Hydrogen production material, system and method based on metal organic framework

Abstract

The invention belongs to the field of air hydrogen production, and provides a metal organic framework (MOF)-based hydrogen production material, which comprises a porous foam base material, and the base material is loaded with an MOF material with a water vapor adsorption function. The invention also provides a preparation method of the hydrogen production material, a hydrogen production system prepared from the hydrogen production material and a hydrogen production method of the hydrogen production system. According to the hydrogen production system and method, clean water can be collected in a low-humidity environment, hydrogen can be produced in low air humidity, and the hydrogen production system and method have the potential of sustainable development and large-scale application.

Description

Technical Field

[0001] The present invention relates to the field of hydrogen production from air, and in particular to a hydrogen production material, system and method based on a metal organic framework. Background Art

[0002] Water shortage and increasing energy demand are two major challenges that complement each other worldwide. Traditional water resources, such as rivers and groundwater, are facing problems of overexploitation and pollution, while the use of fossil fuels has led to serious environmental problems, including climate change. The need for sustainable development has led scientists and engineers to explore innovative solutions, one of which is to extract water from the air and use it to produce hydrogen.

[0003] Water extracted from the air can be used to generate hydrogen through the process of electrolysis. Electrolysis is the process of breaking water molecules into hydrogen and oxygen by applying an electric current. Hydrogen is a clean energy source that can be used in fuel cells, industrial processes or as an energy storage medium.

[0004] At present, although air hydrogen production technology has made certain progress, it still has problems of high energy consumption and high cost, which limits its large-scale application. At the same time, key materials such as adsorbents and membrane materials have technical bottlenecks in terms of cost and life, and further research and development is urgently needed. In addition, the optimization of the process flow is still a challenge, and it is necessary to reduce the overall cost by improving efficiency. To realize the large-scale application of air hydrogen production, it is necessary to overcome technical difficulties, reduce costs, and achieve large-scale production. Summary of the invention

[0005] The present invention provides a metal organic framework-based hydrogen production material, system and method, which aims to solve the problems of high energy consumption, high cost and complex materials in existing hydrogen production technologies.

[0006] To achieve the above object, one of the technical solutions of the present invention is:

[0007] A hydrogen production material based on a metal organic framework comprises a porous foam substrate, wherein the substrate is loaded with a MOF material having a water vapor adsorption function.

[0008] As a preferred solution of the present invention, the porous foam substrate is a three-dimensional porous structure, and is one of melamine foam, sintered glass foam, silica fiber, polyurethane foam, polyethylene foam, polystyrene foam, and polyvinyl chloride foam.

[0009] As a preferred solution of the present invention, the MOF material is one of MOF-303, CAU-10-H, Ni2Cl2 (BTDD), and MOF-801.

[0010] The second technical solution of the present invention is: a method for preparing a hydrogen production material based on a metal organic framework, comprising the following steps:

[0011] The porous foam substrate was ultrasonically cleaned in deionized water;

[0012] The MOF material is loaded by the infiltration and drying method, so that the surface of each fiber is covered with the MOF material with moisture absorption function.

[0013] The third technical solution of the present invention is: a hydrogen production system based on a metal organic framework, comprising

[0014] A liquid storage tank for storing the adsorbed and enriched water;

[0015] The hydrogen production material prepared by the preparation method as described above is placed in the liquid storage tank;

[0016] A transparent cover plate, covering the hydrogen production material, for collecting and exporting hydrogen during the hydrogen production process;

[0017] The alkaline electrolyte is placed in the liquid storage tank and is used to electrolyze the adsorbed water to generate hydrogen.

[0018] As a preferred solution of the present invention, the liquid storage tank is made of an alkali-resistant material, and the material is selected from one of polypropylene, polypropylene homopolymer, polyethylene, and stainless steel.

[0019] As a preferred solution of the present invention, the alkaline electrolyte is selected from one of KOH and NaOH.

[0020] As a preferred solution of the present invention, the concentration of the alkaline electrolyte is 30%-95%.

[0021] As a preferred solution of the present invention, the transparent cover plate is a light-transmitting material selected from one of acrylic plate, glass plate, acrylic plastic and polycarbonate.

[0022] The fourth technical solution of the present invention is: a hydrogen production method based on a metal organic framework hydrogen production system, comprising the following steps of placing the system in a suitable environment so that the MOF material adsorbs water vapor in the air;

[0023] The water vapor is accumulated in the liquid storage tank and converted into liquid water;

[0024] Under light conditions, the MOF material catalyzes the electrolysis of water in an alkaline electrolyte to produce hydrogen;

[0025] The generated hydrogen is guided out and collected through the transparent cover plate.

