Method for hydrogen storage and release based on hydrogen-containing feed gas

Abstract

The present application relates to a kind of hydrogen storage and hydrogen release method based on hydrogen-containing raw gas, wherein, hydrogen storage process includes: a1) select only the non-metallic material of permeating proton;A2) activate non-metallic material to generate catalytic performance;A3) hydrogen-containing raw gas is introduced into one side of non-metallic material;A4) under the catalytic action of activated non-metallic material, hydrogen-containing raw gas is introduced into decomposition into proton and electron;A5) proton and electron permeate into activated non-metallic material, and form pure hydrogen after recombination in non-metallic material and store in non-metallic material, complete hydrogen storage in non-metallic material.The present application provides a kind of method based on hydrogen-containing raw gas generation proton and application, which is not affected by environmental conditions, more widely applicable temperature range and can be more widely used.

Description

TECHNICAL FIELD

[0001] The application relates to a hydrogen storage and release control method, in particular to a hydrogen storage and release method based on a hydrogen-containing raw gas. BACKGROUND

[0002] In 2020, improving the green low-carbon system and seeking new clean energy became a major theme of development. Hydrogen energy is a clean and efficient secondary energy source with a wide range of sources. Hydrogen has a high calorific value, an energy density of 140.4 kJ / kg, and is environmentally friendly. The combustion product has no carbon emissions. Developing and utilizing hydrogen energy is the main strategic direction of global industrial innovation and energy transformation. Currently, hydrogen has been widely used in aerospace, military applications, chemical power sources and other fields.

[0003] From the perspective of development or preparation, in the process of preparing hydrogen by coal gasification, natural gas, methanol, industrial by-product hydrogen and water electrolysis, there are always impurity gases such as oxygen, nitrogen, carbon monoxide, carbon dioxide and methane, which cannot reach the high-precision use standard. In addition, the tail gas discharged by most chemical companies contains a large amount of hydrogen and hydrogen-containing raw gas (such as methane, ammonia, hydrogen chloride, ethane, formaldehyde, etc.). The existing production process directly discharges the tail gas into the flare system. On the one hand, a large amount of hydrogen is consumed in the production process, and on the other hand, a considerable part of the hydrogen is discharged with the tail gas, which not only causes waste of hydrogen resources, but also causes an increase in production costs. Therefore, extracting clean hydrogen from mixed gas and waste gas has become the focus of attention. There are three main methods for purifying and separating hydrogen from mixed gas: cryogenic separation, pressure swing adsorption separation and membrane separation. Cryogenic separation requires the mixed gas to be converted from a gaseous state to a liquid state, which consumes a large amount of energy and cost, and has poor flexibility. The pressure swing adsorption separation method requires controlling the temperature and pressure to achieve pressure swing adsorption to separate hydrogen. The equipment is large and occupies a large area. The membrane separation method has the advantages of simple operation, low energy consumption, small occupied area and continuous operation. The commonly used membranes are metal, zeolite and polymer. The current membrane separation of mixed gas is a complete physical process, which usually uses polymer membranes or amorphous carbon membranes. Therefore, the pore size of the membrane must be controlled, for example, when the pore size is 0.25 nm, H2 can pass through, but CH4 cannot pass through. However, the permeability and diffusion coefficient of the pores are easily affected by environmental factors such as temperature, humidity and pressure, resulting in a decrease in selectivity. Moreover, the above three methods can only be implemented at a specific temperature or at a low temperature, and cannot be implemented over a wide temperature range to separate and purify hydrogen.

[0004] Hydrogen fuel cell is not subject to the Carnot cycle, so the energy conversion efficiency is high, the power and density are large, and the power generation process has little impact on the environment. It is the fourth generation of power generation technology after water power generation, thermal power generation and atomic power generation, and has broad application prospects in distributed power stations, electric vehicles, ships, submarines, aerospace, mobile communications and weapon equipment fields.

[0005] The most widely used in hydrogen fuel cell is proton exchange membrane fuel cell. Compared with other liquid electrolyte fuel cells, the solid proton exchange membrane with good proton conductivity is used, which not only avoids the inconvenience of liquid electrolyte operation, but also can make the proton exchange membrane into a thin film of several tens of microns, thereby improving the energy density of the cell. Therefore, it has the characteristics of high power density, high energy conversion efficiency, room temperature rapid start, no electrolyte leakage, low working temperature and rapid start and stop characteristics, and is recognized as the most promising power source for aerospace, military, electric vehicles and regional power stations. The key materials of proton exchange membrane fuel cell mainly include proton exchange membrane, catalyst, gas diffusion layer, bipolar plate and other main components. When hydrogen is used as raw material, hydrogen at the anode is decomposed into H + and electrons under the catalytic action of the catalyst, and then H + is transmitted to the cathode of the cell through the proton exchange membrane, and the electrons are moved from the anode to the cathode of the cell through the external circuit. However, there are still difficulties in realizing large-scale commercialization of proton exchange membrane fuel cell, mainly in that the cost of key materials such as proton exchange membrane, gas diffusion layer and catalyst is too high. As for the catalyst, the anode catalyst can only use Pt group metals or metal-containing supported materials, and no non-noble metal catalyst has been found. Taking methanol as fuel as an example, Pt cannot completely catalyze methanol, and CO and other small molecular organic hydrocarbon chemicals containing oxygen will be produced, and CO will poison the metal catalyst. The commonly used commercial catalyst is carbon-supported Pt type catalyst, and using Pt nanoparticles supported on carbon carrier is the best choice for proton exchange membrane fuel cell. From a technical point of view, if non-noble metal proton exchange membrane fuel cell can be used, using cheap catalyst instead of noble metal catalyst will be a better choice.

[0006] In addition, the key technology of hydrogen fuel cell is hydrogen storage and release. For pure hydrogen storage, conventional hydrogen storage methods include liquefied hydrogen storage, high-pressure hydrogen storage, non-metallic and metallic material solid hydrogen storage, etc. Among them, solid hydrogen storage is considered as the development trend of future hydrogen storage and transportation and the top technology of hydrogen fuel cell because it has relatively higher volume hydrogen storage density, low hydrogen storage pressure, high safety and less energy consumption. Solid hydrogen storage materials mainly include metal alloy materials, carbon-based materials, inorganic porous materials, chemical hydrogen compound materials and metal organic framework compound materials, etc. However, the performance of various hydrogen storage materials in safety, volume hydrogen storage density and mass hydrogen storage density still needs to be improved, otherwise it cannot meet the requirements of practical use of hydrogen energy. The ideal hydrogen storage material can work under mild conditions and has large weight hydrogen storage density, volume hydrogen storage density and long service life. The most commonly required target is mass hydrogen storage density of more than 6wt%, hydrogen release temperature of less than 250℃ and working pressure of less than 2MPa, etc. With the continuous in-depth research of solid hydrogen storage technology, fullerene, graphene and carbon nanotube materials are expected to become high-efficiency hydrogen storage materials in theory due to their hollow tubular structure and large specific surface area. It is found that the interaction between carbon nanotube material and hydrogen is weak physical adsorption, which is reversible adsorption and easy to desorb, which is beneficial to reduce the hydrogen release temperature, but the disadvantage is that the selectivity is not high, the separation coefficient is small, and the mass hydrogen storage density is only 0.2wt% under normal conditions, which cannot be used as high-efficiency hydrogen storage and transportation. Although the hydrogen storage density of chemical adsorption is improved, the disadvantage is that the desorption of adsorbent is difficult, and due to the strong binding force of some chemical adsorption, the adsorption process is irreversible, the desorption temperature is too high, and the practical application cannot be realized. Therefore, the development of new high-density hydrogen storage technology and reversible hydrogen storage / release technology in solid materials is the research focus at present. SUMMARY

[0007] The technical problem solved by the present application is to provide a hydrogen storage and release method based on hydrogen-containing raw gas, which is not affected by environmental conditions, has a wider applicable temperature range and can be used more widely.

[0008] Technical scheme: In order to solve the above technical problem, the present application provides a hydrogen storage and release method based on hydrogen-containing raw gas, characterized in that the hydrogen storage and release method based on hydrogen-containing raw gas comprises a hydrogen storage process and a hydrogen release process, and the hydrogen storage process comprises the following steps:

[0009] a1) selecting a non-metallic material that can only permeate protons;

[0010] a2) activating the non-metallic material to generate catalytic properties;

[0011] a3) introducing hydrogen-containing raw gas into one side of the non-metallic material;

[0012] a4) the incoming hydrogen-containing feed gas is decomposed into protons and electrons under the catalytic action of the activated non-metallic material;

[0013] a5) the protons and electrons permeate into the activated non-metallic material, recombine in the non-metallic material to form pure hydrogen gas and store in the non-metallic material, completing the hydrogen storage in the non-metallic material;

[0014] The hydrogen release process comprises the following steps:

[0015] b1) activating the non-metallic material containing hydrogen and generating catalytic properties;

[0016] b2) the hydrogen stored in the non-metallic material is decomposed into protons and electrons under the catalytic action of the activated non-metallic material;

[0017] b3) the protons and electrons obtained in step b2) recombine to form pure hydrogen gas after passing through the activated non-metallic material, completing the hydrogen release from the non-metallic material.

[0018] As preferred, the non-metallic material used in the present application is a two-dimensional material thin film layered material or a solid material containing cavities; the two-dimensional material thin film layered material is one or a combination of graphene sheet, hexagonal boron nitride sheet, molybdenum disulfide sheet, tungsten disulfide sheet, molybdenum diselenide sheet, niobium diselenide sheet and tungsten diselenide sheet; the solid material containing cavities is one or a combination of carbon nanotubes, fullerene spheres and boron-nitrogen nanotubes.

[0019] As preferred, when the two-dimensional material thin film layered material used in the present application is graphene sheet, the thickness of the graphene sheet is 2nm-1mm; when the two-dimensional material thin film layered material is hexagonal boron nitride sheet, the thickness of the hexagonal boron nitride sheet is 2nm-1mm; when the two-dimensional material thin film is molybdenum disulfide sheet, the thickness of the molybdenum disulfide sheet is 1.5nm-1mm.

[0020] When the solid material containing cavities is carbon nanotubes, the carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotubes, the tube diameter of the carbon nanotubes is 0.5nm-100nm, preferably the tube diameter is 1nm to 10nm; when the solid material containing cavities is fullerene spheres, the diameter of the fullerene spheres is 0.7nm-10nm, preferably the diameter is 0.7nm to 5nm.

