Bionic flexible photocatalytic membrane and seawater hydrogen production intelligent application system thereof
Patent Information
- Application Number
- CN202610183536.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-30
- Publication Date
- 2026-09-01
AI Technical Summary
然而，粉末态催化剂在实际应用中存在回收困难、易失活、难以连续运行等问题，尤其在动态海水环境中更易发生材料流失与结构破坏
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Abstract
Description
Technical Field
[0001] This invention belongs to the interdisciplinary field of photocatalytic materials, new energy and marine resource utilization. Specifically, it relates to a flexible composite photocatalytic membrane with a biomimetic structural design, its preparation method, and an intelligent system and application method of the membrane in solar-driven direct hydrogen production from seawater. Background Technology
[0002] With the escalating global energy crisis and environmental problems, the development of clean and sustainable new energy technologies has become a key research focus. Hydrogen energy, as a high-energy-density, zero-carbon-emission green energy carrier, has broad application prospects. Photocatalytic water splitting driven by solar energy is considered one of the ideal ways to convert solar energy into chemical energy due to its advantages such as mild reaction conditions, low energy consumption, and environmental friendliness. However, traditional photocatalytic hydrogen production mainly uses freshwater as a raw material, and the scarcity of freshwater resources makes it difficult to support large-scale industrial applications.
[0003] Oceans cover approximately 71% of the Earth's surface, and seawater resources are extremely abundant. If efficient photocatalytic seawater splitting for hydrogen production could be achieved, it would greatly expand the sources of hydrogen production feedstock and be of great significance to promoting the development of the hydrogen energy economy. However, seawater has a complex composition, containing high concentrations of Cl- and Na-. + Mg 2+ Ca 2+ SO4 2- Impurities such as plasma, microorganisms, and organic matter pose serious challenges to the photocatalytic process. On the one hand, salt ions easily deposit on the catalyst surface, leading to blockage of active sites. On the other hand, highly corrosive chloride ions can not only cause catalyst structural degradation but also undergo competitive oxidation reactions under light to generate harmful byproducts such as Cl2 and HClO, severely affecting hydrogen production selectivity and system stability. In addition, most semiconductor photocatalysts (such as TiO2) suffer from high photogenerated electron-hole recombination rates, weak visible light response, and easy aggregation or shedding in electrolyte environments, resulting in rapid performance degradation under real seawater conditions.
[0004] In recent years, graphitic carbon nitride (g-C3N4) has been widely used in photocatalysis research due to its suitable band structure, good chemical stability, and visible light response. Sg-C3N4 formed by sulfur doping can further broaden the light absorption range and improve carrier separation efficiency. ZnIn2S4, as a ternary sulfide narrow bandgap semiconductor, possesses excellent visible light response and a suitable conduction band position, and is often used as a highly efficient hydrogen production co-catalyst. Constructing Sg-C3N4 / ZnIn2S4 heterojunctions helps promote interfacial charge transfer, improves the separation efficiency of photogenerated carriers, and thus enhances catalytic activity. However, powdered catalysts suffer from problems such as difficult recovery, easy deactivation, and difficulty in continuous operation in practical applications, especially in dynamic seawater environments where material loss and structural damage are more likely to occur.
[0005] To address the aforementioned issues, developing self-supporting thin-film photocatalysts has become an important direction. Polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) is a high-molecular polymer with good mechanical strength, hydrophobicity, corrosion resistance, and film-forming properties, making it an ideal substrate material for constructing flexible and stable composite catalytic membranes. This material can not only effectively anchor photocatalyst particles, preventing them from being washed away in seawater, but also inhibit salt crystallization and biofouling by controlling surface wettability, thus improving the long-term stability of the material in complex water conditions. Therefore, developing a photocatalytic material and system that can achieve efficient, stable, safe, and continuous hydrogen production in real seawater environments has become a key technological bottleneck that urgently needs to be overcome in this field.
