Method for generating protons based on a hydrogen-containing feed gas and applications

Abstract

The application relates to a method and application for generating protons based on hydrogen-containing raw gas, which comprises the following steps: 1) selecting a non-metallic material which can only permeate protons; 2) activating the non-metallic material to generate catalytic performance; 3) introducing hydrogen-containing raw gas into one side of the non-metallic material; and 4) under the catalytic action of the activated non-metallic material, the introduced hydrogen-containing raw gas is decomposed into protons and electrons. The application provides a method and application for generating protons based on hydrogen-containing raw gas, which are not affected by environmental conditions, have a wider applicable temperature range and can be used more widely.

Description

TECHNICAL FIELD

[0001] The application relates to a method for generating protons, in particular to a method for generating protons based on hydrogen-containing raw gas and application. BACKGROUND

[0002] Hydrogen energy is a clean and efficient secondary energy source with a wide range of sources. Hydrogen has a high calorific value, with an energy density of 140.4 kJ / kg, and is environmentally friendly, with no carbon emissions from combustion products. Developing and utilizing hydrogen energy is a major strategic direction for global industrial innovation and energy transformation. Hydrogen is currently widely used in aerospace, military applications, and chemical power sources.

[0003] From the perspective of development or production, in the processes of coal gasification hydrogen production, natural gas hydrogen production, methanol hydrogen production, industrial by-product hydrogen production, and water electrolysis hydrogen production, there are always impurity gases such as oxygen, nitrogen, carbon monoxide, carbon dioxide, and methane, which cannot achieve high-precision use standards in terms of purity. In addition, the tail gas emitted 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 this tail gas into the flare system. On the one hand, a large amount of hydrogen is consumed during production, and on the other hand, a considerable amount of hydrogen is discharged with the tail gas, which not only wastes hydrogen resources but also increases production costs. Therefore, extracting clean hydrogen from mixed gas and waste gas has become a 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. Pressure swing adsorption separation requires controlling temperature and pressure to achieve pressure swing adsorption to separate hydrogen, which requires large equipment and occupies a large area. Membrane separation has the unique advantages of simple operation, low energy consumption, small footprint, and continuous operation. Currently, common membranes include metal, zeolite, and polymer. The use of membrane separation for mixed gas is a complete physical process, usually using polymer membranes or amorphous carbon membranes, so 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. However, the permeability and diffusion coefficient of the pores are easily affected by environmental factors such as temperature, humidity, and pressure, resulting in reduced selectivity. Moreover, the above three methods can only be implemented at specific temperatures or low temperatures, and cannot achieve hydrogen separation and purification over a wide temperature range.

[0004] From the perspective of hydrogen energy utilization, hydrogen fuel cells are undoubtedly the key factor to perfect low-carbon clean hydrogen supply system and help carbon neutralization in the vision. Hydrogen fuel cells are not restricted by Carnot cycle, so they have high energy conversion efficiency, high power and density, and little environmental impact during power generation process. They are the fourth generation of power generation technology after water power generation, thermal power generation and atomic power generation, and have broad application prospects in distributed power stations, electric vehicles, ships and submarines, aerospace, mobile communication and weapon equipment, etc.

[0005] The most widely used in hydrogen fuel cells is proton exchange membrane fuel cell. Compared with other liquid electrolyte fuel cells, proton exchange membrane fuel cell uses solid proton exchange membrane with good proton conductivity, 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 transferred to the cathode of the cell through the proton exchange membrane, and the electrons move from the anode to the cathode through the external circuit. However, there are still difficulties in realizing large-scale commercialization of proton exchange membrane fuel cells, mainly due to the high cost of key materials such as proton exchange membrane, gas diffusion layer and catalyst. 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, which will produce CO and other small molecular organic hydrocarbon chemicals containing oxygen, and CO will poison the metal catalyst. The commonly used commercial catalyst is carbon-supported Pt catalyst, and Pt nanoparticle supported on carbon support is the best choice for proton exchange membrane fuel cells. From a technical point of view, if non-noble metal proton exchange membrane fuel cells 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 high 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 DEG C and working pressure of less than 2 MPa, 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 of the material 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 method for generating protons 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 method for generating protons based on hydrogen-containing raw gas, which comprises the following steps:

[0009] 1) Selecting a non-metallic material that can only permeate protons;

[0010] 2) Activating the non-metallic material to generate catalytic performance;

[0011] 3) Introducing hydrogen-containing raw gas to one side of the non-metallic material;

[0012] 4) under the catalysis of the activated non-metallic material, the hydrogen-containing raw material gas is decomposed into protons and electrons.

[0013] As preferred, the non-metallic material used in the present application is a two-dimensional material film or a non-metallic solid material;

[0014] Preferably, 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;

[0015] Preferably, 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;

[0016] Preferably, when the two-dimensional material film layered material is a graphene flake, a hexagonal boron nitride flake, a molybdenum disulfide flake, a tungsten disulfide flake, a molybdenum diselenide flake, a niobium diselenide flake or a tungsten diselenide flake, or a combination thereof;

[0017] Preferably, 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;

[0018] Preferably, when the two-dimensional material film is graphene, the thickness of the graphene is 0.5nm-1mm; when the two-dimensional material film is hexagonal boron nitride, the thickness of the hexagonal boron nitride is 0.5nm-1mm; when the two-dimensional material film is molybdenum disulfide, the thickness of the molybdenum disulfide is 0.7nm-1mm;

[0019] Preferably, the size of the two-dimensional material film is 100nm 2 -1m 2 , preferably the size is 100nm 2 -100cm 2 ;

[0020] Preferably, when the two-dimensional material film layered material is a graphene flake, the thickness of the graphene flake is 2nm-1mm; when the two-dimensional material film layered material is a hexagonal boron nitride flake, the thickness of the hexagonal boron nitride flake is 2nm-1mm; when the two-dimensional material film is a molybdenum disulfide flake, the thickness of the molybdenum disulfide flake is 1.5nm-1mm;

[0021] Preferably, when the cavity-containing solid material is a carbon nanotube, the carbon nanotube is a single-walled carbon nanotube or a multi-walled carbon nanotube, the carbon nanotube has a tube diameter of 0.5 nm to 100 nm, preferably a tube diameter of 1 nm to 10 nm; when the cavity-containing solid material is a fullerene sphere, the fullerene sphere has a diameter of 0.7 nm to 10 nm, preferably a diameter of 0.7 nm to 5 nm;

[0022] Preferably, the cavity-containing solid material has a size of 100 nm 2 ~ 1 m 2 Preferably, the cavity-containing solid material has a size of 100 nm 2 ~ 100 cm 2 .

