A hydrogen production composition, a method for preparing the hydrogen production composition, and a hydrogen production method

Abstract

The present application discloses a hydrogen production composition, a method for preparing the hydrogen production composition, and a hydrogen production method. The hydrogen production composition comprises: a plurality of piezoelectric catalytic particles capable of generating piezoelectric charges under mechanical force; a plurality of organic active particles having a plurality of functional groups for coordinating with metal ions and organic conjugated units, the organic active particles being coordinately bonded to the piezoelectric catalytic particles through the functional groups, the organic conjugated units being conjugated to the functional groups to form a carrier transport path extending from the functional groups to the organic conjugated units, and the organic conjugated units being capable of absorbing light to generate photo-generated carriers, the energy levels of the organic active particles and the piezoelectric catalytic particles being matched to form a heterojunction between the organic active particles and the piezoelectric catalytic particles; and a liposome carrier, the piezoelectric catalytic particles and the organic active particles being dispersed in the liposome carrier.

Description

Technical Field

[0001] This invention relates to the field of biomedical materials, specifically to a hydrogen-generating composition, a method for preparing the hydrogen-generating composition, and a method for generating hydrogen. Background Technology

[0002] In related technologies, hydrogen-rich medical aesthetic products mostly employ hydrogen production technologies such as water electrolysis and metal hydrolysis; however, the hydrogen production efficiency of these technologies is not ideal. In recent years, the industry has also attempted to apply piezoelectric material catalytic hydrogen production technology to the medical field; however, piezoelectric material catalytic hydrogen production still suffers from unstable hydrogen production.

[0003] Therefore, developing a hydrogen-producing composition, a method for preparing the hydrogen-producing composition, and a hydrogen production method to improve the stability of hydrogen production is an urgent problem to be solved in this field. Summary of the Invention

[0004] This invention aims to address, to a certain extent, one of the technical problems in related technologies. To this end, this invention provides a hydrogen-producing composition, a method for preparing the hydrogen-producing composition, and a method for hydrogen production.

[0005] To achieve the above objectives, as a first aspect of the present invention, the present invention provides a hydrogen-producing composition comprising: Multiple piezoelectric catalytic particles, which are capable of generating piezoelectric charges under mechanical force; Multiple organic active particles, each having multiple functional groups for metal ion coordination and organic conjugated units, are provided. The organic active particles are coordinated and bonded to the piezoelectric catalytic particles through the functional groups, and the organic conjugated units are conjugatedly connected to the functional groups to form a carrier transport path extending from the functional groups to the organic conjugated units. The organic conjugated units are capable of absorbing light to generate photogenerated carriers. The energy levels of the organic active particles and the piezoelectric catalytic particles are matched, resulting in a heterojunction at the interface between the organic active particles and the piezoelectric catalytic particles. The piezoelectric catalytic particles and the organic active particles are dispersed in the liposome carrier.

[0006] Furthermore, the mass ratio of the liposome carrier to the piezoelectric catalytic particles is between 100:50 and 100:300, and the mass ratio of the liposome carrier to the organic active particles is between 1000:1 and 100:18.

[0007] Furthermore, the size of the piezoelectric catalytic particles is between 1 μm and 5 μm.

[0008] Furthermore, the material of the organic active particles is selected from at least one of organic conjugated molecules, polyphenolic compounds, flavonoids, quinones, and conjugated aromatic compounds, and the functional group for coordinating metal ions is selected from at least one of β-diketone groups, ortho-phenolic hydroxyl groups, and ortho-quinone groups.

[0009] Furthermore, the material of the organic active particles is selected from at least one of curcumin, curcuminoids, resveratrol, catechins, anthocyanins, coumarin, lutein, quercetin, rutin, tea polyphenols, gallic acid, nicotinamide, retinol, coenzyme Q10, ferulic acid, caffeic acid, chlorogenic acid, emodin, and shikonin.

[0010] Furthermore, the material of the piezoelectric particles is selected from at least one of bismuth-based piezoelectric materials, zinc-based piezoelectric materials, titanium-based piezoelectric materials, niobium-based piezoelectric materials, alkali metals, alkaline earth metal piezoelectric ceramics, and two-dimensional piezoelectric nanomaterials.

[0011] Furthermore, the materials of the liposome carrier include phospholipids, steroidal compounds, and polyethylene glycol modifiers.

[0012] Furthermore, in the liposome carrier, the mass ratio of the phospholipid, steroid compound and polyethylene glycol modifier is between (5-30):(2-10):(1-10).

[0013] Furthermore, the piezoelectric composite also includes a proton donor for providing protons, the material of which is selected from at least one of lactic acid, formic acid, acetic acid, oxalic acid, ascorbic acid, methanol, ethanol, isopropanol, glycerol, triethanolamine, triethylamine, ethylenediaminetetraacetic acid, citrate, glucose, fructose, and biomass-derived small molecule sacrificial agents.

