized water, and then γ-Al2O3 was added. The solution was stirred for 0.5 h, and then placed in a hydrothermal reactor and hydrothermally treated at 100 °C for 16 h. The mixture in the hydrothermal reactor was then cooled to room temperature, vacuum filtered, and washed with deionized water until the solution was colorless. It was dried at 80 °C for 12 h, and the dried powder was ground evenly. It was then calcined at 500 °C for 4 h in a 10% H2 / Ar atmosphere to obtain light gray MnO / Al2O3 powder.

[0077] Preparation of Mn2O3 / Al2O3: Mn(NO3)2 was added to ethanol and stirred until homogeneous. Then, γ-Al2O3 was added to manganese nitrate ethanol solution and stirred for 0.5 h. Subsequently, the mixture was added to a hydrothermal reactor and hydrothermally treated at 120 °C for 12 h. The mixture in the hydrothermal reactor was then cooled to room temperature, vacuum filtered, and washed with deionized water until the solution was colorless. It was dried at 80 °C for 12 h, and the dried powder was ground uniformly and calcined in a muffle furnace at 500 °C for 2 h to obtain Mn2O3 / Al2O3 powder.

[0078] MnO2 / Al2O3 was prepared by evaporation impregnation method: Mn(NO3)2 and γ-Al2O3 were added to H2O and stirred continuously. The mixture was kept in a water bath at 60℃ for 1 h, and then the water was evaporated at the same temperature. Then it was dried at 80℃ overnight. The resulting powder was ground evenly and placed in a muffle furnace and calcined at 400℃ for 4 h to obtain MnO2 / Al2O3 powder.

[0079] In a preferred embodiment, after step S3, the following also needs to be performed:

[0080] Testing Pt-MnO x The dehydrogenation activity of Al2O3 catalyst for organic hydrides at different reaction temperatures of 230℃, 250℃ and 270℃, and the Pt-MO dehydrogenation activity at 250℃ were also tested. x The cyclic catalytic performance of Al2O3 catalyst; and the further analysis of Pt-MnO x A comprehensive characterization analysis of the Al2O3 catalyst was performed, and the Pt-MnO4 catalyst was analyzed. x Structure-activity relationship of Al2O3 catalyst.

[0081] In this embodiment of the invention, a combination of Pt / Al2O3 and Pt-MnO is used. x A comprehensive characterization analysis of the Pt / Al2O3 catalyst was performed. In this embodiment of the invention, a Pt / Al2O3 catalyst was used as a comparison to test the performance of Pt / Al2O3 and Pt-MnO3. x The dehydronaphthalene dehydrogenation activity (mainly including dehydrogenation rate and hydrogen yield) of Pt / Al2O3 catalyst at different reaction temperatures (230, 250 and 270 °C) was tested, and the dehydrogenation activity of Pt / Al2O3 and Pt-MO at 250 °C was also tested. x Cyclic catalytic performance of Pt / Al2O3 catalyst (three cycles); followed by Pt / Al2O3 and Pt-MnO3 catalysts. x A comprehensive characterization analysis was performed on the Pt / Al2O3 catalyst to analyze Pt / Al2O3 and Pt-MnO. x Structure-activity relationship of Al2O3 catalyst.

[0082] Example 3

[0083] The method for preparing the organic hydride dehydrogenation catalyst provided in Example 2 further includes:

[0084] (1) The oxide support MgAl2O4 was prepared by alcoholysis;

[0085] (2) MgAl2O4 catalysts were obtained by loading Pt elements with loading amounts of 0.15 wt.%, 1 wt.% and 1.5 wt.% onto the catalyst MgAl2O4.

[0086] Another alternative is that MgAl2O4 can be replaced by carbon nanofibers (CNF) to obtain a Pt / CNF catalyst.

