JP2018095530A - Hydrogen generator - Google Patents

Abstract

Hydrogen is efficiently generated. A photosensitizer 11 of a hydrogen generator 1 includes a void structure having a plurality of voids capable of taking in ions, atoms, molecules or electrons. The irradiation unit 13 irradiates a predetermined region on the photosensitizer 11 with pulsed laser light, activates the void structure, and generates a radicalized void structure, thereby supplying water supplied from the water supply unit 12. To produce hydrogen. The supply amount adjustment unit 14 adjusts the supply amount of water from the water supply unit 12. In the hydrogen generator 1, at least a part of the radicalized void structure used for generating hydrogen is decomposed by adjusting the amount of water supplied to the photosensitizer 11 by the supply amount adjusting unit 14. Returning to the void structure, it is activated by the pulsed laser light from the irradiation unit 13 and becomes a radicalized void structure again. Thereby, since a void structure can be repeatedly used for the production | generation of hydrogen, hydrogen can be produced | generated efficiently. [Selection] Figure 1

Description

  The present invention relates to a technique for generating hydrogen.

  In recent years, hydrogen has attracted attention as a clean energy source that is more environmentally friendly than petroleum-derived fuels. For example, in a fuel cell vehicle, power is generated by supplying hydrogen stored in an on-vehicle hydrogen tank and oxygen in the air to the fuel cell, and an electric motor as a power source is driven.

  In patent document 1, the manufacturing method of hydrogen which does not use ammonia is proposed. In the manufacturing method, cataite and hydrogen are produced by introducing mayenite and calcium hydroxide into water and reacting with water. Patent Document 2 proposes a method of regenerating mayenite and calcium hydroxide by calcining katoite produced together with hydrogen by the above production method at 300 ° C to 500 ° C.

  On the other hand, Patent Document 3 proposes a technique for generating hydrogen by decomposing water without using a photocatalyst or the like by condensing illumination light with a condensing optical system and irradiating the water in the container. . Examples of the illumination light source include the sun, a lamp light source, and a pulse laser light source.

JP2013-203588A JP2013-203589A JP 2006-306667 A

  By the way, in the hydrogen generator of patent document 3, even if it is a case where a pulse laser light source is used, the light-hydrogen energy conversion efficiency is about 1.4%, and hydrogen generation is performed with high efficiency. It's hard to say. Further, in the hydrogen production methods of Patent Document 1 and Patent Document 2, since mayenite is decomposed into katoite during hydrogen generation, a process of firing katoite to regenerate mayenite is necessary. Therefore, there is a limit to improving the efficiency of hydrogen generation.

  This invention is made | formed in view of the said subject, and aims at producing | generating hydrogen efficiently.

  The invention described in claim 1 is a hydrogen generator, a photosensitizer comprising a void structure having a plurality of voids capable of taking in ions, atoms, molecules or electrons, and water in the photosensitizer. Irradiate a predetermined space including the photosensitizer or a predetermined region on the photosensitizer with a pulsed electromagnetic wave to activate the void structure to generate a radicalized void structure An irradiation unit that generates hydrogen from the water supplied from the water supply unit, and a supply amount adjustment unit that adjusts the supply amount of water from the water supply unit, and the supply amount adjustment unit By adjusting the amount of water supplied to the photosensitizer, at least a part of the radicalized void structure used to generate the hydrogen returns to the void structure without being decomposed, and the irradiation unit Of pulsed electromagnetic waves Again become radicalized void structure and sex of.

According to a second aspect of the invention, a hydrogen generator according to claim 1, wherein the void _structure, a mayenite containing Ca _{12 Al} 14 _{O 33.}

  The invention according to claim 3 is the hydrogen generator according to claim 1 or 2, wherein an electron avalanche occurs in the activation of the void structure by the pulse electromagnetic wave from the irradiation unit.

  The invention according to claim 4 is a hydrogen generator, comprising a photosensitizer, a water supply unit for supplying water to the photosensitizer, a predetermined space containing the photosensitizer, or the photosensitizer. An irradiation unit that generates hydrogen from water supplied from the water supply unit by irradiating a predetermined region on the sensitizer with a pulsed electromagnetic wave to activate the photosensitizer, and from the irradiation unit In the activation of the photosensitizer by pulsed electromagnetic waves, an electronic avalanche occurs.

