TWI803821B - Method, photocatalyst complex and energy power module system for generating hydrogen - Google Patents

Abstract

The present invention involves a method for preparing hydrogen. The method includes the following steps. A hydrogen-generation mixed solution is provided and a light source irradiates the hydrogen-generation mixed solution to generate hydrogen. The hydrogen-generation mixed solution includes a solvent, a photocatalyst complex, an organic acid reactant, a P-ligand and an electron provider. The photocatalyst complex comprises a magnetic metal organic framework and a nitrogen-substituted derivative of alkyldithiolate ruthenium complex fixed on the magnetic metal organic framework.

Description

Hydrogen preparation method, photocatalyst compound and power module system

The invention relates to a method for preparing hydrogen, a power module system and a photocatalyst compound, especially a recyclable photocatalyst compound, a method for preparing hydrogen using the same, and a power module system.

As a fuel energy source, hydrogen has its advantages. According to the analysis, the combustion calorific value of hydrogen is high, and the heat per 1,000 grams of hydrogen combustion is about three times that of gasoline, and the product of hydrogen combustion is only water, which will not pollute the environment. Hydrogen as a fuel energy source does not cause acid rain and smog, nor does it produce any chemicals sufficient to cause greenhouse effects like burning oil and coal. The characteristics of high energy and zero pollution make the research of hydrogen energy the current development direction of various countries, and it is expected that hydrogen energy can be used as an alternative energy source in the future.

At present, the more common methods for preparing hydrogen are as follows. One is natural gas recombination, which is divided into partial oxidation of methane when it is burned in air and recombination of steam. However, this method requires additional energy for heating to increase the temperature, and a high-pressure environment is required. The second is to electrolyze water to generate hydrogen and oxygen. However, this method requires additional power for the electrolysis reaction and the reaction rate is slow, so the efficiency is not good. The third is gasification The method is to use gasification to convert coal or biomass into the final product of syngas, and then generate hydrogen. However, this method requires additional energy to increase the pressure or temperature. The fourth is renewable liquid recombination, that is, after converting biomass into bio-oil or ethanol, and then forming the final product of syngas for hydrogen production reaction. However, this method is cumbersome and requires additional energy to increase pressure or temperature. The fifth is nuclear high-temperature electrolysis of water, which uses the heat energy generated by nuclear energy reactions in the electrolysis of water. However, the nuclear waste generated in this method has great pollution to the environment and the remaining pollution derived from nuclear waste is difficult to remove. The sixth is hydrogen production by algae or microorganisms, which use, for example, green algae or other microorganisms to carry out water splitting reactions, or use their by-products to generate hydrogen, or use extraction methods to directly extract hydrogen from the contained biomass, but This method requires a considerable land area to cultivate microorganisms or algae, and the overall hydrogen production efficiency is not good. The seventh is photoelectrochemical hydrogen production, which places special semiconductor materials under sunlight and uses water cracking to produce hydrogen. However, the semiconductor material preparation process of this method will inevitably cause environmental pollution.

How to efficiently obtain cheap hydrogen is a very important issue. Only by finding an economical hydrogen production method can hydrogen energy become a new alternative energy source. At present, a major research axis of hydrogen production method is "solar hydrogen production". of hydrogen into a source of electricity. However, the current solar hydrogen production technology is still in the development stage, and there are still many problems to be solved, so the hydrogen production technology is still the goal of the academic community.

In view of the deficiencies in the known technology, the applicant of this case finally conceived this case after careful experimentation and research, and with a persistent spirit, which can overcome the deficiencies of the previous technology. The following is a brief description of this case.

This case can provide a photocatalyst compound for preparing hydrogen, a method and a power module system for preparing hydrogen using it. The photocatalyst composite formed by immobilizing the ruthenium-based catalyst on the magnetic metal-organic framework can be conveniently recovered using magnetism, and the recovered photocatalyst composite does not affect the hydrogen production reaction, thereby reducing the cost of the ruthenium-based catalyst.

One of the purposes of this case is to provide a hydrogen production method, including the following steps. A hydrogen-producing mixed solution is provided and a light source is irradiated on the hydrogen-producing mixed solution to generate hydrogen gas. The mixed solution for hydrogen production includes solvent, photocatalyst compound, organic acid reactant, P-ligand and electron provider. The photocatalyst compound comprises a magnetic metal organic framework and a ruthenium azadisulfide complex fixed on the magnetic metal organic framework.

Another object of the present case is to provide a photocatalyst composite for producing hydrogen, which includes a magnetic metal organic framework and a ruthenium azadisulfide complex fixed on the magnetic metal organic framework. In view of the shortcomings of existing photocatalysts used for hydrogen production, the photocatalyst composite provided in this case has the characteristics of strong photosensitivity, high light utilization rate, high catalytic activity, high catalytic efficiency, high stability, and easy recycling and reuse.