[0023] As a preference, the specific implementation of the activation in step 2) of the present application is that: introducing electrons into the non-metallic material, heating the non-metallic material, and / or irradiating the non-metallic material with light;

[0024] Preferably, when the activation in step 2) is introducing electrons into the non-metallic material, the way of introducing electrons is scanning electron microscope electron injection, electrostatic generator electron injection, and / or ordinary power supply electron injection; the current of introducing electrons is 1 pA to 10 A, preferably 5 pA to 5 nA; the voltage used when introducing electrons is 1 V to 50 kV, preferably 1 V to 500 V; the applicable temperature of introducing electrons is -250°C to 1000°C;

[0025] Preferably, when the activation in step 2) is heating the non-metallic material, the temperature used for heating is 30°C to 800°C;

[0026] Preferably, when the activation in step 2) is irradiating the non-metallic material with light, the light is natural light, artificial natural light, and / or laser light;

[0027] Preferably, the wavelength of the light used for irradiation is less than 1000 nm;

[0028] Preferably, the applicable temperature of the irradiation is -250°C to 1000°C;

[0029] Preferably, when the activation in step 2) is irradiating the non-metallic material with light, the surface of the non-metallic material is attached with metal platinum, metal palladium, and / or metal nickel;

[0030] Preferably, the activation in step 2) is heating the non-metallic solid material, and the heating temperature is 30-800°C; preferably, the heating temperature of the graphene sheet and the carbon nanotube is 500-800°C; preferably, the heating temperature of the hexagonal boron nitride sheet is 400-800°C; preferably, the heating temperature of the molybdenum disulfide sheet is 200-500°C; and the heating temperature of the fullerene sphere is 50-300°C.

[0031] As preferred, the hydrogen-containing raw gas in step 3) is one or a combination of hydrogen, argon, ammonia, methane and ethane.

[0032] The method for generating protons based on hydrogen-containing raw gas as described above is used in the preparation of pure hydrogen, the preparation of hydrogen fuel cells or the storage and release of hydrogen.

[0033] As preferred, the method for generating protons based on hydrogen-containing raw gas is used in the preparation of pure hydrogen, and the preparation method comprises the following steps:

[0034] 1) generating protons according to the method for generating protons based on hydrogen-containing raw gas as described above;

[0035] 2) combining the protons and electrons through the activated non-metallic material to form pure hydrogen.

[0036] As preferred, the non-metallic material in step 2) is a two-dimensional material film.

[0037] Preferably, 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.

[0038] Preferably, the thickness of the graphene is 0.5 nm-1 mm; the thickness of the hexagonal boron nitride is 0.5 nm-1 mm; and the thickness of the molybdenum disulfide is 0.7 nm-1 mm.

[0039] Preferably, the size of the two-dimensional material film is 100 nm 2 -1 m 2 , preferably 100 nm 2 -100 cm 2 .

[0040] Preferably, the activation is introducing electrons into the non-metallic material, heating the non-metallic material and / or irradiating the non-metallic material with light.

[0041] As preferred, the method for generating protons based on hydrogen-containing raw gas adopted by the present application is used for preparing hydrogen fuel cell, and the preparation method comprises the following steps:

[0042] 1) generating protons based on hydrogen-containing raw gas according to the method as described above;

[0043] 2) under the driving of concentration difference and potential difference, the protons generated in step 1) are transferred to the cathode of the cell through the non-metallic material, and the electrons are moved from the anode to the cathode of the cell through the external circuit, forming a hydrogen fuel cell.

[0044] As preferred, the non-metallic material in step 2) adopted by the present application is a two-dimensional material film;

[0045] As preferred, 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;

[0046] As preferred, when the two-dimensional material film is graphene, the thickness of the graphene is 0.5nm-1mm; when the two-dimensional material film is hexagonal boron nitride, the thickness of the hexagonal boron nitride is 0.5nm-1mm; when the two-dimensional material film is molybdenum disulfide, the thickness of the molybdenum disulfide is 0.7nm-1mm;

[0047] As preferred, the size of the two-dimensional material film is 100nm 2 -1m 2 , preferably 100nm 2 -100cm 2 ;

[0048] As preferred, the activation mode is introducing electrons into the non-metallic material, heating the non-metallic material and / or irradiating the non-metallic material with light.

[0049] As preferred, the method for generating protons based on hydrogen-containing raw gas adopted by the present application is used for hydrogen storage and release, and the hydrogen storage and release method comprises a hydrogen storage process and a hydrogen release process, and the hydrogen storage process comprises the following steps:

[0050] a1) selecting a non-metallic material capable of permeating only protons;

[0051] a2) activating the non-metallic material to generate catalytic properties;

[0052] a3) introducing hydrogen-containing raw gas to one side of the non-metallic material;

[0053] a4) under the catalytic action of the activated non-metallic material, the introduced hydrogen-containing raw gas is decomposed into protons and electrons;

[0054] a5) the protons and electrons penetrate into the activated non-metallic material, recombine to form pure hydrogen gas in the non-metallic material and store in the non-metallic material, completing the hydrogen storage in the non-metallic material;

[0055] The hydrogen release process comprises the following steps:

[0056] b1) activating the non-metallic material containing hydrogen gas and generating catalytic performance;

[0057] b2) under the catalysis of the activated non-metallic material, the hydrogen gas stored in the non-metallic material is decomposed into protons and electrons;

[0058] b3) the protons and electrons obtained through step b2) recombine to form pure hydrogen gas after penetrating through the activated non-metallic material, completing the hydrogen release from the non-metallic material;

[0059] Preferably, when the non-metallic material is a non-metallic solid material, the non-metallic solid material is a two-dimensional material thin film layered material or a solid material containing cavities;

[0060] Preferably, the two-dimensional material thin film layered material is one or a combination of graphene sheets, hexagonal boron nitride sheets, molybdenum disulfide sheets, tungsten disulfide sheets, molybdenum diselenide sheets, niobium diselenide sheets, and tungsten diselenide sheets;

[0061] Preferably, 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;

[0062] Preferably, when the two-dimensional material thin film layered material is graphene sheets, the thickness of the graphene sheets is 2nm-1mm; when the two-dimensional material thin film layered material is hexagonal boron nitride sheets, the thickness of the hexagonal boron nitride sheets is 2nm-1mm; when the two-dimensional material thin film is molybdenum disulfide sheets, the thickness of the molybdenum disulfide sheets is 1.5nm-1mm;

[0063] Preferably, 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 balls, the diameter of the fullerene balls is 0.7nm-10nm, preferably the diameter is 0.7nm to 5nm;

[0064] Preferably, the size of the solid material containing cavities is 100nm 2 -1m 2 , preferably in the range of 100nm 2 -100cm 2 ;

[0065] Preferably, the activation in a2) is introducing electrons, light and / or heating into the non-metallic material; it is also possible to place the non-metallic material directly into a plasma environment, and use plasma technology to decompose a hydrogen-containing raw material gas to generate protons and electrons, thereby achieving interlayer storage of hydrogen in the non-metallic material.

