Zinc-hydrogen battery iron-based nano-alloy cathode and preparation method and tumor treatment application thereof

Abstract

The invention discloses an iron-based nano-alloy cathode of a zinc-hydrogen battery, a preparation method of the iron-based nano-alloy cathode and application of the iron-based nano-alloy cathode to tumor treatment. The iron-based nano-alloy cathode comprises an iron-based nano-alloy formed by alloying iron and another metal element, and the iron-based nano-alloy is used as a cathode active material; and the other metal element is at least one of chromium, aluminum, platinum and nickel. The solution phase interface reduction method is used for preparing the iron-based nano-alloy, and the method has the advantages of being simple in process, short in preparation period and good in universality. The zinc-hydrogen battery composed of the iron-based nano-alloy cathode and the metal zinc anode has a good hydrogen evolution effect, is implanted into a tumor tissue area through an operation or intervention means, continuously produces enough hydrogen in situ in a body fluid environment, directly acts on a tumor part for a long time, and can remarkably reduce the tumor size.

Description

Technical Field

[0001] The present invention relates to the technical field of biological battery materials, in particular to an iron-based nano alloy cathode for a zinc-hydrogen battery, a preparation method thereof and tumor treatment application thereof. Background Art

[0002] Although existing tumor treatments have achieved certain results in disease control, there are still many problems that need to be solved:

[0003] First, treatments are often accompanied by significant side effects and complications. For example, while radiotherapy can effectively destroy tumor tissue, it can also cause damage to surrounding normal tissues, such as radiation pneumonitis and skin inflammation. Chemotherapy drugs, while also killing tumor cells, can also be toxic to normal cells, triggering a range of adverse reactions such as nausea, vomiting, and bone marrow suppression. These side effects not only reduce patients' quality of life but may also limit the further implementation of treatment strategies.

[0004] Secondly, the selectivity and specificity of existing treatments need to be improved. While attacking tumor cells, radiotherapy and chemotherapy often inevitably damage normal cells. This nonspecific effect can weaken the therapeutic effect and increase treatment risks. Although targeted drugs have emerged in recent years, they can improve treatment specificity to a certain extent, their efficacy is relatively limited and usually needs to be used in combination with other treatments.

[0005] Furthermore, individual patient variability and drug resistance are significant challenges in cancer treatment. Different patients respond significantly to treatments, with some becoming insensitive to certain treatments or developing drug resistance. This complicates treatment planning, requiring careful consideration of individual patient differences and specific disease characteristics.

[0006] Finally, high treatment costs are also a major factor limiting the widespread use of cancer treatments. While some advanced treatments, such as immunotherapy and cell therapy, are highly effective, they are prohibitively expensive, making them unaffordable for many patients.

[0007] Hydrogen therapy is considered a highly targeted, low-cost, and virtually side-effect-free cancer treatment. Currently, the primary challenge with hydrogen therapy is how to continuously deliver hydrogen to tumor cells. Advances in nanotechnology have led to the emergence of a number of nanomedicines capable of in situ release of hydrogen in tumors. However, these nanomedicines have a short residence time in tumors and limited penetration, while increasing the dosage and frequency of injections can lead to side effects. This limits the effectiveness of hydrogen therapy for tumors and remains a current challenge in this field. Summary of the Invention

[0008] In light of the aforementioned shortcomings of the prior art, the present invention provides an iron-based nanoalloy cathode for zinc-hydrogen batteries, a method for its preparation, and its application in tumor treatment. The iron-based nanoalloy cathode exhibits excellent biosafety. Compared to conventional zinc-hydrogen batteries, zinc-hydrogen batteries based on this iron-based nanoalloy cathode exhibit superior hydrogen evolution performance. Implanting this zinc-hydrogen battery in tumor tissue can produce sufficient hydrogen in situ, resulting in significant tumor treatment efficacy.

[0009] To achieve the above object, the present invention provides the following technical solutions:

[0010] In a first aspect, the present invention provides an iron-based nano-alloy cathode for a zinc-hydrogen battery, characterized in that: it comprises an iron-based nano-alloy formed by alloying iron and another metal element as the cathode active material; the other metal element is at least one of chromium, aluminum, platinum, and nickel; and the atomic ratio of iron to the other metal element is 1 to 3:1.