[0021] As preferred, the size of the solid material containing cavities used in the present application is 100nm 2 -1m 2 , preferably in the range of 100nm 2 -100cm 2 .

[0022] As preferred, the activation in step a2) of the present application is placing the non-metallic material in a plasma environment, introducing electrons into the non-metallic material and / or heating the non-metallic material.

[0023] As preferred, the activation in step 2) of the present application is placing the non-metallic material in a plasma environment, the plasma environment is generated by a plasma generator, the plasma generator is an inductively coupled plasma, the power of the plasma generator is 5W-500W, preferably the power is 10W-100W; the pressure of the plasma generator is 10 - 5 Pa-1atm, preferably the pressure is 10 -2 Pa-10 2 Pa; the reaction temperature of the plasma generator is 50℃-800℃, preferably the temperature is 100℃-800℃; the gas flow of the plasma generator is 5-2000sccm, preferably the gas flow is 10sccm-500sccm; the heating time of the plasma generator is 5s-5h, preferably the heating time is 30min-2h; the reaction time of the activation is 5s-7200s, preferably the reaction time of the activation is 30s-1000s.

[0024] As preferred, the activation in step b1) of the present application is introducing electrons into the non-metallic material and / or heating the non-metallic material;

[0025] When the activation mode is introducing electrons into the non-metallic material, the mode of introducing electrons is scanning electron microscope injection of electrons, electrostatic generator injection of electrons and / or ordinary power injection of electrons; the current of introducing electrons is 1pA-10A, preferably 5pA-5nA; the voltage of introducing electrons is 1V-50kV, preferably 1V-500V; the applicable temperature of introducing electrons is -250℃-1000℃;

[0026] When the activation mode is heating the non-metallic material, the temperature of heating is 30℃-800℃;

[0027] When the activation mode is light irradiation to the non-metallic material, the light is natural light, artificial natural light and / or laser light; the wavelength of the light is less than 1000nm; the applicable temperature of the light is -250℃-1000℃.

[0028] As preferred, the heating temperature of the graphene sheet and the carbon nanotube of the present application is 500℃-800℃; the heating temperature of the hexagonal boron nitride sheet is 400℃-800℃; the heating temperature of the molybdenum disulfide sheet is 200℃-500℃; the heating temperature of the fullerene sphere is 50℃-300℃.

[0029] As preferred, the activation in step b1) of the present application is irradiation of the non-metallic material, and the surface of the non-metallic material is attached with metal platinum, metal palladium, and / or metal nickel.

[0030] As preferred, the hydrogen raw gas in step 3) of the present application is one or a combination of hydrogen, argon, ammonia, methane, and ethane.

[0031] Advantages: Compared with the prior art, the present application has the following advantages: the present application provides a method for generating protons based on hydrogen-containing raw gas, which can utilize light energy, heat energy or injected electrons to catalytically decompose hydrogen-containing raw gas in a non-metallic material that can only permeate protons to generate protons, and protons can pass through the non-metallic material that can only permeate protons. At the same time, the present application also provides the method as an application for preparing pure hydrogen, preparing hydrogen fuel cells or storing and releasing hydrogen. In the preparation of pure hydrogen, the present application utilizes the concept that protons can freely pass through graphene, hexagonal boron nitride, molybdenum disulfide and other thin films, and protons pass through two-dimensional materials to recombine with electrons to form hydrogen, thereby realizing the extraction of high-purity hydrogen from mixed gas and waste gas. At the same time, the present application uses two-dimensional thin films with intrinsic structure of graphene, hexagonal boron nitride and other materials with high mechanical properties, excellent chemical stability and thermal stability, which can realize hydrogen separation and purification in a large temperature and pressure range. Compared with other thin films used in common membrane separation methods, the present application has high thermal stability and excellent temperature resistance, so the applicable temperature range is very large. Moreover, the hydrogen-containing raw gas used in the present application includes hydrogen, argon, ammonia, methane, ethane and other hydrogen-containing raw gas, which can separate and purify high-purity hydrogen from a variety of mixed gases, and has exclusivity to other gases. In the present application, by controlling electron injection and light, the hydrogen purification can be switched on and off in nanoseconds, and the present application lays a foundation for the application of hydrogen energy in future spaceflight, military application, fuel cells and other applications. In the preparation and purification process of the present application, no harmful substances are used and no harmful substances are generated, the equipment is simple, the land occupation is small, and the process is simple, efficient and requires less energy.

[0032] In the preparation of hydrogen fuel cells, the present application utilizes light energy, heat energy or injected electrons to catalytically decompose hydrogen-containing fuel in two-dimensional materials to generate protons and electrons, and then under the driving of concentration difference and potential difference, H +The proton exchange membrane fuel cell is realized by that the electrons move from the anode to the cathode of the battery through the external circuit while the protons are transferred to the cathode of the battery through the proton exchange membrane. The present application utilizes the concept that protons can freely cross the thin films of graphene, hexagonal boron nitride, molybdenum disulfide and other materials, while other raw fuels are blocked by the two-dimensional materials to prevent damage to the proton exchange membrane. The hydrogen-containing fuel is catalytically decomposed by the two-dimensional materials to generate protons and electrons, the protons are transferred to the cathode of the battery through the proton exchange membrane, and the electrons move from the anode to the cathode of the battery through the external circuit, thereby realizing the proton exchange membrane fuel cell. The present application can utilize the two-dimensional thin films with intrinsic structure of graphene, hexagonal boron nitride and other materials with high mechanical properties, excellent chemical stability and thermal stability, and can realize the application of hydrogen fuel cells in a large temperature range and pressure range. The two-dimensional materials used in the present application have the characteristics of blocking fuel, preventing fuel from leaking to the proton exchange membrane, and also preventing the poisoning of the catalyst by the byproduct carbon monoxide. In the preparation and use process, no harmful substances are used and no harmful substances are generated, the equipment is simple, the land occupation is small, and it is simple, efficient and requires less energy. By controlling the electron injection and light, it is instantaneous and can realize the switching of the fuel cell within nanoseconds. The present application lays a foundation for the application of hydrogen energy in future spaceflight, military application, fuel cell and other applications.

[0033] In the hydrogen storage and release, the application utilizes the characteristics of solid materials such as graphene sheets, carbon nanotubes, fullerene molecules, hexagonal boron nitride and molybdenum disulfide, which can only permeate protons, and combines hydrogen plasma, light energy, heat energy or electron injection to realize the storage of hydrogen in the interlayer of solid materials or in the cavity. In the hydrogen application (hydrogen release), the above-mentioned solid materials are activated by means of light energy, heat energy or electron injection to catalyze the decomposition of hydrogen to generate protons and electrons, and the permeated protons and electrons recombine to generate hydrogen, which is released from the interlayer of solid materials and / or the cavity to realize the hydrogen storage and release. The application is suitable for layered materials of graphene, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, niobium diselenide, tungsten diselenide and other semi-metals, semiconductors, conductors and insulators, carbon nanotubes, fullerenes, boron-nitrogen nanotubes and other cavity-containing solid materials. The application uses pure solid materials with intrinsic structure of graphene, hexagonal boron nitride and the like, which have high mechanical properties, excellent chemical stability and thermal stability, and does not need any element doping. The intrinsic structure of the solid material is not damaged during the whole hydrogen storage and release process, and the repeated hydrogen storage and release and long service life can be realized. In the hydrogen release process of the application, the electron injection and light are controlled, which is instantaneous and can realize the switching of the hydrogen release process within nanoseconds. In the application, the interlayer and / or cavity space of the solid material is used to store hydrogen. Compared with the commonly used physical adsorption method, the application has higher selectivity because only protons and electrons are allowed to pass through, and is suitable for a variety of hydrogen-containing gases, which has less limitation on raw gas. The working pressure is small, and the hydrogen storage can be realized at normal pressure or even low pressure, and the maximum mass density can exceed 9wt%. In the hydrogen release process of the application, the above-mentioned solid materials are activated by activation, so that the hydrogen release process can be carried out at normal temperature or even low temperature to 200K, and the application temperature range is wider. The whole process is reversible, so that the solid material can be repeatedly used. The application is suitable for hydrogen-containing raw gas, which can include hydrogen, hydrogen-containing natural gas, propane, butane and methanol, etc. Compared with the common adsorption method which can only use hydrogen, the application has wider application range and use value. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 is a principle diagram of the application for preparing pure hydrogen by injecting electrons;

[0035] Figure 2 is a principle diagram of the application for preparing pure hydrogen by heating;

[0036] Figure 3 is a principle diagram of the application for preparing pure hydrogen by light irradiation;

[0037] Figure 4 is a principle diagram of the proton exchange membrane fuel cell anode catalyst of the application using the electron injection implementation;

[0038] Figure 5It is a schematic diagram of the hydrogen storage principle of graphene sheet layer by hydrogen plasma method of the application;

[0039] Figure 6 It is a schematic diagram of the hydrogen storage principle of graphene sheet layer by methane plasma method of the application;

[0040] Figure 7 It is an atomic force microscope picture of the hydrogen storage principle of hexagonal boron-nitrogen layer of the application;

[0041] Figure 8 It is an atomic force microscope picture of the thermal stability of hydrogen storage in graphene layer of the application;

[0042] Figure 9 It is a statistical chart and an atomic force microscope picture of the time stability of hydrogen storage in graphene layer of the application;

[0043] Figure 10 It is a Raman picture of hydrogen storage in graphene layer of the application. DETAILED DESCRIPTION

[0044] The application provides a method for generating protons based on hydrogen-containing raw gas, and the method comprises the following steps:

[0045] 1) selecting a non-metallic material capable of permeating only protons, wherein the non-metallic material is a two-dimensional material film or a non-metallic solid material;

[0046] When the non-metallic material is a two-dimensional material film, the two-dimensional material film is one or a combination of graphene, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, niobium diselenide and tungsten diselenide; when the non-metallic material is a non-metallic solid material, the non-metallic solid material is a two-dimensional material film layered material or a solid material containing cavities; the two-dimensional material film layered material is one or a combination of graphene sheet, hexagonal boron nitride sheet, molybdenum disulfide sheet, tungsten disulfide sheet, molybdenum diselenide sheet, niobium diselenide sheet and tungsten diselenide sheet; when the solid material is a solid material containing cavities, the solid material containing cavities is one or a combination of carbon nanotubes, fullerene balls and boron-nitrogen nanotubes; when the two-dimensional material film is graphene, the thickness of the graphene is 0.5 nm to 1 mm; when the two-dimensional material film is hexagonal boron nitride, the thickness of the hexagonal boron nitride is 0.5 nm to 1 mm; when the two-dimensional material film is molybdenum disulfide, the thickness of the molybdenum disulfide is 0.7 nm to 1 mm; the size of the two-dimensional material film is 100 nm 2 to 1 m 2 , preferably 100 nm 2 to 100 cm 2; when the two-dimensional material thin film layered material is hexagonal boron nitride sheet, the thickness of the hexagonal boron nitride sheet is 2nm-1mm; when the two-dimensional material thin film layered material is molybdenum disulfide sheet, the thickness of the molybdenum disulfide sheet is 1.5nm-1mm; when the solid material containing cavities is carbon nanotube, the carbon nanotube is single-walled carbon nanotube or multi-walled carbon nanotube, the tube diameter of the carbon nanotube is 0.5nm-100nm, and preferably the tube diameter is 1nm to 10nm; when the solid material containing cavities is fullerene ball, the diameter of the fullerene ball is 0.7nm-10nm, and preferably the diameter is 0.7nm to 5nm; the size of the solid material containing cavities is 100nm 2 ~1m 2 , preferably in the range of 100nm 2 ~100cm 2 .