[0006] This invention proposes a novel Sg-C3N4 / ZnIn2S4@PVDF-HFP biomimetic flexible photocatalytic membrane. Through the rational design of a multi-component synergistic structure, it achieves efficient visible light response and efficient carrier separation. Furthermore, the PVDF-HFP matrix provides mechanical support and environmental tolerance, significantly enhancing the catalytic activity and long-term stability of the material in real seawater environments. A biomimetic flexible photocatalytic membrane intelligent application system for seawater hydrogen production is constructed. Its core is the use of flexibly arranged composite membrane modules, in conjunction with hole sacrificial agents, controllable illumination, and gas collection units. This achieves continuous hydrogen production, monitorable operating status, and adaptive system control, providing a feasible solution for the practical application of solar-driven seawater hydrogen production technology. Summary of the Invention
[0007] Based on the design concepts of structural biomimicry, functional synergy, and system intelligence, this invention provides a method for preparing a biomimetic flexible photocatalytic membrane and an intelligent application system for seawater hydrogen production, starting from practical engineering problems.
[0008] One of the technical solutions of the present invention is to provide a method for preparing a biomimetic flexible photocatalytic membrane, wherein the method for preparing the catalytic membrane includes the following steps:
[0009] (1) Sulfur-containing precursors were placed in a closed ceramic boat and calcined to obtain Sg-C3N4 powder;
[0010] (2) Zinc source, indium source, sulfur source and Sg-C3N4 powder were mixed and dispersed in ethanol, and Sg-C3N4 / ZnIn2S4 composite material was synthesized by hydrothermal method.
[0011] (3) The Sg-C3N4 / ZnIn2S4 composite material, PVDF powder and ammonia water were dispersed in a solvent, heated and stirred to form a uniform solution, and the Sg-C3N4 / ZnIn2S4@PVDF-HFP biomimetic flexible photocatalytic membrane was prepared by phase inversion method. The material was washed and stored in deionized water.
[0012] Furthermore, in the above-mentioned Sg-C3N4 / ZnIn2S4@PVDF-HFP biomimetic flexible photocatalytic membrane, step (1) includes the following steps: placing trithiocyanate in a sealed ceramic boat, raising the temperature to 550℃ at a rate of 5℃ / min and continuing for 2h to obtain reddish Sg-C3N4, which is then ground and collected.
[0013] Further, in the above-mentioned Sg-C3N4 / ZnIn2S4@PVDF-HFP biomimetic flexible photocatalytic membrane, step (2) includes the following steps: zinc chloride, indium trichloride tetrahydrate and thioacetamide are dissolved in 40mL of ethanol and stirred for 1.5h, then a certain amount of Sg-C3N4 powder is added and stirred for 0.5h, the suspension is placed in a hydrothermal box for hydrothermal reaction, the hydrothermal reaction time is 5h, the reaction temperature is 180℃, after cooling to room temperature, centrifugation, washing and drying are performed to obtain Sg-C3N4 / ZnIn2S4 composite photocatalytic material.
[0014] Furthermore, by controlling the mass of the added Sg-C3N4 powder, the Sg-C3N4 and ZnIn2S4 in the Sg-C3N4 / ZnIn2S4 composite material can have different mass percentages.
[0015] Further, in the aforementioned Sg-C3N4 / ZnIn2S4@PVDF-HFP biomimetic flexible photocatalytic membrane, step (3) includes the following steps: 0.5g of PVDF powder is added to 9.5mL of N-methylpyrrolidone and completely dissolved in a water bath at 80°C; 15mg of Sg-C3N4 / ZnIn2S4 powder and 0.2μL of ammonia water are added and stirred for 6h; the completely dissolved PVDF-HFP solution is poured onto a glass substrate; the size of the film scraper is set, and then the film scraper is gently pushed. It is slowly placed into deionized water, gradually forming a gel; the membrane is gently peeled off from the glass substrate and rinsed several times with deionized water to obtain the final product.
