JP2017104848A - Silicon nanoparticles and/or aggregate thereof, hydrogen generating material for organism and production method for the same, and hydrogen water and production method and production apparatus for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide hydrogen water having a prescribed hydrogen concentration at a low cost, safely, and on site by generating hydrogen by contacting silicon nanoparticles and/or silicon nanoparticles having a portion thereof aggregated with or dispersing the same in water or an aqueous solution.SOLUTION: Hydrogen water having a prescribed and controlled hydrogen concentration in aqueous solution is obtained by generating hydrogen by contacting silicon nanoparticles, or silicon nanoparticles pulverized in ethanol solvent by a bead mill, and/or silicon nanoparticles having a portion thereof aggregated, in which a portion or all of surface silicon oxide film is treated with hydrogen peroxide aqueous solution, with or dispersing the same in water or an aqueous solution in a sealed vessel. In the production method of hydrogen water, use of silicon nanoparticles as a starting material enables safe and efficient production of hydrogen water containing dissolved hydrogen in a concentration and amount sufficient for practical use.SELECTED DRAWING: Figure 9b

Description

The present invention relates to silicon fine nanoparticles and / or aggregates thereof, a biogenic hydrogen generating material, a production method thereof, hydrogen water, a production method thereof, and a production apparatus.

Hydrogen water in which hydrogen is dissolved in water requires a dissolved hydrogen concentration of 1 ppm or more, and it is possible to remove active oxygen. Health drinking water, facial wash water, bath water, medical field and electronic component washing water Moreover, the utilization of various fields such as plant growth promoting water is progressing, but hydrogen water production technology and production equipment are carried out by introducing hydrogen gas into water or by electrolysis of water (for example, Patent Document 1).

    Patent Document 1: Japanese Patent Laid-Open No. 2006-95389

 However, the technique for producing hydrogen water disclosed in the prior art requires a process of directly introducing hydrogen gas, and there are problems in its control and handling. Furthermore, there is a need for a simple on-site hydrogen water, a method for producing the same, and a device for producing the same by using a hydrogen generating material that is low in cost and highly safe for living bodies.

The present invention eliminates at least one of the above technical problems, makes effective use of silicon fine particles, and generates hydrogen by a production method excellent in safety, economy, and industriality, thereby providing a simple and safe hydrogen. It greatly contributes to water production and its production equipment.

The inventors of the present application have been researching effective use of silicon fine particles in semiconductors and light emitting devices. On the other hand, intensive research was carried out on hydrogen production technology with excellent practicality and industriality from such silicon fine particles. As a result, it was found that even under mild conditions at room temperature, silicon fine particles, which are low-cost and safe materials, can be dispersed in water to generate hydrogen from the water, and this hydrogen is dissolved in water. And have found that hydrogen water having a controlled hydrogen concentration can be realized.

The present invention has been created based on the above viewpoint.

One aspect of the present invention is that silicon fine particles or silicon fine particles obtained by further pulverizing silicon fine particles (hereinafter referred to as silicon fine nanoparticles) and / or aggregates thereof are contacted or dispersed in water to generate generated hydrogen, Hydrogen water directly dissolved in the water and sealed in a container.

One apparatus for producing hydrogen water according to the present invention comprises a pulverized portion for forming silicon fine particles or silicon fine nanoparticles obtained by further pulverizing silicon fine particles, and the silicon fine nanoparticles and / or aggregates thereof in water or an aqueous solution. And a hydrogen water generating unit that is dissolved in the water and sealed by contact or dispersion.

According to this hydrogen water production apparatus, silicon fine nanoparticles and / or aggregates thereof are brought into contact with or dispersed in water or an aqueous solution in a sealed container, so that the hydrogen concentration and amount of hydrogen water that can withstand practical use are highly accurate. It can be manufactured on-site safely at low cost. According to this hydrogen water production apparatus, industrial productivity in the production of hydrogen water can be significantly improved.

Further, one method for producing hydrogen water according to the present invention includes a pulverization step for forming silicon fine particles, silicon fine nanoparticles and / or aggregates thereof are contacted or dispersed with water or an aqueous solution, and hydrogen is generated. A step of generating hydrogen water in which hydrogen is dissolved in the water and sealed.