[0014] As a second aspect of this application, a method for preparing a hydrogen-producing composition is disclosed, the method comprising: Liposome carriers are mixed and dissolved with organic active powder to obtain a first mixture. The organic active powder includes multiple organic active particles. Each organic active particle has multiple functional groups for metal ion coordination and organic conjugated units. The organic conjugated units are conjugated with the functional groups to form a carrier transport path extending from the functional groups to the organic conjugated units. The organic conjugated units can absorb light to generate photogenerated carriers. The organic active particles can coordinate and bond with the piezoelectric catalytic particles through the functional groups. The energy levels of the organic active particles and the piezoelectric catalytic particles are matched, enabling the organic active particles to form a heterojunction with the piezoelectric catalytic particles. The first mixture is desolventized and then hydrated to form a first intermediate complex, the first intermediate complex comprising a liposome dispersion loaded with a plurality of the organic active particles; The piezoelectric catalytic powder is mixed with the first intermediate complex to obtain the above composition, wherein the piezoelectric catalytic powder comprises a plurality of piezoelectric catalytic particles; Further, the step of mixing the piezoelectric catalytic powder with the first intermediate complex to obtain the composition includes: mixing and dispersing the piezoelectric catalytic component powder with a sacrificial agent in a solvent, wherein the sacrificial agent includes a proton donor.

[0015] Furthermore, before mixing the piezoelectric catalytic powder with the first intermediate complex, the method further includes: Piezoelectric metal salts are mixed in a solvent to form a piezoelectric metal mixture; The piezoelectric metal mixture is placed in a reaction vessel and reacted at a set temperature and pressure to generate piezoelectric crystals, wherein the set temperature is between 100°C and 200°C. The piezoelectric crystal is cooled, separated, washed, and dried to obtain the piezoelectric catalytic powder.

[0016] As a third aspect of this application, a method for producing hydrogen is disclosed, the method comprising: A hydrogen-producing stock solution is prepared using a hydrogen-producing composition, wherein the hydrogen-producing composition is the aforementioned hydrogen-producing composition; The hydrogen-producing stock solution is subjected to ultrasonic treatment, which causes the hydrogen-producing stock solution to generate hydrogen gas under the action of ultrasound.

[0017] The hydrogen production composition provided by this invention constructs a stable organic-inorganic hybrid heterojunction at the interface through coordination bonding and energy level matching between organic active particles and piezoelectric catalytic particles, significantly improving the efficiency of mechanically driven hydrogen production. On the one hand, the conjugated units of the organic active particles are conjugatedly connected with the coordinating functional groups, forming a carrier transport path extending from the anchoring point to the entire conjugated system, reducing the interfacial charge transport resistance, forcibly separating ultrasonically excited electron-hole pairs, and effectively suppressing carrier recombination. On the other hand, the organic conjugated units can absorb visible light to generate photogenerated carriers, forming a photogenerated and piezoelectric synergistic supply with the piezoelectric charge, further improving the hydrogen production rate. Simultaneously, the rigid heterojunction interface anchored by the coordination bonds maintains structural stability under ultrasonic vibration, ensuring long-term reliability. Furthermore, liposome carriers can co-disperse and encapsulate piezoelectric catalytic particles and organic active particles, which not only achieves stable loading and sustained release of active ingredients (such as polyphenols and flavonoids), but also endows the composition with good biocompatibility and skin adaptability. It can be easily compounded into cosmetics, masks or ultrasonic beauty instrument matching formulations, and has integrated application prospects in the fields of clean energy production and medical aesthetics anti-oxidation, anti-inflammatory repair.

[0018] These features and advantages of the present invention will be disclosed in detail in the following specific embodiments and accompanying drawings. The preferred embodiments or means of the present invention will be shown in detail in conjunction with the accompanying drawings, but are not intended to limit the technical solutions of the present invention. In addition, each of these features, elements and components appearing in the following text and drawings is a plurality of, and different symbols or numbers are used for convenience of representation, but all represent parts with the same or similar construction or function. Attached Figure Description

[0019] The present invention will be further described below with reference to the accompanying drawings: Figure 1 A schematic diagram illustrating one embodiment of the hydrogen-producing composition provided by the present invention; Figure 2 A schematic flowchart of one embodiment of the method for preparing the hydrogen-producing composition provided by the present invention; Figure 3 This is a hydrogen production test graph for Example 1 of the present invention; Figure 4 This is a graph showing the hydrogen production test results of Example 2 of the present invention; Figure 5 This is a hydrogen production test graph from Example 1 of the present invention; Figure 6 This is a hydrogen production test graph from Example 2 of the present invention; Figure 7 This is a hydrogen production test graph from Example 3 of the present invention; Figure 8 This is a hydrogen production test graph from Example 4 of the present invention; Figure 9 This is a hydrogen production test graph from Example 5 of the present invention.