[0026] The beneficial effects achieved by the present invention are:

[0027] On the one hand, the present invention proposes a hydrogen production material based on metal organic frameworks (MOFs), which can efficiently adsorb water vapor in the air under low humidity conditions and catalytically electrolyze to generate hydrogen under light conditions. The high specific surface area and pore structure of the MOF material provide a large number of active sites, thereby greatly improving the efficiency of water electrolysis. This material can perform water electrolysis reaction at a low overpotential, which can not only significantly improve the efficiency of hydrogen production, but also reduce overall energy consumption, making the hydrogen production process more energy-saving and environmentally friendly. In addition, the excellent stability of the MOF material allows the system to maintain catalytic activity for a long time, prolongs the service life of the system and the liquid storage tank, and reduces maintenance costs. The structure and properties of the MOF material can be adjusted by selecting different metal centers and organic connectors, which provides great flexibility for optimizing the process of water electrolysis and hydrogen production.

[0028] MOF materials may allow liquid reservoirs to operate under a wider range of operating conditions, such as different pH values, temperatures, and pressures, thus adapting to different application scenarios.

[0029] On the other hand, the hydrogen production system proposed in the present invention has the ability to produce hydrogen from air within a wide humidity range. The system uses MOF materials to adsorb water vapor in the air and enrich the water vapor in a liquid storage tank. The liquid storage tank design can produce hydrogen by photocatalysis without the need for additional energy input. This design enables the system to adapt to different humidity environments, so it is widely used in air hydrogen production under various working conditions, and has the potential for sustainable development and large-scale application. The combined design of the system's transparent gas collecting plate, liquid storage tank and catalytic components effectively improves the ease of operation and energy efficiency.

[0030] In addition, through this method, the system can adsorb and enrich water vapor from the air to generate high-purity hydrogen without relying on traditional water sources, achieving sustainable hydrogen production without energy input. This innovative hydrogen production method not only improves the operational flexibility of the system, but also shows excellent results in optimizing electrolysis efficiency, reducing energy consumption, and improving system stability, meeting the needs of large-scale low-cost applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] like Figure 1 is an enlarged schematic diagram of a hygroscopic material;

[0032] Figure 2 This is a schematic diagram of the structure of a hydrogen production system based on a metal-organic framework.

[0033] In the figure, 1. porous foam substrate; 2. MOF material; 3. alkaline electrolyte; 4. transparent cover; 5. liquid storage tank; 6. through hole. DETAILED DESCRIPTION

[0034] like Figure 1 , Figure 2 As shown, a hydrogen production material based on a metal organic framework comprises a porous foam substrate 1, on which a MOF material 2 having the function of adsorbing water vapor is loaded.

[0035] Preferably, the porous foam substrate 1 is a three-dimensional porous structure, and is made of one of melamine foam, sintered glass foam, silica fiber, polyurethane foam, polyethylene foam, polystyrene foam, and polyvinyl chloride foam.

[0036] Preferably, the MOF material 2 is one of MOF-303, CAU-10-H, Ni2Cl2 (BTDD), and MOF-801.

[0037] A method for preparing a hydrogen production material based on a metal organic framework comprises the following steps:

[0038] The porous foam substrate 1 is ultrasonically cleaned in deionized water;

[0039] The MOF material 2 is loaded by a wet-drying method, so that the surface of each fiber is covered with the MOF material 2 having a moisture absorption function.

[0040] A hydrogen production system based on a metal organic framework, comprising

[0041] A liquid storage tank 5, used to store the adsorbed and enriched water;

[0042] The hydrogen production material prepared by the preparation method as described above is placed in the liquid storage tank 5;

[0043] A transparent cover plate 4, covering the hydrogen production material, for collecting and exporting hydrogen during the hydrogen production process;

[0044] The alkaline electrolyte 3 is placed in the liquid storage tank 5 and is used to electrolyze the adsorbed water to generate hydrogen.

[0045] It should be noted that the transparent cover plate 4 only covers the top of the hydrogen production material, and moisture can be adsorbed through the side. Since hydrogen is lighter than air, it can be discharged from the through hole 6 of the transparent cover plate 4 after being generated. This method is simple and easy to operate, realizes clean production, and can produce clean hydrogen more conveniently.

[0046] Preferably, the liquid storage tank 5 is made of an alkali-resistant material, and the material is selected from one of polypropylene, polypropylene homopolymer, polyethylene, and stainless steel.