[0087] The preparation of the Pt / MgAl2O4 catalyst with a Mn content of 0% includes:

[0088] The preparation of Pt / MgAl2O4 and Pt / CNF includes the following steps:

[0089] (1) Preparation of MgAl2O4 and CNF supports

[0090] The steps for preparing MgAl₂O₄ using the alcoholysis method are as follows: Magnesium acetate as the magnesium source and aluminum isopropoxide as the aluminum source are mixed in anhydrous ethanol and placed in a micro high-pressure reactor; the mixture is continuously stirred and heated to 120℃ and held for 10 h, then the temperature is increased to 160℃ and held for 10 h; after cooling to room temperature, the mixture in the reactor is centrifuged, washed multiple times with deionized water and ethanol, dried at 100℃, and finally calcined in a muffle furnace at 700℃. CNF is prepared by chemical vapor deposition, and residual metal impurities in the CNF are removed with HCl solution before loading Pt.

[0091] (2) Pt element loading

[0092] Chloroplatinic acid hexahydrate (Pt ≥ 37.5% wt.%) was prepared into an ethanol solution, and Pt / MgAl2O4 and Pt / CNF catalysts were prepared by impregnation. The specific impregnation steps are as follows: the appropriate loading amount of chloroplatinic acid ethanol solution was added dropwise to the catalyst support, stirred evenly with a glass rod, aged at room temperature for 12 h, and dried at 80 °C overnight; finally, the catalyst was reduced at 300 °C in a tube furnace using H2 / Ar gas.

[0093] In this embodiment, Pt / MgAl2O4 and Pt / CNF catalysts were prepared by impregnation for the dehydronaphthalene dehydrogenation reaction. The dehydrogenation performance evaluation results showed that, compared with Pt / CNF, the Pt / MgAl2O4 catalyst exhibited superior dehydrogenation activity and stability for dehydronaphthalene.

[0094] In the structure-activity relationship of the catalysts in this invention, extensive characterization analyses were performed on Pt / MgAl2O4 and Pt / CNF catalysts. NH3-TPD, H2-TPR, and XPS confirmed the presence of positively valence Pt in the Pt / MgAl2O4 catalyst. Through model statistical analysis of Pt nanoparticles in the Pt / MgAl2O4 catalyst, the presence of Pt in the Pt nanoparticles was determined. edgeThe active sites are the dominant source of active sites in the catalyst. The reason why the partially positively charged Pt species in the Pt / MgAl2O4 catalyst improves the dehydrogenation reaction performance is explained by temperature-programmed surface reaction and CO-DRIFTS. The partially positively charged Pt is more conducive to the desorption of the dehydrogenation product naphthalene, which is conducive to the rapid release of active sites and multiple decahydronaphthalene dehydrogenation cycles.

[0095] Example 4

[0096] This invention provides a Pt-MnO x The preparation method of / MO / honeycomb ceramic catalyst, wherein the Pt-MnO x The preparation method of / MO / honeycomb ceramic catalyst includes the following steps:

[0097] (1) Pretreatment of the monolithic catalyst matrix: use hydrochloric acid or acetic acid with a mass fraction of 10% to 30% as a pretreatment agent, treat at 60 to 80°C for 3 hours, wash with water until neutral after acid treatment, dry and weigh for later use.

[0098] (2) Preparation of active component catalyst powder;

[0099] (3) Preparation of binder: Weigh Al2O3 sol and surfactant polyethylene glycol according to the weight of active component powder. The weight ratio of active component powder to binder is 1:1 to 3, and the weight ratio of active component powder to polyethylene glycol is 1:0.1 to 0.3.

[0100] (4) Preparation of coating slurry: Based on the mass of cordierite honeycomb ceramics, the weight ratio of active component and binder is as follows: 9-11 parts by weight of active component, 10-25 parts by weight of binder mixture, and 64-77 parts by weight of water. The active component powder is added to a ball mill and ground for 1 hour. The binder is dissolved in water and mixed to prepare a coating slurry. The solid content of the coating slurry is 20%-50%.

[0101] (5) Coating operation: The cordierite honeycomb ceramic pretreated in step (1) is immersed in the coating slurry prepared in step (4) for 30 minutes. After removal, excess slurry is blown off, dried at 80 degrees Celsius for 2 hours, and calcined at 300 degrees Celsius for 3 hours. The weight is measured and the above operation is repeated until the required weight is achieved on the honeycomb ceramic to obtain Pt-MnO. x / MO / Cellular Ceramic Catalyst. The beneficial effect of this invention is that the catalyst is composed of a cellular ceramic cordierite support, a binder, and an active component, the active component including Pt. To increase coating adhesion, this invention employs acid treatment of the cordierite cellular ceramic support to increase its surface area and surface roughness; this is achieved through a dual approach using alumina sol and surfactants. The catalyst preparation method includes pretreatment of the cellular ceramic cordierite, preparation of the active component catalyst powder, preparation of the binder, preparation of the coating slurry, coating operation, drying, and calcination steps, resulting in a Pt-MnO catalyst. x / MO / Cellular ceramics.