[0020] Explanation of reference numerals in the attached figures 1: Hydrogen-producing composition; 10: Liposome carrier; 11: Piezoelectric catalytic particles; 12: Organic active particles. Detailed Implementation

[0021] Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described are intended to explain the present invention and should not be construed as limiting the invention.

[0022] The terms "an embodiment," "example," or "example" used in this specification refer to a particular feature, structure, or characteristic described in connection with the embodiment itself that may be included in at least one embodiment disclosed in this application. The phrase "in an embodiment" appearing in various places throughout the specification does not necessarily refer to the same embodiment.

[0023] The inventors of this application have discovered that the separation efficiency of single piezoelectric carriers is extremely low, resulting in insufficient hydrogen production kinetics. Existing research indicates that pure piezoelectric materials have weak polarization electric fields and small piezoelectric potential differences, leading to high recombination rates of photogenerated and piezoelectric carriers. Relying solely on intrinsic structures cannot achieve efficient water splitting for hydrogen production, resulting in defects such as slow hydrogen production rate, low hydrogen production volume, and lag response, making it difficult to meet the real-time and stable hydrogen supply requirements of medical and aesthetic scenarios. This invention enhances the internal electric field at the interface by constructing heterojunction structures and micron-sized reactors, thereby achieving efficient carrier separation and migration and fundamentally improving the piezoelectric hydrogen production kinetics. The existing hydrogen production technology for medical aesthetics has poor adaptability, insufficient safety and portability. Most existing hydrogen-rich medical aesthetic products use water electrolysis or metal hydrolysis to produce hydrogen. Electrolysis hydrogen production is energy-intensive, expensive, and requires bulky equipment. It is also prone to producing harmful byproducts such as ozone and residual chlorine, posing safety hazards. Metal hydrolysis hydrogen production is a violent reaction with an uncontrollable rate, making it incompatible with portable medical aesthetic devices. This invention uses mechanical force to drive piezoelectric hydrogen production. The reaction is mild, has no byproducts, and produces high-purity hydrogen. It can be directly compounded into medical aesthetic matrix and is compatible with portable devices such as handheld ultrasonic beauty instruments. Loading active ingredients is difficult, and it's hard to balance piezoelectric properties and biocompatibility. Natural medical aesthetic active ingredients such as curcumin have extremely poor water solubility and are easily oxidized, aggregated, and deactivated. Conventional physical doping and surface loading can easily damage the crystal structure and piezoelectric properties of piezoelectric materials, and the biocompatibility and skin tolerance of the components cannot meet the standards. This invention uses liposomes as a carrier to achieve stable encapsulation and sustained release of natural active ingredients such as curcumin, balancing the dual requirements of catalytic modification and medical aesthetic biocompatibility. It does not damage piezoelectric properties and significantly improves piezoelectric properties and skin compatibility. Piezoelectric hydrogen production materials have a single function and cannot achieve the integration of "hydrogen production + medical aesthetics". Existing piezoelectric hydrogen production materials only focus on the clean energy field, without additional medical aesthetic bioactivity, resulting in single function and limited application scenarios. Hydrogen-rich medical aesthetic products only store hydrogen and have no in-situ hydrogen production capability, resulting in easy hydrogen loss and poor efficacy duration. This invention achieves synergistic effects of piezoelectric in-situ hydrogen production and the antioxidant, anti-inflammatory, and anti-aging properties of curcumin, breaking through industry technical barriers and achieving an integrated approach of "in-situ hydrogen production + skin repair".

[0024] To address the aforementioned problems, as a first aspect of the present invention, the present invention provides a hydrogen-producing composition, such as... Figure 1 As shown, hydrogen-producing composition 1 comprises: Multiple piezoelectric catalytic particles 11, which can generate piezoelectric charges under mechanical force; Multiple organic active particles 12 have multiple functional groups and organic conjugated units that can provide coordination for metal ions. The organic active particles are coordinated and bonded to the piezoelectric catalytic particles through the functional groups. The organic conjugated units are conjugated and connected to the functional groups to form a carrier transport path extending from the functional groups to the organic conjugated units. The organic conjugated units can absorb light to generate photogenerated carriers. The energy levels of the organic active particles and the piezoelectric catalytic particles are matched, so that a heterojunction is formed at the interface between the organic active particles and the piezoelectric catalytic particles. Liposome carrier 10, piezoelectric catalytic particles and organic active particles are dispersed in liposome carrier.