According to this method for producing hydrogen water, it is possible to produce hydrogen water having a hydrogen concentration and amount that can withstand practical use using silicon fine particles as a starting material. Effective use of water makes a great contribution to environmental protection, as well as drinking water. The production cost of the hydrogen water can be greatly reduced, and industrial productivity can be significantly improved.

The fine silicon nanoparticles and / or aggregates thereof used for the production of one hydrogenous water of the present invention have a crystallite size distribution of 100 nm (nanometers) or less, preferably 50 nm or less. It is suitable for the production of hydrogen water in which hydrogen is generated in water, the hydrogen is dissolved in the water and sealed in a container.

Among the silicon fine nanoparticles, those that have been chemically treated (typically, removal of the oxide film with a hydrofluoric acid aqueous solution and / or an ammonium fluoride aqueous solution in each embodiment described later) are hydrogen. It is an example suitable as silicon fine nanoparticles for water production, and one method for producing hydrogen water of the present invention includes a pulverization step for forming silicon fine nanoparticles.

In addition, among the silicon fine nanoparticles, those subjected to chemical treatment (typically heat treatment with an aqueous hydrogen peroxide solution in each embodiment described later) are silicon for producing living body and hydrogen water in the living body. It is an example suitable as a fine nanoparticle, and one manufacturing method of hydrogen water of the present invention includes a crushing process in ethanol which forms a silicon fine nanoparticle.

According to the above-mentioned silicon fine nanoparticles for producing hydrogen water and the production method thereof, the living body for efficiently producing hydrogen water having a hydrogen concentration and quantity that can be practically used by the silicon fine nanoparticles and / or aggregates thereof. It is provided as a material having safety.

According to one hydrogen water production apparatus of the present invention and one hydrogen water production method of the present invention, hydrogen fine water particles having a hydrogen concentration and amount that can be practically used as a starting material for the production of hydrogen water. Is used for on-site manufacturing with high accuracy, low cost and safety. Therefore, silicon fine nanoparticles and / or aggregates thereof are effectively used to contribute to environmental protection and biological safety, and to greatly reduce the production cost of hydrogen water.

It is a cross-sectional TEM (transmission electron microscope) photograph figure which shows the crystal structure example of the silicon | silicone fine nanoparticle after the one-step grinding | pulverization in an Example. FIG. 4 is an enlarged TEM photograph focusing on individual silicon fine nanoparticles. It is a crystallite diameter distribution map by the X-ray-diffraction apparatus (XRD) of the silicon | silicone fine nanoparticle obtained by the one-step grinding | pulverization of an Example. It is a crystallite size distribution map by XRD of the silicon fine nanoparticle obtained by the two-step grinding | pulverization of an Example. It is a dissolved hydrogen concentration characteristic figure in hydrogen water obtained in an example. It is a dissolved hydrogen concentration characteristic figure in hydrogen water obtained in an example. It is a dissolved hydrogen concentration characteristic figure in hydrogen water obtained in an example. It is a dissolved hydrogen concentration characteristic figure in hydrogen water obtained in an example. It is the dissolved hydrogen concentration characteristic figure and hydrogen generation amount characteristic figure in the hydrogen water obtained in another Example. In the hydrogen generation amount characteristic diagram in hydrogen water obtained in other examples, there is a hydrogen generation amount converted per gram of Si.

Embodiments of the present invention will be described in detail with reference to the accompanying drawings.

For silicon fine particles, commercially available high-purity silicon (Si) powder (particle size distribution <φ; 0.5 μm, purity 99.9%, i-type silicon, manufactured by High-Purity Chemical Co., Ltd.) and bead mill method from high-purity Si powder Using the fine silicon nanoparticles prepared in step 1, the aqueous solution was mixed with a weakly alkaline potassium borate buffer solution at pH 8; ultrapure water at pH 7; and standard tap water at pH 7.1 to 7.3. Select and use in a sealed container.