Another object of the present case is to provide a hydrogen production system, which includes a reaction tank and a light source system. The reaction tank is configured to accommodate a hydrogen-producing mixed solution, which includes a solvent, a photocatalyst compound, an organic acid reactant, a P-ligand, and an electron provider, wherein the photocatalyst compound includes a magnetic metal organic framework and a ruthenium azadisulfide complex anchored to the magnetic metal organic framework. The light source system is configured so that the light source irradiates the hydrogen-producing mixed solution to generate hydrogen gas.

In some embodiments, a dual-axis heliostat is used as the light source system The system can automatically and continuously focus sunlight on the hydrogen production mixed solution in the reaction tank, thereby improving the convenience of hydrogen production and saving a lot of manpower.

In some embodiments, a light-emitting device including a transparent insulating element and a light-emitting unit (such as a low-wattage bulb) is used as a light source system to improve the convenience of hydrogen production and to produce hydrogen in an environment with no or insufficient external light source.

4: Hydrogen preparation system

40:Light source system

41: formic acid storage tank

42: Ruthenium azadisulfide complex storage tank

43: Tri(o-tolyl)phosphine storage tank

44: Triethylamine storage tank

45: Pumping equipment

46: Reaction tank

461: hydrogen production mixed solution

47: Air valve equipment

48: Gas separation equipment

49: Hydrogen storage tank

5: Two-axis sun tracking device

51: base

52: Concentrating lens

53: Angle adjustment lever

54: Sensor

71: Transparent insulating element

72: Lighting unit

The above objects and advantages of the present invention will become more immediately apparent to those of ordinary skill in the art after referring to the following detailed description and accompanying drawings.

FIG. 1 shows a schematic diagram of a scheme for preparing a photocatalyst composite using a ruthenium azadisulfide complex.

Fig. 2 shows a flowchart of a hydrogen production method according to an embodiment of the present invention.

Fig. 3 shows the hydrogen production of Example 1, Comparative Examples 1-4 and Comparative Examples in Table 1 over time.

Fig. 4 shows a schematic diagram of a hydrogen production power module system according to an embodiment of the present invention.

Fig. 5 shows a light source system according to an embodiment of the present invention.

Fig. 6 shows the hydrogen production amount of hydrogen production cycle in Example 2 of the present invention.

Fig. 7 shows a light source system according to another embodiment of the present invention.

8A and 8B show schematic diagrams of the application of the hydrogen production system according to an embodiment of the present invention.

The invention proposed in this case can be fully understood by the description of the following examples, so that those with ordinary knowledge in the technical field can complete it. However, the implementation of this case can not be limited to its implementation form by the following examples. Those skilled in the art can still deduce other embodiments according to the spirit of the disclosed embodiments, and these embodiments all belong to the scope of the present invention.

Unless otherwise limited or stated in a particular example, the following definitions apply to terms used throughout this specification.

The term "Metal Organic Framework (MOF)" used herein refers to an organic-inorganic hybrid material with intramolecular pores formed by the self-assembly of organic ligands and inorganic metal ions or clusters through coordination bonds. The organic ligands in the MOF are the linkers of the MOF, and the metal ions or clusters are the nodes of the MOF. The two are mainly self-assembled into a coordination compound with a periodic structure.

The term "magnetic MOF" used in this article is a combination of MOF materials and magnetic materials (especially magnetic particle materials), which not only retains the structure and properties of MOF materials, but also adds the magnetism of magnetic particle materials. Magnetic MOF can be made by at least one of the following methods: embedding magnetic granular materials on the surface of MOF; covering and superimposed growth of MOF layers on the surface of functionalized magnetic granular materials; growing MOF materials around magnetic particles and surrounding them Embedded; polymerize MOF and magnetic particle materials by physical or chemical action.

The term "photocatalyst composite" used herein refers to "magnetic MOF composite", which means a composite formed by immobilizing a photocatalyst on a magnetic MOF. have Features and Benefits.

The ruthenium azadisulfide complex of the present invention has the general formula [(Ru) _X (CO) _Y (μ-SCH ₂ CH(NHZ) CH ₂ S], wherein X is an integer from 1 to 6, and Y is an integer from 1 to is an integer of 9, and Z can be CO ₂ (C(CH ₃ ) ₃ ) or CO ₂ CH ₃ or other substituted functional groups.