[0025] The hydrogen production composition provided by this invention constructs a stable organic-inorganic hybrid heterojunction at the interface through coordination bonding and energy level matching between organic active particles and piezoelectric catalytic particles, significantly improving the efficiency of mechanically driven hydrogen production. On the one hand, the conjugated units of the organic active particles are conjugatedly connected with the coordinating functional groups, forming a carrier transport path extending from the anchoring point to the entire conjugated system, reducing the interfacial charge transport resistance, forcibly separating ultrasonically excited electron-hole pairs, and effectively suppressing carrier recombination. On the other hand, the organic conjugated units can absorb visible light to generate photogenerated carriers, forming a photogenerated and piezoelectric synergistic supply with the piezoelectric charge, further improving the hydrogen production rate. Simultaneously, the rigid heterojunction interface anchored by the coordination bonds maintains structural stability under ultrasonic vibration, ensuring long-term reliability. Furthermore, liposome carriers can co-disperse and encapsulate piezoelectric catalytic particles and organic active particles, which not only achieves stable loading and sustained release of active ingredients (such as polyphenols and flavonoids), but also endows the composition with good biocompatibility and skin adaptability. It can be easily compounded into cosmetics, masks or ultrasonic beauty instrument matching formulations, and has integrated application prospects in the fields of clean energy production and medical aesthetics anti-oxidation, anti-inflammatory repair.

[0026] Preferably, the mass ratio of liposome carrier to piezoelectric catalytic particles is between 100:50 and 100:300, and the mass ratio of liposome carrier to organic active particles is between 1000:1 and 100:18. This invention precisely controls the mass ratio range between liposome carriers, organic active particles, and piezoelectric catalytic particles. A low amount of organic active particles is sufficient to form a monolayer on the surface of the piezoelectric particles for coordination and anchoring, ensuring the integrity of the heterojunction interface and efficient carrier transport while avoiding increased interfacial charge transport resistance or blockage of active sites due to excessive organic molecule accumulation. Secondly, a large amount of liposome carriers ensures that the piezoelectric and organic active particles are fully encapsulated and uniformly dispersed, forming a stable nanoreactor configuration, preventing particle aggregation and precipitation, and endowing the composition with excellent biocompatibility and skin permeability. Furthermore, this ratio range balances hydrogen production efficiency and economy, achieving efficient hydrogen production under ultrasound drive while significantly reducing the amount of expensive natural active ingredients, thus saving raw material costs. Finally, the composition at this ratio exhibits good formulation compatibility and can be directly compounded in cosmetics, mask bases, or gels for ultrasonic beauty devices, maintaining structural integrity and functional stability under long-term storage and mechanical stimulation.

[0027] Preferably, the size of the piezoelectric catalytic particles is between 1 μm and 5 μm. Compared to smaller nanoparticles or larger aggregates, this micron-sized particle size range allows for stronger piezoelectric polarization under ultrasonic mechanical forces. This is because the piezoelectric output is related to the deformation volume of the particle; appropriately sized particles can undergo more effective lattice distortion in an ultrasonic field, resulting in a higher piezoelectric potential difference and more piezoelectric charge. Secondly, this size range matches the encapsulation capacity and vesicle size of the liposome carrier (liposomes are typically 100 nm to 500 nm). While the size is small (nm), micron-sized liposomes or multilayer lipid vesicles can be obtained through preparation methods, allowing piezoelectric particles to be stably dispersed and encapsulated within the aqueous phase or lipid bilayer of the liposome, preventing particle leakage or sedimentation. Furthermore, the micron-sized piezoelectric particles have a moderate specific surface area, ensuring an effective interface for coordination bonding with organic active particles (the specific surface area is not too low), while avoiding the problem of nanoparticles easily agglomerating due to excessively high surface energy and being difficult to disperse uniformly in liposomes. This ensures the colloidal stability of the composite material during storage and use. Within this size range, the organic-inorganic hybrid heterojunction interface formed by the piezoelectric particles and organic active particles has a low defect density, effectively suppressing interfacial charge recombination, thereby improving the hydrogen production rate and long-term cycling stability under ultrasonic drive.

[0028] This application does not impose special limitations on the selection of organic active particles, as long as the above-mentioned relationships are satisfied. Preferably, the material of the organic active particles is selected from at least one of organic conjugated molecules, polyphenolic compounds, flavonoids, quinones, and conjugated aromatic compounds, and the functional group for metal ion coordination is selected from at least one of β-diketone groups, ortho-phenolic hydroxyl groups, and ortho-quinone groups. In some specific embodiments, the material of the organic active particles is selected from at least one of curcumin, curcuminoids, resveratrol, catechins, anthocyanins, coumarin, lutein, quercetin, rutin, tea polyphenols, gallic acid, nicotinamide, retinol, coenzyme Q10, ferulic acid, caffeic acid, chlorogenic acid, emodin, and shikonin.

[0029] This application does not impose special limitations on the selection of piezoelectric particles, as long as they are metallic or ceramic piezoelectric materials. Preferably, the material of the piezoelectric particles is selected from at least one of bismuth-based piezoelectric materials, zinc-based piezoelectric materials, titanium-based piezoelectric materials, niobium-based piezoelectric materials, alkali metals, alkaline earth metal piezoelectric ceramics, and two-dimensional piezoelectric nanomaterials. In some specific embodiments, the material of the piezoelectric particles includes at least one of bismuth oxychloride, bismuth oxybromide, bismuth oxyiodide, zinc oxide, barium titanate, potassium niobate, barium strontium metaniobate, strontium titanate, barium strontium titanate, barium strontium niobate, zinc oxide-based composites, and bismuth oxychloride-based composites.