The above-mentioned silicon fine nanoparticles were dispersed in 300 ml of 99% or more of isopropyl alcohol (IPA) using a bead mill apparatus (IMEX Co., Ltd .: RMB type badge-type ready mill), φ: 0 .5 μm zirconia beads (capacity 300 ml) were added and pulverized at a rotational speed of 2500 rpm (one-stage pulverization) for 4 hours, and the average crystallite diameter (volume distribution) was measured by X-ray diffractometer (XRD). 0 nm was obtained. Further, φ: 0.3 mm zirconia beads (capacity: 300 ml) were pulverized at a rotational speed of 2500 rpm (two-stage pulverization) for 4 hours, and the average crystallite diameter (volume distribution) was measured by XRD. 9 nm was obtained.

FIG. 1 is a cross-sectional TEM (transmission electron microscope) photograph showing an example of the crystal structure of silicon fine nanoparticles obtained after the one-step grinding process of the bead mill in this example. FIG. 1 shows a state in which silicon fine nanoparticles are partially agglomerated to form irregularly large particles of about 0.5 μm or less. FIG. 2 is an enlarged TEM photograph focusing on individual silicon fine nanoparticles. As shown by being surrounded by a white line in FIG. 2, silicon fine nanoparticles having a size of about 5 nm to 10 nm were confirmed. Further, it was confirmed that the silicon fine particles had crystallinity ((111) plane). The appearance is irregular, and some silicon agglomerates are also found. Although not shown, TEM analysis after two-stage pulverization yielded silicon fine nanoparticles having a crystallinity (about (111) plane) of about ½ or less after one-stage pulverization.

FIG. 3 is a diagram showing the results of measurement and analysis of the crystallite size distribution of the silicon fine nanoparticles obtained in the example by one-step pulverization using an X-ray diffractometer (Smart Lab manufactured by Rigaku Electric Co., Ltd.). In FIG. 3, the horizontal axis represents the crystallite diameter (nm), and the vertical axis represents the frequency. The solid line indicates the crystallite size distribution based on the number distribution, and the broken line indicates the crystallite size distribution based on the volume distribution. In the number distribution, the mode diameter was 0.29 nm, the median diameter (50% crystallite diameter) was 0.75 nm, and the average diameter was 1.2 nm. In the volume distribution, the mode diameter was 4.9 nm, the median diameter was 12.5 nm, and the average diameter was 20.0 nm as described above.

FIG. 4 is a diagram showing the result of measurement and analysis of the crystallite size distribution of the silicon fine nanoparticles obtained in the example in the two-stage pulverization using an X-ray diffractometer. In FIG. 4, the horizontal axis represents the crystallite diameter (nm), and the vertical axis represents the frequency. The solid line indicates the crystallite size distribution based on the number distribution, and the broken line indicates the crystallite size distribution based on the volume distribution. In the number distribution, the mode diameter was 0.14 nm, the median diameter (50% crystallite diameter) was 0.37 nm, and the average diameter was 0.6 nm. In the volume distribution, the mode diameter was 2.6 nm, the median diameter was 6.7 nm, and the average diameter was 10.9 nm as described above. From these results, it was found that the silicon fine nanoparticles obtained after the two-stage pulverization had a fineness of about ½ or less achieved by the one-stage pulverization. It was confirmed that fine silicon nanoparticles having a crystallite size in the range of 100 nm or less, particularly 50 nm or less, can be obtained by the pulverization treatment by these bead mill methods.

Hereinafter, the generation of hydrogen water using silicon fine nanoparticles produced by one-step pulverization and two-step pulverization and control of the dissolved hydrogen concentration will be described in detail.

Silicon fine nanoparticles containing beads prepared by the above-mentioned one-stage grinding and two-stage grinding are SUS filters (φ: 0.5 mm beads in the case of beads of φ: 0.5 mm) attached to a bead separation container (made by Imex Co., Ltd.). Is 0.35 mm, φ: 0.3 mm beads are used, and mesh 0.06 mm is used), and an isopropyl alcohol (IPA) solution containing silicon fine nanoparticles containing beads is poured from the top to classify the particles. After processing, suction filtration was performed to separate the beads to obtain an IPA solution containing silicon fine nanoparticles. Thereafter, IPA was evaporated at 40 ° C. using a vacuum evaporator to obtain silicon fine nanoparticles.