[0066] As a preference, the non-metallic material is placed in a plasma environment, which is generated by a plasma generator, the plasma generator is an inductively coupled plasma, the power of the plasma generator is 5 W to 500 W, preferably the power is 10 W to 100 W; the pressure of the plasma generator is 10 -5 Pa to 1 atm, preferably the pressure is 10 -2 Pa to 10 2 Pa; the reaction temperature of the plasma generator is 50°C to 800°C, preferably the temperature is 100°C to 800°C; the gas flow of the plasma generator is 5 to 2000 sccm, preferably the gas flow is 10 sccm to 500 sccm; the heating time of the plasma generator is 5 s to 5 h, preferably the heating time is 30 min to 2 h; the reaction time of the activation is 5 s to 7200 s, preferably the reaction time of the activation is 30 s to 1000 s;

[0067] Preferably, the activation in b1) is introducing electrons, light and / or heating into the non-metallic material.

[0068] Beneficial effects: 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 and other means to catalytically decompose hydrogen-containing raw gas to generate protons in non-metallic materials 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 gas, 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 the thin films used in other common membrane separation methods, the present application has high thermal stability and excellent temperature resistance, so the applicable temperature range is very large. Compared with the common metal catalyst, the suitable active temperature is required, such as the working temperature of the raw gas and the palladium film body needs to be higher than 300 DEG C, and the temperature stability will affect the purification performance of the metal. In addition, the hydrogen-containing raw gas used in the present application includes hydrogen, argon, ammonia, methane, ethane and other hydrogen-containing raw gas, which is separated and purified from a variety of mixed gas to obtain high-purity hydrogen, which is unique and exclusive to other gases. In the present application, by controlling the electron injection and light, it has instantaneous nature and can realize the switching of hydrogen purification in nanoseconds. The present application lays a foundation for the support of hydrogen energy in the future application of spaceflight, military application, fuel cell and the like. 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 area is small, and the present application is simple, efficient and requires less energy.

[0069] In the preparation of hydrogen fuel cells, the present application utilizes light energy, heat energy or injected electrons and other means, and two-dimensional materials catalytically decompose hydrogen-containing fuel to generate protons and electrons, and then 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.

[0070] 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 hydrogen storage between the layers 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 layers of solid materials and / or the cavity to realize the hydrogen storage and release. The application is suitable for layered materials such as graphene, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, niobium diselenide, tungsten diselenide and other semimetals, 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 require any element doping. The intrinsic structure of the solid material is not damaged during the entire hydrogen storage and release process, and the hydrogen storage and release can be repeated and the service life is long. 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, which has higher selectivity than the commonly used physical adsorption method 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. At the same time, since hydrogen is not allowed to pass through the material used, the sealing performance is excellent during hydrogen storage. The working pressure is small, and hydrogen storage can be realized at normal pressure or even low pressure, and the maximum mass density can exceed 9wt%. In the application, the above-mentioned solid materials are activated in the hydrogen release process, so that the hydrogen release process can be carried out at room temperature or even low temperature to 200K, and the temperature range is wider. The overall 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 a wider application range and use value. BRIEF DESCRIPTION OF DRAWINGS

[0071] Figure 1 is the principle diagram of the application for preparing pure hydrogen by injecting electrons;

[0072] Figure 2 is the principle diagram of the application for preparing pure hydrogen by heating;

[0073] Figure 3 is the principle diagram of the application for preparing pure hydrogen by light irradiation;

[0074] Figure 4 is the principle diagram of the proton exchange membrane fuel cell anode catalyst of the application using the electron injection embodiment.

[0075] Figure 5 is the schematic diagram of the hydrogen storage principle of the graphene sheet layer by the hydrogen plasma method of the present application;

[0076] Figure 6 is the schematic diagram of the hydrogen storage principle of the graphene sheet layer by the hydrogen plasma method of the present application;

[0077] Figure 7 is the atomic force microscope picture of the hydrogen storage principle of the hexagonal boron-nitrogen layer of the present application;

[0078] Figure 8 is the atomic force microscope picture of the thermal stability of the hydrogen storage principle of the graphene layer of the present application;

[0079] Figure 9 is the atomic force microscope picture of the thermal stability of the hydrogen storage principle of the graphene layer of the present application;

[0080] Figure 10 is the Raman picture of the graphene layer when storing hydrogen. DETAILED DESCRIPTION

[0081] The present application provides a method for generating protons based on hydrogen-containing raw gas, which comprises the following steps:

[0082] 1) selecting a non-metallic material capable of permeating only protons, which is a two-dimensional material film or a non-metallic solid material;

[0083] 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 a cavity; 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 a cavity, the solid material containing a cavity 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 0.5nm-1mm; when the two-dimensional material film is hexagonal boron nitride, the thickness of the hexagonal boron nitride is 0.5nm-1mm; when the two-dimensional material film is molybdenum disulfide, the thickness of the molybdenum disulfide is 0.7nm-1mm; the size of the two-dimensional material film is 100nm 2 -1m 2 , preferably the size is 100nm 2 -100cm 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 .

[0084] 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;

[0085] When the activation is introducing electrons into the non-metallic material, the way of introducing electrons is scanning electron microscope electron injection, electrostatic generator electron injection, and / or ordinary power supply electron injection; the current of the introduced electrons is 1pA-10A, preferably 5pA-5nA; the voltage used when introducing electrons is 1V-50kV, preferably 1V-500V; the applicable temperature of the introduced 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℃.

[0086] 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.

[0087] 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.

[0088] The method for generating protons based on the hydrogen-containing raw gas provided by the application has the following application schemes, specifically:

[0089] Application A

[0090] The method for generating protons based on the hydrogen-containing raw gas is used for preparing pure hydrogen, and specifically includes the following contents:

[0091] 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. For example, the thickness of the graphene is single-layer to 1 mm, and 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. For example, 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. For example, 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 .

[0092] 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 ).

[0093] 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℃.

[0094] 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.

[0095] 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;

[0096] 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;

[0097] 5) the protons and the electrons recombine after passing through the activated two-dimensional material film to form pure hydrogen.

[0098] The technical solutions provided by the present application are further explained below in combination with the drawings:

[0099] Referring to Figure 1 , the hydrogen is purified by injecting electrons, specifically:

[0100] 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;

[0101] 2) separating and purifying under the condition of injecting electrons to obtain pure hydrogen on the other side.

[0102] Referring to Figure 2 , the hydrogen is purified by heating, specifically:

[0103] 1) heating the two-dimensional material film, and introducing a hydrogen-containing raw material gas into one side of the two-dimensional material film;

[0104] 2) Separation and purification under heating conditions, and pure hydrogen gas is obtained on the other side.

[0105] Referring to Figure 3 , the purification of hydrogen gas is achieved by means of light irradiation, specifically:

[0106] 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;

[0107] 2) Separation and purification under light conditions, and pure hydrogen gas is obtained on the other side.