[0016] The second technical solution of the present invention is to provide a biomimetic flexible photocatalytic membrane seawater hydrogen production intelligent application system, including the biomimetic flexible photocatalytic membrane, a sacrificial agent, a simulated seawater reaction liquid, a light source system, a gas collection and online detection unit, and a circulating flow simulation device;
[0017] The biomimetic flexible photocatalytic membrane is the aforementioned catalytic membrane.
[0018] The sacrificial agent is triethanolamine.
[0019] The method for preparing the simulated seawater is as follows:
[0020] (1) Take 800 mL of deionized water and dissolve NaCl, MgCl2·6H2O and KCl in sequence, stirring until completely dissolved.
[0021] (2) Add CaCl2 to avoid reaction with SO4. 2- It forms a precipitate.
[0022] (3) Add NaHCO3 and adjust the pH to 8.0±0.2 (fine-tune with 0.1M NaOH).
[0023] (4) Make up to 1L, filter with a 0.22μm filter membrane, and use immediately after preparation.
[0024] By mixing the sacrificial agent and simulated seawater, placing the biomimetic flexible photocatalytic membrane in a circulating flow device, and irradiating the biomimetic flexible photocatalytic membrane with light, hydrogen gas can be generated.
[0025] Furthermore, the reaction system is evacuated for 30 minutes before light exposure.
[0026] Furthermore, the system can monitor hydrogen production rate and system parameters in real time, and achieve intelligent control of the hydrogen production process by adjusting light intensity, liquid flow rate or sacrificial agent concentration.
[0027] The present invention discloses the following technical effects:
[0028] The core challenges in seawater-based hydrogen production lie in the contradictions between highly active catalysts and highly stable supports; between efficient charge separation and suppression of harmful side reactions; and between laboratory performance and engineering applicability. Therefore, ideal materials should simultaneously possess: broad spectral response and efficient charge separation capabilities; excellent chemical and mechanical stability; resistance to ion contamination and bioattachment; and ease of large-scale preparation and system integration.
[0029] The materials and structural design have the following technical advantages:
[0030] Photoactive layer design: Sg-C3N4 and ZnIn2S4 were selected to construct a type II heterojunction charge transfer pathway, which effectively promoted the spatial separation of photogenerated electron-hole pairs. Under illumination, electrons are enriched in the conduction band of ZnIn2S4 for hydrogen evolution reaction, while holes are rapidly captured and oxidized by TEOA, which greatly suppresses carrier recombination and significantly improves quantum efficiency and hydrogen production rate.
[0031] Biomimetic carrier design: Drawing inspiration from the hydrophobic and anti-adhesion properties of marine organism surfaces, PVDF-HFP is selected as the flexible substrate, endowing the membrane material with hydrophobicity, mechanical strength, corrosion resistance, and anti-fouling properties. This flexible membrane structure not only prevents the nanocatalyst particles from being washed away and detached in seawater, but also effectively inhibits Mg... 2+ Ca 2+ Plasma-induced surface scaling prevents the deactivation of active sites, enabling long-term stable operation in high ionic strength environments.
[0032] Multi-level composite structure: Through the multi-level construction of heterojunction nanounits-polymer network-porous membrane layer, the functions of light absorption, charge transfer, reaction mass transfer and mechanical support are integrated.
[0033] A biomimetic flexible photocatalytic membrane seawater hydrogen production intelligent application system has the following technical advantages:
[0034] By designing the composite membrane as a floating or fixed module and combining it with a hole sacrificial agent, a light system, and a gas collection device, an intelligent photocatalytic hydrogen production system that can operate continuously, be monitored in real time, and be adaptively controlled can be constructed, achieving full-chain innovation from materials to devices.