[0047] 2) activating the non-metallic material to generate catalytic properties, and the specific implementation of the activation is: introducing electrons into the non-metallic material, heating the non-metallic material and / or irradiating the non-metallic material with light;

[0048] When the activation is introducing electrons into the non-metallic material, the way of introducing electrons is scanning electron microscope injection, electrostatic generator injection and / or ordinary power injection; the current of introducing electrons is 1pA-10A, preferably 5pA-5nA; the voltage used when introducing electrons is 1V-50kV, preferably 1V-500V; the applicable temperature of introducing electrons is -250℃-1000℃; when the activation is heating the non-metallic material, the temperature used for heating is 30℃-800℃; when the activation is irradiating the non-metallic material with light, the light is natural light, artificial natural light and / or laser light; the wavelength of the light used for irradiation is less than 1000nm; the applicable temperature of the light irradiation is -250℃-1000℃; when the activation is irradiating the two-dimensional material thin film with light, the surface of the two-dimensional material thin film is attached with metal platinum, metal palladium and / or metal nickel, which can accelerate the decomposition of the hydrogen-containing raw material gas; when the activation is heating the non-metallic solid material, the heating temperature is 30℃-800℃; preferably, the heating temperature of the graphene sheet and the carbon nanotube is 500℃-800℃; preferably, the heating temperature of the hexagonal boron nitride sheet is 400℃-800℃; preferably, the heating temperature of the molybdenum disulfide sheet is 200℃-500℃; the heating temperature of the fullerene ball is 50℃-300℃.

[0049] 3) introducing hydrogen-containing raw material gas into one side of the non-metallic material, and the hydrogen-containing raw material gas is one or a combination of hydrogen, argon, ammonia, methane and ethane.

[0050] 4) the hydrogen-containing raw gas is decomposed into protons and electrons under the catalysis of the activated non-metallic material. Based on the above, the application of the method for generating protons based on the hydrogen-containing raw gas in the preparation of pure hydrogen, the preparation of hydrogen fuel cells or the storage and release of hydrogen is also provided.

[0051] The method for generating protons based on the hydrogen-containing raw gas provided by the application has the following application schemes, specifically:

[0052] Application A

[0053] When the method for generating protons based on the hydrogen-containing raw gas is used for preparing pure hydrogen, the following content is specifically included:

[0054] 1) Select a two-dimensional material film. The two-dimensional material film is graphene, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, niobium diselenide, and tungsten diselenide, and other two-dimensional materials of semimetals, semiconductors, conductors and insulators. When the two-dimensional material film is graphene, the thickness of the graphene is 0.5 nm to 1 mm. Exemplarily, the thickness of the graphene is single layer to 1 mm, or two layers to 100 nm. When the two-dimensional material film is hexagonal boron nitride, the thickness of the hexagonal boron nitride is 0.5 nm to 1 mm. Exemplarily, the thickness of the hexagonal boron nitride is single layer to 1 mm, or single layer to 50 nm. When the two-dimensional material film is molybdenum disulfide, the thickness of the molybdenum disulfide is 0.7 nm to 1 mm. Exemplarily, the thickness of the molybdenum disulfide is single layer to 1 mm, or single layer to 50 nm. The size of the two-dimensional material film is 100 nm 2 to 1 m 2 , preferably 100 nm 2 to 100 cm 2 .

[0055] 2) Activate the two-dimensional material film to generate catalytic activity. The specific activation methods are: introducing electrons into the two-dimensional material film (as shown in Figure 1 ), heating the two-dimensional material film (as shown in Figure 2 ), and / or irradiating the two-dimensional material film with light (as shown in Figure 3 ).

[0056] Wherein, when the activation mode is to introduce electrons, the introduced electrons are injected by a scanning electron microscope, an electrostatic generator and / or a common power supply; the current of the introduced electrons is 1pA-10A, preferably 5pA-5nA; the voltage used in the introduction of the electrons is 1V-50kV, preferably 1V-500V; the applicable temperature of the introduced electrons is -250℃-1000℃. When the activation mode is to heat the two-dimensional material film, the temperature used for heating is 30℃-800℃, the preferred temperature range of graphene is 500℃-800℃, the preferred temperature range of hexagonal boron nitride is 400℃-800℃, and the preferred temperature range of molybdenum disulfide is 200℃-500℃. When the activation mode is to irradiate the two-dimensional material film, the light irradiation is natural light, artificial natural light and / or laser light; preferably, the wavelength of the light used for irradiation is less than 1000nm; preferably, the applicable temperature of the light irradiation is -250℃-1000℃.

[0057] When the activation mode is to irradiate the two-dimensional material film, the surface of the two-dimensional material film is attached with metal platinum, metal palladium and / or metal nickel, and the metal platinum, metal palladium and / or metal nickel and other metals with catalytic ability can accelerate the hydrogen purification rate.

[0058] 3) introducing a hydrogen-containing raw material gas into the two-dimensional material film, wherein the hydrogen-containing raw material gas includes hydrogen, argon, ammonia, methane, ethane and other hydrogen-containing raw material gases;

[0059] 4) under the catalytic action of the activated two-dimensional material film, the hydrogen-containing raw material gas introduced into the two-dimensional material film is decomposed into protons and electrons;

[0060] 5) the protons and the electrons recombine after passing through the activated two-dimensional material film to form pure hydrogen.

[0061] The technical solutions provided by the present application are further explained below in combination with the drawings:

[0062] Referring to Figure 1 , the hydrogen is purified by injecting electrons, specifically:

[0063] 1) injecting electrons into the two-dimensional material film, and introducing a hydrogen-containing raw material gas into one side of the two-dimensional material film;

[0064] 2) separating and purifying under the condition of injecting electrons to obtain pure hydrogen on the other side.

[0065] Referring to Figure 2 , the hydrogen is purified by heating, specifically:

[0066] 1) heating the two-dimensional material film, and introducing a hydrogen-containing raw material gas into one side of the two-dimensional material film;

[0067] 2) Separation and purification under heating conditions, and pure hydrogen gas is obtained on the other side.

[0068] Referring to Figure 3 , the purification of hydrogen gas is achieved by means of light irradiation, specifically:

[0069] 1) The two-dimensional material film is placed under light, and the hydrogen-containing raw material gas is introduced into one side of the two-dimensional material film;

[0070] 2) Separation and purification under light conditions, and pure hydrogen gas is obtained on the other side.

[0071] In the following, the specific technical solutions of the method for preparing pure hydrogen gas based on the production of protons from hydrogen-containing raw material gas will be described in detail in combination with specific embodiments:

[0072] Embodiment 1

[0073] Hydrogen gas is purified by injecting electrons into double-layer graphite using hydrogen-containing mixed gas of hydrogen, nitrogen and argon as raw material, specifically: the hydrogen-containing mixed gas is sent into one side of the double-layer graphene, the gas pressure is 1 MPa, the temperature is 200°C, the two-dimensional material film is double-layer graphene, the thickness of the double-layer graphene is about 1 nm, and the size area is 100 nm 2 , the double-layer graphene is activated by injecting electrons into the double-layer graphene through an electrostatic generator, the current of the electrostatic generator is 5 nA, and the voltage is 100 V. Under the catalytic action of the activated double-layer graphene, the hydrogen atoms in the mixed gas are decomposed into protons and electrons, and the protons and electrons can freely pass through the double-layer graphene. After the protons and electrons pass through the activated double-layer graphene, the protons and electrons combine to form hydrogen gas again. The double-layer graphene completely blocks other non-proton particles, achieving the extraction of pure hydrogen gas. Since the current experiment confirms that the graphene honeycomb structure only allows the smallest particle protons to penetrate, the purity of the purified hydrogen gas can reach more than 99.99%.

[0074] Based on the foregoing other conditions being unchanged, on the basis of the two-dimensional material film being double-layer graphene, the size area of the double-layer graphene can also be selected from any one of 500 nm 2 , 10 μm 2 , 100 μm 2 , 500 μm 2 , 1 cm 2 , 10 cm 2 , 100 cm 2 , 500 cm 2 , and 1 m 2 .

[0075] Embodiment 2

[0076] The hydrogen-containing raw gas is sent to one side of the double-layer graphene, the gas pressure of the mixed gas is 1 MPa, the temperature is 200 DEG C, the two-dimensional material film is double-layer graphene, the thickness of the double-layer graphene is about 1 nm, and the size area is 100 nm 2 The double-layer graphene is activated by injecting electrons into the double-layer graphene through an electrostatic generator, the current of the electrostatic generator is 5 nA, and the voltage is 100 V. Under the catalysis of the activated double-layer graphene, the hydrogen atoms in the methane are decomposed into protons and electrons, and the protons and electrons can freely pass through the double-layer graphene. After the protons and electrons pass through the activated double-layer graphene, the protons and electrons combine to form hydrogen gas again. The double-layer graphene completely blocks other non-proton particles, and pure hydrogen gas is extracted. Since the current experiment proves that the graphene honeycomb structure only allows the smallest particle protons to penetrate, the purity of the purified hydrogen gas can reach more than 99.99%.

[0077] Based on the foregoing other conditions being unchanged, on the basis of the two-dimensional material film being double-layer graphene, the size area of the double-layer graphene can also be selected from any one of 500 nm 2 , 10 μm 2 , 100 μm 2 , 500 μm 2 , 1 cm 2 , 10 cm 2 , 100 cm 2 , 500 cm 2 and 1 m 2 .