Next, when the hydrofluoric acid treatment was performed, the following treatment was added. The obtained silicon fine nanoparticles were immersed in a 5% concentration hydrofluoric acid solution for 10 minutes. Thereafter, filtration in air was performed with a 100 nm fluororesin membrane filter, and silicon fine nanoparticles were trapped on the membrane filter and left in layers. When the silicon fine nanoparticles on the membrane filter were held on a fluororesin beaker and hydrofluoric acid treatment was performed, ethanol was dropped from above to remove the hydrofluoric acid component. Silicon fine nanoparticles on the membrane filter were dried in air for about 30 minutes to obtain hydrofluoric acid-treated silicon fine nanoparticles.

The silicon oxide film thickness on the surface of these silicon fine nanoparticles was measured by XPS method. When hydrofluoric acid treatment is not performed, a silicon oxide film having a thickness of about 1.6 nm is provided. In the case of hydrofluoric acid treatment, the oxide film was removed by etching, and the thickness was 0.07 nm or less, and it was found that the oxide film was hardly present.

10 mg of the obtained silicon fine nanoparticles were put into a glass bottle with a capacity of 30 ml (borosilicate glass thickness of about 1 mm, Labone screw tube manufactured by ASONE), and then 1 ml of ethanol was added and dispersed, About 29 ml of a predetermined aqueous solution was added so that the volume became 30 ml, the mouth of the glass bottle was filled up, the inner lid was closed so as not to enter air, a cap (length 1 cm) was attached, and the bottle was completely sealed. The cap was polypropylene (thickness 2 mm), and the inner lid was made of polyethylene and polypropylene multilayer filters. By these, the permeation | transmission and leakage of the generated hydrogen were fully suppressed.

While maintaining this state, hydrogen is gradually generated from the silicon fine nanoparticles in a closed glass bottle at room temperature, and hydrogen having a predetermined concentration can be dissolved in the aqueous solution to obtain safe hydrogen water. I was able to.

A portable dissolved hydrogen concentration meter manufactured by Toa DKK was used to measure the reaction time dependence of the dissolved hydrogen concentration in the aqueous solution. First, FIG. 5 shows the measurement result in the case of ultrapure water at pH 7 using fine silicon nanoparticles without hydrofluoric acid treatment.

The dissolved hydrogen concentration in the ultrapure aqueous solution in FIG. 5 is the measured value in unground high-purity Si powder, one-stage pulverization (average crystal particle diameter 20.0 nm) and two-stage pulverization (average crystal particle diameter 10.9 nm). Show. It can be seen that as the particle size (crystallite size) decreases, the surface area of the silicon fine nanoparticles increases, the amount of hydrogen generated on the surface increases, and the dissolved hydrogen concentration increases. Moreover, the dissolved hydrogen concentration obtained with the increase in the reaction time increased, and the dissolved hydrogen concentration of about 0.4 ppm was achieved even in ultrapure water by the reaction of about 400 minutes (about 7 hours).
In order to obtain a dissolved hydrogen concentration of 1 ppm or more, the amount of silicon fine nanoparticles may be increased.

The dissolved hydrogen concentration in the aqueous solution also depends on the pH value of the aqueous solution. When the pH value is 8.0, it is clear that the dissolved hydrogen concentration in the aqueous solution is greatly increased compared to ultrapure water. Became.

FIG. 6 shows a comparison between a case where a silicon fine nanoparticle of one-step pulverization (average crystallite diameter 20.0 nm) is immersed in a hydrofluoric acid solution to remove an oxide film and a case where it is not.

When silicon fine nanoparticles treated with hydrofluoric acid were used, a dissolved hydrogen concentration exceeding 1 ppm in about 20 minutes and exceeding 1.4 ppm in 100 minutes was achieved. If it is desired to further shorten the time, the amount of silicon fine nanoparticles added may be increased.

In addition, using fine drinking tap water (pH value of about 7.1 to 7.3), silicon fine nanoparticles without hydrofluoric acid treatment of one-step pulverization (average crystallite diameter of 20.0 nm) Was mixed with tap water to prepare hydrogen water. FIG. 7 shows the measured values.