[0047] Preferably, the alkaline electrolyte 3 is selected from one of KOH and NaOH.

[0048] Preferably, the concentration of the alkaline electrolyte 3 is 30%-95%.

[0049] Preferably, the transparent cover plate 4 is made of a light-transmitting material selected from one of acrylic plate, glass plate, acrylic plastic, and polycarbonate, and the light transmittance is preferably above 90%.

[0050] A method for producing hydrogen based on a metal organic framework-based hydrogen production system comprises the following steps: placing the system in a suitable environment so that the MOF material 2 absorbs water vapor in the air;

[0051] The water vapor is accumulated in the liquid storage tank 5 and converted into liquid water;

[0052] Under light conditions, the MOF material 2 catalyzes the electrolysis of water in the alkaline electrolyte 3 to produce hydrogen;

[0053] The generated hydrogen is guided out and collected through the through holes 6 provided on the transparent cover plate 4 .

[0054] In order to further illustrate the present invention, the invention and its application are described in detail in combination with the embodiments below. However, it should be understood that these embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operation processes are given only to further illustrate the features and advantages of the present invention, rather than to limit the claims of the present invention. The protection scope of the present invention is not limited to the following embodiments.

[0055] All raw materials of the present invention have no particular limitation on their sources, and can be purchased from the market or prepared according to conventional methods known to those skilled in the art.

[0056] There is no particular limitation on the purity of all raw materials in the present invention, and analytically pure or prepared raw materials are preferred.

[0057] All raw materials and process steps of the present invention, their brands or abbreviations are conventional brands or abbreviations in the art, and each brand or abbreviation is clear and definite in the field of its related use. Those skilled in the art can purchase them from the market or prepare them by conventional methods, or implement them with corresponding equipment according to the brands, abbreviations and corresponding uses.

[0058] Example 1: Hydrogen production material based on melamine foam substrate and MOF-303

[0059] This embodiment uses a three-dimensional porous melamine foam substrate as a carrier of MOF material. First, the melamine foam substrate is ultrasonically cleaned in deionized water for 30 minutes to remove surface impurities. The cleaned foam substrate is placed in a MOF-303 solution (20 mg / mL) and soaked for 2 hours to ensure uniform adsorption of the MOF material. Subsequently, the foam substrate is taken out and dried at 60°C for 6 hours to complete the loading of MOF-303.

[0060] The prepared material has good hygroscopic properties and can absorb water vapor in the air at low relative humidity (10% RH). The material can catalyze the electrolysis of water to generate hydrogen under light conditions. After testing, the hydrogen production rate is 50mL / h·g and the hygroscopic capacity is 20mg / g.

[0061] Example 2: Hydrogen production material based on sintered glass foam substrate and Ni2Cl2 (BTDD)

[0062] This embodiment uses a sintered glass foam substrate as a carrier of MOF material. First, the sintered glass foam substrate is ultrasonically cleaned in deionized water for 40 minutes to remove surface impurities. The cleaned foam substrate is placed in a Ni2Cl2(BTDD) solution (25 mg / mL) and soaked for 3 hours to ensure uniform adsorption of the MOF material. Then, the foam substrate is dried at 70°C for 4 hours to complete the loading of Ni2Cl2(BTDD).

[0063] The prepared material exhibits high hygroscopic properties at low relative humidity (10% RH). The material catalyzes water decomposition to generate hydrogen under light conditions. Tests show that its hydrogen production rate is 60 mL / h·g and its hygroscopic capacity is 25 mg / g.

[0064] Example 3: Hydrogen production material based on silica fiber substrate and MOF-801

[0065] This example uses a silica fiber substrate as a carrier of MOF material. First, the silica fiber substrate is ultrasonically cleaned in deionized water for 20 minutes to remove surface impurities. Then, the cleaned foam substrate is placed in a MOF-801 solution (30 mg / mL) and soaked for 1.5 hours. After taking out the foam, it is dried at 50°C for 5 hours to complete the loading of MOF-801.

[0066] The prepared material exhibits good hygroscopic properties at low relative humidity (10% RH). The material is used to generate hydrogen by water electrolysis under light conditions, and the test results show that the hydrogen production rate is 55mL / h·g and the hygroscopic capacity is 22mg / g.

[0067] Example 4: Hydrogen production material based on polyurethane foam substrate and MOF-303

[0068] This example uses a three-dimensional porous polyurethane foam substrate as a carrier of MOF material. First, the polyurethane foam substrate is ultrasonically cleaned in deionized water for 40 minutes to remove surface impurities. After the cleaned foam substrate is dried, it is immersed in a MOF-303 solution (15 mg / mL) for 3 hours to ensure uniform adsorption of the material. Then it is dried at 60°C for 6 hours to complete the loading of MOF-303.