[0030] This application does not impose any special limitations on the selection of liposome carriers. Preferably, the materials of liposome carriers include phospholipids, steroidal compounds, and polyethylene glycol modifiers. Preferably, in the liposome carrier, the mass ratio of phospholipids, steroidal compounds, and polyethylene glycol modifiers is between (5-30):(2-10):(1-10).

[0031] In some specific embodiments, the phospholipid is selected from at least one of dipalmitoylphosphatidylcholine (DPPC), distearylphosphatidylcholine (DSPC), dimyristoylphosphatidylcholine (DMPC), 1-palmitoyl-2-oleoyllecithin (POPC), and distearylphosphatidylethanolamine (DSPE); the steroid compound is cholesterol or a derivative thereof; and the polyethylene glycol modifier is selected from at least one of distearylphosphatidylethanolamine-polyethylene glycol 2000 (DSPE-PEG2000), distearylphosphatidylethanolamine-polyethylene glycol 5000 (DSPE-PEG5000), distearylphosphatidylethanolamine-polyethylene glycol (DPPE-PEG), DSPE, and polyethylene glycol 2000 (PEG2000).

[0032] In some embodiments, the piezoelectric composite further includes a proton donor for providing protons, which can further improve the hydrogen production efficiency of the piezoelectric material. Preferably, the proton donor is selected from at least one of lactic acid, formic acid, acetic acid, oxalic acid, ascorbic acid, methanol, ethanol, isopropanol, glycerol, triethanolamine, triethylamine, ethylenediaminetetraacetic acid, citrate, glucose, fructose, and biomass-derived small molecule sacrificial agents. This application does not specifically limit the use of the hydrogen-generating composition. Preferably, the hydrogen-generating composition is used in cosmetics, skin care products, topical skin compositions, functional layer materials of face masks, bioactive repair materials, antioxidant skin care preparations, or anti-inflammatory and soothing preparations.

[0033] As a second aspect of this application, a method for preparing a hydrogen-producing composition is disclosed, such as... Figure 2 As shown, the preparation method includes: S100. The liposome carrier is mixed and dissolved with the organic active powder to obtain a first mixture. The organic active powder includes multiple organic active particles. The organic active particles have multiple functional groups for metal ion coordination and organic conjugated units. The organic conjugated units are conjugated with the functional groups to form a carrier transport path extending from the functional groups to the organic conjugated units. The organic conjugated units can absorb light to generate photogenerated carriers. The organic active particles can coordinate and bond with the piezoelectric catalytic particles through the functional groups. The energy levels of the organic active particles and the piezoelectric catalytic particles are matched, so that the organic active particles can form a heterojunction with the piezoelectric catalytic particles. S200. The first mixture is desolventized and then hydrated to form a first intermediate complex, the first intermediate complex comprising a liposome dispersion loaded with multiple organic active particles. S300. The piezoelectric catalytic powder is mixed with the first intermediate complex to obtain the above composition, wherein the piezoelectric catalytic powder comprises a plurality of piezoelectric catalytic particles.

[0034] In steps S100 and S200, specifically, the liposome carrier component and the organic active particles are dissolved together in an organic solvent, the solvent is removed by vacuum distillation to form a composite film, and then the liposome dispersion loaded with organic active particles is obtained by hydration and dispersion. In step S300, specifically, it includes: mixing and dispersing the piezoelectric catalytic component powder with a sacrificial agent in a solvent, the sacrificial agent including a proton donor.

[0035] Preferably, before mixing the piezoelectric catalytic powder with the first intermediate complex, the method further includes: Piezoelectric metal salts are mixed in a solvent to form a piezoelectric metal mixture; A mixture of piezoelectric metals is placed in a reaction vessel and reacted at a set temperature and pressure to generate piezoelectric crystals. The set temperature is between 100°C and 200°C. The piezoelectric crystal was cooled, separated, washed, and dried to obtain piezoelectric catalytic powder.

[0036] This invention involves blending natural active ingredients, such as curcumin, with liposome carrier components in ethanol, followed by solvent removal via rotary evaporation to achieve homogeneous composite composition. This avoids the problems of heterojunction interface dissociation, phase separation, and particle aggregation caused by subsequent hydration processes, ensuring a consistently good contact interface. Furthermore, the stable and compact interface structure allows for direct transfer of piezoelectric charges excited by ultrasound, eliminating additional interfacial barriers, significantly improving carrier separation efficiency, and promoting rapid electron migration to the reaction interface, thus efficiently driving the water splitting and hydrogen production process.

[0037] As a third aspect of this application, a method for producing hydrogen is disclosed, the method comprising: A hydrogen-producing stock solution is prepared using a hydrogen-producing composition, wherein the hydrogen-producing composition is the aforementioned hydrogen-producing composition; The hydrogen-producing stock solution is subjected to ultrasonic treatment, which causes the stock solution to produce hydrogen gas under the action of ultrasound.