The above-mentioned ruthenium azadisulfide complexes may include at least one of the complexes of the following chemical formulas, for example, the ruthenium azadisulfide complexes include other chemical formulas (1) to (3) other than chemical formula (2) complexes, or only complexes of formula (1). In conclusion, the present invention is not limited by the types and combinations of ruthenium azadisulfide complexes.

[Ru ₃ (CO) ₉ (μ-SCH ₂ CH(NHCO ₂ (C(CH ₃ ) ₃ ))CH ₂ S)] Chemical formula (1)

[Ru ₂ (CO) ₆ (μ-SCH ₂ CH(NHCO ₂ (C(CH ₃ ) ₃ ))CH ₂ S)] Chemical formula (2)

[Ru ₂ (CO) ₅ (μ-SCH ₂ CH(NHCO ₂ (C(CH ₃ ) ₃ ))CH ₂ S)] Chemical formula (3)

[Ru ₃ (CO) ₉ (μ-SCH ₂ CH(NHCO ₂ CH ₃ ))CH ₂ S)] Chemical formula (4)

Referring to FIG. 1 , it shows a scheme for preparing a photocatalyst composite using a ruthenium azadisulfide complex. This scheme prepares magnetic MOFs through a simple strategy and immobilizes photocatalysts on the magnetic MOFs. In some preferred embodiments, the magnetic MOF is a magnetic phosphorus metal organic framework PPh ₂ -MOF, and the photocatalyst is a biomimetic ruthenium azadisulfide complex. The ruthenium azadisulfide complex [Ru ₃ (Boc-NS ₂ C ₃ H ₈ ) (CO) ₉ ] (hereinafter abbreviated as Ru ₃ S ₂ Boc) is used as an example of a photocatalyst, but the method in this case does not Not limited to this. First, under an argon atmosphere at 70°C, in 40mL of 100mg FeCl ₃ . 6H ₂ O ethanol solution, add 100mg of Fe ₃ O ₄ and 100mg of 2-(diphenylphosphine) terephthalic acid (PPh ₂ -bdc) to synthesize 80mg of Fe ₃ O ₄ @LSK-15(Fe ) (the schematic diagram of its three-dimensional structure is shown in Figure 1). Next, 10 mg of Ru ₃ S ₂ Boc, 120.4 mg of Fe ₃ O ₄ @LSK-15(Fe) were suspended in 1.5 mL of dichloromethane (DCM) solution under an argon atmosphere. The suspension was left under static condition at room temperature for 24 hours, _the solid was isolated via decantation, washed with DCM, and finally dried under reduced pressure at room temperature to obtain ₁₀₀ mg of photocatalyst composite _Fe3O4 @ _Ru3S2 Boc-LSK-15(Fe) (hereinafter abbreviated as HJC101, its schematic diagram is shown in Figure 1). HJC101 is a new material formed by immobilizing photocatalyst on magnetic MOF, also known as "photocatalyst composite" or "magnetic MOF composite". The Ru ₃ S ₂ Boc in the scheme of FIG. 1 can also be replaced by other ruthenium azadisulfide complexes mentioned above. The method of preparing the magnetic MOF composite in this example is a method with a simple preparation process and is easy to prepare a large amount of magnetic MOF composites, and the obtained magnetic MOF composite materials are uniform in size and strong in magnetism. On the other hand, the magnetic MOF composite of this example avoids the characteristics of easy aggregation of magnetic nanoparticles in the past due to the magnetism of Fe ₃ O ₄ , and can be easily separated from reactants and products for recycling and reuse.

Next, it is detected and analyzed by infrared spectroscopy (ATR-FT-IR), and the absorption wavenumber is 500cm ^-1 to 2500cm ^-1 . Put the HJC101 magnetic sample with a mass of 2 mg, Ru ₃ S ₂ Boc, LSK-15(Fe)(C-3) and its Fe ₃ O ₄ precursor on the detection mirror of SHIMADZU IRTracer-100, and measure the background with air, And scan the product 64 times. Comparing the obtained FTIR spectra can confirm that the Ru ₃ S ₂ Boc catalyst in HJC101 has indeed been immobilized on the MOF. In addition, observing the HJC101 magnetic sample by scanning electron microscopy (SEM), it can be seen that its shape is an octahedral structure (as shown in the schematic diagram of the structure in Figure 1), and each side is about 256nm. Using a high-resolution field emission transmission electron microscope to further analyze the morphology of the HJC101 magnetic sample, two-dimensional lattice fringes can be clearly observed, and the lattice spacing is about 0.263nm. The atomic percentages of C, O, N, P, S, Fe and Ru in HJC101 were 2.77%, 33.40%, 1.86%, 1.45%, 0.65%, 58.90% and 0.14%, respectively. Since the photocatalyst composite material disclosed in this embodiment has the above-mentioned structural characteristics, it can achieve good catalytic performance while having the advantage of recyclability (that is, the characteristics of recycling and reuse).