[0069] The prepared material exhibits excellent hygroscopic properties under low relative humidity (10% RH) conditions. Tests show that under light conditions, the material can catalyze the electrolysis of water to generate hydrogen, with a hydrogen production rate of 62 mL / h·g and a hygroscopic capacity of 28 mg / g.

[0070] Example 5: Hydrogen production material based on polyethylene foam substrate and CAU-10-H

[0071] This example uses polyethylene foam as a porous substrate. First, the polyethylene foam substrate is ultrasonically cleaned in deionized water for 30 minutes to remove surface impurities. The cleaned foam substrate is placed in a CAU-10-H solution (20 mg / mL) and soaked for 2 hours to ensure uniform adsorption of the MOF material. Subsequently, the foam substrate is taken out and dried at 60°C for 4 hours to complete the loading of CAU-10-H.

[0072] The material can absorb water vapor in the air at low relative humidity (10% RH) and catalyze the electrolysis of water to generate hydrogen under light conditions. Its moisture absorption capacity is 26 mg / g and the hydrogen production rate is 58 mL / h·g.

[0073] Example 6: Hydrogen production material based on polystyrene foam substrate and Ni2Cl2 (BTDD)

[0074] This embodiment uses a polystyrene foam substrate as a carrier of MOF material. First, the polystyrene foam substrate is ultrasonically cleaned in deionized water for 35 minutes to remove surface impurities. Then, the cleaned foam substrate is placed in a Ni2Cl2(BTDD) solution (25 mg / mL) and soaked for 2.5 hours. The foam substrate is taken out and dried at 70°C for 5 hours to complete the loading of Ni2Cl2(BTDD).

[0075] The material exhibits good hygroscopicity under low relative humidity conditions, can effectively absorb water vapor in the air, and can be used to produce hydrogen under light. According to tests, the hygroscopicity is 24 mg / g and the hydrogen production rate is 57 mL / h·g.

[0076] Example 7: Hydrogen production system based on the material of Example 1

[0077] This example is based on the melamine foam substrate prepared in Example 1 loaded with MOF-303 material.

[0078] The hydrogen production system consists of a liquid storage tank 5 made of polypropylene, which is filled with 50% KOH solution as an alkaline electrolyte 3. The top of the system is covered with an acrylic transparent cover plate 4 with a light transmittance of 90%. In a 12% RH environment, the system uses MOF-303 material to absorb water vapor in the air and electrolyzes it to generate hydrogen under light conditions, with a hydrogen generation rate of 50 mL / h·g.

[0079] Example 8: Hydrogen production system based on the material of Example 2

[0080] This example is based on the sintered glass foam substrate loaded with Ni2Cl2 (BTDD) material prepared in Example 2.

[0081] The hydrogen production system consists of a polyethylene liquid storage tank 5 filled with 80% NaOH solution. The top of the system uses a glass cover with a light transmittance of 90%. In a 12% RH environment, MOF material 2 is used to adsorb water vapor in the air and generate hydrogen through photocatalytic electrolysis, with a hydrogen generation rate of 60 mL / h·g.

[0082] Example 9: Hydrogen production system based on the material of Example 3

[0083] This example is based on the silica fiber substrate loaded with MOF-801 material prepared in Example 3.

[0084] The hydrogen production system consists of a stainless steel liquid storage tank 5 filled with 60% KOH solution. The top of the system is covered with a transparent acrylic cover plate 4 with a light transmittance of 95%. Under a 10% RH environment, the MOF material 2 can absorb water vapor in the air and generate hydrogen through a photocatalytic reaction, with a hydrogen generation rate of 55 mL / h·g.

[0085] Example 10: Hydrogen production system based on the material of Example 4

[0086] This example is based on the polyurethane foam substrate prepared in Example 4 loaded with MOF-303 material.

[0087] The hydrogen production system consists of a polypropylene liquid storage tank 5 filled with a 50% KOH solution. The top of the system is covered with an acrylic transparent cover plate 4 with a light transmittance of 90%. The system uses MOF-303 material to adsorb water vapor under a 10% RH environment, and catalyzes water decomposition to generate hydrogen under light conditions, with a hydrogen generation rate of 62 mL / h·g.

[0088] Example 11: Hydrogen production system based on the material of Example 5

[0089] This example is based on the polyethylene foam substrate prepared in Example 5 loaded with CAU-10-H material.