[0078] Embodiment 3

[0079] The hydrogen-containing raw gas is sent to one side of the double-layer graphene, the gas pressure of the mixed gas is 1 MPa, the temperature is 200 DEG C, the two-dimensional material film is double-layer graphene, the thickness of the double-layer graphene is about 1 nm, and the size area is 100 nm 2 The double-layer graphene is activated by injecting electrons into the double-layer graphene through an electrostatic generator, the current of the electrostatic generator is 5 nA, and the voltage is 100 V. Under the catalysis of the activated double-layer graphene, the hydrogen atoms in the methane are decomposed into protons and electrons, and the protons and electrons can freely pass through the double-layer graphene. After the protons and electrons pass through the activated double-layer graphene, the protons and electrons combine to form hydrogen gas again. The double-layer graphene completely blocks other non-proton particles, and pure hydrogen gas is extracted. Since the current experiment proves that the graphene honeycomb structure only allows the smallest particle protons to penetrate, the purity of the purified hydrogen gas can reach more than 99.99%.

[0080] Based on the foregoing other conditions remain unchanged, on the basis of two-dimensional material thin film for three layers of hexagonal boron nitride, the size of three layers of hexagonal boron nitride area can also be selected from any one of the following dimensions: 500 nm 2 , 10 μm 2 , 100 μm 2 , 500 μm 2 , 1 cm2, 10 cm 2 , 100 cm 2 , 500 cm 2 and 1 m 2 .

[0081] Example 4

[0082] The hydrogen-containing raw gas is used as raw material to purify hydrogen by injecting electrons into a single-layer molybdenum disulfide. Specifically, hydrogen, nitrogen and argon are sent to one side of the single-layer molybdenum disulfide, the mixed gas pressure is 1 MPa, the temperature is 200°C, the two-dimensional material thin film is a single-layer molybdenum disulfide, the thickness of the single-layer molybdenum disulfide is about 1 nm, and the size area is 100 nm 2 . Electrons are injected into the single-layer molybdenum disulfide by an electrostatic generator to activate the single-layer molybdenum disulfide. The current of the electrostatic generator is 5 nA, and the voltage is 100 V. Under the catalytic action of the activated single-layer molybdenum disulfide, the hydrogen atoms in the hydrogen are decomposed into protons and electrons, which can freely pass through the single-layer molybdenum disulfide. After the protons and electrons pass through the activated single-layer molybdenum disulfide, the protons and electrons combine to form hydrogen again. The single-layer molybdenum disulfide completely blocks other non-proton particles, realizing the extraction of pure hydrogen. Since the current experiment proves that the structure of three atoms of molybdenum disulfide only allows the smallest particle protons to penetrate, the purity of the purified hydrogen can reach more than 99.99%.

[0083] Based on the foregoing other conditions remain unchanged, on the basis of two-dimensional material thin film for single-layer molybdenum disulfide, the size of single-layer molybdenum disulfide area can also be selected from any one of the following dimensions: 500 nm 2 , 10 μm 2 , 100 μm 2 , 500 μm 2 , 1 cm 2 , 10 cm 2 , 100 cm 2 , 500 cm 2 and 1 m 2 .

[0084] Example 5

[0085] The hydrogen-containing raw gas is used as raw material to purify hydrogen by heating the single-layer molybdenum disulfide (the energy used in this embodiment is heat energy), specifically, the hydrogen, nitrogen and argon are sent to one side of the single-layer molybdenum disulfide, the mixed gas pressure is 1 MPa, the temperature is 200°C, the two-dimensional material film is single-layer molybdenum disulfide, the thickness of the single-layer molybdenum disulfide is about 1 nm, and the size area is 100 nm 2 The single-layer molybdenum disulfide is activated by heating (a small amount of hot electrons is generated by heating), and the heating temperature is 300°C. Under the catalysis of the heated single-layer molybdenum disulfide, the hydrogen is decomposed into protons and electrons, and the protons and electrons can freely pass through the single-layer molybdenum disulfide. After the protons and electrons pass through the activated single-layer molybdenum disulfide, the protons and electrons combine to re-form hydrogen. The single-layer molybdenum disulfide completely blocks other non-proton particles, realizing the extraction of pure hydrogen. At present, experiments have proved that the structure of three-layer atoms of molybdenum disulfide only allows the penetration of the smallest particle protons, and the purity of the purified hydrogen can reach more than 99.99%.

[0086] Based on the foregoing other conditions being unchanged, on the basis of the two-dimensional material film being single-layer molybdenum disulfide, the size area of the single-layer molybdenum disulfide can also be selected from any one of 500 nm 2 , 10 μm 2 , 100 μm 2 , 500 μm 2 , 1 cm 2 , 10 cm 2 , 100 cm 2 , 500 cm 2 and 1 m 2 .

[0087] Embodiment 6

[0088] The hydrogen-containing raw gas is used as raw material to purify hydrogen by laser irradiation of single-layer molybdenum disulfide (the energy used in this embodiment is laser, i.e. the electrons are generated by laser irradiation), specifically, the hydrogen, nitrogen and argon are sent to one side of the single-layer molybdenum disulfide, the mixed gas pressure is 1 MPa, the temperature is 200°C, the two-dimensional material film is single-layer molybdenum disulfide, the thickness of the single-layer molybdenum disulfide is about 1 nm, and the size area is 100 nm 2, the single-layer molybdenum disulfide is activated by laser irradiation, and the wavelength of the laser is 532 nm. Under the catalysis of the activated single-layer molybdenum disulfide irradiated by the laser, hydrogen is decomposed into protons and electrons, and the protons and electrons can freely pass through the single-layer molybdenum disulfide. After the protons and electrons pass through the activated single-layer molybdenum disulfide, the protons and the electrons combine to re-form hydrogen. The single-layer molybdenum disulfide completely blocks other non-proton particles, realizing the extraction of pure hydrogen. Since experiments have confirmed that the structure of three-layer atoms of molybdenum disulfide only allows the smallest particle protons to penetrate, the purity of the purified hydrogen can reach more than 99.99%.

[0089] Based on the foregoing other conditions being unchanged, on the basis of the two-dimensional material thin film being single-layer molybdenum disulfide, the size area of the single-layer molybdenum disulfide can also be selected from any one of 500 nm 2 , 10 μm 2 , 100 μm 2 , 500 μm 2 , 1 cm 2 , 10 cm 2 , 100 cm 2 , 500 cm 2 , and 1 m 2 . When laser irradiation is used, the wavelength of the laser can also be selected from any one of wavelengths below 1000 nm.

[0090] Example 7

[0091] The natural light is used to irradiate the single-layer molybdenum disulfide to realize the purification of hydrogen-containing raw material gas to obtain hydrogen (the energy used in this embodiment is natural light). Specifically, hydrogen, nitrogen and argon are sent to one side of the single-layer molybdenum disulfide, the mixed gas pressure is 1 MPa, the temperature is 200°C, the two-dimensional material thin film is single-layer molybdenum disulfide, the thickness of the single-layer molybdenum disulfide is about 1 nm, and the size area is 100 nm 2 . The single-layer molybdenum disulfide is activated by natural light irradiation. Under the catalysis of the activated single-layer molybdenum disulfide irradiated by the natural light, hydrogen is decomposed into protons and electrons, and the protons and electrons can freely pass through the single-layer molybdenum disulfide. After the protons and electrons pass through the activated single-layer molybdenum disulfide, the protons and the electrons combine to re-form hydrogen. The single-layer molybdenum disulfide completely blocks other non-proton particles, realizing the extraction of pure hydrogen. Since experiments have confirmed that the structure of three-layer atoms of molybdenum disulfide only allows the smallest particle protons to penetrate, the purity of the purified hydrogen can reach more than 99.99%.

[0092] Based on the foregoing other conditions being unchanged, on the basis of the two-dimensional material thin film being single-layer molybdenum disulfide, the size area of the single-layer molybdenum disulfide can also be selected from any one of 500 nm 2 , 10 μm 2 , 100 μm 2, 500 pm 2 , 1 cm 2 , 10 cm 2 , 100 cm 2 , 500 cm 2 and 1 m 2 .

[0093] Example 8

[0094] A hydrogen-containing raw gas is used as a raw material to purify hydrogen gas by laser irradiation of double-layer graphene covering platinum nanoparticles (exemplarily, double-layer graphene covering platinum nanoparticles is used in this embodiment, and of course, covering metal platinum also has the same effect). Specifically, hydrogen gas, nitrogen gas, and argon gas are sent into one side of the double-layer graphene, and the other side of the graphene covers platinum nanoparticles. The mixed gas pressure is 1 MPa, and the temperature is 200°C. The two-dimensional material thin film is double-layer graphene covering platinum nanoparticles, the height of the platinum nanoparticles is 0.5-10 nm, and the size is 10 nm-500 nm. The side of the graphene covering the platinum nanoparticles is activated by laser irradiation with a wavelength of 532 nm. Under the catalytic action of the double-layer graphene covering the platinum nanoparticles after being affected by the laser, the hydrogen gas is decomposed into protons and electrons, which can freely pass through the double-layer graphene. After the protons and electrons pass through the double-layer graphene, the protons combine with the electrons to re-form hydrogen gas. The double-layer graphene completely blocks other non-proton particles, achieving the extraction of pure hydrogen gas. Since the current experiments have confirmed that the graphene honeycomb atomic structure only allows the smallest particle protons to penetrate, the purity of the purified hydrogen gas can reach more than 99.99%. Based on the foregoing conditions, on the basis of using a two-dimensional material thin film as a single-layer molybdenum disulfide, when laser irradiation is used, the wavelength of the laser can also be selected from any wavelength below 1000 nm.

[0095] Application B

[0096] The method for generating protons based on a hydrogen-containing raw gas is used to prepare a hydrogen fuel cell. The principle is as follows: using light energy, heat energy, or injecting electrons, a two-dimensional material thin film catalytically decomposes hydrogen-containing substances to generate protons. Combining the characteristics of the two-dimensional material thin film that can only permeate protons and block hydrogen-containing fuels, H + is transferred to the cathode of the cell through the proton exchange membrane, and electrons move from the anode to the cathode through the external circuit, thereby realizing a proton exchange membrane fuel cell.