[0102] In the above embodiments, the descriptions of each embodiment have different focuses. For parts that are not described in detail or recorded in a certain embodiment, please refer to the relevant descriptions of other embodiments.

[0103] II. The technical solution of the present invention will be further described below with reference to the embodiments and specific principle analysis.

[0104] Example 5

[0105] The technical solution of the present invention will be further described below using the catalytic performance of the decahydronaphthalene dehydrogenation reaction as an example.

[0106] In Pt / MgAl2O4 and Pt / CNF catalysts, the partially positively charged Pt / MgAl2O4 catalysts can promote the desorption of the dehydrogenation product naphthalene, facilitating the rapid release of active sites, improving the catalytic efficiency of active sites, and enhancing the dehydronaphthalene dehydrogenation catalytic performance. However, partially positively charged Pt nanoparticles not only promote the rapid desorption of naphthalene but also inhibit the activation of the reactant dehydronaphthalene, negatively impacting the dehydronaphthalene dehydrogenation reaction. Therefore, this invention introduces a novel species into the support to regulate the degree of Pt's positive charge, enabling the catalyst to simultaneously promote the desorption of naphthalene and the activation of the reactant, thus achieving optimal dehydronaphthalene dehydrogenation activity. Transition metal oxides (TMOs) are widely used in heterogeneous catalytic reaction processes due to their diverse and tunable electronic structures. Therefore, the strategy adopted in this invention is to introduce a suitable transition metal oxide to regulate the Pt-TMO interface, optimize the electronic structure of Pt and its surrounding environment, and promote optimal catalytic performance in the dehydronaphthalene dehydrogenation reaction.

[0107] In this embodiment of the invention, a self-made γ-Al₂O₃ catalyst support was used. Three manganese oxides were first introduced onto an alumina support to prepare MnO. x / Al2O3, then load Pt elements onto MnO x Three types of Pt-MnO were prepared on Al2O3. x / Al2O3 catalyst; using Pt / Al2O3 catalyst as a comparison, Pt / Al2O3 and Pt-MnO were tested.x The dehydronaphthalene dehydrogenation activity (mainly including dehydrogenation rate and hydrogen yield) of Pt / Al2O3 catalyst at different reaction temperatures (230, 250 and 270 °C) was tested, and the dehydrogenation activity of Pt / Al2O3 and Pt-MO at 250 °C was also tested. x Cyclic catalytic performance of Pt / Al2O3 catalyst (three cycles); followed by Pt / Al2O3 and Pt-MnO3 catalysts. x A comprehensive characterization analysis was performed on the Pt / Al2O3 catalyst to analyze Pt / Al2O3 and Pt-MnO. x Structure-activity relationship of Al2O3 catalyst.

[0108] In this embodiment of the invention, Pt-MnO x The catalytic performance analysis of Al2O3 and Pt / Al2O3 catalysts includes:

[0109] Dehydrogenation temperature is a crucial factor for the application of decahydronaphthalene as an organic hydrogen storage medium. Therefore, the dehydrogenation activities of four catalysts at different temperatures were first analyzed. Figure 2(a) shows the dehydrogenation activities of Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3, and Pt-MnO2 / Al2O3 catalysts at reaction temperatures of 230, 250, and 270 °C. Observation shows that all curves in the figure are linear, indicating that each catalyst maintains a relatively stable dehydrogenation rate for decahydronaphthalene. The average hydrogen evolution rate over 30 min was calculated, and the results are shown in Figure 2(b). The relationship between hydrogen evolution rate and reaction temperature shows that the hydrogen evolution rate of the four catalysts catalyzing the dehydronaphthalene dehydrogenation reaction increases with increasing temperature. At different reaction temperatures, the order of hydrogen evolution rate from high to low for the four catalysts is: Pt-Mn2O3 / Al2O3 > Pt / Al2O3 > Pt-MnO2 / Al2O3 > Pt-MnO / Al2O3. At temperatures of 230, 250, and 270 °C, the hydrogen evolution rates of the Pt-Mn2O3 / Al2O3 catalyst are 4.01, 8.38, and 11.0 mol H2·g, respectively. Pt -1 ·s -1The hydrogen evolution rates of both Pt-MnO / Al2O3 and Pt-MnO2 / Al2O3 catalysts were higher than those of the Pt / Al2O3 catalyst at the corresponding temperatures. However, the hydrogen evolution rates of Pt-MnO / Al2O3 and Pt-MnO2 / Al2O3 catalysts were lower than those of the Pt / Al2O3 catalyst. For example, at 250℃, the hydrogen yields of Pt-MnO / Al2O3 and Pt-MnO2 / Al2O3 catalysts were 0.3 times and 0.9 times that of the Pt / Al2O3 catalyst, respectively. The difference in hydrogen evolution rates indicates that the Pt-Mn2O3 / Al2O3 catalyst exhibited superior catalytic efficiency at different reaction temperatures. The hydrogen yields of the four catalysts for the dehydronaphthalene dehydrogenation are shown in the bar chart of Figure 2(c). As can be seen from the figure, the hydrogen yields of the four catalysts for the dehydronaphthalene dehydrogenation all increase with increasing reaction temperature. At the three reaction temperatures, the hydrogen yield of the Pt-Mn2O3 / Al2O3 catalyst is higher than that of the Pt / Al2O3 catalyst at the corresponding temperatures.

[0110] Analysis of the above reaction results shows that among the four catalysts, the Pt-Mn2O3 / Al2O3 catalyst exhibits superior dehydronaphthalene dehydrogenation activity. The introduction of Mn2O3 enhances the catalytic activity, making it superior to the Pt-MO catalyst. x / Al2O3 catalyst is the preferred choice, while the decahydronaphthalene dehydrogenation activity of Pt-MnO / Al2O3 and Pt-MnO2 / Al2O3 catalysts is lower than that of Pt / Al2O3 catalyst. This indicates that the introduction of MnO and MnO2 is not conducive to improving catalyst activity.

[0111] In this embodiment of the invention, XRD and elemental analysis of the catalyst were performed.

[0112] Figure 3The XRD patterns of the reduced Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3, and Pt-MnO2 / Al2O3 catalysts are shown in the figure. From the XRD pattern of Pt / Al2O3, three distinct diffraction peaks at 2θ = 37.6°, 45.8°, and 66.8° can be observed, corresponding to the (311), (400), and (440) crystal planes of γ-Al2O3 (JCPDS: 29-0063), respectively. From the XRD pattern of Pt-MnO / Al2O3 in the figure, in addition to the diffraction peaks of Al2O3, diffraction peaks at 2θ = 34.9°, 40.5°, 58.7° and 66.8° can also be observed, corresponding to the (111), (200), (220) and (311) crystal planes of MnO (JCPDS: 07-0230) respectively. From the XRD pattern of Pt-Mn2O3 / Al2O3 in the figure, in addition to the diffraction peaks of Al2O3, diffraction peaks at 2θ = 18.0°, 28.8°, 32.6° and 36.2° can also be observed, corresponding to the (111), (202), (221) and (203) crystal planes of Mn2O3 (JCPDS: 06-0540) respectively. From the XRD pattern of Pt-MnO2 / Al2O3 in the figure, in addition to the diffraction peaks of Al2O3, diffraction peaks at 2θ = 28.7°, 37.4° and 56.6° can also be observed, which correspond to the (110), (101) and (211) crystal planes of MnO2 (JCPDS: 24-0735), respectively. The XRD analysis shows that the corresponding manganese oxides are loaded in all four catalysts as expected in the experiment.

[0113] Table 1 shows the ICP-OES results of the reduced Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3 and Pt-MnO2 / Al2O3 catalysts. As can be seen from the table, the Pt content in all catalysts is slightly lower than the theoretical Pt element loading (1 wt.%), and the Mn element content in the Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3 and Pt-MnO2 / Al2O3 catalysts is around 3 wt.%.