  Invention of Claim 5 is a hydrogen generator of Claim 4, Comprising: The water storage part which stores the water supplied from the said water supply part is further provided, The said photosensitizer is granular , Dispersed in the water in the water reservoir.

  A sixth aspect of the present invention is the hydrogen generator according to any one of the first to fourth aspects, wherein water supplied from the water supply unit to the photosensitizer is mist or gaseous. .

  A seventh aspect of the present invention is the hydrogen generator according to any one of the first to fourth aspects, wherein the water supplied from the water supply unit to the photosensitizer is solid.

  The invention described in claim 8 is the hydrogen generator according to any one of claims 1 to 7, wherein the irradiation unit is a scanner that scans a pulse electromagnetic wave two-dimensionally or three-dimensionally.

  In the present invention, hydrogen can be generated efficiently.

It is a figure showing the composition of the hydrogen generator concerning a 1st embodiment. It is a figure which shows the structure of the hydrogen generator based on 2nd Embodiment.

FIG. 1 is a diagram showing a configuration of a hydrogen generator 1 according to a first embodiment of the present invention. The hydrogen generator 1 is an apparatus that decomposes water to generate hydrogen (H ₂ ). The hydrogen generator 1 includes a photosensitizer 11, a water supply unit 12, an irradiation unit 13, a supply amount adjustment unit 14, and a photosensitizer storage unit 15.

  The photosensitizer 11 is accommodated in the internal space of the photosensitizer accommodating portion 15. In the example shown in FIG. 1, the photosensitizer 11 has a substantially rectangular parallelepiped shape, and is placed on the bottom surface of the photosensitizer accommodating portion 15. The photosensitizer 11 is preferably a porous member. Note that the structure, size, and shape of the photosensitizer 11 may be variously changed.

The photosensitizer 11 includes a void structure. The void structure is a crystal structure having a plurality of voids (also referred to as cages) that can take in ions, atoms, molecules, or electrons. In the void structure, the plurality of voids are connected, for example, three-dimensionally. The void structure contained in the photosensitizer 11 is, for example, mayenite. Mayenite is a compound having a crystal structure in which voids having a diameter of about 0.4 nm (nanometers) are three-dimensionally connected (that is, a mayenite type crystal structure), and is also called a mayenite type compound. The mayenite is, for example, a composite oxide containing at least one of calcium element (Ca) and aluminum element (Al). Specifically, the mayenite is a compound mainly containing Ca ₁₂ Al ₁₄ O ₃₃ (also expressed as 12CaO · 7Al ₂ O ₃ ). In other words, mayenite has Ca ₁₂ Al ₁₄ O ₃₃ as a representative composition. The molar ratio of calcium and aluminum in the mayenite is preferably 13:12 to 11:16. In the mayenite, some of the calcium atoms and aluminum atoms may be substituted with other atoms. Further, some or all of the free oxygen ions in the void may be substituted with other anions.

  The water supply unit 12 supplies water to the photosensitizer 11 in the photosensitizer storage unit 15. The water supplied from the water supply unit 12 is, for example, ion exchange water. In the example illustrated in FIG. 1, the water supply unit 12 is disposed on the top of the photosensitizer housing unit 15 and supplies mist-like water to the upper surface of the photosensitizer 11. In FIG. 1, the outline of the mist-like water injected from the water supply part 12 is shown with a broken line. The supply amount adjustment unit 14 adjusts the supply amount of water supplied from the water supply unit 12 to the photosensitizer 11 in the photosensitizer storage unit 15 (that is, the amount of water supplied per unit time). To do. The supply amount adjustment unit 14 adjusts the supply amount of water from the water supply unit 12 based on characteristics such as the material, size, and shape of the photosensitizer 11. Specifically, the supply amount adjusting unit 14 adjusts the water amount so that the amount of water supplied from the water supply unit 12 is equal to the supply amount that is predetermined according to the characteristics of the photosensitizer 11. The supply unit 12 is controlled.