As shown in FIG. 7, it showed a marked increase over the dissolved hydrogen concentration when mixed with ultrapure water (pH value 7.0), and achieved 1 ppm in about 200 minutes.

In addition, when silicon water was prepared by mixing two-stage pulverized silicon nanoparticles (average crystallite diameter 10.9 nm) with tap water, although not shown, one-stage pulverized silicon fine nanoparticles It was found that the concentration increased by about 1.4 to 1.6 times the concentration of dissolved hydrogen when using.

It has been found that it is possible to obtain hydrogen water having a hydrogen concentration of 1 ppm or more at low cost without using hydrofluoric acid treatment using tap water. If it is desired to further shorten the time, the amount of silicon fine nanoparticles to be charged can be increased.

FIG. 8 shows the measurement results of dissolved hydrogen concentration over a long period of time when dispersed in ultrapure water (pH value 7.0) using one-step pulverized silicon fine nanoparticles. In the case of hydrofluoric acid treatment, 1 ppm was achieved in 20 hours. When hydrofluoric acid treatment was not performed, 1 ppm was achieved in 160 hours or more (about 1 week).

This is because the hydrogen generation reaction in the ultrapure water by the silicon fine nanoparticles without hydrofluoric acid treatment has a silicon oxide film on the surface, so the silicon oxide film is gradually dissolved in the ultrapure water. , Which occurs very slowly, indicating that the hydrogen concentration is expected to persist for an extended period of time.

Another embodiment (Example 2) of the present invention will be described in detail with reference to the accompanying drawings.

Silicon fine nanoparticles can be obtained by using a bead mill (IMEX Co., Ltd .: RMB type badge-type ready mill) and using high-purity silicon (Si) powder (manufactured by High-Purity Chemical Co., Ltd., particle size distribution <φ0.5 μm, purity 99.9%. , I-type silicon))) is dispersed in 250 ml of 99.5 wt% ethanol, φ: 0.5 μm zirconia beads (capacity: 300 ml) are added, and pulverization (one-step pulverization) is performed at 2500 rpm for 4 hours. Produced.

The volume distribution obtained after the one-step grinding process of the bead mill in this example and the crystal structure of the silicon fine nanoparticles are considered to give almost the same results as in Example 1.

Hereinafter, the generation of hydrogen water using silicon fine nanoparticles prepared by one-step pulverization in ethanol and treated with hydrogen peroxide, and the control of the dissolved hydrogen concentration and the amount of hydrogen generation will be described in detail.

Silicon fine nanoparticles containing beads produced by one-step grinding in ethanol as described above are SUS filters (φ: 0.5 mm beads in the case of beads of φ: 0.5 mm) attached to a bead separation container (made by Imex Corporation). 0.35mm, φ: Use a mesh of 0.06mm in the case of 0.3mm mm), and pour an ethanol solution containing fine silicon nanoparticles containing beads from the top, classify and suction filter The beads were separated to obtain an ethanol solution containing fine silicon nanoparticles. Then, ethanol was evaporated at 30 ° C. to 35 ° C. using a vacuum evaporator to obtain silicon fine nanoparticles and / or aggregates thereof (hereinafter also referred to as silicon fine nanoparticles).

The obtained silicon fine nanoparticles were put into a heat-resistant glass containing hydrogen peroxide (3.5 wt%, 100 ml) and subjected to a heat treatment (temperature: about 75 ° C.) for 30 minutes. The treated silicon fine nanoparticles are transferred to a centrifuge tube, separated into solid and liquid by centrifugation, the liquid is discarded, and ethanol (3.5% 100ml) is newly added to stir the silicon fine nanoparticles. Then, the same centrifugation was performed and the same treatment was performed. Thereafter, similarly, the same amount of ethanol was added and the same centrifugation treatment was performed to obtain silicon fine nanoparticles.
Then, natural drying was performed for about a day for a long time. In this state, it is considered that ethanol and hydrogen peroxide water are completely removed. Further, a hydrogen peroxide solution was heat-treated for 60 minutes (temperature: about 75 ° C.), and the same centrifugal separation treatment was performed to obtain silicon fine particles.