[0114] Table 1. Elemental content of Pt and Mn in the catalyst

[0115]

[0116] a Determined by ICP-OES

[0117] HRTEM and HAADF-STEM analysis of the catalyst

[0118] Figure 4 shows the HAADF-STEM images of the reduced Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3, and Pt-MnO2 / Al2O3 catalysts (Figure 4(a)). Observation of the images reveals that a large number of Pt nanoparticles are uniformly dispersed in all catalysts. The size distribution of Pt nanoparticles in each sample was analyzed using Nano Measure software. The sizes of more than 500 Pt nanoparticles were counted to obtain the Pt nanoparticle size distribution of each catalyst and calculate the average Pt particle size of each catalyst. The average particle sizes of Pt nanoparticles in the Pt / Al₂O₃, Pt-MnO / Al₂O₃, Pt-Mn₂O₃ / Al₂O₃, and Pt-MnO₂ / Al₂O₃ catalysts were 1.56±0.33 nm, 1.26±0.28 nm, 1.51±0.31 nm, and 1.32±0.36 nm, respectively. This indicates that the introduction of manganese oxide did not significantly affect the size of the Pt nanoparticles. Correlating the dehydronaphthalene dehydrogenation activities of the four catalysts, the Pt-Mn₂O₃ / Al₂O₃ and Pt / Al₂O₃ catalysts showed similar reactivity, and the Pt nanoparticles in these catalysts also had similar sizes. This may be due to the size matching between the reactant dehydronaphthalene molecules and the Pt nanoparticles; Pt nanoparticles of this size may better adsorb and activate dehydronaphthalene molecules, promoting the dehydrogenation reaction.

[0119] Figure 4(b) shows HRTEM images of the reduced Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3 and Pt-MnO2 / Al2O3 catalysts. Obvious lattice fringes can be observed in all the images. The lattice spacing was measured to determine the exposed surface in the catalyst. Figure (1) shows the HRTEM of Pt / Al2O3. The lattice measurement results show that the lattice spacing d = 0.232 nm corresponds to the Pt (111) plane, the lattice spacing d = 0.239 nm corresponds to the Al2O3 (311) plane and the diffraction peak of Al2O3 at 37.6° in the XRD pattern; Figure (2) shows the HRTEM of Pt-MnO / Al2O3 catalyst. The lattice measurement results show that the lattice spacing d = 0.232 nm corresponds to the Pt (111) plane, the lattice spacing d = 0.222 nm corresponds to the MnO (200) plane and the diffraction peak of MnO at 40.5° in the XRD pattern, the lattice spacing d = 0.198 nm corresponds to the Al2O3 (400) plane and the XRD pattern. The diffraction peak of Al2O3 at 45.8° in the D spectrum; Figure (3) shows the HRTEM of Pt-Mn2O3 / Al2O3 catalyst. The lattice measurement results show that the lattice spacing d = 0.232nm corresponds to the Pt (111) plane, the lattice spacing d = 0.248nm corresponds to the (203) plane of Mn2O3, and the diffraction peak of Mn2O3 at 36.2° in the XRD spectrum; Figure (4) shows the HRTEM of Pt-MnO2 / Al2O3 catalyst. The lattice measurement results show that the lattice spacing d = 0.232nm corresponds to the Pt (111) plane, the lattice spacing d = 0.311nm corresponds to the (110) plane of MnO2, and the diffraction peak of MnO2 at 28.7° in the XRD spectrum.