[0108] 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:

[0109] Embodiment 1

[0110] Hydrogen gas is purified by injecting electrons into double-layer graphite using hydrogen-containing raw material gas, specifically: hydrogen-containing mixed gas of hydrogen, nitrogen and argon is introduced into one side of double-layer graphene, the mixed 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 hydrogen gas 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 experiments have confirmed that the honeycomb structure of graphene only allows the smallest particle protons to penetrate, the purity of the purified hydrogen gas can reach more than 99.99%.

[0111] 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 .

[0112] Embodiment 2

[0113] 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%.

[0114] 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 size 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 .

[0115] Embodiment 3

[0116] 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%.

[0117] 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 cm 2 , 10 cm 2 , 100 cm 2 , 500 cm 2 and 1 m 2 .

[0118] Example 4

[0119] 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%.

[0120] 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 .

[0121] Example 5

[0122] 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 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%.

[0123] 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 .

[0124] Embodiment 6

[0125] 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 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%.

[0126] 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.

[0127] Example 7

[0128] 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%.

[0129] 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 .

[0130] Example 8

[0131] A hydrogen-containing raw gas is used as a raw material to purify hydrogen gas by using laser irradiation to cover platinum nanoparticles on double-layer graphene (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. One 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. The protons and electrons 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, thereby achieving the extraction of pure hydrogen gas. Since 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.

[0132] Application B

[0133] 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 the barrier of hydrogen-containing fuel, H + is transferred to the cathode of the cell through the proton exchange membrane, and electrons are moved from the anode to the cathode of the cell through the external circuit, thereby realizing a proton exchange membrane fuel cell.

[0134] Exemplarily, a method for forming a hydrogen fuel cell by catalytically decomposing hydrogen-containing fuel by graphene is shown in Figure 4 , and specifically includes:

[0135] 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;

[0136] 2) Under conditions of electron injection or heating, graphene catalyzes the decomposition of hydrogen-containing fuels into H2O. + And electrons, and then, driven by the concentration difference and potential difference, H + Electrons are transferred to the cathode of the battery through a proton exchange membrane, while electrons move from the anode to the cathode through an external circuit, forming a hydrogen fuel cell.

[0137] An exemplary method for catalytically decomposing hexagonal boron nitride into hydrogen-containing fuels to form hydrogen fuel cells includes:

[0138] 1) Electrons are injected or heated into a preferred thickness of hexagonal boron nitride, where applicable, to pass hydrogen-containing fuel through one side of the boron nitride;

[0139] 2) Under conditions of electron injection or heating, boron nitride catalytically decomposes hydrogen-containing fuels into H2O. + And electrons, and then, driven by the concentration difference and potential difference, H + Electrons are transferred to the cathode of the battery through a proton exchange membrane, while electrons move from the anode to the cathode through an external circuit, forming a hydrogen fuel cell.

[0140] An exemplary method for forming a hydrogen fuel cell by catalytic decomposition of hydrogen-containing fuels using thin films of two-dimensional materials such as molybdenum disulfide includes:

[0141] 1) In the case of application, hydrogen-containing fuel is passed through one side of molybdenum disulfide by injecting electrons, heating, or sunlight, etc., into a preferred thickness of molybdenum disulfide.

[0142] 2) Under the influence of electron injection, heating, or sunlight, molybdenum disulfide catalytically decomposes hydrogen-containing fuels into H2O. + And electrons, and then, driven by the concentration difference and potential difference, H + Electrons are transferred to the cathode of the battery via a proton exchange membrane, while electrons move from the anode to the cathode through an external circuit, forming a hydrogen fuel cell. The concentration difference refers to the proton concentration difference across the two-dimensional material. The potential difference is the potential difference resulting from the decomposition of electrons.

[0143] The applicable two-dimensional material films are exactly the same as those in Application A, and will not be repeated in this Application B.

[0144] Example 9

[0145] Using electron injection into bilayer graphene to catalytically decompose hydrogen fuel into H2O + Specifically, hydrogen gas is introduced into one side of the bilayer graphene at a pressure of 1 MPa and a temperature of -20°C. The catalytic anode film is a bilayer graphene with a thickness of approximately 1 nm (bilayer graphene is too thin and easily affected by external factors, so the measured range is 1 nm-1.5 nm, the same below), and an area of ​​100 nm.2 , the hydrogen-containing fuel is methane, and the hydrogen-containing fuel is sent to one side of the double-layer graphene, the gas pressure of the methane is 1 MPa, the temperature is 30°C, the catalytic anode film is the double-layer graphene, the thickness is about 1 nm, the area is 100 nm + , and the current is 5 nA, and the voltage is 100 V. Under the catalytic action of the activated double-layer graphene, the hydrogen is decomposed into H + and electrons, and then under the driving of the concentration difference and the potential difference, the H 2 is transmitted to the cathode of the battery through the double-layer graphene, and the electrons are moved from the anode of the battery to the cathode through an external circuit.

[0146] Based on the foregoing other conditions remain unchanged, on the basis of the two-dimensional material thin film as the double-layer graphene, according to the applicable environment adjustment, 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 and 1 mm + .

[0147] Example 10

[0148] The hydrogen-containing fuel is methane, and the hydrogen-containing fuel is sent to one side of the double-layer graphene, the gas pressure of the methane is 1 MPa, the temperature is 30°C, the catalytic anode film is the double-layer graphene, the thickness is about 1 nm, the area is 100 nm 2 , and the current is 5 nA, and the voltage is 100 V. Under the catalytic action of the activated double-layer graphene, the hydrogen is decomposed into H + and electrons, and then under the driving of the concentration difference and the potential difference, the H + is transmitted to the cathode of the battery through the double-layer graphene, and the electrons are moved from the anode of the battery to the cathode through an external circuit.

[0149] Based on the foregoing other conditions remain unchanged, on the basis of the two-dimensional material thin film as the double-layer graphene, according to the applicable environment adjustment, 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 and 1 mm 2 .

[0150] Example 11

[0151] The hydrogen-containing fuel is methane, and the hydrogen-containing fuel is sent to one side of the double-layer graphene, the gas pressure of the methane is 1 MPa, the temperature is 30°C, the catalytic anode film is the double-layer graphene, the thickness is about 1 nm, the area is 100 nm +and electrons, specifically: hydrogen gas is sent into one side of the three-layer hexagonal boron nitride, the hydrogen gas pressure is 1 MPa, the temperature is 30°C, and electrons are injected into the three-layer hexagonal boron nitride by an electrostatic generator, the thickness is about 1.6 nm, and the area is 100 nm 2 , the current is 5 nA, and the voltage is 100 V. Under the catalytic action of the activated three-layer hexagonal boron nitride, the hydrogen gas 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.

[0152] Based on the foregoing other conditions being unchanged, 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 500 nm 2 , 10 μm 2 , 100 μm 2 , 500 μm 2 , and 1 mm 2 .