11 mg of the obtained silicon nano-particles (hydrogen peroxide solution treated for 30 minutes) was placed in a glass bottle with a capacity of 115 ml (borosilicate glass thickness of about 1 mm, Labone screw tube manufactured by ASONE) and dispersed. Add about 115 ml of a predetermined aqueous solution and sodium bicarbonate (about 20 g of Japanese Pharmacopoeia compliant to make 1.88 wt% and obtain pH of about 8.3) so that it reaches 115 ml. Then, the inner lid was closed so that air could not enter, and the cap (length 1 cm) was put on, which was completely sealed. The cap was polypropylene (thickness 2 mm), and the inner lid was made of polyethylene and polypropylene multilayer filters. By these, the permeation | transmission and leakage of the generated hydrogen were fully suppressed. The silicon fine nanoparticles were mixed uniformly in the entire aqueous solution as they were. This is thought to be because the silicon fine nanoparticles are effectively made hydrophilic by the hydrogen peroxide treatment.
In the hydrogen peroxide solution treatment for 60 minutes, hydrogen generation experiment was conducted using 5 mg of silicon fine nanoparticles.

While maintaining this state, hydrogen is gradually generated from the silicon fine nanoparticles in a sealed glass bottle at room temperature, and hydrogen having a predetermined concentration can be dissolved in the aqueous solution, as in Example 1. Since IPA and hydrofluoric acid are not used, it is worthy of special mention that silicon fine nanoparticles and hydrogen water can be obtained by a safer and safer chemical solution and process in the living body and in vivo.

A portable dissolved hydrogen concentration meter manufactured by Toa DKK was used to measure the reaction time dependence of the dissolved hydrogen concentration in the aqueous solution. In each of FIGS. 9a and 9b, silicon fine nanoparticles without hydrogen peroxide solution treatment, silicon fine nanoparticles treated with hydrogen peroxide solution for 30 minutes, and silicon fine nanoparticles treated with hydrogen peroxide solution for 60 minutes are shown. The measurement results of the dissolved hydrogen concentration using the particles are shown, and in FIG. 9b, each is shown by the amount of hydrogen generation converted per gram of Si. 9a and 9b, the vertical axis represents the dissolved hydrogen concentration, and the horizontal axis represents the reaction time (h: time). Hydrogen peroxide treatment has been shown to accelerate and increase hydrogen generation. This is because the silicon fine nanoparticles became hydrophilic and were uniformly dispersed in the aqueous solution. Treatment with hydrogen peroxide for 30 minutes gave a remarkable concentration of 400 ppb in 2 hours and nearly 1000 ppm in 4 hours. It reached 2000 ppm in 24 hours. In the 60-minute treatment, the hydrogen generation amount was reduced from 30 minutes. It is considered that the surface oxide film of silicon fine nanoparticles was thicker than 30 minutes by the 60-minute treatment, and the amount of hydrogen generation was suppressed. Although not shown in the figure, the same experiment was performed with a 15-minute treatment, but almost the same experimental result as that obtained for 30 minutes was obtained. The treatment for 1 minute to 2 minutes did not produce hydrogen as effectively as no treatment. Therefore, the hydrogen peroxide treatment time is suitably 5 minutes to 30 minutes. Incorporation of sodium hydrogen carbonate is usually comparable to the pH state of the small intestine of a living body, and effective hydrogen generation occurs in the body. FIG. 9b shows the hydrogen generation amount converted per gram of Si. The vertical axis represents the amount of hydrogen generated per gram of Si (ml), and the horizontal axis represents the reaction time (h: time). A very effective hydrogen generation amount (40 ml) is continuously obtained in 2 hours or longer after 30 minutes of treatment.
From this experimental result, even if it is used for a living body without using IPA or hydrofluoric acid, safer and more reliable silicon fine nanoparticles can be produced, and hydrogen can be safely generated in the living body. Furthermore,
Using these silicon fine nanoparticles, it is possible to produce a biogenic hydrogen generating material by adding it to a known additive or food.
In order to obtain a dissolved hydrogen concentration of 1 ppm or more within a reaction time of several hours, the amount of silicon fine nanoparticles may be increased.