  The irradiation unit 13 irradiates a predetermined region on the photosensitizer 11 with a pulse laser beam substantially in a planar shape. In the example shown in FIG. 1, the irradiation unit 13 irradiates the upper surface of the photosensitizer 11 with pulsed laser light. The irradiation unit 13 is, for example, a scanner that scans a pulsed laser beam two-dimensionally on the photosensitizer 11. As the irradiation unit 13, for example, a biaxial galvano scanner is used.

  In the example illustrated in FIG. 1, the irradiation unit 13 includes a laser light source 131, a reflection unit 132, and a reflection control unit 133. The laser light source 131 emits pulsed laser light toward the reflection unit 132. As the laser light source 131, for example, a femtosecond laser device or a picosecond laser device is used. The reflection unit 132 includes two mirrors 134 and two motors 135. The pulsed laser light from the laser light source 131 is reflected by the two mirrors 134 of the reflecting portion 132 and guided to the photosensitizer 11. The two motors 135 are controlled by the reflection control unit 133 and change the angles of the two mirrors 134 independently of each other. As a result, the pulse laser beam from the laser light source 131 is scanned two-dimensionally on the photosensitizer 11. In the hydrogen generator 1, for example, about 2000 positions on the photosensitizer 11 are irradiated with pulsed laser light per second.

By irradiating the photosensitizer 11 with pulsed laser light, the above-described void structure contained in the photosensitizer 11 is activated (that is, electrons in the void structure are excited), and a radicalized void structure is formed. Is generated. At this time, the electrons excited by the pulse laser beam pump up other electrons in a chain. That is, an electron avalanche (Avalanche phenomenon) occurs in the activation of the void structure by the pulse laser beam. The radicalized void structure decomposes the water supplied to the photosensitizer 11 from the water supply unit 12 to generate hydrogen and oxygen (O ₂ ).

  As described above, when the void structure is mayenite, radicalized mayenite is generated by activation with pulsed laser light. During the activation, the above-described electronic avalanche is generated, and, for example, 12 radicals (free electrons) are generated per 1 mol (mol) of mayenite. As shown in Equation 1, the radicalized mayenite decomposes water supplied to the photosensitizer 11 to generate hydrogen and oxygen. The generated hydrogen and oxygen are separated by, for example, the separation unit 16 and sent to the hydrogen storage unit 171 and the oxygen storage unit 172, respectively, to be stored.

In the hydrogen generator 1, the amount of water supplied to the photosensitizer 11 is adjusted by the supply amount adjusting unit 14. The photosensitizer 11 is continuously irradiated with pulsed laser light from the irradiation unit 13. As a result, the radicalized mayenite used for the generation of hydrogen returns to mayenite without being decomposed to cathoite (Ca ₃ Al ₂ (OH) ₁₂ ), which is a precursor of mayenite. It is activated by the pulse laser beam from the part 13 and becomes radicalized mayenite again.

  In other words, in the hydrogen generator 1, the mayenite that has been used to generate hydrogen and is no longer in the activated state is reactivated by the pulsed laser light and returned to the radicalized mayenite before being decomposed to katoite. . Thereby, mayenite can be repeatedly utilized for the production | generation of hydrogen.

  In the hydrogen generator 1, a part of the radicalized mayenite used for generating hydrogen may be decomposed to cataite. Even in this case, as described above, mayenite can be repeatedly used for the production of hydrogen.

  As described above, when the photosensitizer 11 is porous, the light from the irradiation unit 13 is diffusely reflected in the pores of the photosensitizer 11, thereby causing the inside of the pores of the photosensitizer 11. Is irradiated over a wide area. Accordingly, since the mayenite that forms the pores is also radicalized, the water supplied into the pores is also decomposed to generate hydrogen.

  When 12 radicals are generated in 1 mol of radicalized mayenite in contact with water, the amount of water supplied to the photosensitizer 11 is 6 mol or less with respect to 1 mol of radicalized mayenite. It is preferable. In other words, the amount of water supplied to the photosensitizer 11 is such that N radicals (N is an integer of, for example, 6 or more and 12 or less) are generated in 1 mole of radicalized mayenite in contact with water. When it exists, it is preferable that it is N / 2 mol or less with respect to the said 1 mol radicalized mayenite. Thereby, decomposition | disassembly of mayenite can be prevented or suppressed.