[0035] Unlike traditional powdered catalysts that require centrifugation for recovery and are prone to loss, the Sg-C3N4 / ZnIn2S4@PVDF-HFP of this invention is a flexible, self-supporting film that can be directly floated or fixed on the seawater surface for photocatalytic reaction without additional filtration or recovery steps. This facilitates the construction of continuous and modular solar hydrogen production devices and has promising engineering application prospects. Furthermore, the biomimetic flexible photocatalytic membrane seawater hydrogen production intelligent application system integrates a floatable / fixed composite membrane module, a hole sacrificial agent, controllable illumination, and a gas collection device, constructing an intelligent photocatalytic hydrogen production system with continuous operation, real-time monitoring, and adaptive control capabilities. Attached Figure Description
[0036] Figure 1This is a schematic diagram of a biomimetic flexible photocatalytic membrane seawater hydrogen production intelligent application system. The diagram includes: a gas cylinder (1); a hydrogen generator (2); a 300W xenon lamp light source (3); a magnetic stirrer / ultrasonic machine (4); a quartz reactor (5); an intelligent controller (6), which controls a pH sensor probe (7), a light intensity sensor (8), and a temperature sensor (9); an online sample collection injector (10); a gas chromatograph (11); and a condensate circulator (11).
[0037] Figure 2 The graph shows the hydrogen production yield of SCN / ZIS-2 and SCN / ZIS-20@PVDF-HFP biomimetic flexible photocatalytic membranes for pure water and simulated seawater under light and ultrasound conditions.
[0038] Figure 3 This is a schematic diagram of the preparation steps of the SCN / ZIS@PVDF-HFP biomimetic flexible photocatalytic membrane.
[0039] Figure 4 X-ray diffraction patterns of SCN, ZIS, PVDF, SCN / ZIS, and SCN / ZIS@PVDF-HFP samples.
[0040] Figure 5 Contact angle diagrams for SCN, ZIS, SCN / ZIS-20, and SCN / ZIS-20@PVDF-HFP.
[0041] Figure 6 This is a scanning electron microscope image of the SCN / ZIS@PVDF-HFP biomimetic flexible photocatalytic membrane sample.
[0042] Figure 7 The graph shows the yield of hydrogen production from pure water for SCN, ZIS, PVDF, SCN / ZIS-10, SCN / ZIS-20, SCN / ZIS-30, and SCN / ZIS-20@PVDF-HFP photocatalysts under light irradiation and stirring conditions. Detailed Implementation
[0043] Example 1
[0044] Intelligent application system for seawater hydrogen production using biomimetic flexible photocatalytic membrane at ambient temperature and pressure ( Figure 1 Sg-C3N4 / ZnIn2S4-20 powdered photocatalyst and Sg-C3N4 / ZnIn2S4-20@PVDF-HFP biomimetic flexible photocatalytic membrane were added to prepare simulated seawater. 10 mL of triethanolamine was added as a sacrificial agent. A 300W xenon lamp equipped with an AM 1.5 filter was used as the light source, and hydrogen was produced from the simulated seawater under ultrasonic treatment. The specific steps are as follows:
[0045] (1) The prepared Sg-C3N4 / ZnIn2S4-20 powder photocatalyst and Sg-C3N4 / ZnIn2S4-20@PVDF-HFP biomimetic flexible photocatalytic membrane were added to 90 mL of simulated seawater, and then 10 mL of sacrificial agent triethanolamine was added. The mixture was ultrasonicated to make it uniform.
[0046] (2) Add the above mixture into the reactor, evacuate the system and turn on the 300W xenon lamp equipped with an AM1.5 filter to simulate sunlight as the energy source for the photocatalytic reaction.
[0047] (3) During the entire photocatalytic reaction process, a circulating water cooling system and an ultrasonic machine were used to collect gas samples generated in the reaction system every half hour and analyze the hydrogen production using an online gas chromatograph.
[0048] (4) Discharge the solution that has been reacted in the reactor and recycle the photocatalyst.