[0097] Exemplarily, the method for forming a hydrogen fuel cell by catalytically decomposing hydrogen-containing fuel by graphene is shown in Figure 4 , and specifically includes:

[0098] 1) Injecting electrons or heating in graphene with a preferred thickness in a suitable occasion, and passing hydrogen-containing fuel through one side of the graphene;

[0099] 2) Under the condition of injecting electrons or heating, the boron nitride catalytically decomposes the hydrogen-containing fuel into H + and electrons, and then under the driving of the concentration difference and the potential difference, H + transfers to the cathode of the battery through the proton exchange membrane, and the electrons move to the cathode from the anode of the battery through the external circuit, forming a hydrogen fuel cell.

[0100] Exemplarily, the method for catalytically decomposing the hydrogen-containing fuel into a hydrogen fuel cell by hexagonal boron nitride includes:

[0101] 1) Under the condition of injecting electrons or heating, the boron nitride catalytically decomposes the hydrogen-containing fuel into H

[0102] 2) Under the condition of injecting electrons or heating, the boron nitride catalytically decomposes the hydrogen-containing fuel into H + and electrons, and then under the driving of the concentration difference and the potential difference, H + transfers to the cathode of the battery through the proton exchange membrane, and the electrons move to the cathode from the anode of the battery through the external circuit, forming a hydrogen fuel cell.

[0103] Exemplarily, the method for catalytically decomposing the hydrogen-containing fuel into a hydrogen fuel cell by hexagonal boron nitride includes:

[0104] 1) Under the condition of injecting electrons or heating, the boron nitride catalytically decomposes the hydrogen-containing fuel into H

[0105] 2) Under the condition of injecting electrons or heating, the boron nitride catalytically decomposes the hydrogen-containing fuel into H + and electrons, and then under the driving of the concentration difference and the potential difference, H + transfers to the cathode of the battery through the proton exchange membrane, and the electrons move to the cathode from the anode of the battery through the external circuit, forming a hydrogen fuel cell.

[0106] The two-dimensional material film suitable for use is completely the same as the two-dimensional material film suitable for use in application A, and will not be described again in application B.

[0107] Example 9

[0108] Under the condition of injecting electrons into double-layer graphene, the hydrogen-containing fuel is catalytically decomposed into H + and electrons, specifically: hydrogen gas is sent to one side of the double-layer graphene, the gas pressure of the hydrogen gas is 1 MPa, the temperature is-20°C, the catalytic anode film is double-layer graphene, the thickness is about 1 nm (double-layer graphene is too thin to be easily affected by the outside world, so the measured range value is 1 nm-1.5 nm, the same below), and the area is 100 nm2 Electrons were injected into the bilayer graphene using an electrostatic generator at a current of 5 nA and a voltage of 100 V. Under the catalytic action of the activated bilayer graphene, hydrogen gas was decomposed into H+ and electrons. Then, driven by the concentration and potential differences, H+... + Electrons are transferred to the cathode of the battery through bilayer graphene, while electrons move from the anode to the cathode through the external circuit.

[0109] With all other conditions remaining unchanged, and based on using a two-dimensional material film as the bilayer graphene, the size and area of ​​the bilayer graphene can also be selected from 500 nm, depending on the applicable environment. 2 10μm 2 100μm 2 500μm 2 and 1mm 2 Any size in the range.

[0110] Example 10

[0111] Using electron injection into bilayer graphene to catalytically decompose hydrogen fuel into H2O + Specifically, the process involves feeding hydrogen-containing methane fuel into one side of a bilayer graphene film. The methane gas pressure is 1 MPa, the temperature is 30°C, and the catalytic anode film is a bilayer graphene film with a thickness of approximately 1 nm and an area of ​​100 nm. 2 Electrons were injected into the bilayer graphene using an electrostatic generator at a current of 5 nA and a voltage of 100 V. Under the catalytic action of the activated bilayer graphene, hydrogen was decomposed into H₂. + And electrons, and then, driven by the concentration difference and potential difference, H + Electrons are transferred to the cathode of the battery through bilayer graphene, while electrons move from the anode to the cathode through the external circuit.

[0112] With all other conditions remaining unchanged, and based on using a two-dimensional material film as the bilayer graphene, the size and area of ​​the bilayer graphene can also be selected from 500 nm, depending on the applicable environment. 2 10μm 2 100μm 2 500μm 2 and 1mm 2 Any size in the range.

[0113] Example 11

[0114] Using hydrogen fuel containing hexagonal boron nitride injected with electrons as feedstock, catalytically decomposes it into H2O. + The electron injection process involves introducing hydrogen gas into one side of a triple-layered hexagonal boron nitride structure at a pressure of 1 MPa and a temperature of 30°C. Electrons are then injected into the boron nitride structure via an electrostatic generator. The structure is approximately 1.6 nm thick and has an area of ​​100 nm.2 , the current is 5nA and the voltage is 100V. Under the catalysis of the activated three-layer hexagonal boron nitride, the hydrogen is decomposed into H + and electrons. Then, under the driving of the concentration difference and the potential difference, H + is transferred to the cathode of the battery through the three-layer hexagonal boron nitride, and the electrons are moved from the anode to the cathode of the battery through the external circuit.

[0115] Based on the foregoing conditions, on the basis of the two-dimensional material thin film being the three-layer hexagonal boron nitride, according to the applicable environment adjustment, the size area of the three-layer hexagonal boron nitride can also be selected from any one of 500nm 2 , 10μm 2 , 100μm 2 , 500μm 2 and 1mm 2 .

[0116] Example 12

[0117] Catalytic decomposition of hydrogen-containing fuel into H + and electrons is realized by injecting electrons into a single-layer molybdenum disulfide, specifically: hydrogen is sent to one side of a single-layer molybdenum disulfide with a thickness of about 0.7nm and an area of 100nm 2 , the gas pressure of the hydrogen is 1MPa, the temperature is 30℃, electrons are injected into the single-layer molybdenum disulfide by an electrostatic generator, the current is 5nA, and the voltage is 100V. Under the catalysis of the activated single-layer molybdenum disulfide, the hydrogen is decomposed into H + and electrons. Then, under the driving of the concentration difference and the potential difference, H + is transferred to the cathode of the battery through the single-layer molybdenum disulfide, and the electrons are moved from the anode to the cathode of the battery through the external circuit. Based on the foregoing conditions, on the basis of the two-dimensional material thin film being the single-layer molybdenum disulfide, according to the applicable environment adjustment, the size area of the single-layer molybdenum disulfide can also be selected from any one of 500nm 2 , 10μm 2 , 100μm 2 , 500μm 2 and 1mm 2 .

[0118] Example 13

[0119] Catalytic decomposition of hydrogen-containing fuel into H + and electrons is realized by heating a single-layer molybdenum disulfide (the energy used in this embodiment is heat energy), specifically: hydrogen is sent to one side of a single-layer molybdenum disulfide with a thickness of about 0.7nm and an area of 100nm 2Hydrogen gas at a pressure of 1 MPa and a temperature of 30°C is heated to 300°C using a monolayer of molybdenum disulfide. Under the catalytic action of the activated molybdenum disulfide, hydrogen is decomposed into H₂. + And electrons, and then, driven by the concentration difference and potential difference, H + Electrons are transferred to the cathode of the battery via a monolayer of molybdenum disulfide, while electrons move from the anode to the cathode via an external circuit. Under the premise that other conditions remain unchanged, and using a two-dimensional material film as the monolayer of molybdenum disulfide, the size and area of ​​the monolayer can also be selected from 500 nm. 2 10μm 2 100μm 2 500μm 2 1cm 2 10cm², 100cm 2 500cm 2 and 1m 2 Any size in the range.

[0120] Example 14

[0121] Using laser irradiation of monolayer molybdenum disulfide to catalytically decompose hydrogen-containing fuels into H2O + And electrons (in this embodiment, the energy source is a laser), specifically: hydrogen gas is introduced into one side of a monolayer of molybdenum disulfide, with a thickness of about 0.7 nm and an area of ​​100 nm. 2 Adjusted according to the applicable environment, the hydrogen gas pressure is 1 MPa, the temperature is -30℃, and a single layer of molybdenum disulfide is irradiated with a laser at a wavelength of 532 nm. Under the catalytic action of the activated single layer of molybdenum disulfide, hydrogen is decomposed into H₂. + And electrons, and then, driven by the concentration difference and potential difference, H + Electrons are transferred to the cathode of the battery via a monolayer of molybdenum disulfide, while electrons move from the anode to the cathode via an external circuit. Under the premise that other conditions remain unchanged, and using a two-dimensional material film as the monolayer of molybdenum disulfide, the size and area of ​​the monolayer can also be selected from 500 nm. 2 10μm 2 100μm 2 500μm 2 1cm 2 10cm 2 100cm 2 500cm 2 and 1m 2 Any size within the range. When using laser irradiation, the laser wavelength can also be selected from any wavelength below 1000 nm.

[0122] Example 15

[0123] The hydrogen-containing fuel is used as raw material to realize catalytic decomposition into H + and electron (the energy used in this embodiment is sunlight), specifically: hydrogen is sent to one side of the monolayer molybdenum disulfide with a thickness of about 0.7 nm and an area of 100 nm 2 , the gas pressure of hydrogen is 1 MPa, the temperature is 30°C, and the monolayer molybdenum disulfide is irradiated by sunlight. Under the catalytic action of the activated monolayer molybdenum disulfide, hydrogen is decomposed into H + and electron, then H + is transferred to the cathode of the battery through the monolayer molybdenum disulfide, and the electron moves from the anode to the cathode of the battery through the external circuit.

[0124] Based on the foregoing other conditions being unchanged, on the basis of the two-dimensional material thin film being the monolayer molybdenum disulfide, the size area of the monolayer molybdenum disulfide can also be selected from any one of 500 nm 2 , 10 μm 2 , 100 μm 2 , 500 μm 2 , 1 cm 2 , 10 cm 2 , 100 cm 2 , 500 cm 2 and 1 m 2 .

[0125] Embodiment 16

[0126] The hydrogen-containing fuel is used as raw material to realize catalytic decomposition into H + and electron, specifically: hydrogen is sent to one side of the double-layer graphene covered with platinum nanoparticles with a thickness of about 1 nm and an area of 100 nm 2 , the gas pressure of hydrogen is 1 MPa, the temperature is 30°C, the height of the platinum nanoparticles is 0.5-10 nm, the size is 10 nm-50 nm, and the double-layer graphene covered with platinum nanoparticles is irradiated by laser with a wavelength of 532 nm. Under the synergistic catalytic action of the activated double-layer graphene and platinum nanoparticles, hydrogen is decomposed into H + and electron, then H + is transferred to the cathode of the battery through the double-layer graphene covered with platinum nanoparticles, and the electron moves from the anode to the cathode of the battery through the external circuit.