[0038] The present invention will be further described below with reference to preparation examples and embodiments.

[0039] Preparation Example Preparation Example 1 A piezoelectric catalytic powder is provided. Specifically, zinc acetate (1.1 g) and NaOH (4.0 g) are dissolved in a solvent mixture of 30 ml anhydrous ethanol and 7.5 ml polyethylene glycol to obtain a mixture. The mixture is continuously magnetically stirred for 5 hours to homogenize it. The homogenized mixture is then heated to 120°C in a sealed container for hydrothermal reaction for 12 hours. Afterward, it is centrifuged at 8000 r / min for 3 minutes to obtain the separated ZnO nanorods (piezoelectric catalytic powder). Then, the ZnO nanorods are purified by multiple washing cycles with deionized water and anhydrous ethanol to remove residual reactants, finally obtaining ZnO piezoelectric catalytic powder sample 1.

[0040] Preparation Example 2 A piezoelectric catalytic powder is provided. Specifically, 0.367 g of anhydrous zinc acetate and 0.02 g of cetyltrimethylammonium bromide (CTAB) are dissolved in 30 mL of water and stirred continuously at room temperature for 60 min. Then, the mixture is transferred to a reaction vessel and heated to 180 °C for 18 h to obtain initial ZnO powder. The powder is washed three times alternately with water and ethanol and dried at 60 °C overnight to finally obtain ZnO piezoelectric catalytic powder sample 2.

[0041] Preparation Example 3 A piezoelectric catalytic powder is provided. Specifically, bismuth nitrate and sodium chloride are dissolved in deionized water at a molar ratio of 1:1. After stirring, the mixture is transferred to a high-pressure reactor and heated to 160°C for hydrothermal reaction for 24 hours. After cooling, centrifugation, washing, and drying, bismuth oxychloride piezoelectric catalytic powder sample 3 is obtained.

[0042] Example Example 1 This embodiment provides a hydrogen-producing composition and its preparation method, specifically including: Take 5 mg of ZnO piezoelectric catalytic powder sample 2 prepared in Preparation Example 2, disperse it in 2 ml of water containing 0.044 mg of coumarin, add 3 mL of water containing 100 μL of ethylene glycol, mix well to obtain hydrogen production composition 1, and sonicate it with an ultrasonic power of 480 W and an ultrasonic frequency between 20 kHz and 40 kHz, and detect its hydrogen production content.

[0043] Example 2 This embodiment provides a hydrogen-producing composition and its preparation method, specifically including: 17 mg of dipalmitoylphosphatidylcholine (DPPC), 6 mg of cholesterol, 1.5 mg of distearate phosphatidylethanolamine (DSPE), 4 mg of polyethylene glycol 2000 (PEG2000) and 0.44 mg of coumarin were dissolved in 20 mL of ethanol, and the mixture was rotary evaporated to form a film. Then, 20 mL of hydration solution was added, and the mixture was ultrasonically hydrated to form a liposome dispersion. Take 5 mg of ZnO piezoelectric catalytic powder sample 2 prepared in Preparation Example 2, disperse it in the above 2 ml liposome dispersion, add 3 mL of water containing 100 μL ethylene glycol, mix evenly to obtain hydrogen production composition 2, and sonicate it with an ultrasonic power of 480 W and an ultrasonic frequency between 20 kHz and 40 kHz, and detect its hydrogen production content.

[0044] Example 3 This embodiment provides a hydrogen-producing composition and its preparation method, specifically including: 17 mg dipalmitoylphosphatidylcholine (DPPC), 6 mg cholesterol, 1.5 mg distearate phosphatidylethanolamine (DSPE), 4 mg polyethylene glycol 2000 (PEG2000) and 0.44 mg curcumin were dissolved in 20 mL ethanol, and the mixture was rotary evaporated to form a film. Then, 20 mL of hydration solution was added, and the mixture was ultrasonically hydrated to form a liposome dispersion.

[0045] Take 5 mg of bismuth oxychloride piezoelectric catalytic powder sample 3 from Preparation Example 3, disperse it in the above 2 ml liposome dispersion, add 3 mL of water containing 100 μL ethylene glycol, mix evenly to obtain hydrogen production composition 3, and sonicate it with an ultrasonic power of 480 W and an ultrasonic frequency between 20 kHz and 40 kHz, and detect its hydrogen production content.

[0046] Example 4 This embodiment uses the same preparation method as Example 3, except that ethylene glycol is replaced with lactic acid. Other steps are the same as in Example 3 to obtain hydrogen-producing composition 4. It is then subjected to ultrasonic treatment with an ultrasonic power of 480W and an ultrasonic frequency between 20kHz and 40kHz, and its hydrogen production content is detected.