[0049] The results are as follows Figure 2 As shown, the SCN / ZIS-20@PVDF-HFP biomimetic flexible photocatalytic membrane still produces 16252 μmol·g of hydrogen in seawater. -1 ·h -1 The hydrogen production rate in freshwater is 18025 μmol·g⁻¹. -1 ·h -1 The hydrogen production rate of the SCN / ZIS-20 powder catalyst decreased by only 9.8%, while the hydrogen production rate of the SCN / ZIS-20 powder catalyst in seawater decreased by 30.7%. This result is attributed to the enhanced catalyst stability and corrosion resistance achieved by the addition of the PVDF-HFP membrane. The PVDF-HFP membrane effectively isolates the catalyst active sites from corrosive ions (especially Cl-) in simulated seawater. - This significantly slows down the corrosion, dissolution, and deactivation processes of the catalyst.
[0050] Example 2
[0051] Preparation of Sg-C3N4 powder photocatalyst. 5g of trithiocyanate was placed in a sealed ceramic boat, and the temperature was raised to 550℃ at a rate of 5℃ / min and maintained for 2h to obtain reddish blocky Sg-C3N4. After grinding, the Sg-C3N4 powder photocatalyst was collected.
[0052] Example 3
[0053] Preparation of ZnIn2S4 powder photocatalyst: 1 mmol zinc chloride (0.1363 g), 2 mmol (0.5865 g) indium trichloride tetrahydrate, and 4 mmol thioacetamide (0.3005 g) were weighed and dissolved in 40 mL ethanol and stirred for 1.5 h. The suspension was placed in a hydrothermal chamber for hydrothermal reaction for 5 h at a reaction temperature of 180 °C. After cooling to room temperature, the solution was centrifuged, washed, and dried to obtain the ZnIn2S4 powder photocatalyst.
[0054] Example 4
[0055] Prepared Sg-C3N4 / ZnIn2S4 composite powder photocatalysts. 5g of trithiocyanate was placed in a sealed ceramic boat and heated to 550℃ at a rate of 5℃ / min for 2h to obtain reddish Sg-C3N4, which was then ground and collected. 1mmol of zinc chloride (0.1363g), 2mmol (0.5865g) of indium trichloride tetrahydrate, and 4mmol of thioacetamide (0.3005g) were dissolved in 40mL of ethanol and stirred for 1.5h. Then, 10%, 20%, and 30% by mass of pre-synthesized Sg-C3N4 were added to the mixture and stirred for 0.5h. The suspensions were then placed in a hydrothermal oven for a hydrothermal reaction at 180℃ for 5h. After cooling to room temperature, the mixture was centrifuged, washed, and dried to obtain Sg-C3N4 / ZnIn2S4 composite powder photocatalysts with different composite ratios.
[0056] Example 5
[0057] The Sg-C3N4 / ZnIn2S4-20@PVDF-HFP biomimetic flexible photocatalytic membrane was prepared, and the preparation schematic is shown in Figure 1. Figure 3As shown. 5g of trithiocyanate was placed in a sealed ceramic boat, and the temperature was raised to 550℃ at a rate of 5℃ / min and maintained for 2h to obtain reddish Sg-C3N4, which was then ground and collected. 1mmol of zinc chloride (0.1363g), 2mmol (0.5865g) of indium trichloride tetrahydrate and 4mmol of thioacetamide (0.3005g) were weighed and dissolved in 40mL of ethanol and stirred for 1.5h. Then, 20% by mass of the pre-synthesized Sg-C3N4 was added to the mixture and stirred for 0.5h. The suspension was placed in a hydrothermal chamber for hydrothermal reaction for 5h at a temperature of 180℃. After cooling to room temperature, the mixture was centrifuged, washed, and dried to obtain the Sg-C3N4 / ZnIn2S4-20 composite powder photocatalyst. 0.5 g of PVDF powder was added to 9.5 mL of N-methylpyrrolidone and completely dissolved in a water bath at 80 °C. 15 mg of Sg-C3N4 / ZnIn2S4-20 powder and 0.2 μL of ammonia were added and the mixture was stirred for 6 h. The completely dissolved PVDF-HFP solution was poured onto a glass substrate. The film scraper size was set, and the scraper was gently pushed. The substrate was slowly immersed in deionized water, gradually forming a gel. The membrane was gently peeled off the glass substrate and rinsed several times with deionized water to obtain the final product, the Sg-C3N4 / ZnIn2S4-20@PVDF-HFP biomimetic flexible photocatalytic membrane.