[0127] Based on the foregoing other conditions being unchanged, on the basis of the two-dimensional material thin film being the double-layer graphene, the size area of the double-layer graphene can also be selected from any one of 500 nm 2 , 10 μm 2 , 100 μm 2 , 500 μm 2, 10 cm 2 , 100 cm 2 , 500 cm 2 , 1 m 2 , and 1 m 2 . When laser irradiation is used, the wavelength of the laser can also be selected from any wavelength below 1000 nm.

[0128] Example 17

[0129] Catalytic decomposition of hydrogen-containing fuel into H + and electrons is achieved by injecting electrons into bilayer graphene. Specifically, a hydrogen-containing mixed gas fuel of methanol is fed into one side of bilayer graphene (in this example, hydrogen-containing fuels including natural gas, ethane, propane, butane, and methanol are used), which has a thickness of about 1 nm and an area of 100 nm 2 . The mixed gas has a pressure of 1 MPa and a temperature of 30°C. Electrons are injected into the bilayer graphene by an electrostatic generator, with a current of 5 nA and a voltage of 100 V. Under the catalytic action of the activated bilayer graphene, hydrogen is decomposed into H + and electrons. Then, under the driving force of the concentration difference and the potential difference, H + is transferred through the bilayer graphene to the cathode of the battery, and the electrons move from the anode to the cathode through the external circuit.

[0130] Based on the foregoing other conditions being unchanged, on the basis of a two-dimensional material thin film as bilayer graphene, the size area of the bilayer graphene can also be selected from any one of 500 nm 2 , 10 μm 2 , 100 μm 2 , 500 μm 2 , 1 cm 2 , 10 cm 2 , 100 cm 2 , 500 cm 2 , and 1 m 2 .

[0131] C

[0132] The method for generating protons based on hydrogen-containing raw material gas is used for hydrogen storage and release. The principle is as follows: using the characteristics that solid-state materials such as graphene sheets, carbon nanotubes, fullerene molecules, hexagonal boron nitride, and molybdenum disulfide can only permeate protons, combined with hydrogen plasma, light energy, thermal energy, or electron injection, hydrogen is stored in the interlayer or cavity of the solid-state material. When hydrogen is used, the above-mentioned solid-state materials are activated by means such as light energy, thermal energy, or electron injection to catalytically decompose hydrogen into protons and electrons. The permeated protons and electrons recombine to generate hydrogen, which is released from the interlayer and / or cavity of the solid-state material, achieving hydrogen storage and release.

[0133] The specific method includes a hydrogen storage process and a hydrogen release process. The hydrogen storage process includes the following steps:

[0134] a1) Select a non-metallic material that can only be permeated by protons;

[0135] a2) Activating non-metallic materials to produce catalytic properties;

[0136] a3) Introduce hydrogen-containing raw material gas into the non-metallic material side;

[0137] a4) Under the catalytic action of activated non-metallic materials, the introduced hydrogen-containing raw material gas is decomposed into protons and electrons; or hydrogen plasma technology is directly used to generate protons and electrons from the hydrogen-containing raw material gas.

[0138] a5) Protons and electrons permeate into the activated non-metallic material, recombine in the non-metallic material to form pure hydrogen gas, and are stored in the non-metallic material, thus completing the hydrogen storage in the non-metallic material.

[0139] The hydrogen release process includes the following steps:

[0140] b1) Activates non-metallic materials containing hydrogen and produces catalytic properties;

[0141] b2) Under the catalysis of activated non-metallic materials, the hydrogen gas stored in the non-metallic materials is decomposed into protons and electrons;

[0142] b3) The protons and electrons obtained in step b2) pass through the activated non-metallic material and recombine to form pure hydrogen gas, thus completing the hydrogen release from the non-metallic material.

[0143] Taking two-dimensional material sheets such as graphene sheets, hexagonal boron nitride sheets, or molybdenum disulfide sheets as examples, the following explanation is provided:

[0144] The high-density hydrogen storage and reversible hydrogen absorption / desorption in graphene sheets utilize the following hydrogen storage mechanism:

[0145] 1) In a graphene sheet of preferred thickness for the applicable application, hydrogen gas is introduced into the space where the graphene sheet is located, and then plasma, thermal energy or electron injection are applied.

[0146] 2) Under plasma conditions, hydrogen-containing gases (such as...) Figure 5 Hydrogen or Figure 6 The methane in the solution is decomposed into H2O. + And electrons, H +and electrons cross into the graphene interlayer, recombine to form pure hydrogen gas, and are stored in the graphene interlayer; at this time, specifically, the hydrogen gas stored in the graphene interlayer of the graphene sheet with a thickness of 50-100 nm has excellent thermal stability, and the hydrogen gas in the graphene interlayer does not decrease after heating at 150°C, 300°C, and 400°C in vacuum for 4 hours, respectively (as shown in Figure 8 ); and the time stability is very good, and the hydrogen gas does not decrease after the four samples with different heights are stored in the air for 3-4 months (as shown in Figure 9 ). Similarly, under the conditions of injecting electrons or heating, the activated graphene catalytically decomposes the hydrogen-containing gas into H + and electrons, and then, driven by the concentration difference and the potential difference, H + and electrons cross into the graphene interlayer, recombine to form hydrogen gas, and are stored in the graphene interlayer, which also has excellent thermal stability and time stability.

[0147] The hydrogen release process is as follows:

[0148] During hydrogen release, the graphene sheet is activated by means such as light energy, heat energy, or electron injection, catalytically decomposes the interlayer hydrogen gas into protons and electrons, and the permeated protons and electrons recombine to generate hydrogen gas, thereby releasing hydrogen gas from the interlayer and / or cavity of the solid material. The entire process of hydrogen storage and release does not damage the intrinsic structure of the graphene material (as shown in Figure 10 ), and the graphene material can be reused and has a long service life.

[0149] The process of high-density hydrogen storage and reversible absorption / release in the hexagonal boron nitride sheet is as follows:

[0150] Hydrogen storage:

[0151] 1) In the hexagonal boron nitride sheet with a preferred thickness in a suitable application, a hydrogen-containing gas is introduced into the space where the hexagonal boron nitride sheet is located, and then a means such as plasma, heat energy, or electron injection is applied;

[0152] 2) Under the condition of plasma, the hydrogen-containing gas is decomposed into H + and electrons, H + and electrons cross into the interlayer of the hexagonal boron nitride, recombine to form hydrogen gas, and are stored in the interlayer of the hexagonal boron nitride; under the conditions of injecting electrons or heating, the activated hexagonal boron nitride catalytically decomposes the hydrogen-containing gas into H + and electrons, and then, driven by the concentration difference and the potential difference, H + and electrons cross into the interlayer of the hexagonal boron nitride, recombine to form hydrogen gas, and are stored in the interlayer of the hexagonal boron nitride, as shown in Figure 7 , which is an atomic force microscope image of hydrogen storage in the interlayer of hexagonal boron nitride.

[0153] Hydrogen release:

[0154] The hexagonal boron nitride flake is activated by means of light energy, heat energy or injected electrons, etc. to catalytically decompose the interlayer hydrogen to generate protons and electrons, and the penetrated protons and electrons recombine to generate hydrogen, thereby realizing the release of hydrogen from the interlayer of solid material and / or the cavity.

[0155] The process of high-density hydrogen storage and reversible hydrogen absorption / desorption in two-dimensional material flake such as molybdenum disulfide is:

[0156] Hydrogen storage:

[0157] 1) In the molybdenum disulfide of the preferred thickness under the applicable occasion, hydrogen-containing gas is introduced into the space where the molybdenum disulfide flake is located under the light irradiation of plasma, injected electrons or heating or sunlight, etc.

[0158] 2) Under the condition of plasma, the hydrogen-containing gas is decomposed into H + and electrons, H + and electrons penetrate into the interlayer of molybdenum disulfide, and recombine to form hydrogen, which is stored in the interlayer of molybdenum disulfide; under the condition of injected electrons or heating or sunlight, etc., the activated molybdenum disulfide catalytically decomposes the hydrogen-containing gas into H + and electrons, and then under the driving of the concentration difference and the potential difference, H + and electrons penetrate into the interlayer of hexagonal boron nitride, and recombine to form hydrogen, which is stored in the interlayer of hexagonal boron nitride.

[0159] Hydrogen release:

[0160] The molybdenum disulfide flake is activated by means of heat energy or injected electrons, etc. to catalytically decompose the interlayer hydrogen to generate protons and electrons, and the penetrated protons and electrons recombine to generate hydrogen, thereby realizing the release of hydrogen from the interlayer of solid material and / or the cavity.

[0161] The process of high-density hydrogen storage and reversible hydrogen absorption / desorption in low-dimensional cavity-containing material such as carbon nanotubes, fullerenes and boron-nitrogen tubes is:

[0162] Hydrogen storage:

[0163] 1) In the cavity-containing material of the preferred diameter under the applicable occasion, hydrogen-containing gas is introduced into the space where the cavity-containing material is located, and then plasma, heat energy or injected electrons, etc. are applied;

[0164] 2) Under the condition of plasma, the hydrogen-containing gas is decomposed into H + and electrons, H + and electrons penetrate into the cavity of the cavity-containing material, and recombine to form hydrogen, which is stored in the cavity of the cavity-containing material; under the condition of injected electrons or heating, etc., the activated cavity-containing material catalytically decomposes the hydrogen-containing gas into H + and electrons, and then under the driving of the concentration difference and the potential difference, H +And the electrons pass into the cavity of the cavity material, recombine to form hydrogen gas, stored in the cavity of the cavity material.

[0165] Hydrogen release:

[0166] The cavity material is activated by means of light energy, heat energy or electron injection, etc. to catalyze the decomposition of hydrogen gas in the cavity to generate protons and electrons, and the permeated protons and electrons recombine to generate hydrogen gas, realizing the release of hydrogen gas from the interlayer and / or cavity of the solid material layer.

[0167] The solid material film is graphene, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, niobium diselenide, tungsten diselenide, and other layered materials of semimetals, semiconductors, conductors and insulators, carbon nanotubes, fullerene, boron-nitrogen nanotubes, etc. Contain cavity solid materials.