[0011] Furthermore, the iron-based nano-alloy cathode includes a mixture of an iron-based nano-alloy, a binder and a conductive agent.

[0012] In a second aspect, the present invention provides a method for preparing an iron-based nano-alloy cathode for a zinc-hydrogen battery, characterized in that the method comprises the following steps:

[0013] S1. Dissolving an iron source precursor, wherein the iron source precursor is at least one of ferric sulfate and ferric acetylacetonate; then adding another metal element precursor and stirring evenly; the other metal element precursor is at least one of chromium, aluminum, platinum, and nickel; and the atomic ratio of iron to the other metal element is 1 to 3:1;

[0014] S2. Centrifugally filter the product obtained in step S1, add a polymer compound, and stir evenly; the polymer compound is at least one of PE, PVC, PVE, and PVP;

[0015] S3, adding a strong reducing agent to the product obtained in step S2, stirring, collecting the product by centrifugation, and drying to obtain an iron-based nano alloy;

[0016] S1 to S3 were performed in an inert gas environment;

[0017] S4, dispersing the Fe-based nano alloy material using a solvent, then adding a binder and stirring evenly;

[0018] S5. Adding a conductive agent to the product obtained in step S4 to prepare a slurry;

[0019] S6. Evenly brush the slurry obtained in step S5 onto carbon paper to prepare an iron-based nano alloy cathode for a zinc-hydrogen battery.

[0020] Furthermore, the strong reducing agent is at least one of benzenesulfonic acid, potassium iodide, potassium bisulfite, and sodium borohydride.

[0021] Furthermore, the drying is freeze-drying.

[0022] Furthermore, the binder is at least one of PAN, PAA, CMC, and PTFE; and the conductive agent is at least one of Ketjen black, carbon nanotubes, graphene, and acetylene black.

[0023] In a third aspect, the present invention provides an iron-based nano alloy cathode for a zinc-hydrogen battery, characterized in that it is prepared by the above-mentioned preparation method.

[0024] In a fourth aspect, the present invention provides a zinc-hydrogen battery, characterized in that it comprises a zinc anode, a glass fiber separator and the zinc-hydrogen battery iron-based nano-alloy cathode as described above, which are stacked in sequence.

[0025] In the final aspect, the present invention provides an application of the zinc-hydrogen battery for in situ treatment of tumors, characterized in that body fluid is used as the electrolyte of the zinc-hydrogen battery.

[0026] Furthermore, the zinc-hydrogen battery as described above is implanted into the tumor tissue area through surgery or interventional means.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) The Fe-based nanoalloy of the present invention has good biocompatibility. The Fe-based nanoalloy is prepared by a solution phase interface reduction method, which has the characteristics of simple process, short preparation cycle and good versatility.

[0029] (2) Since the d-band center of the Fe-based nanoalloy is farther away from the Fermi level and the hydrogen adsorption free energy of the Fe-based nanoalloy is closer to 0, the zinc-hydrogen battery composed of the Fe-based nanoalloy cathode and the metal zinc anode of the present invention has a good hydrogen evolution effect.

[0030] (3) The zinc-hydrogen battery of the present invention performs well in a body fluid environment, directly acts on the tumor site for a long time, has a good therapeutic effect, can significantly reduce the tumor size of tumor-bearing mice, and ultimately achieve tumor cure. When the zinc-hydrogen battery of the present invention is precisely implanted near the tumor tissue, the generated hydrogen can directly act on the tumor cells in situ, triggering a series of biochemical effects. The tiny molecules of hydrogen can penetrate into the tumor cells, destroy their mitochondrial function, and lead to energy metabolism disorders; at the same time, hydrogen can also cause lysosome rupture, further aggravating cell damage; in addition, hydrogen can also destroy key cell components such as cytochrome, and ultimately lead to the death of tumor cells. The local release of hydrogen can not only minimize damage to normal tissues, but also ensure that hydrogen effectively kills tumor cells. In addition, because hydrogen is a non-toxic and harmless gas, this treatment method has fewer side effects and higher safety than traditional chemotherapy, radiotherapy and other means. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The present invention and its features and advantages will become more apparent upon reading the detailed description of non-limiting embodiments with reference to the following drawings. Like reference numerals indicate like parts throughout the drawings. The drawings are not necessarily drawn to scale, emphasis being placed on illustrating the subject matter of the present invention.