[0153] Example 12

[0154] Hydrogen-containing fuel is used as a raw material to realize catalytic decomposition into H + and electrons by injecting electrons into a single-layer molybdenum disulfide, specifically: hydrogen gas is sent into one side of the single-layer molybdenum disulfide, the thickness is about 0.7 nm, and the area is 100 nm 2 , the hydrogen gas pressure is 1 MPa, the temperature is 30°C, and electrons are injected into the single-layer molybdenum disulfide by an electrostatic generator, the current is 5 nA, and the voltage is 100 V. Under the catalytic action of the activated single-layer molybdenum disulfide, the hydrogen gas is decomposed into H + and electrons. Then, under the driving of the concentration difference and the potential difference, H 2 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 other conditions being unchanged, 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 500 nm 2 , 10 μm 2 , 100 μm 2 , 500 μm 2 , and 1 mm + .

[0155] Example 13

[0156] Hydrogen-containing fuel is used as a raw material to realize catalytic decomposition into H +and electrons (the energy used in this embodiment is heat energy), specifically: hydrogen gas is sent to one side of the monolayer molybdenum disulfide, the thickness is about 0.7 nm, and the area is 100 nm 2 . The hydrogen gas pressure is 1 MPa, and the temperature is 30°C. The monolayer molybdenum disulfide is heated to a temperature of 300°C. Under the catalytic action of the activated monolayer molybdenum disulfide, the hydrogen gas is decomposed into H + and electrons. Then, under the driving of the concentration difference and the potential difference, the H + is transferred to the cathode of the battery through the monolayer molybdenum disulfide, and the electrons are moved from the anode to the cathode of the battery through the external circuit. 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 .

[0157] Embodiment 14

[0158] Catalytic decomposition of hydrogen-containing fuel into H + and electrons (the energy used in this embodiment is laser) is realized by laser irradiation of monolayer molybdenum disulfide, specifically: hydrogen gas is sent to one side of the monolayer molybdenum disulfide, the thickness is about 0.7 nm, and the area is 100 nm 2 . According to the adjustment of the applicable environment, the hydrogen gas pressure is 1 MPa, and the temperature is -30°C. The monolayer molybdenum disulfide is irradiated by a laser with a wavelength of 532 nm. Under the catalytic action of the activated monolayer molybdenum disulfide, the hydrogen gas is decomposed into H + and electrons. Then, under the driving of the concentration difference and the potential difference, the H + is transferred to the cathode of the battery through the monolayer molybdenum disulfide, and the electrons are moved from the anode to the cathode of the battery through the external circuit. 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 2any size in the range of 100 nm to 1 m. When laser irradiation is used, the wavelength of the laser can also be selected from any wavelength below 1000 nm.

[0159] Example 15

[0160] Catalytic decomposition of hydrogen-containing fuel into H + and electrons (solar light is used as the energy source in this embodiment) is achieved by sending hydrogen gas to one side of monolayer molybdenum disulfide with a thickness of about 0.7 nm and an area of 100 nm 2 , the hydrogen gas has a gas pressure of 1 MPa and a temperature of 30°C, and monolayer molybdenum disulfide is irradiated with solar light. Under the catalytic action of the activated monolayer molybdenum disulfide, the hydrogen gas is decomposed into H + and electrons, and then, driven by the concentration difference and the potential difference, H + is transferred to the cathode of the battery through the monolayer molybdenum disulfide, and the electrons are moved from the anode to the cathode of the battery through an external circuit.

[0161] Based on the foregoing other conditions being unchanged, on the basis of the two-dimensional material thin film being monolayer molybdenum disulfide, the size of the monolayer molybdenum disulfide can also be selected from any size in the range 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 .

[0162] Example 16

[0163] Catalytic decomposition of hydrogen-containing fuel into H + and electrons is achieved by using laser irradiation to cover platinum nanoparticles with double-layer graphene, specifically by sending hydrogen gas to one side of double-layer graphene covering platinum nanoparticles with a thickness of about 1 nm and an area of 100 nm 2 , the hydrogen gas has a gas pressure of 1 MPa and a temperature of 30°C, the platinum nanoparticles have a height of 0.5-10 nm and a size of 10 nm-50 nm, and double-layer graphene covering platinum nanoparticles is irradiated with a laser with a wavelength of 532 nm. Under the synergistic catalytic action of the activated double-layer graphene and platinum nanoparticles, the hydrogen gas is decomposed into H + and electrons, and then, driven by the concentration difference and the potential difference, H + is transferred to the cathode of the battery through the double-layer graphene covering platinum nanoparticles, and the electrons are moved from the anode to the cathode of the battery through an external circuit.

[0164] Based on the foregoing other conditions being unchanged, on the basis of the two-dimensional material thin film being 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 . When laser irradiation is used, the wavelength of the laser can also be selected from any one of wavelengths below 1000 nm.

[0165] Example 17

[0166] Catalytic decomposition of hydrogen-containing fuel into H + and electrons is achieved by injecting electrons into bilayer graphene, specifically: hydrogen-containing mixed gas fuel of methanol is sent into one side of the bilayer graphene (hydrogen-containing fuels used in this example include natural gas, ethane, propane, butane, and methanol), the thickness is about 1 nm, the area is 100 nm 2 , the mixed gas pressure is 1 MPa, the temperature is 30°C, electrons are injected into the bilayer graphene by an electrostatic generator, the current is 5 nA, and the voltage is 100 V. Under the catalytic action of the activated bilayer graphene, hydrogen is decomposed into H + and electrons, and then driven by the concentration difference and the potential difference, H + is transferred to the cathode of the battery through the bilayer graphene, and the electrons are moved from the anode to the cathode of the battery through the external circuit.

[0167] Based on the foregoing other conditions being unchanged, on the basis of the two-dimensional material thin film being 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 .

[0168] C

[0169] The method for generating protons based on hydrogen-containing raw gas is used for hydrogen storage and hydrogen release. The principle is that solid-state materials such as graphene sheets, carbon nanotubes, fullerene molecules, hexagonal boron nitride, and molybdenum disulfide can only permeate protons. By combining hydrogen plasma, light energy, heat energy, or electron injection, hydrogen can be stored between the layers of solid-state materials or in cavities. When hydrogen is used, the above-mentioned solid-state materials are activated by light energy, heat energy, or electron injection to catalyze the decomposition of hydrogen to generate protons and electrons. The permeated protons and electrons recombine to generate hydrogen, which is released from the solid-state material layers and / or cavities, achieving hydrogen storage and hydrogen release.