[0168] The plasma is provided by an auxiliary chemical vapor deposition device (prior art), which includes a plasma generator, a dry pump, a molecular pump, a graphite heating plate, etc. The plasma generator is an inductively coupled plasma, with a power adjustable range of 5W-500W, equipped with a pressure adjustable range of 10 -5 Pa-1atm, equipped with a controllable temperature range of 20℃-800℃. In the hydrogen storage process using plasma, the preferred power is 10W-100W. The plasma technology adjusts the temperature, pressure, reaction gas flow, heating time, plasma intensity and reaction time of the reaction, the reaction temperature is 50℃-800℃, the preferred range is 100℃-800℃; the pressure is 10 -5 Pa-1atm, the preferred range is 10 -2 Pa-10 2 Pa; the carrier gas can be methane, nitrogen, argon, oxygen, hydrogen, etc.; the gas flow is 5-2000sccm, the preferred range is 10sccm-500sccm; the heating time is 5s-5h, the preferred range is 30min-2h; the reaction time is 5s-7200s, the preferred range is 30s-1000s.

[0169] The method of injecting electrons is exactly the same as in application A, and this application C will not be repeated.

[0170] When activated by heating, the heating temperature is 30℃-800℃, when graphene sheets or carbon nanotubes are used, the heating temperature is preferably 500℃-800℃; when hexagonal boron nitride sheets are used, the heating temperature is preferably 400℃-800℃; when molybdenum disulfide sheets are used, the heating temperature is preferably 200℃-500℃; when fullerene sheets are used, the heating temperature is preferably 50℃-300℃.

[0171] Example 17

[0172] The hydrogen is stored in the graphene sheet by plasma assistance, and the graphene is activated by electron injection to release hydrogen, specifically: the graphene sheet is placed in a plasma assisted chemical vapor deposition device, the graphene sheet is four layers thick (about 2nm thick), and the size area is preferably 100μm 2 . When the pressure in the reaction chamber is less than 10 -4 Pa, hydrogen is introduced, specifically 180sccm of hydrogen, the pressure in the reaction chamber is stabilized by a pressure regulating valve to 6Pa, the temperature is raised to 500℃, and then maintained for 10min to ensure uniform heating of the substrate. Turn on the inductively coupled plasma generator, specifically at a power of 10W, and control the hydrogen storage content in the graphene sheet by changing the plasma time, the time used in this embodiment is 300s. After completion, turn off the heating and naturally cool down, and finally take out the sample. The prepared sample is observed by atomic force microscope to observe the number and size of hydrogen bubbles in the graphene sheet. According to the number and size of the bubbles, the hydrogen storage content in the graphene sheet can be calculated, and the highest hydrogen mass density is 9wt%.

[0173] When releasing hydrogen, electrons are injected into the graphene sheet sample obtained by the above method to activate the graphene by an electrostatic generator, the current of the electrostatic generator is 5nA, and the voltage is 100V. Under the catalytic action of the activated graphene, the hydrogen atoms of hydrogen are decomposed into protons and electrons, and the protons and electrons can freely pass through the graphene. After the protons and electrons pass through the activated graphene, the protons and electrons combine to form hydrogen again, realizing the release of pure hydrogen.

[0174] Embodiment 18

[0175] The hydrogen is stored in the graphene sheet by plasma assistance, and the graphene is activated by electron injection to release hydrogen, specifically: the graphene sheet is placed in a plasma assisted chemical vapor deposition device, the graphene sheet is four layers thick (about 2nm thick), and the size area is preferably 100μm 2 . When the pressure in the reaction chamber is less than 10 -4 Pa, hydrogen is introduced, specifically 180sccm of hydrogen, the pressure in the reaction chamber is stabilized by a pressure regulating valve to 6Pa, the temperature is raised to 500℃, and then maintained for 10min to ensure uniform heating of the substrate. Turn on the inductively coupled plasma generator, specifically at a power of 10W, and control the hydrogen storage content in the graphene sheet by changing the plasma time, the time used in this embodiment is 300s. After completion, turn off the heating and naturally cool down, and finally take out the sample. The prepared sample is observed by atomic force microscope to observe the number and size of hydrogen bubbles in the graphene sheet. According to the number and size of the bubbles, the hydrogen storage content in the graphene sheet can be calculated, and the highest hydrogen mass density is 9wt%.

[0176] When hydrogen is released, the graphene sample obtained above is activated by injecting electrons into it through an electrostatic generator, the current of which is 5 nA and the voltage is 100 V. Under the catalysis of the activated graphene, hydrogen atoms in hydrogen are decomposed into protons and electrons, which can freely pass through the graphene. After the protons and electrons pass through the activated graphene, the protons combine with the electrons to re-form hydrogen, thereby releasing pure hydrogen.

[0177] Example 19

[0178] Hydrogen is stored in the hexagonal boron nitride flakes by plasma assistance, and the hexagonal boron nitride is activated by electron injection to release hydrogen, specifically: the hexagonal boron nitride flakes are placed in a plasma-assisted chemical vapor deposition device, the hexagonal boron nitride flakes are four layers thick (about 2 nm thick), and the size area is preferably 100 μm 2 When the pressure in the reaction chamber is less than 10 -4 Pa, hydrogen is introduced, specifically 180 sccm of hydrogen, the pressure in the reaction chamber is stabilized by a pressure regulating valve to 6 Pa, and the temperature is raised to 500°C, and then maintained for 10 min to ensure uniform heating of the substrate. The inductively coupled plasma generator is turned on, specifically at a power of 30 W, and the hydrogen storage content in the interlayer of the hexagonal boron nitride flakes is controlled by changing the plasma time, which is 60 s. After completion, the heating is turned off and the sample is naturally cooled, and finally the sample is taken out. The prepared sample is observed by atomic force microscopy to observe the number and size of hydrogen bubbles in the interlayer of the hexagonal boron nitride flakes. According to the number and size of the bubbles, the hydrogen storage content in the interlayer of the hexagonal boron nitride flakes can be calculated, and the highest hydrogen mass density is 9.5 wt%.

[0179] When hydrogen is released, the hexagonal boron nitride sample obtained above is activated by injecting electrons into it through an electrostatic generator, the current of which is 5 nA and the voltage is 100 V. Under the catalysis of the activated hexagonal boron nitride, hydrogen atoms in hydrogen are decomposed into protons and electrons, which can freely pass through the hexagonal boron nitride. After the protons and electrons pass through the activated hexagonal boron nitride, the protons combine with the electrons to re-form hydrogen, thereby releasing pure hydrogen.

[0180] Example 20

[0181] Hydrogen is stored in the molybdenum disulfide flakes by plasma assistance, and the molybdenum disulfide is activated by laser to release hydrogen, specifically: the molybdenum disulfide flakes are placed in a plasma-assisted chemical vapor deposition device, the molybdenum disulfide flakes are 2 nm thick, and the size area is preferably 100 μm 2 When the pressure in the reaction chamber is less than 10 -4Pa, and then hydrogen gas was introduced, specifically 180 seem of hydrogen gas, the pressure in the reaction chamber was stabilized at 6 Pa by a pressure regulating valve, and the temperature was raised to 500°C, and then maintained for 10 min to ensure uniform heating of the substrate. The inductively coupled plasma generator was turned on, specifically at a power of 10 W, and the interlayer hydrogen storage content of the molybdenum disulfide sheet was controlled by changing the plasma time, and the general time was 600 s. After completion, the heating was turned off and the sample was naturally cooled, and finally the sample was taken out. The prepared sample was observed by atomic force microscopy to observe the number and size of hydrogen gas bubbles in the interlayer of the molybdenum disulfide sheet. According to the number and size of the bubbles, the hydrogen storage content of the molybdenum disulfide sheet can be calculated, and the highest hydrogen mass density is 2.8wt%.

[0182] When hydrogen is released, the hydrogen storage molybdenum disulfide sheet sample obtained above is activated by laser irradiation by an electrostatic generator, and the laser wavelength is 532 nm. Under the catalysis of the activated molybdenum disulfide, the hydrogen atoms of hydrogen gas are decomposed into protons and electrons, and the protons and electrons can freely pass through the molybdenum disulfide. After the protons and electrons pass through the activated molybdenum disulfide, the protons and electrons combine to form hydrogen gas again, and pure hydrogen gas is released.

[0183] When laser irradiation is used, the wavelength of the laser can also be selected from any wavelength below 1000 nm.

[0184] Example 21

[0185] Hydrogen was stored in the molybdenum disulfide sheet by plasma assistance, and the molybdenum disulfide was activated by natural light to release hydrogen, specifically: the molybdenum disulfide sheet was placed in a plasma assisted chemical vapor deposition device, the molybdenum disulfide sheet was 2 nm thick, and the size area was preferably 100 cm 2 When the pressure in the reaction chamber was <10 -4 Pa, and then hydrogen gas was introduced, specifically 180 seem of hydrogen gas, the pressure in the reaction chamber was stabilized at 6 Pa by a pressure regulating valve, and the temperature was raised to 400°C, and then maintained for 10 min to ensure uniform heating of the substrate. The inductively coupled plasma generator was turned on, specifically at a power of 20 W, and the interlayer hydrogen storage content of the molybdenum disulfide sheet was controlled by changing the plasma time, and the general time was 200 s. After completion, the heating was turned off and the sample was naturally cooled, and finally the sample was taken out. The prepared sample was observed by atomic force microscopy to observe the number and size of hydrogen gas bubbles in the interlayer of the molybdenum disulfide sheet. According to the number and size of the bubbles, the hydrogen storage content of the molybdenum disulfide sheet can be calculated, and the highest hydrogen mass density is 2.8wt%.

[0186] When hydrogen is released, the hydrogen atoms of hydrogen gas are decomposed into protons and electrons by natural light irradiation through an electrostatic generator in the above-obtained hydrogen-stored molybdenum disulfide flake sample, the protons and electrons can freely pass through the molybdenum disulfide, and after the protons and electrons pass through the activated molybdenum disulfide, the protons and electrons combine to re-form hydrogen gas, thereby realizing the release of pure hydrogen gas.

[0187] Example 22

[0188] Hydrogen is stored in the molybdenum disulfide flake by plasma assistance, and hydrogen is released by heating to activate the molybdenum disulfide. Specifically, the molybdenum disulfide flake is placed in a plasma-assisted chemical vapor deposition device, the molybdenum disulfide flake is 2 nm thick, and the size area is preferably 100 μm 2 When the reaction chamber pressure is <10 -4 Pa, hydrogen is introduced, specifically 180 sccm of hydrogen, the reaction chamber pressure is stabilized to 6 Pa by a pressure regulating valve, and the temperature is raised to 200°C, and then maintained for 10 min to ensure uniform heating of the substrate. The inductively coupled plasma generator is turned on, and the hydrogen storage content in the molybdenum disulfide flake layer is controlled by changing the plasma time, generally for 600 s. After completion, the heating is turned off and the sample is naturally cooled, and finally the sample is taken out. The prepared sample is observed by atomic force microscopy to observe the number and size of hydrogen gas bubbles in the molybdenum disulfide flake layer. According to the number and size of the bubbles, the hydrogen storage content in the molybdenum disulfide flake layer can be calculated, and the highest hydrogen mass density is 2.8 wt%.