The void structure contained in the photosensitizer 11 may be other than mayenite. For example, the void structure includes [HN (CH ₂ CH ₂ ) 3 NH) K _1.35 [V ₅ O ₉ (PO ₄ ) ₂ ] · xH ₂ O, or (CS ₃ [V ₅ O ₉ (PO _4). ) ₂ ] · xH ₂ O may be included.

  As described above, the hydrogen generator 1 includes the photosensitizer 11, the water supply unit 12, the irradiation unit 13, and the supply amount adjustment unit 14. The photosensitizer 11 includes a void structure. The void structure has a plurality of voids that can take in ions, atoms, molecules, or electrons. The water supply unit 12 supplies water to the photosensitizer 11. The irradiation unit 13 irradiates a predetermined region on the photosensitizer 11 with pulsed laser light, activates the void structure, and generates a radicalized void structure, thereby supplying water supplied from the water supply unit 12. To produce hydrogen. The supply amount adjustment unit 14 adjusts the supply amount of water from the water supply unit 12. In the hydrogen generator 1, at least a part of the radicalized void structure used for generating hydrogen is decomposed by adjusting the amount of water supplied to the photosensitizer 11 by the supply amount adjusting unit 14. Returning to the void structure, it is activated by the pulsed laser light from the irradiation unit 13 and becomes a radicalized void structure again.

  Thus, by adjusting the amount of water supplied to such an extent that the radicalized void structure used for hydrogen generation is not decomposed, the void structure can be repeatedly used for hydrogen generation. As a result, hydrogen can be generated efficiently.

  Further, in the hydrogen generator 1, an electron avalanche occurs when the void structure is activated by the pulse laser beam from the irradiation unit 13. Thereby, in a void structure, multiphoton absorption and / or multielectron excitation can be generated, and the quantum yield in the photosensitizer 11 can be increased. As a result, hydrogen can be generated more efficiently. In the hydrogen generator 1, it is not always necessary to generate an electronic avalanche when the void structure is activated.

  In the hydrogen generator 1, the water supplied from the water supply unit 12 to the photosensitizer 11 is mist. Thereby, the contact area of the photosensitizer 11 and water can be increased. As a result, hydrogen can be generated more efficiently.

  In the hydrogen generator 1, the water supplied from the water supply unit 12 is not limited to a mist shape, and may be, for example, a droplet shape or a liquid column shape. The water supplied from the water supply unit 12 is not limited to a liquid state, and may be a gaseous state (that is, water vapor) or a solid state (that is, ice). When the water supplied from the water supply unit 12 is gaseous, the contact area between the photosensitizer 11 and water can be increased in substantially the same manner as when the water is mist. As a result, hydrogen can be generated more efficiently. When the water supplied from the water supply unit 12 is solid, for example, fine granular ice may be supplied from the water supply unit 12 to the photosensitizer 11. Since the water supplied to the photosensitizer 11 from the water supply unit 12 is solid, the photosensitizer 11 can be maintained at a relatively low temperature. Thereby, the void structure (in the above example, mayenite) can be activated efficiently by the pulse laser beam. Furthermore, decomposition of the void structure can be suppressed.

  As described above, the photosensitizer 11 is porous. Thereby, not only on the surface of the photosensitizer 11 but also inside the photosensitizer 11, the water and the photosensitizer 11 come into contact with each other, and the pulse laser beam is applied to the photosensitizer 11 in contact with the water. Is irradiated. As a result, since hydrogen is also generated inside the photosensitizer 11, hydrogen can be generated more efficiently.

  In the hydrogen generator 1, the irradiation unit 13 is a scanner that scans the pulsed laser beam two-dimensionally. Thereby, it is possible to easily irradiate a predetermined region on the photosensitizer 11 with pulsed laser light. The irradiation region of the pulse laser beam on the surface of the photosensitizer 11 (in the example shown in FIG. 1, the irradiation region in plan view) preferably includes the entire water supply region on the surface of the photosensitizer 11. . Thereby, the water supplied to the photosensitizer 11 can be efficiently used for hydrogen generation.

  In the hydrogen generator 1, the irradiation unit 13 may be a scanner that three-dimensionally scans the pulsed laser light on the photosensitizer 11. As the irradiation unit 13, for example, a 3D galvano scanner is used, and pulsed laser light is irradiated onto the photosensitizer 11 in a substantially three-dimensional shape. Thereby, it is possible to easily irradiate a predetermined region on the photosensitizer 11 with pulsed laser light.