[0120] In this embodiment of the invention, H2-TPR analysis

[0121] like Figure 5 As shown in the figure, the embodiments of the present invention provide H2-TPR results for Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3, and Pt-MnO2 / Al2O3 catalysts; overall, Pt-MnO xThe Pt / Al2O3 catalyst and the Pt / Al2O3 catalyst exhibit similar hydrogen reduction properties to the analyzed Pt / MgAl2O4 catalyst. The low-temperature reduction peaks indicate the reduction of the Pt precursor in the catalyst, while a peak indicating that Pt is more difficult to reduce exists around 400℃. Based on the analysis of the hydrogen reduction properties of the Pt / MgAl2O4 catalyst in the previous chapter, the more difficult-to-reduce Pt reflects, to some extent, the strong interaction between Pt and the support. The higher the reduction temperature of the more difficult-to-reduce Pt, the stronger the interaction between Pt and the support. The order of the temperatures of the most difficult-to-reduce Pt in the H2-TPR spectra of Pt / MgAl2O4, Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3 and Pt-MnO2 / Al2O3 catalysts from high to low is: Pt-Mn2O3 / Al2O3 (424℃) > Pt-MnO / Al2O3 (413℃) > Pt / Al2O3 (403℃) > Pt / MgAl2O4 (400℃) > Pt-MnO2 / Al2O3 (326℃), indicating that the Pt-Mn2O3 / Al2O3 catalyst has the strongest metal-support interaction. The activity of the associated catalysts was found to be the highest in the Pt-Mn2O3 / Al2O3 catalyst for decahydronaphthalene dehydrogenation. This may be due to the fact that Mn2O3 in the catalyst enhances the strong metal-support interaction, thereby creating a more favorable Pt coordination environment for the decahydronaphthalene dehydrogenation reaction. This has also been reported in previous literature. For example, Yang et al. previously reported that the introduction of MnO into the Rh / SiO2 catalyst led to a partial increase in the Rh reduction temperature. The formation of Rh-MnO interface sites is the reason for the improved activity and selectivity of the syngas conversion reaction.

[0122] In this embodiment of the invention, Figure 6(a) is the XPS spectrum of the catalyst Pt 4d provided in this embodiment of the invention; Figure 6(b) is the XPS spectrum of the catalyst Pt 4d provided in this embodiment of the invention, which is obtained by fitting the main peak and convolving it into three peaks, corresponding to Pt respectively. 0 (~331.1eV), Pt 2+ (~332.3eV) and Pt 4+ (~334.1 eV), the content of Pt in each valence state was calculated based on the peak area ratio; Figure 6(c) is the Mn 2p XPS spectrum of the catalyst provided in the embodiment of the present invention, which is formed by fitting the main peak and convolving it into three peaks, corresponding to Mn respectively. 2+ (~653eV), Mn 3+ (~653.5eV) and Mn 4+ (~654eV), the content of Mn in each valence state was calculated based on the proportion of peak area.

[0123] XPS analysis was used to analyze the valence states and electronic structures of relevant elements in the catalyst, thereby analyzing the electronic properties of the catalyst. Figure 6(a) shows the Pt 4d XPS spectra of Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3, and Pt-MnO2 / Al2O3 catalysts. The Pt 4d XPS spectra of all Pt-based catalysts contain two peaks, representing the Pt 4d... 5 / 2 (~314.2 eV) and Pt4d 3 / 2 (~332 eV), Pt 4d 3 / 2 Peak fitting, as shown in Figure 6(b), shows that the main peak convolution consists of three peaks, corresponding to Pt respectively. 0 (~331.1eV), Pt 2+ (~332.3eV) and Pt 4+ (~334.1 eV), the content of Pt in each valence state was calculated based on the proportion of peak area, and the results are shown in Table 2; Mn 2p 3 / 2 Peak fitting was performed on the XPS spectrum, as shown in Figure 6(c). The main peak convolved into three peaks, corresponding to Mn, respectively. 2+ (~653eV), Mn 3+ (~653.5eV) and Mn 4+ (~654eV), the content of Mn in each valence state was calculated based on the proportion of peak area, and the results are shown in Table 2.

[0124] Table 2 XPS data of Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3 and Pt-MnO2 / Al2O3 catalysts

[0125]

[0126] In the embodiments of the present invention, the results are as follows: Figure 7 As shown, Pt in Pt / Al2O3, Pt-MnO / Al2O3, Pt-Mn2O3 / Al2O3 and Pt-MnO2 / Al2O3 catalysts 0 The content of Pt gradually increased. Avs As the number of electrons gradually decreases, the electron transfer from Pt to the carrier gradually weakens.

[0127] The results show that when the number of surface oxygen vacancies increases, the metallic Pt in the Pt / Al2O3 catalyst... 0 As the proportion decreases and the number of surface oxygen vacancies decreases, the metallic Pt in the Pt / Al2O3 catalyst... 0 The proportion has increased.