In some embodiments, there is provided a photocatalyst compound for producing hydrogen, comprising a magnetic MOF and a ruthenium azadisulfide complex immobilized on the magnetic MOF, the magnetic MOF has an octahedral structure, and the octahedral The bulk structure approaches the regular octahedral structure. In some embodiments, the photocatalyst composite is in the form of nanoparticles. In some embodiments, the nanoparticles can have an average diameter of less than about 270 nm. In some embodiments, the average diameter is between about 20 nm and about 270 nm. In some embodiments, the photocatalyst composite has a core-shell structure comprising a core layer and a shell layer, wherein the core layer comprises a nanoparticle structure of ferric oxide, the shell layer comprises an octahedral MOF framework, and the light A catalyst system is attached to the nanoparticle structure of the Fe3O4.

Hydrogen production method

Please refer to FIG. 2 , which is a flowchart of a hydrogen production method according to an embodiment of the present invention. First, in step S21, a hydrogen production mixed solution including a solvent, a photocatalyst compound, an organic acid reactant, a P-ligand, and an electron provider is provided. The photocatalyst composite includes a magnetic MOF and a photocatalyst (ruthenium azadisulfide complex) immobilized on the magnetic MOF, which can be prepared using the scheme shown in Figure 1, but is not limited thereto.

As an example, the solvent is dimethylformamide (DMF), the organic acid reactant is formic acid (FA), the P-part is tri-o-tolylphosphine (tri-o-tolylphosphine, (P( o -tol) ₃ )), the electron donor is triethylamine (TEA), and the magnetic MOF is a magnetic MOF comprising Fe ₃ O ₄ nanoparticles. In some preferred embodiments, the electron provider comprises TEA and ascorbic acid (AA).

Thereafter, in step S22, the light source is irradiated with the hydrogen-producing mixed solution to generate hydrogen gas. The light source used in step S22 may be sunlight or other visible light sources with a wavelength greater than 420 nm (eg, visible light sources with a wavelength close to ultraviolet rays). When the light source is sunlight, in some embodiments, a light source system configured to irradiate the hydrogen-producing mixed solution with sunlight can be used, preferably the light source system concentrates sunlight on the hydrogen-producing mixed solution, so as to Accelerates the production of hydrogen gas. For example, the light source system may include a solar tracking system (such as a single-axis or dual-axis tracking system), a condenser lens (such as a Nefer lens) or a combination thereof. According to tests, the efficiency of hydrogen production in step S22 is not good in an environment with a temperature lower than 100°C. Step S22 is preferably carried out in an environment of 125-145°C, and most preferably carried out in an environment of about 145°C. Finally, in step S23, any method known in the art may be used to collect the hydrogen generated in step S22 for subsequent processing or use.

In one example, a mixed solution for hydrogen production was prepared by adding 10 mg of photocatalyst complex and 7.74 μmol of P( o -tol) ₃ to 1 mL of DMF and 4 mL of FA and TEA mixture. In addition, the mixed solution for hydrogen production also contains 40 mg of ascorbic acid (AA). AA may be added in an amount between about 40 mg to 160 mg. The molar ratio of FA:TEA in 4 mL of FA and TEA mixture was 9:1. Since the magnetic MOF composite contains Fe ₃ O ₄ , it will be oxidized in an alkaline environment and cause magnetic loss. Therefore, when the molar ratio of FA:TEA in 4 mL of FA and TEA mixture is 5:2, the magnetic MOF The composite cannot maintain good magnetic properties, which will lead to the inability to effectively recover the magnetic MOF composite from the hydrogen production mixed solution after hydrogen production. Therefore, the molar ratio of FA and TEA is very important for the efficient recovery of magnetic MOF composites. According to experiments, the molar ratio of FA:TEA in 4 mL of FA and TEA mixture is preferably between about 4:1 and 19:1, preferably between about 5:1 and 14:1, and more preferably about 7:1 to 11:1, the optimum is about 9:1, within these ranges the purpose of efficient recovery of magnetic MOF composites can be achieved.

Table 1 shows the composition of the 5 mL hydrogen production mixed solution of Example 1, Comparative Examples 1-4 and Comparative Example. In the comparative example in Table 1, no magnetic MOF composite was added, but only magnetic MOF was added, in other words, there was no Ru-based catalyst in the comparative example.