[0058] Figure 4 The X-ray diffraction patterns of the photocatalytic materials in Examples 2-5 demonstrate the successful preparation of the materials.
[0059] Figure 5 The contact angle diagrams for the photocatalytic materials in Examples 2-5 demonstrate that the introduction of the PVDF-HFP membrane imparts hydrophobicity to the biomimetic flexible photocatalytic membrane.
[0060] Figure 6 Scanning electron microscope image of the Sg-C3N4 / ZnIn2S4-20@PVDF-HFP biomimetic flexible photocatalytic membrane.
[0061] Example 6
[0062] Under normal temperature and pressure, the photocatalysts of Examples 2, 3, 4, and 5 were added, along with 10 mL of the sacrificial agent triethanolamine. A 300W xenon lamp equipped with an AM 1.5 filter was used as the light source, and hydrogen was precipitated from pure water under magnetic stirring. The specific steps are as follows:
[0063] (1) The prepared Sg-C3N4, ZnIn2S4, Sg-C3N4 / ZnIn2S4 powder photocatalysts and Sg-C3N4 / ZnIn2S4-20@PVDF-HFP biomimetic flexible photocatalytic membrane were added to 90 mL of deionized water, and then 10 mL of sacrificial agent triethanolamine was added. The mixture was ultrasonicated to make it uniform.
[0064] (2) Add the above suspension mixture into the reactor, evacuate the system and turn on the 300W xenon lamp equipped with an AM1.5 filter to simulate sunlight as the energy source for the photocatalytic reaction;
[0065] (3) During the entire photocatalytic reaction process, a circulating water cooling system and a magnetic stirrer were used to assist in collecting gas samples generated in the reaction system every half hour and analyzing the hydrogen production using an online gas chromatograph.
[0066] (4) Discharge the solution that has been reacted in the reactor and recycle the photocatalytic film agent.
[0067] The results are as follows Figure 7 As shown, SCN and ZIS alone exhibited poor photocatalytic activity, with hydrogen production rates of 2084 μmol·g⁻¹, respectively. -1 ·h -1 and 6613 μmol·g -1 ·h -1 However, when combined, the hydrogen production rate was significantly improved, with the SCN / ZIS-20 combination achieving a hydrogen production rate of 14347 μmol·g⁻¹. -1· h -1 The results showed that the charge carriers were 6.9 times that of pure SCN and 2.2 times that of pure ZIS, respectively. This indicates that the composite of the two single materials forms a heterojunction, and the successful separation of charge carriers at the interface between SCN and ZIS greatly improves the photocatalytic activity.
[0068] Example 7
[0069] Under normal temperature and pressure, Sg-C3N4 / ZnIn2S4-20 powdered photocatalyst and Sg-C3N4 / ZnIn2S4-20@PVDF-HFP biomimetic flexible photocatalytic membrane were added, along with 10 mL of sacrificial triethanolamine. A 300W xenon lamp equipped with an AM 1.5 filter was used as the light source, and hydrogen evolution was achieved under ultrasonic treatment. The specific steps are as follows:
[0070] (1) The prepared Sg-C3N4 / ZnIn2S4-20 powder photocatalyst and Sg-C3N4 / ZnIn2S4-20@PVDF-HFP biomimetic flexible photocatalytic membrane were added to 90 mL of deionized water, and then 10 mL of sacrificial agent triethanolamine was added. The mixture was ultrasonicated to make it uniform.