[0128] Furthermore, in Pt-MnO xIn the structure-activity relationship analysis of Al2O3 and Pt / Al2O3 catalysts, experimental results show that the introduction of MnO, Mn2O3, and MnO2 did not significantly affect the size of Pt nanoparticles in the catalyst, but it did significantly affect the electronic structure of Pt nanoparticles. The introduction of manganese oxides can occupy some oxygen vacancies on the surface of the Al2O3 support, changing the probability of Pt nanoparticles binding to oxygen vacancies, thereby regulating the electronic structure of Pt nanoparticles. The metal average valence state descriptor (AvS) was defined to analyze the changes in the metal's electronic structure. The introduction of MnO, Mn2O3, and MnO2 affected the electronic structure of Pt nanoparticles. Avs The charge gradually decreases. The introduction of Mn2O3 optimizes the positive charge state of Pt nanoparticles, and the average valence state of Pt nanoparticles in the Pt-Mn2O3 / Al2O3 catalyst is Pt. Avs =0.9, thus balancing reactant activation and product desorption. Catalytic activity analysis of the associated catalyst, Pt-MnO x The reactivity of the / Al2O3 catalyst is also affected by the alteration of the coordination environment around the Pt nanoparticles by manganese oxides. The introduction of MnO and MnO2 inhibited the enhancement of decahydronaphthalene dehydrogenation activity, while the introduction of Mn2O3 promoted the enhancement of decahydronaphthalene dehydrogenation activity. At different reaction temperatures, the Pt-Mn2O3 / Al2O3 catalysts all exhibited superior decahydronaphthalene dehydrogenation activity.

[0129] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications, equivalent substitutions and improvements made by those skilled in the art within the scope of the technology disclosed in the present invention and within the spirit and principles of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A hydrogen storage and release device for decahydronaphthalene, with an organic hydride dehydrogenation catalyst as the core material, characterized in that, The organic hydride dehydrogenation catalyst comprises Pt element, Mn2O3, and γ-Al2O3 oxide support. The Pt element is supported on Mn2O3 / Al2O3 composite powder made from Mn2O3 and γ-Al2O3 oxide support to obtain a Pt-Mn2O3 / Al2O3 catalyst, with a Pt element content of 0.5 wt.%~1.5 wt.%. The Pt element is Pt 0 Pt 2+ and Pt 4+ It exists in the form of; The preparation methods of Pt-Mn2O3 / Al2O3 catalysts include: Preparation of S1,γ-Al2O3: Materials with a specific surface area ≥250m² 2 / g of pseudoboehmite was placed in a muffle furnace and heated to 600℃-800℃ at a certain heating rate. Then, the temperature was kept constant for 4h-12h and cooled to room temperature to obtain γ-Al2O3. Preparation of S2, Mn2O3 / Al2O3: Mn(NO3)2 was added to ethanol and stirred until homogeneous. Then, γ-Al2O3 was added to manganese nitrate ethanol solution and stirred for 0.5 h. Subsequently, the mixture was added to a hydrothermal reactor and hydrothermally treated at 120 °C for 12 h. The mixture in the hydrothermal reactor was then cooled to room temperature, vacuum filtered, and washed with deionized water until the solution was colorless. It was dried at 80 °C for 12 h. The dried powder was ground uniformly and calcined in a muffle furnace at 500 °C for 2 h to obtain Mn2O3 / Al2O3 powder. S3, Pt element is loaded onto Mn2O3 / Al2O3 to prepare Pt-Mn2O3 / Al2O3 catalyst.

2. The hydrogen storage and release device for decahydronaphthalene, with the organic hydride dehydrogenation catalyst as the core material according to claim 1, is characterized in that, To obtain the Pt-Mn2O3 / Al2O3 catalyst, the following steps are also required: The dehydronaphthalene dehydrogenation activity of the Pt-Mn2O3 / Al2O3 catalyst was tested at reaction temperatures of 230℃, 250℃ and 270℃, and the cyclic catalytic performance of the Pt-Mn2O3 / Al2O3 catalyst at 250℃ was also tested. The Pt-Mn2O3 / Al2O3 catalyst was then comprehensively characterized and analyzed to determine its structure-activity relationship.

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