Using the hydrogen production mixed solution shown in Table 1, a 500W xenon (Xe) lamp (which can emit light with a light wavelength of 250nm to 1800nm) was used as a light source to produce hydrogen in an environment of 145° C. The results are shown in FIG. 3 . Please refer to FIG. 3 , which shows the hydrogen production of Example 1, Comparative Examples 1-4 and Comparative Examples in Table 1 over time. From the comparative example in Figure 3, it can be seen that the hydrogen production mixed solution with only magnetic MOF but no embedded catalyst cannot produce hydrogen; in addition, the experimental results of comparative examples 1 to 4 prove that it cannot or is difficult to produce hydrogen effectively. Therefore, it can be deduced that for the mixed solution of hydrogen production, ruthenium azadisulfide complex, P-ligand and ascorbic acid are all necessary for efficient hydrogen generation. In this organic phase system, a magnetic MOF composite containing a catalyst reacts with P(o-tol) ₃ , and ascorbic acid has two functions: one is as an antioxidant that can prevent the oxidation of the catalyst in an alkaline environment, and the other is is to act as electron donor and catalyze the production of hydrogen gas.

Returning to the process flow of the method in Figure 2, after generating hydrogen in step S22, step S24 can also be optionally performed to magnetically recover the photocatalyst compound in the hydrogen production mixed solution, whereby the method in Figure 2 can be recycled back to step S21 to Hydrogen is produced continuously. For example, in step S24, the magnetic MOF composite in the hydrogen production mixed solution is recovered by the magnetic force of the magnet.

Please refer to FIG. 4 , which shows a schematic diagram of a hydrogen production system according to an embodiment of the present invention. The hydrogen production system 4 includes a formic acid storage tank 41, a ruthenium azadisulfide complex storage tank 42, a tri(o-tolyl)phosphine storage tank 43, a triethylamine storage tank 44, a pumping device 45, a reaction tank 46, Gas valve equipment 47, gas separation equipment 48 and hydrogen storage tank 49. Formic acid storage tank 41, ruthenium azadisulfide complex storage tank 42, tri(o-tolyl)phosphine storage tank 43 and triethylamine storage tank 44 are used to store formic acid, ruthenium azadisulfide complex, Tris(o-tolyl)phosphine and triethylamine.

The pumping device 45 has a plurality of pumping units to store the formic acid storage tank 41, the ruthenium azadisulfide complex storage tank 42, the tri(o-tolyl)phosphine storage tank 43 and the triethylamine storage tank 44 respectively. The formic acid, ruthenium azadisulfide complex, tri(o-tolyl)phosphine and triethylamine are sent to the reaction tank 46. The reaction tank 46 is configured to accommodate the hydrogen production mixed solution 461 . In some embodiments, the solute of the hydrogen-producing mixed solution 461 includes formic acid, ruthenium azadisulfide complex, ascorbic acid, tri(o-tolyl)phosphine, and triethylamine, and the solvent of the hydrogen-producing mixed solution 461 is Dimethylformamide. The light source system 40 is arranged near, above or in the reaction tank 46, so that the light source irradiates the hydrogen-producing mixed solution 461 to generate hydrogen gas. Preferably, the hydrogen production system 4 can also include dimethylformyl An amine storage tank (not shown in the figure), and the pumping device 45 can send the dimethylformamide it stores to the reaction tank 46.

The environment in the reaction tank 46 or the environment where the reaction tank 46 is located can be an environment of normal temperature and pressure, and there is no need to set up pressure control equipment and heating equipment for pressurization and heating. The formic acid in the hydrogen production mixed solution 461 in the reaction tank 46 will start to catalyze the decomposition of the formic acid into hydrogen and carbon dioxide when the ruthenium azadisulfide complex is irradiated by light from the light source system 40 . The gas valve device 47 can discharge the generated hydrogen and carbon dioxide from the reaction tank 46 to the gas separation device 48 through the control of the valve. The gas separation device 48 can physically or chemically separate the hydrogen from the carbon dioxide, and the separated hydrogen can be sent to the hydrogen storage tank 49 for storage. In some embodiments, the gas separation device 48 is connected to the rear end of the condensing device of the reaction tank, and can separate the hydrogen from the organic gas, alkali vapor and water to obtain the produced hydrogen. The hydrogen in the hydrogen storage tank 49 can be extracted by various application equipment (not shown in the figure) and used as energy fuel. In some embodiments, the gas separation device 48 may include a hydrogen filter device (not shown in the figure) to remove impurities or mixed gases (such as organic gases, carbon dioxide, etc.). In some embodiments, the hydrogen production system 4 further includes a recovery device (not shown) connected to the reaction tank 46 to recover the photocatalyst compound from the hydrogen production mixed solution 461 .