[0170] The specific method includes a hydrogen storage process and a hydrogen release process. The hydrogen storage process includes the following steps:

[0171] a1) Selecting a non-metallic material that can only permeate protons;

[0172] a2) Activating the non-metallic material to generate catalytic properties;

[0173] a3) Introducing hydrogen-containing raw gas to one side of the non-metallic material;

[0174] a4) Under the catalytic action of the activated non-metallic material, the introduced hydrogen-containing raw gas is decomposed into protons and electrons; or directly using hydrogen plasma technology to make the hydrogen-containing raw gas generate protons and electrons;

[0175] 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;

[0176] The hydrogen release process includes the following steps:

[0177] b1) Activating the non-metallic material containing hydrogen and generating catalytic properties;

[0178] b2) Under the catalysis of the activated non-metallic material, the hydrogen stored in the non-metallic material is decomposed into protons and electrons;

[0179] 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.

[0180] Taking graphene sheets, hexagonal boron nitride sheets, or molybdenum disulfide sheets as examples, the following is described:

[0181] The high-density hydrogen storage and reversible hydrogen absorption / release in graphene sheets are as follows:

[0182] 1) in the graphene sheet of the preferred thickness, hydrogen-containing gas is introduced into the space where the graphene sheet is located, followed by the application of plasma, thermal energy or injection of electrons, etc.

[0183] 2) under the condition of plasma, hydrogen-containing gas (such as hydrogen in Figure 5 or methane in Figure 6 ) is decomposed into H + and electrons, H + and electrons penetrate into the graphene interlayer to recombine to form pure hydrogen gas and store in the graphene interlayer; at this time, specifically, the hydrogen gas stored in the graphene interlayer of the graphene sheet of 50-100 nm has excellent thermal stability, and the hydrogen gas in the graphene interlayer does not decrease after heating at 150℃, 300℃, 400℃ in vacuum for 4 hours, respectively (as shown in Figure 8 ); and the time stability is very good, and the hydrogen gas of the four samples with different heights does not decrease after being stored in the atmosphere for 3-4 months (as shown in Figure 9 ). Similarly, under the condition of injection of electrons or heating, the activated graphene catalytically decomposes the hydrogen-containing gas into H + and electrons, and then H + and electrons penetrate into the graphene interlayer to recombine to form pure hydrogen gas and store in the graphene interlayer, and the interlayer hydrogen gas also has excellent thermal stability and time stability.

[0184] The process of hydrogen release is:

[0185] When hydrogen is released, the graphene sheet is activated by means of light energy, thermal energy or injection of electrons, etc. to catalytically decompose the interlayer hydrogen gas into protons and electrons, and the penetrated protons and electrons recombine to generate hydrogen gas, realizing the release of 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 ), which can be reused and achieve long service life.

[0186] The process of high-density hydrogen storage and reversible absorption / release of hydrogen in the hexagonal boron nitride sheet is:

[0187] Hydrogen storage:

[0188] 1) in the hexagonal boron nitride sheet of the preferred thickness, hydrogen-containing gas is introduced into the space where the hexagonal boron nitride sheet is located, followed by the application of plasma, thermal energy or injection of electrons, etc.

[0189] 2) under the condition of plasma, hydrogen-containing gas is decomposed into H + and electrons, H +and electrons, then under the driving of the concentration difference and the potential difference, H + and electrons, then under the driving of the concentration difference and the potential difference, H + and electrons, then under the driving of the concentration difference and the potential difference, H Figure 7 Figure 5 is an atomic force microscope picture of the hydrogen storage in the hexagonal boron nitride interlayer.

[0190] Hydrogen release:

[0191] Using light energy, heat energy or electron injection, etc. to activate the hexagonal boron nitride sheet, catalyze the decomposition of interlayer hydrogen to generate protons and electrons, and the penetrated protons and electrons recombine to generate hydrogen, realizing the release of hydrogen from the interlayer and / or cavity of solid material.

[0192] The process of high-density hydrogen storage and reversible absorption / release in two-dimensional material sheets such as molybdenum disulfide is:

[0193] Hydrogen storage:

[0194] 1) In the preferred thickness of molybdenum disulfide under suitable conditions, hydrogen-containing gas is introduced into the space where the molybdenum disulfide sheet is located under the irradiation of plasma, electron injection or heating or sunlight, etc.

[0195] 2) Under the condition of plasma, the hydrogen-containing gas is decomposed into H + and electrons, H + and electrons, then under the driving of the concentration difference and the potential difference, H + and electrons, then under the driving of the concentration difference and the potential difference, H + and electrons, then under the driving of the concentration difference and the potential difference, H

[0196] Hydrogen release:

[0197] Using heat energy or electron injection, etc. to activate the molybdenum disulfide sheet, catalyze the decomposition of interlayer hydrogen to generate protons and electrons, and the penetrated protons and electrons recombine to generate hydrogen, realizing the release of hydrogen from the interlayer and / or cavity of solid material.

[0198] The process of high-density hydrogen storage and reversible absorption / release in low-dimensional materials with cavities such as carbon nanotubes, fullerenes and boron-nitrogen tubes is:

[0199] Hydrogen storage:

[0200] 1) In the preferred diameter of the cavity material, the hydrogen-containing gas is introduced into the space where the cavity material is located, and then plasma, heat energy or injection of electrons is applied;

[0201] 2) In the condition of plasma, the hydrogen-containing gas is decomposed into H + and electrons, H + and electrons enter the cavity of the cavity material, and recombine to form hydrogen gas and store in the cavity of the cavity material; under the condition of injection of electrons or heating, the activated cavity material catalytically decomposes the hydrogen-containing gas into H + and electrons, and then H + and electrons enter the cavity of the cavity material under the driving of concentration difference and potential difference, and recombine to form hydrogen gas and store in the cavity of the cavity material.

[0202] Hydrogen release:

[0203] The cavity material is activated by means of light energy, heat energy or injection of electrons, catalyzing 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.

[0204] The solid material film is graphene, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, niobium diselenide, tungsten diselenide and other layered materials of various semi-metals, semiconductors, conductors and insulators, carbon nanotubes, fullerene, boron-nitrogen nanotubes and other cavity-containing solid materials.

[0205] 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, and 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 reaction temperature, pressure, reaction gas flow, heating time, plasma intensity and reaction time, with the reaction temperature being 50℃-800℃, and the preferred range being 100℃-800℃; the pressure being 10 -5 Pa-1atm, and the preferred range being 10 -2 Pa-10 2 Pa; the carrier gas can be methane, nitrogen, argon, oxygen, hydrogen, etc.; the gas flow is 5-2000sccm, and the preferred range is 10sccm-500sccm; the heating time is 5s-5h, and the preferred range is 30min-2h; the reaction time is 5s-7200s, and the preferred range is 30s-1000s.

[0206] The way of injecting electrons is the same as in application A, and this application C will not be repeated.

[0207] 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℃.