As described above, the void structure is mayenite containing Ca ₁₂ Al ₁₄ O ₃₃ . Mayenite can be produced at a relatively low cost by heating inexpensive materials such as cathoite and aluminum oxide (Al ₂ O ₃ ). Specifically, mayenite is produced by heating a mixed material of katoite and aluminum oxide to about 1250 ° C. with a microwave or a heater, for example. Therefore, the manufacturing cost of the hydrogen generator 1 can be reduced. Further, even when a part of mayenite is decomposed into katoite with the generation of hydrogen, new mayenite can be supplied to the photosensitizer housing 15 at a relatively low cost. Therefore, the running cost of the hydrogen generator 1 can be reduced.

  In the hydrogen generator 1, the pulsed laser light from the irradiation unit 13 does not necessarily have to be applied to a predetermined area on the photosensitizer 11, and may be applied to a predetermined space including the photosensitizer 11. For example, the pulse laser beam from the irradiation unit 13 may be irradiated in a substantially planar or three-dimensional manner on a region that is larger than the photosensitizer 11 and that includes the entire photosensitizer 11. Thus, even when the pulse laser beam is irradiated to the predetermined space containing the photosensitizer 11, the radicalized void structure used for generating hydrogen is not decomposed to the extent that it is decomposed as described above. By adjusting the supply amount of the void structure, the void structure can be repeatedly used for generating hydrogen. As a result, hydrogen can be generated efficiently.

  Hydrogen and oxygen generated in the hydrogen generator 1 may be used for various purposes. For example, hydrogen and oxygen stored in the hydrogen storage unit 171 and the oxygen storage unit 172 are supplied to the fuel cell and used for power generation in the fuel cell. Water generated from hydrogen and oxygen in the fuel cell is returned to the hydrogen generator 1 and supplied from the water supply unit 12 to the photosensitizer 11. Thereby, as shown in Formula 3, since the photosensitizer 11 and water can be circulated and reused for hydrogen generation, hydrogen can be generated more efficiently.

  Next, a hydrogen generator according to the second embodiment of the present invention will be described. FIG. 2 is a diagram illustrating a configuration of the hydrogen generator 1a according to the second embodiment. The hydrogen generator 1a has substantially the same structure as the hydrogen generator 1 shown in FIG. 1 except that the photosensitizer 11a has a different shape and the supply amount adjusting unit 14 is omitted. . In the following description, among the configurations of the hydrogen generator 1a, configurations corresponding to the configurations of the hydrogen generator 1 shown in FIG.

  In the hydrogen generator 1 a shown in FIG. 2, the water supplied from the water supply unit 12 is stored inside the photosensitizer storage unit 15. That is, the photosensitizer storage unit 15 is a water storage unit that stores the water supplied from the water supply unit 12. Further, the granular photosensitizer 11 a is dispersed in the water in the photosensitizer accommodating portion 15. The photosensitizer 11a is an assembly of a plurality of relatively small sensitizer particles 111. The sensitizer particle 111 is, for example, substantially spherical. In FIG. 2, the sensitizer particles 111 are drawn larger than the actual size, and the density of the sensitizer particles 111 in water is drawn lower than the actual density. The size and shape of the sensitizer particle 111 and the structure, size and shape of the photosensitizer 11a may be variously changed.

The photosensitizer 11a is not limited to the void structure, and may be formed of various materials. For example, the photosensitizer 11a may be formed of a general photocatalytic material such as titanium oxide (TiO ₂ ) or tungsten oxide (WO ₃ ). The photosensitizer 11a is, for example, metal, metal nitride, metal phosphide, metal arsenide, metal oxide, metal hydroxide, metal sulfide, metal fluoride, metal chloride, metal bromide, metal iodide. Among the organometallic compounds, at least one kind may be included.