Please refer to FIG. 5 , which shows a light source system according to an embodiment of the present invention, which can be used as the light source in step S22 in FIG. 2 . The light source system includes a dual-axis solar tracking device 5 that can automatically move or rotate following the sunlight irradiation angle. The dual-axis solar tracking device 5 includes a base 51 configured to carry the reaction tank 46 , a condenser lens 52 , and a plurality of angle adjustment rods 53 connected between the base 51 and the condenser lens 52 . The length and number of the angle adjustment rods 53 vary according to the size and shape of the condenser lens 52 . Spotlight The lens 52 (which is preferably a Nefer lens, but not limited thereto) is configured to focus sunlight on the hydrogen-producing mixed solution in the reaction tank 46 . The dual-axis solar tracking device 5 also includes a sensor 54 configured to obtain a position signal of the sun relative to the condenser lens, a power unit (not shown) configured to drive the plurality of angle adjustment rods 53 and coupled to the Sensors and the controller of the power unit (not shown). The controller is configured to make the power unit drive a plurality of angle adjustment rods 53 according to the position signal, through which the angle of the condenser lens 52 is controlled through the plurality of angle adjustment rods 53, so as to guide sunlight to pass through the condenser lens 52 and focus The mixed solution for hydrogen production in the reaction tank 46 generates hydrogen gas and sends it to the hydrogen storage tank 49 for storage. Accordingly, the controller can control the condensing lens 52 to automatically face the sun at any time, so as to be fully irradiated by sunlight.

In some embodiments, the sensor 54 can sense the angle of the condenser lens 52 (including the azimuth angle and the altitude angle, the azimuth angle is the angle of swinging from the south or the north to the east or west, and the altitude angle is the angle from the horizontal plane upward swing angle), and send a signal about the angle of the condenser lens 52 to the controller. Use the controller to compare the angle information of the condenser lens 52 with the known sun angle information at the current time, and when the two are different, the power unit drives the angle adjustment lever 53 and the condenser lens 52 to rotate to the azimuth and altitude at the present time Angle, when both are the same, then make the power unit stop driving the rotation of the angle adjustment lever 53 and the condenser lens 52. Accordingly, the power unit can be controlled by the controller according to the known sunlight irradiation angle, so as to continuously drive the condensing lens 52 to swing to the position facing the sun.

In some embodiments, the sensor 54 is a light sensor. The position and angle of the sun (including azimuth and altitude) can be detected by the light sensor, and the signal about the position and angle of the sun can be sent to the controller. Thereafter, the controller will make the power unit drive the angle adjustment lever 53 and the condenser lens 52 to rotate according to the signal of the sun position and angle. Move to a position facing the sun.

In some embodiments, the angle adjusting rod 53 can be adjusted manually or the rotation angle can be automatically controlled by the controller according to the known sunshine hours and sun angles. Optionally, the dual-axis tracking device 5 may also include a wheel set connected to the base 51, the power unit and the controller, so that it can drive the dual-axis tracking device 5 to move under the control of the controller.

According to the dual-axis solar tracking device in the embodiment of the present invention, it can automatically control the condenser lens 52 to automatically face the sun at any time, so as to achieve the purpose of absorbing solar energy with the highest efficiency. In other words, compared with the manual Fresnel solar tracking system that needs to constantly adjust the focusing focal length according to the sun’s moving angle, the dual-axis solar tracking device according to the embodiment of the present invention can improve the convenience of the overall hydrogen production system, and thus reduce a lot of Labor costs.

Example 2 is an example of using the same hydrogen production mixed solution as in Example 1 and using a 500W xenon (Xe) lamp as a light source to produce hydrogen in an environment of 145°C. That is, step S22 is performed under photocatalysis at 145° C., and then the photocatalyst composite is recovered by magnetic force for the first time in step S24 , and then the photocatalyst composite recovered for the first time is used in step S21 . Steps S21, S22 and S24 shown in FIG. 2 are repeatedly executed to recover the secondary photocatalyst composite in total, and the amount of hydrogen produced is shown in FIG. 6 . As can be seen from Figure 6, the photocatalyst composite (C-2) recovered for the first time and the photocatalyst composite (C-3) recovered for the second time can reach the same level as the 10mg photocatalyst composite (C-1) used for the first time. ) similar hydrogen production.

The various conditions of Example 3 are the same as those of Example 2, except that the photocatalyst composite is recovered three times in total. In terms of turnover frequency (TOF) of the catalyst, the 10mg photocatalyst composite used for the first time can reach 1199h ^-1 , but the TOF of the photocatalyst composite recovered for the third time drops to 293h ^-1 . After multiple recovery times (especially when the number of recovery reaches more than the third time), the hydrogen production efficiency of the catalyst will gradually decrease as the number of times the catalyst is used increases. According to experiments, when using the photocatalyst compound recovered for the third time, increasing the amount of AA from 40mg to 80mg and 160mg respectively can increase TOF to 473h ^-1 and 698h ^-1 respectively. It can be seen that increasing the amount of electron donors in the hydrogen production mixed solution can improve the TOF of the catalyst.