[0208] Example 17

[0209] Hydrogen is stored in graphene sheets by plasma assistance, and graphene is activated to release hydrogen by electron injection. Specifically, graphene sheets are placed in a plasma-assisted chemical vapor deposition device, the graphene sheets are four layers thick (about 2nm thick), and the size area is preferably 100μm 2 When the reaction chamber pressure is <10 -4 Pa, hydrogen is introduced, specifically 180sccm of hydrogen, the reaction chamber pressure is stabilized by a pressure regulating valve to 6Pa, and the temperature is raised to 500℃, then maintained for 10min to ensure uniform heating of the substrate. Turn on the inductively coupled plasma generator, the power is 10W, and the hydrogen storage content in the graphene sheet layer is controlled 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 gas bubbles in the graphene sheet layer. According to the number and size of the bubbles, the hydrogen storage content in the graphene sheet layer can be calculated, and the highest hydrogen mass density is 9wt%.

[0210] When releasing hydrogen, electrons are injected into the above-mentioned hydrogen-stored graphene sheet sample by an electrostatic generator to activate the graphene, the current of the electrostatic generator is 5nA, and the voltage is 100V. Under the catalytic action of the activated graphene, hydrogen atoms of hydrogen gas 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 gas, realizing the release of pure hydrogen gas.

[0211] Example 18

[0212] Hydrogen is stored in graphene sheets by plasma assistance, and graphene is activated to release hydrogen by electron injection. Specifically, graphene sheets are placed in a plasma-assisted chemical vapor deposition device, the graphene sheets are four layers thick (about 2nm thick), and the size area is preferably 100μm 2 When the reaction chamber pressure is <10 -4Pa, and then hydrogen-containing gas (such as methane or ethane) is introduced, specifically, 100 sccm of methane, the pressure in the reaction chamber is stabilized to 6 Pa by a pressure regulating valve, 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, and the power is specifically 10 W. The hydrogen content in the graphene sheet is controlled by changing the plasma time, and the time is 300 s. After completion, the heating is turned off and the sample is naturally cooled down, 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 between the graphene sheets. 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 9 wt%.

[0213] When hydrogen is released, electrons are injected into the graphene sheet sample obtained above by an electrostatic generator to activate the graphene, and the current of the electrostatic generator 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, 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, and pure hydrogen is released.

[0214] Example 19

[0215] Hydrogen is stored in the hexagonal boron nitride sheet by plasma assistance, and the hexagonal boron nitride is activated by electron injection to release hydrogen, specifically: the hexagonal boron nitride sheet is placed in a plasma assisted chemical vapor deposition device, the thickness of the four layers of the hexagonal boron nitride sheet is about 2 nm, and the size area is preferably 100 μm 2 When the pressure in the reaction chamber is <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, 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, and the power is specifically 30 W. The hydrogen content in the hexagonal boron nitride sheet is controlled by changing the plasma time, and the time is 60 s. After completion, the heating is turned off and the sample is naturally cooled down, 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 between the hexagonal boron nitride sheets. According to the number and size of the bubbles, the hydrogen storage content in the hexagonal boron nitride sheet can be calculated, and the highest hydrogen mass density is 9.5 wt%.

[0216] When hydrogen is released, the hydrogen stored in the above-obtained hexagonal boron nitride flake sample is activated by injecting electrons into the hexagonal boron nitride flake sample 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 hexagonal boron nitride, hydrogen atoms in hydrogen are decomposed into protons and electrons, and the protons and the electrons can freely pass through the hexagonal boron nitride. After the protons and the electrons pass through the activated hexagonal boron nitride, the protons and the electrons combine to re-form hydrogen, and pure hydrogen is released.

[0217] Example 20

[0218] The hydrogen is stored in the molybdenum disulfide flake by plasma assistance, and the molybdenum disulfide is activated by laser irradiation to release hydrogen, 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 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 through a pressure regulating valve, 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, and the power is 10 W. The hydrogen storage content in the molybdenum disulfide flake layer is controlled by changing the plasma time, and the general 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 observed by atomic force microscopy to observe the number and size of hydrogen 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%.

[0219] When hydrogen is released, the hydrogen stored in the above-obtained molybdenum disulfide flake sample is activated by laser irradiation, and the wavelength of the laser is 532 nm. Under the catalysis of the activated molybdenum disulfide, hydrogen atoms in 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 and the electrons combine to re-form hydrogen, and pure hydrogen is released.

[0220] When laser irradiation is used, the wavelength of the laser can also be selected from any wavelength below 1000 nm.

[0221] Example 21

[0222] The hydrogen is stored in the molybdenum disulfide flake by plasma assistance, and the molybdenum disulfide is activated by natural light to release hydrogen, 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 pressure in the reaction chamber is less than 10 -4Pa, then hydrogen gas is introduced, specifically 180 sccm of hydrogen gas, the pressure in the reaction chamber is stabilized to 6 Pa by a pressure regulating valve, the temperature is raised to 400°C, and then maintained for 10 min to ensure that the substrate is uniformly heated. The inductively coupled plasma generator is turned on, specifically at a power of 20 W, and the interlayer hydrogen storage content of the molybdenum disulfide sheet is controlled by changing the plasma time, generally for 200 s. After completion, the heating is turned off and the sample is naturally cooled and then removed. The prepared sample is observed for the number and size of hydrogen gas bubbles in the interlayer of the molybdenum disulfide sheet using an atomic force microscope. According to the number and size of the bubbles, the interlayer hydrogen storage content of the molybdenum disulfide sheet can be calculated, and the highest hydrogen mass density is calculated to be 2.8 wt%.

[0223] When hydrogen is released, the hydrogen atoms in the hydrogen-stored molybdenum disulfide sheet sample obtained above are decomposed into protons and electrons by activating the molybdenum disulfide by a static electricity generator and irradiating with natural light. The protons and electrons can freely pass through the activated molybdenum disulfide. After the protons and electrons pass through the activated molybdenum disulfide, the protons and electrons combine to reform hydrogen gas, achieving the release of pure hydrogen gas.

[0224] Example 22

[0225] Hydrogen is stored in the molybdenum disulfide sheet by plasma assistance, and hydrogen is released by heating to activate the molybdenum disulfide, specifically: the molybdenum disulfide sheet is placed in a plasma-assisted chemical vapor deposition device, the molybdenum disulfide sheet is 2 nm thick, and the size area is preferably 100 μm 2 When the pressure in the reaction chamber is <10 -4 Pa, then hydrogen gas is introduced, specifically 180 sccm of hydrogen gas, the pressure in the reaction chamber is stabilized to 6 Pa by a pressure regulating valve, the temperature is raised to 200°C, and then maintained for 10 min to ensure that the substrate is uniformly heated. The inductively coupled plasma generator is turned on, specifically at a power of 10 W, and the interlayer hydrogen storage content of the molybdenum disulfide sheet 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 then removed. The prepared sample is observed for the number and size of hydrogen gas bubbles in the interlayer of the molybdenum disulfide sheet using an atomic force microscope. According to the number and size of the bubbles, the interlayer hydrogen storage content of the molybdenum disulfide sheet can be calculated, and the highest hydrogen mass density is calculated to be 2.8 wt%.