[0090] The hydrogen production system consists of a stainless steel liquid storage tank 5 filled with 60% KOH solution. The top of the system uses an acrylic transparent cover plate 4 with a light transmittance of 90%. Under 8% RH conditions, the MOF material 2 adsorbs water vapor in the air and catalyzes electrolysis to generate hydrogen, and the hydrogen generation rate is 58 mL / h·g.

[0091] Example 12: Hydrogen production system based on the material of Example 6

[0092] This example is based on the polystyrene foam substrate loaded with Ni2Cl2 (BTDD) material prepared in Example 6.

[0093] The hydrogen production system consists of a polyethylene liquid storage tank 5 filled with 80% NaOH solution. The top of the system is covered with an acrylic transparent cover plate 4 with a light transmittance of 90%. Under an 8% RH environment, the MOF material 2 adsorbs water vapor in the air and generates hydrogen through photocatalysis, with a hydrogen generation rate of 57 mL / h·g.

[0094] In summary, the embodiments of the present invention demonstrate a variety of hydrogen production materials and systems based on different substrates and MOF materials 2. In a low humidity environment, each material exhibits good hygroscopic properties and high hydrogen production efficiency.

[0095] In the actual application of hydrogen production system, each material can effectively adsorb water vapor in the air under different relative humidity conditions and efficiently catalyze the generation of hydrogen under light conditions. Examples 7 to 12 show the specific performance of the system under 12%, 10%, and 8% relative humidity, with the highest hydrogen production rate reaching 62mL / h·g, indicating that this series of materials and systems can maintain stable and efficient hydrogen production capabilities under different humidity conditions and are suitable for a variety of application environments.

[0096] The above is a detailed description of the present invention, the purpose of which is to enable people familiar with the technology in this field to understand the content of the present invention and implement it, and it is not intended to limit the scope of protection of the present invention. The present invention is not limited to the above-mentioned embodiments. Any equivalent changes or modifications made according to the spirit of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A hydrogen production material based on a metal organic framework, characterized in that: The invention comprises a porous foam substrate, wherein the substrate supports a MOF material having a function of adsorbing water vapor.

2. The metal organic framework-based hydrogen production material according to claim 1, characterized in that: The porous foam substrate is a three-dimensional porous structure, and is one of melamine foam, sintered glass foam, silicon dioxide fiber, polyurethane foam, polyethylene foam, polystyrene foam, and polyvinyl chloride foam.

3. The metal organic framework-based hydrogen production material according to claim 1, characterized in that: The MOF material is one of MOF-303, CAU-10-H, Ni2Cl2 (BTDD), and MOF-801.

4. A method for preparing a hydrogen production material based on a metal organic framework, characterized in that: The following steps are involved: The porous foam substrate was ultrasonically cleaned in deionized water; The MOF material is loaded by the infiltration and drying method, so that the surface of each fiber is covered with the MOF material with moisture absorption function.

5. A hydrogen production system based on a metal organic framework, characterized in that: include A liquid storage tank for storing the adsorbed and enriched water; The hydrogen production material as described in claims 1 to 3 or prepared by the preparation method as described in claim 4 is placed in the liquid storage tank; A transparent cover plate, covering the hydrogen production material, for collecting and exporting hydrogen during the hydrogen production process; The alkaline electrolyte is placed in the liquid storage tank and is used to electrolyze the adsorbed water to generate hydrogen.

6. A hydrogen production system based on a metal organic framework according to claim 5, characterized in that: The liquid storage tank is made of an alkali-resistant material, and the material is selected from one of polypropylene, polypropylene homopolymer, polyethylene, and stainless steel.

7. The metal organic framework-based hydrogen production system according to claim 5, characterized in that: The alkaline electrolyte is selected from one of KOH and NaOH.

8. A hydrogen production system based on a metal organic framework according to claim 7, characterized in that: The concentration of the alkaline electrolyte is 30%-95%.

9. The metal organic framework-based hydrogen production system according to claim 5, characterized in that: The transparent cover plate is made of a light-transmitting material, selected from one of acrylic plate, glass plate, acrylic plastic and polycarbonate.

10. A method for producing hydrogen based on a metal organic framework hydrogen production system, characterized in that: The method comprises the following steps: placing the system in a suitable environment so that the MOF material adsorbs water vapor in the air; The water vapor is accumulated in the liquid storage tank and converted into liquid water; Under light conditions, the MOF material catalyzes the electrolysis of water in an alkaline electrolyte to produce hydrogen; The generated hydrogen is guided out and collected through the transparent cover plate.

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