Example 4 is an example of using the same hydrogen production mixed solution as in Example 1 and using the light source system in FIG. 5 (temperature is about 153° C.) to produce hydrogen in circulation. Steps S21, S22 and S24 shown in FIG. 2 are repeatedly executed, and the photocatalyst composite is recovered three times in total. As shown in Table 4, the 10 mg photocatalyst composite used for the first time can reach a TOF of 49108h ^-1 , and as the number of recycling increases, the TOF of the recycled photocatalyst composite decreases gradually, but the photocatalyst composite recycled for the third time TOF still has 16369h ^-1 .

From Examples 2 to 4, it can be seen that compared with the case of not recovering the photocatalyst composite, the effective recovery of the photocatalyst composite by using magnetism can reduce the cost to a quarter.

Please refer to FIG. 7 , which shows a light source system according to another embodiment of the present invention, which can be used as the light source in step S22 in FIG. 2 . The light source system includes a light emitting device, and the light emitting device includes a transparent insulating element 71 and a light emitting unit 72 disposed in the transparent insulating element 71 . The transparent insulating element 71 is made of a material that transmits light and can isolate the mixed solution of hydrogen production, such as glass. The light-emitting device is placed in the reaction tank 46, so that the light-emitting unit 72 in the transparent insulating element 71 can emit light to pass through the transparent insulating element 71 and irradiate the hydrogen-producing mixed solution 461 in the reaction tank 46 to generate hydrogen gas. Preferably, the light-emitting unit 72 is disposed in the hydrogen-producing mixed solution 461 via the transparent insulating element 71 . Through the transparent insulating element 71 , the light-emitting unit 72 can irradiate the hydrogen-producing mixed solution 461 with high-intensity light at close range, but avoid direct contact with the hydrogen-producing mixed solution 461 . In a preferred embodiment, the light emitting unit 72 not only emits high intensity light, but also generates enough heat to use the catalyst without using a heating system. In a preferred embodiment, the light emitting unit 72 is a low wattage light emitting unit between 30 and 100 watts. In a preferred embodiment, the light emitting unit 72 is a low power halogen lamp. In a preferred embodiment, the reaction tank 46 is made of a transparent material, and a silver mirror is used on its outer surface to reflect the light emitted by the light emitting unit 72 completely. Injected into the mixed solution of hydrogen production. Through the light-emitting device, the light source system can not only operate when the sunlight is insufficient (such as cloudy, rainy, nighttime, or in a dark environment), but also this type of light source system is easy to move and carry, so the manufacture of this type of light source system Hydrogen systems are very beneficial for transportation vehicles (such as cars, bicycles, etc.) that use hydrogen fuel cells.

Please refer to FIG. 8A and FIG. 8B , which illustrate a schematic diagram of an application manner of a hydrogen production system according to an embodiment of the present invention. The hydrogen production system of this embodiment uses two kinds of light source systems at the same time, for example, two light source systems similar in concept to the two light source systems shown in Fig. 5 and Fig. The battery has enough power to power the car under all conditions. Specifically, when using the hydrogen production system of this embodiment, an automatic solar tracking system can be used to provide a light source for hydrogen production during the day when the sun is sufficient (as shown in Figure 8A, the automatic tracking system is not shown for clarity. All the components of the solar system); and in an environment with insufficient sunlight or darkness, for example, the light source system shown in FIG. 7 can be used for hydrogen production (as shown in FIG. 8B ). The electric energy generated by the hydrogen production during the day can also be used by the light emitting unit 72 in the light source system shown in FIG. 7 , so as to emit light in an environment with insufficient sunlight or darkness. In response to different application environments (such as automobiles), those skilled in the art can make adaptive adjustments on the basis of the two light source systems shown in FIG. 5 and FIG. 7 to facilitate use in the application environment. For example, if it is to be applied to an automobile, the transparent insulating element 71 and the reaction tank 46 used in the light source system shown in FIG. The transparent insulating element 71 is separated, or the hydrogen-producing mixed solution 461 overflows the reaction tank 46 . In addition, when applied to automobiles, in some embodiments, the hydrogen produced by the hydrogen-producing mixed solution of the present invention is further purified through a conventional air filtration system, so as to avoid direct use and damage to fuel cells. The aforementioned air filtration system will be high Warm alkali vapor, organic gas, carbon dioxide and other harmful gases are removed to avoid damage to the fuel cell or harm the environment during use.