In addition to high-purity silicon (Si) powder as a silicon fine particle, hydrogen water can also be generated by using silicon chips generated from cutting of a solar cell grade silicon substrate or semiconductor grade polishing scraps. . Further, not only i-type but also n-type and p-type can be used.

The present invention can produce fine silicon nanoparticles having biosafety, and can be effectively utilized to develop hydrogen water excellent in safety, practicality and economics and its manufacturing technology, It can be used for hydrogen generating materials (agents) containing fine silicon nanoparticles for health and medical use, health and medical foods such as washing water and health drinking water, and product fields.

Claims (11)

Silicon fine particles or silicon fine nanoparticles obtained by further pulverizing silicon fine particles and / or pseudo-aggregates thereof are brought into contact with and / or dispersed in water to generate hydrogen, and the hydrogen is directly dissolved in the water. Hydrogen water characterized by being sealed. Silicon fine particles or silicon fine nanoparticles obtained by further pulverizing silicon fine particles and / or pseudo-aggregates thereof are brought into contact with and / or dispersed in tap water to generate hydrogen, and the hydrogen is dissolved in the tap water and sealed in a container. Hydrogen water characterized by Silicon fine particles or silicon fine nanoparticles obtained by further pulverizing silicon fine particles, silicon fine particles obtained by further pulverizing silicon fine particles or silicon fine particles and / or pseudo-aggregates thereof are contacted or dispersed in water or an aqueous solution. And a method for producing hydrogen water, the method comprising directly generating hydrogen water. The silicon fine particles or the silicon fine nanoparticles obtained by further pulverizing the silicon fine particles or the silicon fine particles and / or the pseudo-aggregates thereof are further provided with a step of removing the surface silicon oxide film by contacting with hydrofluoric acid or ammonium fluoride aqueous solution. Item 3. A method for producing hydrogen water according to Item 2. A pulverization step of forming silicon fine particles or silicon fine nanoparticles obtained by further pulverizing silicon fine particles, silicon fine particles obtained by further pulverizing the silicon fine particles or silicon fine particles and / or pseudo-aggregates thereof with neutral water of pH 7 or A method for producing hydrogen water, comprising the step of contacting and / or dispersing in an aqueous solution having a pH of 8 to 9 to generate hydrogen to dissolve the hydrogen in the neutral water or the aqueous solution. Hydrogen comprising a step of dissolving hydrogen in the tap water by generating and generating silicon by contacting and / or dispersing silicon fine nanoparticles and / or pseudo-aggregates thereof finely pulverized with silicon fine particles or silicon fine particles. Water production method. Contact and / or dispersion of silicon fine particles or fine silicon nanoparticles obtained by further pulverizing silicon fine particles and / or pseudo-aggregates thereof with neutral water of pH 7, aqueous solution of pH 8-9 or tap water of pH 7.1-7.5 Hydrogen water is generated by dissolving hydrogen in the neutral water, the aqueous solution, or tap water. The crystallite size distribution by XRD of silicon fine nanoparticles and / or their pseudo-aggregates is 100 nm.
The hydrogen water according to claim 1, 2, or 7, preferably 50 nm or less. Silicon fine particles or silicon fine nanoparticles obtained by further pulverizing silicon fine particles, and silicon fine nanoparticles obtained by further pulverizing the silicon fine particles or silicon fine particles and / or pseudo-aggregates thereof are contacted in water or an aqueous solution. Alternatively, a hydrogen generation unit that generates hydrogen by dispersing, and an apparatus for producing hydrogen water in which the hydrogen is directly dissolved in the water and sealed in a container. Silicon fine particles or silicon fine particles are further pulverized in ethanol, and hydrogen fine water-treated silicon fine nanoparticles and / or pseudo-aggregates thereof are brought into contact with and / or dispersed in water to generate hydrogen, and the hydrogen is removed. Hydrogen water characterized by being dissolved directly in the water and sealed in a container. Silicon fine particles or silicon fine particles obtained by further pulverizing silicon fine particles in ethanol and treating with hydrogen peroxide water, and / or aggregates thereof, and a biogenic hydrogen generating material containing them