[0032] Figure 1 This is a transmission electron microscope photograph of the FePt nanoalloy in Example 1 of the present invention.

[0033] Figure 2 Graph showing the change in hydrogen evolution concentration over time in the zinc-hydrogen battery in Example 4 of the present invention.

[0034] Figure 3 This is a biological electron microscope photograph of the killing effect of tumor cells by in situ hydrogen production by the zinc-hydrogen battery in Example 5 of the present invention.

[0035] Figure 4 These are photos of tumors in the control group, comparative example 1, comparative example 2 and example 5 after 16 days. DETAILED DESCRIPTION

[0036] The structure of the present invention is further described below with reference to the accompanying drawings and specific embodiments, but is not intended to limit the present invention.

[0037] The reaction devices, compounds, solvents, etc. involved in the following embodiments and examples are all commercially available, and their preparation methods are not described in detail in the present invention.

[0038] The detection instruments and detection reagents involved in the following effect embodiments are all commercially available, and the detection methods adopted are the existing technologies that can be retrieved.

[0039] The present invention provides an iron-based nano-alloy cathode for a zinc-hydrogen battery, comprising an iron-based nano-alloy formed by alloying iron with another metal element as a cathode active material; the other metal element is at least one of chromium, aluminum, platinum, and nickel; and the atomic ratio of iron to the other metal element is 1 to 3:1.

[0040] A zinc-hydrogen battery can be made by stacking a zinc anode, a glass fiber separator, and the aforementioned iron-based nanoalloy cathode. When implanted into tumor tissue, the zinc-hydrogen battery can generate hydrogen in situ in the tumor tissue area, thereby inducing apoptosis and killing the tumor cells.

[0041] The d-band center of the above Fe-based nano-alloy is farther away from the Fermi level, and the hydrogen adsorption free energy of the Fe-based nano-alloy is closer to 0, which is conducive to improving the hydrogen evolution performance. Therefore, it has a better hydrogen evolution effect than the traditional zinc-hydrogen battery. The principle of the zinc-hydrogen battery is as follows: Fe-based nano-alloy is prepared to form the cathode, Zn is used as the anode, and a battery separator is added to form the battery. The battery uses animal body fluids as the electrolyte, and the Fe-based nano-alloy in the positive electrode produces H2 in situ based on the electrochemical HER (hydrogen evolution reaction) effect. The chemical reaction equation of the battery discharge process is as follows:

[0042] Cathode: 2H + +2e→H2

[0043] Anode: Zn-2e→Zn 2+

[0044] The iron-based nano alloy can be prepared by a solution phase interface reduction method, comprising the following steps:

[0045] S1. Dissolve an iron source precursor, wherein the iron source precursor is at least one of ferric sulfate and ferric acetylacetonate; then add another metal element precursor and stir evenly; the other metal element precursor is at least one of chromium, aluminum, platinum, and nickel; the atomic ratio of iron to the other metal element is 1~3:1; the solvent of the precursor is anhydrous ethanol.

[0046] S2. Centrifuge the product obtained in step S1, add a polymer compound, and stir until uniform. The polymer compound is at least one of PE, PVC, PVE, and PVP, depending on the other metal element precursor raw material. The polymer compound helps control the size, morphology, and dispersibility of the nanoparticles.

[0047] S3. A strong reducing agent is added to the product obtained in step S2, and the mixture is stirred, centrifuged, and dried to obtain an iron-based nanoalloy. Preferably, the strong reducing agent is at least one of benzenesulfonic acid, potassium iodide, potassium bisulfite, and sodium borohydride. The drying method is freeze-drying. It is understood that the drying method may also be other drying methods that maintain the nanostructure of the alloy after drying.

[0048] S1 to S3 were performed in an inert gas environment;

[0049] The further preparation of the zinc-hydrogen battery iron-based nano alloy cathode also includes the following steps:

[0050] S4, dispersing the Fe-based nano alloy material using a solvent, then adding a binder and stirring evenly;

[0051] S5. Adding a conductive agent to the product obtained in step S4 to prepare a slurry;

[0052] S6. Evenly brush the slurry obtained in step S5 onto carbon paper to prepare an iron-based nano alloy cathode for a zinc-hydrogen battery.