  In the hydrogen generator 1a, the pulse laser beam is emitted from the irradiation unit 13 toward the water in the photosensitizer housing unit 15, and the pulse laser beam is substantially emitted into a predetermined space including the granular photosensitizer 11a. Irradiation is planar or solid. Thereby, the photosensitizer 11a is activated (that is, the electrons of the photosensitizer 11a are excited), and other electrons are pumped up in a chain. That is, an electron avalanche occurs in the activation of the photosensitizer 11a by the pulse laser beam. The activated photosensitizer 11a decomposes the water supplied to the photosensitizer 11a from the water supply unit 12 to generate hydrogen and oxygen. The generated hydrogen and oxygen are separated by, for example, the separation unit 16 and sent to the hydrogen storage unit 171 and the oxygen storage unit 172, respectively, to be stored. When the water in the photosensitizer housing 15 decreases due to the generation of hydrogen, water is supplied from the water supply unit 12 into the photosensitizer housing 15.

  As described above, the hydrogen generator 1a includes the photosensitizer 11a, the water supply unit 12, and the irradiation unit 13. The water supply unit 12 supplies water to the photosensitizer 11a. The irradiation unit 13 generates hydrogen from the water supplied from the water supply unit 12 by irradiating a predetermined space including the photosensitizer 11a with pulsed laser light to activate the photosensitizer 11a. In the hydrogen generator 1a, an electron avalanche occurs when the photosensitizer 11a is activated by the pulse laser beam from the irradiation unit 13. Thereby, in the photosensitizer 11a, multiphoton absorption and / or multielectron excitation can be generated, and the quantum yield in the photosensitizer 11a can be increased. As a result, hydrogen can be generated efficiently.

  The hydrogen generator 1a further includes a photosensitizer storage unit 15 that is a water storage unit that stores the water supplied from the water supply unit 12. The photosensitizer 11a is granular and is dispersed in water in the photosensitizer accommodating portion 15. Thereby, the contact area of the photosensitizer 11a and water can be increased. As a result, hydrogen can be generated more efficiently.

  As described above, the irradiation unit 13 is a scanner that scans a pulsed laser beam two-dimensionally or three-dimensionally. Thereby, it is possible to easily irradiate a predetermined space including the photosensitizer 11a with pulsed laser light.

  In the hydrogen generator 1a, the pulsed laser light from the irradiation unit 13 does not necessarily have to be applied to a predetermined space including the photosensitizer 11a, and may be applied to a predetermined region on the photosensitizer 11a. For example, instead of the granular photosensitizer 11a, a relatively large substantially rectangular parallelepiped photosensitizer 11a is disposed in the water stored in the photosensitizer accommodating portion 15, and the upper surface of the photosensitizer 11a is arranged. The predetermined region may be irradiated with pulsed laser light in a substantially planar or three-dimensional manner. As described above, even when the pulse laser beam is applied to a predetermined region on the photosensitizer 11a, an electron avalanche is generated in the activation of the photosensitizer 11a by the pulse laser beam as described above. Thereby, the quantum yield in the photosensitizer 11a can be increased. As a result, hydrogen can be generated efficiently.

  In the hydrogen generator 1a, the photosensitizer 11a does not necessarily need to be placed in water, and it is not necessary to store water in the photosensitizer storage unit 15. For example, the photosensitizer 11a having a granular shape, a substantially rectangular parallelepiped shape, or another shape is placed on the bottom of the photosensitizer housing 15 where no water is stored, and the water supply unit 12 applies the photosensitizer 11a to the photosensitizer 11a. Mist water may be supplied. By supplying mist-like water, the contact area between the photosensitizer 11a and water can be increased. As a result, hydrogen can be generated efficiently. Alternatively, instead of mist-like water, solid water (for example, fine granular ice) may be supplied to the photosensitizer 11a. Thereby, the photosensitizer 11a can be maintained at a low temperature, and the photosensitizer 11a can be efficiently activated by the pulse laser beam.

  Various modifications can be made in the above-described hydrogen generators 1 and 1a.

  For example, the irradiation unit 13 is not limited to a galvano scanner, and may be another scanner that scans a pulse laser beam two-dimensionally or three-dimensionally on the photosensitizers 11 and 11a. Moreover, the structure of the irradiation part 13 may be variously changed if the photosensitizers 11 and 11a can be effectively irradiated with the pulse laser light in a planar shape or a three-dimensional shape.