[0071] (2) Add the above mixture into the reactor, evacuate the system and turn on the 300W xenon lamp equipped with an AM1.5 filter to simulate sunlight as the energy source for the photocatalytic reaction.
[0072] (3) During the entire photocatalytic reaction process, a circulating water cooling system and an ultrasonic machine were used to collect gas samples generated in the reaction system every half hour and analyze the hydrogen production using an online gas chromatograph.
[0073] (4) Discharge the solution that has been reacted in the reactor and recycle the photocatalyst.
[0074] The results are as follows Figure 2 As shown, the yields of both SCN / ZIS-20 and SCN / ZIS-20@PVDF-HFP were improved, with SCN / ZIS-20@PVDF-HFP showing a greater improvement, reaching 18025 μmol·g⁻¹. -1 ·h -1 This indicates that ultrasonic vibration can not only accelerate mass transfer, but also induce periodic deformation of the PVDF film, generating a piezoelectric field that promotes the directional transfer of charge carriers.
Claims
1. A biomimetic flexible photocatalytic membrane and its intelligent application system for seawater hydrogen production, characterized in that, The photocatalytic membrane comprises a PVDF-HFP substrate and an Sg-C3N4 / ZnIn2S4 composite photocatalytic material supported thereon. The composite material is formed by a type II heterojunction constructed from Sg-C3N4 and ZnIn2S4. The intelligent application system based on the biomimetic flexible photocatalytic membrane includes the photocatalytic membrane, a sacrificial agent, a simulated seawater reaction solution, a light source system, a gas collection and online detection unit, and a circulating flow simulation device.
2. The biomimetic flexible photocatalytic membrane according to claim 1, characterized in that, The PVDF-HFP substrate is prepared by a phase inversion method, specifically: PVDF powder is dissolved in N-methylpyrrolidone, Sg-C3N4 / ZnIn2S4 composite photocatalyst material and ammonia are added, stirred and poured onto a glass substrate, and obtained by coating, gelling, peeling and rinsing.
3. The biomimetic flexible photocatalytic membrane according to claim 1, characterized in that, The biomimetic flexible photocatalytic membrane is hydrophobic, has a contact angle greater than 90°, and has good mechanical strength, allowing it to withstand seawater erosion without falling off.
4. The intelligent application system for photocatalytic seawater hydrogen production according to claim 1, characterized in that, include: Gas cylinder (1); hydrogen generator (2); 300W xenon lamp light source (3); magnetic stirrer / ultrasonic machine (4); quartz reactor (5); intelligent controller (6) which controls pH sensor probe (7), light intensity sensor (8), and temperature sensor (9); online sample collection injector (10); gas chromatograph (11); condensate circulator (11).
5. The reactor according to claim 4, characterized in that, The gas cylinder (1) is filled with argon gas.
6. The reactor according to claim 4, characterized in that, The 300W xenon lamp light source (3) is equipped with an AM 1.5 filter to simulate natural light.
7. The reactor according to claim 4, characterized in that, The quartz reactor (5) contains simulated seawater, photocatalytic materials, and triethanolamine sacrificial agent.
8. The reactor according to claim 4, characterized in that, The online sample collection injector (10) cycles every half hour.
9. The reactor according to claim 4, characterized in that, The condensate circulator (11) is set to a temperature of 15°C.
10. A method for producing hydrogen using the photocatalyst of claim 1, characterized in that, The process includes the following steps: mixing the sacrificial agent and simulated seawater, placing the photocatalyst in a circulating flow device, evacuating the reaction system for 30 minutes, and irradiating the photocatalyst with light to generate hydrogen.
11. The method according to claim 10, characterized in that, The system can monitor hydrogen production rate and system parameters in real time, and achieve intelligent control of the hydrogen production process by adjusting light intensity, liquid flow rate or sacrificial agent concentration.