[0047] Example 5 This embodiment uses the same preparation method as Example 4, except that it is subjected to ultrasonic treatment with an ultrasonic power of 5W and an ultrasonic frequency of 1MHz, and the hydrogen production content is detected. Test case The ultrasonic hydrogen production capacity of the samples from the preparation examples and embodiments was tested, and the test results are shown in [the table below]. Figures 3 to 9 As shown, it should be noted that Figures 3 to 9 The x-axis represents “Time (min)”, indicating the hydrogen production time in minutes; the y-axis represents “Hydrogen content (%)”, “Hydrogen production rate (%)”, or “H2Production (mmol / g / h)”, all indicating the amount of hydrogen produced. “Hydrogen content (%)” is a percentage of hydrogen content, while “Hydrogen production rate (%)” or “H2Production (mmol / g / h)” is expressed in “mmol / g / h” and “μmol / g / h”, respectively, representing the millimoles or micromoles of hydrogen produced per gram of the hydrogen-producing composition per hour. Figure 3 The "ZnO+EG" indicates that zinc oxide (ZnO) piezoelectric catalytic powder is mixed with ethylene glycol (EG) solvent. Figure 7 The term “BiOCl-Cur-Lip+EG” indicates that bismuth oxychloride (BiOCl) piezoelectric catalytic powder is dispersed in a liposome dispersion containing curcumin (Cur), and then ethylene glycol (EG) is added to the system as a sacrificial agent.

[0048] according to Figure 3 and Figure 4 The results show that the zinc oxide piezoelectric catalytic powder samples obtained under different preparation conditions in Preparation Example 1 and Preparation Example 2 have significantly different hydrogen production rates.

[0049] according to Figure 5 The results showed that the addition of coumarin increased the hydrogen production of the piezoelectric catalytic powder under ultrasound by 17%.

[0050] according to Figure 6 The results showed that after the piezoelectric catalytic powder was dispersed in a liposome dispersion loaded with organic active particles, the hydrogen production under ultrasound increased by 56%.

[0051] according to Figure 7 The results showed that the hydrogen production rate of the bismuth oxychloride piezoelectric catalytic powder was the highest, reaching 0.34 mmol / g / h, after 5 minutes of sonication.

[0052] according to Figure 7 and Figure 8 The results show that when the proton donor was changed from ethylene glycol to lactic acid, the hydrogen production rate reached its maximum of 10.9 mmol / g / h at 2 min. Therefore, it can be inferred that lactic acid is more effective as a proton donor than ethylene glycol. This may be because lactic acid has a stronger hole-trapping ability: the α-hydroxy structure of lactic acid is more easily oxidized by holes generated by the piezoelectric effect than the terminal hydroxyl group of ethylene glycol, resulting in higher hole-trapping efficiency. This more effectively suppresses carrier recombination, allowing more electrons to participate in the water splitting reaction and fundamentally improving the hydrogen production rate. Furthermore, the lactic acid molecule contains a carboxyl group, which can ionize into a negative charge, allowing it to adsorb onto the surface of the positively charged piezoelectric catalytic particles in this invention. This enriches the proton donor near the catalytic reaction site, allowing holes to be captured as soon as they are generated, significantly improving the capture efficiency. Ethylene glycol, being a neutral molecule, cannot accumulate at the catalytic interface; holes need to diffuse into the solution to be captured, and recombination loss is more likely during this process.

[0053] according to Figure 8 and Figure 9 The results show that, compared to the laboratory-grade high-power broadband ultrasound (480 W, 20–40 kHz) used in Example 4, the 5 W, 1 MHz ultrasound beauty device used in Example 5 is closer to the equipment parameters for civilian medical aesthetic scenarios, belonging to low-intensity, high-frequency gentle ultrasound. Test results show that the system can reach a peak hydrogen production rate of 1.08 mmol / g / h within 2 minutes, verifying its excellent piezoelectric catalytic hydrogen production activity under low-power, high-frequency ultrasound conditions. This indicates that the catalytic system has good adaptability to ultrasound excitation of different intensities, breaking through the application limitations of traditional piezoelectric catalysis relying on high-power ultrasound equipment, and providing key performance support for its application in portable medical aesthetic devices and home care scenarios.

[0054] The above are merely specific embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that the present invention includes, but is not limited to, the contents described in the accompanying drawings and the specific embodiments above. Any modifications that do not depart from the functional and structural principles of the present invention will be included within the scope of the claims.

Claims

1. A hydrogen-producing composition, characterized in that, The hydrogen-producing composition (1) comprises: Multiple piezoelectric catalytic particles (11) are capable of generating piezoelectric charges under mechanical force; Multiple organic active particles (12) have multiple functional groups and organic conjugated units for metal ion coordination. The organic active particles are coordinated and bonded to the piezoelectric catalytic particles through the functional groups. The organic conjugated units are conjugated and connected to the functional groups to form a carrier transport path extending from the functional groups to the organic conjugated units. The organic conjugated units are capable of absorbing light to generate photogenerated carriers. The energy levels of the organic active particles and the piezoelectric catalytic particles are matched, so that a heterojunction is formed at the interface between the organic active particles and the piezoelectric catalytic particles. The piezoelectric catalytic particles and the organic active particles are dispersed in the liposome carrier (10).