[0189] When hydrogen is released, the hydrogen atoms of hydrogen gas are decomposed into protons and electrons by heating to activate the molybdenum disulfide in the above-obtained hydrogen-stored molybdenum disulfide flake sample, the protons and electrons can freely pass through the molybdenum disulfide, and after the protons and electrons pass through the activated molybdenum disulfide, the protons and electrons combine to re-form hydrogen gas, thereby realizing the release of pure hydrogen gas.

[0190] Example 23

[0191] Hydrogen is stored in the molybdenum disulfide flake by injecting electrons, and hydrogen is released by laser to activate the molybdenum disulfide. Specifically, hydrogen is introduced into one side of the molybdenum disulfide flake, the hydrogen pressure is 3 MPa, the molybdenum disulfide is about 10 nm thick, and the size area is 100 nm 2, the current of the electrostatic generator is 5 nA, and the voltage is 100 V. Under the catalysis of the single-layer molybdenum disulfide subjected to the electron injection, hydrogen is decomposed into protons and electrons, and the protons and the electrons can freely pass through the molybdenum disulfide under the driving of the concentration difference. After the protons and the electrons pass through the molybdenum disulfide, the protons combine with the electrons to re-form hydrogen. The prepared sample is observed by an atomic force microscope to observe the number and size of hydrogen bubbles between the molybdenum disulfide sheet layers. According to the number and size of the bubbles, the hydrogen storage content of the molybdenum disulfide sheet layers can be calculated, and the highest hydrogen mass density is 2.8 wt%.

[0192] When hydrogen is released, the molybdenum disulfide in the above-obtained hydrogen storage molybdenum disulfide sheet sample is activated by laser irradiation through an electrostatic generator, and the wavelength of the laser is 532 nm. Under the catalysis of the activated molybdenum disulfide, hydrogen atoms of hydrogen are decomposed into protons and electrons, and the protons and the electrons can freely pass through the molybdenum disulfide. After the protons and the electrons pass through the activated molybdenum disulfide, the protons combine with the electrons to re-form hydrogen, thereby realizing the release of pure hydrogen. When the laser irradiation is used, the wavelength of the laser can also be selected from any wavelength below 1000 nm.

[0193] Example 24

[0194] Hydrogen is stored in a hollow cavity of a single-walled carbon nanotube by plasma assistance, and the single-walled carbon nanotube is activated by electron injection to release hydrogen, specifically as follows. The single-walled carbon nanotube is placed in a plasma-assisted chemical vapor deposition device, the tube diameter of the single-walled carbon nanotube is 1 nm-3 nm, and the size area of the laid carbon nanotube film is preferably 500 μm 2 , and the film thickness is 3 nm. After the pressure in the reaction chamber is less than 10 -4 Pa, hydrogen is introduced, specifically 180 sccm of hydrogen, the pressure in the reaction chamber is stabilized to 6 Pa by a pressure regulating valve, the temperature is raised to 800 ℃, and then kept for 10 min to ensure the uniformity of the substrate. The inductively coupled plasma generator is turned on, and the power is 10 W. The hydrogen storage content of the graphene sheet layers is controlled by changing the plasma time, and the time is 600 s. After completion, the heating is turned off and the sample is naturally cooled, and finally the sample is taken out. The prepared sample is weighed by using a high-precision balance, and the mass density is calculated to be about 5 wt%.

[0195] When hydrogen is released, the single-walled carbon nanotube in the above-obtained hydrogen storage single-walled carbon nanotube sample is activated by injecting electrons through an electrostatic generator, the current of the electrostatic generator is 5 nA, and the voltage is 100 V. Under the catalysis of the activated single-walled carbon nanotube, hydrogen atoms of hydrogen are decomposed into protons and electrons, and the protons and the electrons can freely pass through the single-walled carbon nanotube. After the protons and the electrons pass through the activated single-walled carbon nanotube, the protons combine with the electrons to re-form hydrogen, thereby realizing the release of pure hydrogen.

[0196] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Various simple modifications can be made to the technical solutions of the present application within the technical concept of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A method for hydrogen storage and release based on a hydrogen- containing feed gas, characterized by, The hydrogen storage and release method based on the hydrogen-containing raw gas includes a hydrogen storage process and a hydrogen release process, and the hydrogen storage process includes the following steps: a1) selecting a non-metallic material capable of permeating only protons; the non-metallic material is a two-dimensional material thin film layered material or a solid material containing cavities; the two-dimensional material thin film layered material is one or a combination of graphene sheet, hexagonal boron nitride sheet, molybdenum disulfide sheet, tungsten disulfide sheet, molybdenum diselenide sheet, niobium diselenide sheet and tungsten diselenide sheet; the solid material containing cavities is one or a combination of carbon nanotubes, fullerene balls and boron-nitrogen nanotubes; a2) activating the non-metallic material to generate catalytic properties; the activation is placing the non-metallic material in a plasma environment, introducing electrons into the non-metallic material and / or heating the non-metallic material; a3) introducing the hydrogen-containing raw gas into one side of the non-metallic material; a4) under the catalytic action of the activated non-metallic material, the introduced hydrogen-containing raw gas is decomposed into protons and electrons; a5) the protons and electrons permeate into the activated non-metallic material, recombine in the non-metallic material to form pure hydrogen gas and store in the non-metallic material, and complete the hydrogen storage in the non-metallic material; The hydrogen release process includes the following steps: b1) activating the non-metallic material containing hydrogen and generating catalytic properties; the activation is introducing electrons into the non-metallic material and / or heating the non-metallic material and / or irradiating the non-metallic material with light; b2) under the catalysis of the activated non-metallic material, the hydrogen stored in the non-metallic material is decomposed into protons and electrons; b3) the protons and electrons obtained through step b2) recombine to form pure hydrogen gas after passing through the activated non-metallic material, and complete the hydrogen release from the non-metallic material.

2. The method for hydrogen storage and release based on hydrogen- containing feed gas according to claim 1, characterized in that, When the two-dimensional material thin film layered material is a graphene sheet, the thickness of the graphene sheet is 2nm-1mm; when the two-dimensional material thin film layered material is a hexagonal boron nitride sheet, the thickness of the hexagonal boron nitride sheet is 2nm-1mm; when the two-dimensional material thin film is a molybdenum disulfide sheet, the thickness of the molybdenum disulfide sheet is 1.5nm-1mm; When the solid material containing cavities is a carbon nanotube, the carbon nanotube is a single-walled carbon nanotube or a multi-walled carbon nanotube, and the tube diameter of the carbon nanotube is 0.5nm-100nm; when the solid material containing cavities is a fullerene ball, the diameter of the fullerene ball is 0.7nm-10nm.

3. The method for hydrogen storage and release based on hydrogen- containing feed gas according to claim 2, characterized in that, The tube diameter of the carbon nanotube is 1nm-10nm; the diameter of the fullerene ball is 0.7nm-5nm.

4. The method for hydrogen storage and release based on hydrogen- containing feed gas according to claim 3, characterized in that, The area of the solid material containing the cavity is 100 nm 2 1 m 2 .

5. The method for hydrogen storage and release based on hydrogen- containing feed gas according to claim 4, characterized in that, The area of the solid material containing the cavity is 100 nm 2 ~100 cm 2 .

6. The method for hydrogen storage and release based on hydrogen- containing feed gas according to any one of claims 1-5, characterized in that, The activation in the step a2) is that the non-metallic material is placed in a plasma environment, the plasma environment is prepared by a plasma generator, the plasma generator is an inductively coupled plasma, the power of the plasma generator is 5W~500W; the pressure of the plasma generator is 10 -5 Pa~1atm; the reaction temperature of the plasma generator is 50℃~800℃; the gas flow of the plasma generator is 5~2000sccm; the heating time of the plasma generator is 5s~5h; the reaction time of the activation is 5s~7200s.

7. The method for hydrogen storage and release based on hydrogen- containing feed gas according to claim 6, characterized in that, The power of the plasma generator is 10W~100W; the pressure of the plasma generator is 10 -2 Pa~10 2 Pa; the reaction temperature of the plasma generator is 100℃~800℃; the gas flow of the plasma generator is 10sccm~500sccm; the heating time of the plasma generator is 30min~2h; the activated reaction time is 30s~1000s.

8. The method for hydrogen storage and release based on hydrogen- containing feed gas according to claim 7, characterized in that, The activation in step b1) is introducing electrons into the non-metallic material and / or heating the non-metallic material and / or irradiating the non-metallic material with light; When the activation method is introducing electrons into the non-metallic material, the method of introducing electrons is scanning electron microscope injection, electrostatic generator injection and / or ordinary power injection; the current for introducing electrons is 1pA-10A; the voltage used for introducing electrons is 1V-50kV; the suitable temperature for introducing electrons is -250℃-1000℃; When the activation mode is heating the non-metallic material, the temperature for heating is 30℃-800℃; When the activation mode is light irradiation on the non-metallic material, the light irradiation is natural light irradiation, artificial natural light irradiation, and / or laser light irradiation; the wavelength of the light is less than 1000nm; the applicable temperature of the light irradiation is -250℃-1000℃.

9. The method for hydrogen storage and release based on hydrogen- containing feed gas according to claim 8, characterized in that, The current for introducing electrons is 5pA-5nA; the voltage for introducing electrons is 1V-500V.

10. The method for hydrogen storage and release based on hydrogen- containing feed gas according to claim 9, characterized in that, The heating temperature of the graphene sheet and the carbon nanotube is 500℃-800℃; the heating temperature of the hexagonal boron nitride sheet is 400℃-800℃; the heating temperature of the molybdenum disulfide sheet is 200℃-500℃; the heating temperature of the fullerene sphere is 50℃-300℃.

11. The method for hydrogen storage and release based on hydrogen- containing feed gas according to claim 10, characterized in that, When the activation in the step b1) is light irradiation on the non-metallic material, the surface of the non-metallic material is attached with metal platinum, metal palladium, and / or metal nickel.

12. The method for hydrogen storage and release based on hydrogen-containing feed gas according to claim 11, characterized in that: The hydrogen raw gas in the step a3) is one or a combination of hydrogen, ammonia, methane, and ethane.

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