The present invention is really an impossible innovative invention with great industrial value, and the application is filed according to the law. In addition, the present invention can be modified in any way by those skilled in the art without departing from the scope of protection as claimed in the appended claims.

Claims (11)

A hydrogen production method, comprising the following steps: providing a hydrogen production mixed solution, the hydrogen production mixed solution contains a solvent, a photocatalyst complex, an organic acid reactant, an ascorbic acid, a P-ligand and an electron supply and making a light source irradiate the hydrogen-producing mixed solution to generate a hydrogen gas, wherein the photocatalyst composite includes: a magnetic metal organic framework; and a ruthenium azadisulfide complex fixed on the magnetic metal organic framework . The hydrogen production method as described in claim item 1, wherein: the solvent is dimethylformamide, the organic acid reactant is formic acid, and the P-part is three (o-tolylphosphine) ), the electron donors are triethylamine and an ascorbic acid, and the magnetic metal organic framework comprises Fe ₃ O ₄ nanoparticles; and the ruthenium azadisulfide complex is [(Ru) _X (CO) _Y (μ-SCH ₂ CH(NHZ)CH ₂ S], wherein X is an integer from 1 to 6, Y is an integer from 1 to 9, and Z is CO ₂ (C(CH ₃ ) ₃ ) or CO ₂ CH ₃ . The hydrogen production method according to claim 2, wherein in the hydrogen production mixed solution, the molar ratio of the formic acid to the triethylamine is in the range of 4:1 to 19:1. The method for producing hydrogen gas according to claim 1, wherein the step of irradiating the hydrogen-producing mixed solution with the light source includes: focusing a sunlight to the hydrogen-producing mixed solution through a biaxial solar tracking device. The hydrogen production method as described in Claim 1, wherein the step of irradiating the hydrogen production mixed solution with the light source comprises: activating a light emitting device, the light emitting device comprising: a transparent insulating element configured in the hydrogen-producing mixed solution; and a light-emitting unit configured in the transparent insulating element to avoid contact with the hydrogen-producing mixed solution; and The light-emitting unit irradiates the hydrogen-producing mixed solution through the transparent insulating element. The hydrogen production method as described in claim 1, further comprising: A magnet is used to recover the photocatalyst complex from the hydrogen-producing mixed solution. A photocatalyst complex for producing hydrogen, comprising: a magnetic metal organic framework having an octahedral structure; and A ruthenium azadisulfide complex fixed on the magnetic metal organic framework. A hydrogen production system, comprising: a reaction tank configured to hold a hydrogen production mixed solution, the hydrogen production mixed solution includes a solvent, a photocatalyst compound, an organic acid reactant, an ascorbic acid, a P-ligand and an electron provider, Wherein the photocatalyst composite comprises a magnetic metal organic framework and a ruthenium azadisulfide complex fixed on the magnetic metal organic framework; and A light source system configured so that a light source irradiates the hydrogen-producing mixed solution to generate hydrogen gas. The hydrogen production system as described in claim item 8, wherein the light source system includes a dual-axis solar tracking device, and the dual-axis solar tracking device includes: a base configured to carry the reaction tank; a condensing lens configured to focus a sunlight on the hydrogen-producing mixed solution in the reaction tank; a plurality of angle adjustment rods connected between the base and the condenser lens; a sensor configured to obtain a position signal; a power unit configured to drive the plurality of angle adjustment rods to adjust an angle of the condenser lens; and a controller, coupled to the sensor and the power unit, the controller is configured to control the angle of the condenser lens through the plurality of angle adjustment rods according to the position signal, so as to guide the sunlight through the Concentrating lens. The hydrogen production system as claimed in item 8, wherein the light source system includes a light emitting device, and the light emitting device includes: a transparent insulating element configured in the hydrogen-producing mixed solution; and A light-emitting unit is arranged in the transparent insulating element to avoid contact with the hydrogen-producing mixed solution, so that the light-emitting unit irradiates the hydrogen-producing mixed solution through the transparent insulating element. The hydrogen production system as described in claim item 8, further comprising: a plurality of storage tanks configured to respectively store the solvent, the organic acid reactant, the P-ligand and the electron provider; a pumping device connected to the plurality of storage tanks and configured to the solvent, the The organic acid reactant, the P-ligand and the electron provider are respectively sent from the plurality of storage tanks to the reaction tank; a gas separation device, connected to the reaction tank and configured to separate the hydrogen produced; a hydrogen storage tank connected to the gas separation device and configured to store the separated hydrogen; and A recovery device is connected to the reaction tank and configured to recover the photocatalyst compound from the hydrogen production mixed solution.

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