2. The hydrogen-producing composition according to claim 1, characterized in that, The mass ratio of the liposome carrier to the piezoelectric catalytic particles is between 100:50 and 100:300, and the mass ratio of the liposome carrier to the organic active particles is between 1000:1 and 100:

18.

3. The hydrogen-producing composition according to claim 1, characterized in that, The size of the piezoelectric catalytic particles is between 1 μm and 5 μm.

4. The hydrogen-producing composition according to any one of claims 1 to 3, characterized in that, The material of the organic active particles is selected from at least one of organic conjugated molecules, polyphenolic compounds, flavonoids, quinones, and conjugated aromatic compounds, and the functional group that provides coordination for metal ions is selected from at least one of β-diketone groups, ortho-phenolic hydroxyl groups, and ortho-quinone groups.

5. The hydrogen-producing composition according to claim 4, characterized in that, The organic active particles are made from at least one of the following: curcumin, curcuminoids, resveratrol, catechins, anthocyanins, coumarin, lutein, quercetin, rutin, tea polyphenols, gallic acid, nicotinamide, retinol, coenzyme Q10, ferulic acid, caffeic acid, chlorogenic acid, emodin, and shikonin.

6. The hydrogen-producing composition according to any one of claims 1 to 3, characterized in that, The material of the piezoelectric particles is selected from at least one of bismuth-based piezoelectric materials, zinc-based piezoelectric materials, titanium-based piezoelectric materials, niobium-based piezoelectric materials, alkali metals, alkaline earth metal piezoelectric ceramics, and two-dimensional piezoelectric nanomaterials.

7. The hydrogen-producing composition according to any one of claims 1 to 3, characterized in that, The materials of the liposome carrier include phospholipids, steroidal compounds, and polyethylene glycol modifiers.

8. The hydrogen-producing composition according to claim 7, characterized in that, In the liposome carrier, the mass ratio of the phospholipid, steroid compound and polyethylene glycol modifier is between (5-30): (2-10): (1-10).

9. The hydrogen-producing composition according to any one of claims 1 to 3, characterized in that, The piezoelectric composite further includes a proton donor for providing protons, the material of which is selected from at least one of lactic acid, formic acid, acetic acid, oxalic acid, ascorbic acid, methanol, ethanol, isopropanol, glycerol, triethanolamine, triethylamine, ethylenediaminetetraacetic acid, citrate, glucose, fructose, and biomass-derived small molecule sacrificial agents.

10. A method for preparing a hydrogen-producing composition, characterized in that, The preparation method includes: Liposome carriers are mixed and dissolved with organic active powder to obtain a first mixture. The organic active powder includes multiple organic active particles. Each organic active particle has multiple functional groups for metal ion coordination and organic conjugated units. The organic conjugated units are conjugated with the functional groups to form a carrier transport path extending from the functional groups to the organic conjugated units. The organic conjugated units can absorb light to generate photogenerated carriers. The organic active particles can coordinate and bond with the piezoelectric catalytic particles through the functional groups. The energy levels of the organic active particles and the piezoelectric catalytic particles are matched, enabling the organic active particles to form a heterojunction with the piezoelectric catalytic particles. The first mixture is desolventized and then hydrated to form a first intermediate complex, the first intermediate complex comprising a liposome dispersion loaded with a plurality of the organic active particles; The piezoelectric catalytic powder is mixed with the first intermediate complex to obtain the composition according to any one of claims 1 to 9, wherein the piezoelectric catalytic powder comprises a plurality of piezoelectric catalytic particles.

11. The preparation method according to claim 10, characterized in that, The step of mixing the piezoelectric catalytic powder with the first intermediate complex to obtain the composition includes: mixing and dispersing the piezoelectric catalytic component powder with a sacrificial agent in a solvent, wherein the sacrificial agent includes a proton donor.

12. The preparation method according to any one of claims 10 or 11, characterized in that, Before mixing the piezoelectric catalytic powder with the first intermediate complex, the method further includes: Piezoelectric metal salts are mixed in a solvent to form a piezoelectric metal mixture; The piezoelectric metal mixture is placed in a reaction vessel and reacted at a set temperature and pressure to generate piezoelectric crystals, wherein the set temperature is between 100°C and 200°C. The piezoelectric crystal is cooled, separated, washed, and dried to obtain the piezoelectric catalytic powder.

13. A method for producing hydrogen, characterized in that, The hydrogen production method includes: A hydrogen-producing stock solution is prepared using a hydrogen-producing composition, wherein the hydrogen-producing composition is the hydrogen-producing composition according to any one of claims 1 to 9; The hydrogen-producing stock solution is subjected to ultrasonic treatment, which causes the hydrogen-producing stock solution to generate hydrogen gas under the action of ultrasound.

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