[0226] When hydrogen is released, the hydrogen atoms in the hydrogen-stored molybdenum disulfide sheet sample obtained above are decomposed into protons and electrons by activating the molybdenum disulfide by a static electricity generator and irradiating with natural light. The protons and electrons can freely pass through the activated molybdenum disulfide. After the protons and electrons pass through the activated molybdenum disulfide, the protons and electrons combine to reform hydrogen gas, achieving the release of pure hydrogen gas.

[0227] Example 23

[0228] The hydrogen is stored in the molybdenum disulfide sheet by means of electron injection, and the molybdenum disulfide is activated by means of laser, specifically, the hydrogen is sent to one side of the molybdenum disulfide sheet, the hydrogen pressure is 3 MPa, the thickness of the molybdenum disulfide is about 10 nm, and the size area of the molybdenum disulfide sheet is 100 nm 2 The molybdenum disulfide is activated by means of electron injection, 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, the 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 the hydrogen. The prepared sample is observed by means of an atomic force microscope to observe the number and size of the 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%.

[0229] When the hydrogen is released, the molybdenum disulfide in the above-mentioned hydrogen-stored molybdenum disulfide sheet sample is activated by means of laser irradiation, and the wavelength of the laser is 532 nm. Under the catalysis of the activated molybdenum disulfide, the hydrogen atoms of the 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 the hydrogen, thereby realizing the release of pure hydrogen. When the laser irradiation is adopted, the wavelength of the laser can also be selected from any wavelength below 1000 nm.

[0230] Example 24

[0231] The hydrogen is stored in the single-walled carbon nanotube cavity by means of plasma assistance, and the single-walled carbon nanotube is activated by means of electron injection to release the hydrogen, specifically, the single-walled carbon nanotube is placed into a plasma-assisted chemical vapor deposition device, the tube diameter of the single-walled carbon nanotube is 1 nm-3 nm, 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, the hydrogen flow is 180 sccm, the pressure in the reaction chamber is stabilized to 6 Pa by means of a pressure regulating valve, the temperature is raised to 800 ℃, and then the temperature is 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 the completion, the heating is turned off, the temperature is naturally reduced, and finally the sample is taken out. The prepared sample is weighed by means of a high-precision balance, and the mass density is calculated to be about 5 wt%.

[0232] When hydrogen is released, the single-walled carbon nanotube sample obtained above is activated by injecting electrons into it through an electrostatic generator, the current of the electrostatic generator being 5 nA and the voltage being 100 V. Under the catalysis of the activated single-walled carbon nanotube, hydrogen atoms of hydrogen are decomposed into protons and electrons, which can freely pass through the single-walled carbon nanotube. After the protons and electrons pass through the activated single-walled carbon nanotube, the protons combine with the electrons to re-form hydrogen, thereby releasing pure hydrogen.

[0233] The above describes the preferred embodiments of the present application in detail, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions 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 the disclosed content of the present application and fall within the protection scope of the present application.

Claims

1. A method for generating protons based on hydrogen-containing feed gas, characterized in that, The method for generating protons based on hydrogen-containing feed gas includes the following steps: 1) Select a non-metallic material that can only be permeated by protons; the non-metallic material is a two-dimensional thin film or a non-metallic solid material; when the non-metallic material is a two-dimensional thin film, the two-dimensional thin 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 thin film layered material or a solid material containing cavities; the two-dimensional thin film layered material is one or a combination of graphene sheets, hexagonal boron nitride sheets, molybdenum disulfide sheets, tungsten disulfide sheets, molybdenum diselenide sheets, niobium diselenide sheets, and tungsten diselenide sheets; when the solid material is a solid material containing cavities, the solid material containing cavities is one or a combination of carbon nanotubes, fullerene spheres, and boron nitride nanotubes. 2) Activating non-metallic materials to produce catalytic properties; the specific methods of activation are: introducing electrons into the non-metallic material, heating the non-metallic material, and / or subjecting the non-metallic material to light radiation; 3) Introduce hydrogen-containing raw material gas into the non-metallic material side; 4) Under the catalytic action of activated non-metallic materials, the introduced hydrogen-containing feed gas is decomposed into protons and electrons.

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

3. The method for generating protons based on hydrogen-containing feed gas according to claim 2, characterized in that, The area of ​​the two-dimensional material film is 100 nm. 2 ~100cm 2 The diameter of the carbon nanotubes is 1 nm to 10 nm; the diameter of the fullerene spheres is 0.7 nm to 5 nm; the area of ​​the hollow solid material is 100 nm. 2 ~100cm 2 .

4. The method for generating protons based on hydrogen-containing feed gas according to claim 3, characterized in that, The activation in step 2) is the introduction of electrons into the non-metallic material. The electrons are introduced by means of scanning electron microscope injection, electrostatic generator injection and / or ordinary power supply injection; the current for introducing electrons is 1pA~10A; the voltage used for introducing electrons is 1V~50kV; the applicable temperature for introducing electrons is -250℃~1000℃. The activation in step 2) refers to heating non-metallic materials at a temperature of 30℃ to 800℃. The activation in step 2) refers to irradiating non-metallic materials with light, where the light is natural light, artificial natural light, and / or laser light; the wavelength of the light used in the irradiation is less than 1000nm; and the applicable temperature for the irradiation is -250℃ to 1000℃. The activation in step 2) is when the non-metallic solid material is heated, and the heating temperature is 30℃~800℃; the heating temperature of the fullerene spheres is 50℃~300℃.

5. The method for generating protons based on hydrogen-containing feed gas according to claim 4, characterized in that, The current for introducing electrons is 5pA~5nA; the voltage used for introducing electrons is 1V~500V; the heating temperature of the graphene sheet and carbon nanotube is 500℃~800℃; the heating temperature of the hexagonal boron nitride sheet is 400℃~800℃; and the heating temperature of the molybdenum disulfide sheet is 200℃~500℃.

6. The method for generating protons based on hydrogen-containing feed gas according to claim 5, characterized in that, In step 2), activation refers to irradiating a non-metallic material with light, wherein the surface of the non-metallic material is coated with platinum, palladium, and / or nickel.

7. The method for generating protons based on hydrogen-containing feed gas according to claim 6, characterized in that: The hydrogen feed gas in step 3) is one or a combination of hydrogen, ammonia, methane, and ethane.

8. The application of the method for generating protons based on hydrogen-containing feedstock gas as described in claim 7 in the preparation of pure hydrogen, the preparation of hydrogen fuel cells, or the storage and release of hydrogen.

9. The application according to claim 8, characterized in that: When the method for generating protons based on hydrogen-containing feed gas is used to prepare pure hydrogen, the preparation method includes the following steps: 1) Protons are prepared using the method for generating protons based on hydrogen-containing feed gas according to claim 7; 2) Protons and electrons recombine after passing through the activated non-metallic material to form pure hydrogen gas.

Images