  The method of supplying water to the photosensitizers 11 and 11a by the water supply unit 12 may be variously changed. For example, before the photosensitizers 11 and 11a are irradiated with pulsed laser light, water is supplied in advance from the water supply unit 12 to the porous photosensitizers 11 and 11a, and water is contained therein. By cooling the photosensitizers 11 and 11a, the photosensitizers 11 and 11a having solid water (that is, ice) inside and on the surface are prepared. Then, hydrogen may be generated by irradiating the photosensitizers 11 and 11a with pulsed laser light from the irradiation unit 13. In the hydrogen generators 1, 1 a, water from the water supply unit 12 is supplied to at least one of the surface and the inside of the photosensitizers 11, 11 a, and the state of the water is gaseous, liquid (mist-like) Or a solid form.

  The water supplied from the water supply unit 12 is not limited to ion exchange water. The water supplied from the water supply unit 12 to the photosensitizers 11 and 11a is, for example, at least one of ion exchange water, distilled water, purified water, tap water, industrial water, well water, river water, and seawater. May be included. Moreover, the water simple substance may be supplied from the water supply part 12 to the photosensitizers 11 and 11a as mentioned above, and the raw material containing water may be supplied. The raw material may be gaseous, liquid, or solid.

  What is irradiated to the photosensitizers 11 and 11a from the irradiation unit 13 in the hydrogen generators 1 and 1a may be a pulsed electromagnetic wave, and is not limited to pulsed laser light. The wavelength of the pulse electromagnetic wave irradiated from the irradiation part 13 is 190 nm or more and 3000 nm or less, for example. In the hydrogen generators 1 and 1a, by irradiating the photosensitizers 11 and 11a with the pulse electromagnetic waves from the irradiation unit 13, hydrogen can be efficiently generated as described above.

  The configurations in the above-described embodiments and modifications may be combined as appropriate as long as they do not contradict each other.

DESCRIPTION OF SYMBOLS 1,1a Hydrogen generator 11, 11a Photosensitizer 12 Water supply part 13 Irradiation part 14 Supply amount adjustment part 15 Photosensitizer storage part

Claims (8)

A hydrogen generator,
A photosensitizer comprising a void structure having a plurality of voids capable of capturing ions, atoms, molecules or electrons;
A water supply unit for supplying water to the photosensitizer;
By irradiating a predetermined space containing the photosensitizer or a predetermined region on the photosensitizer with a pulsed electromagnetic wave and activating the void structure to generate a radicalized void structure, the water supply unit An irradiation unit for generating hydrogen from water supplied from
A supply amount adjusting unit for adjusting the amount of water supplied from the water supply unit;
With
By adjusting the supply amount of water to the photosensitizer by the supply amount adjustment unit, at least a part of the radicalized void structure used for the generation of hydrogen is void structure without being decomposed. The hydrogen generating device is characterized in that it is activated by a pulsed electromagnetic wave from the irradiation unit and becomes a radicalized void structure again. The hydrogen generator according to claim 1,
The hydrogen generating apparatus, wherein the void structure is mayenite containing Ca ₁₂ Al ₁₄ O ₃₃ . The hydrogen generator according to claim 1 or 2,
An electron avalanche occurs in the activation of the void structure by a pulsed electromagnetic wave from the irradiation unit. A hydrogen generator,
A photosensitizer,
A water supply unit for supplying water to the photosensitizer;
By irradiating pulsed electromagnetic waves to a predetermined space containing the photosensitizer or a predetermined area on the photosensitizer to activate the photosensitizer, hydrogen is supplied from water supplied from the water supply unit. An irradiator to generate;
With
An electron avalanche occurs in activation of the photosensitizer by pulsed electromagnetic waves from the irradiation unit. The hydrogen generator according to claim 4, wherein
A water storage part for storing the water supplied from the water supply part;
The hydrogen generating apparatus, wherein the photosensitizer is granular and dispersed in water in the water reservoir. The hydrogen generator according to any one of claims 1 to 4,
The hydrogen generator supplied to the photosensitizer from the water supply unit is in the form of mist or gas. The hydrogen generator according to any one of claims 1 to 4,
The hydrogen generator is characterized in that the water supplied from the water supply unit to the photosensitizer is solid. The hydrogen generator according to any one of claims 1 to 7,
The hydrogen generating apparatus, wherein the irradiation unit is a scanner that scans a pulsed electromagnetic wave two-dimensionally or three-dimensionally.

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