[0053] As a preferred technical solution, further: the binder is at least one of PAN, PAA, CMC, and PTFE; the conductive agent is at least one of Ketjen black, carbon nanotubes, graphene, and acetylene black.

[0054] The solution-phase interfacial reduction method provided by the present invention prepares alloy nanoparticles by reducing a mixed solution of multiple metal ions. Compared with traditional physical synthesis methods, it has the following advantages:

[0055] 1. The raw material cost is low and the versatility is strong.

[0056] 2. Simple operation, no complicated operation required.

[0057] 3. Low requirements on equipment, only the reaction S1~S3 environment needs to be an inert gas environment.

[0058] Below, the technical solution of the present invention is described in detail with reference to specific embodiments and comparative examples.

[0059] Example 1

[0060] The preparation of a zinc-hydrogen battery Fe-based nano alloy cathode comprises the following steps:

[0061] Step 1: Dissolve iron acetylacetonate (0.05 g-0.15 g) in 100 mL of anhydrous ethanol in a nitrogen atmosphere.

[0062] Step 2: Dissolve the material obtained in step 1 in a N2 atmosphere, add a platinum precursor (tetrachloroplatinic acid) with an atomic ratio of iron to platinum of 1:1, and add a polymer compound PE (0.05g-0.12g) and stir evenly;

[0063] Step 3: Dissolve the substance obtained in step 2 in a N2 atmosphere, add potassium bisulfite in an amount twice the total amount of the previous iron acetylacetonate and platinum metal precursor, stir and centrifuge, and freeze-dry. The obtained product is shown in the electron microscope image. Figure 1 As shown in FIG, the particle size of the obtained FePt nano-alloy particles is 2-5 nm.

[0064] Step 4: Disperse the Fe-based nano-alloy material obtained in step 3, add PAA (0.15 g to 0.25 g), and stir evenly;

[0065] Step 5, adding graphene (0.10 g to 0.12 g) to the product obtained in step 4 to prepare a slurry;

[0066] Step 6: Evenly brush the slurry obtained in step 5 onto carbon paper to prepare a battery cathode.

[0067] Example 2

[0068] The preparation of a zinc-hydrogen battery Fe-based nano alloy cathode comprises the following steps:

[0069] Step 1: Dissolve iron acetylacetonate (0.05 g-0.15 g) in 100 mL of anhydrous ethanol in an Ar atmosphere.

[0070] Step 2: In an Ar atmosphere, dissolve the material obtained in step 1, add aluminum precursor (aluminum chloride), with an iron to aluminum atomic ratio of 3:1, and add a polymer compound PVC (0.06g-0.12g) and stir evenly;

[0071] Step 3, in an Ar atmosphere, dissolve the substance obtained in step 2, add benzenesulfonic acid in an amount twice the total amount of the previous iron acetylacetonate and aluminum precursor substances, stir and collect by centrifugation, and freeze-dry.

[0072] Step 4: Disperse the iron-aluminum nano alloy material obtained in step 3, add PAN (0.14 g-0.21 g), and stir evenly;

[0073] Step 5: Add the product obtained in step 4 and a conductive agent (0.11 g to 0.21 g) Ketjen black to form a slurry;

[0074] Step 6: Evenly brush the slurry obtained in step 5 onto carbon paper to prepare a battery cathode.

[0075] Example 3

[0076] The preparation of a zinc-hydrogen battery Fe-based nano alloy cathode comprises the following steps:

[0077] Step 1: Dissolve iron acetylacetonate (0.05 g-0.12 g) in 100 mL of anhydrous ethanol in a nitrogen atmosphere.

[0078] Step 2: Dissolve the material obtained in step 1 in a N2 atmosphere, add nickel precursor (nickel acetylacetonate), with an iron to nickel atomic ratio of 2.5:1, and add a polymer compound PVP (0.06g-0.10g) and stir;

[0079] Step 3, in a N2 atmosphere, dissolve the substance obtained in step 2, add sodium borohydride in an amount twice the total amount of the previous iron acetylacetonate and nickel precursor substances, stir and collect by centrifugation, and freeze-dry.

[0080] Step 4, dispersing the iron-nickel nano alloy material obtained in step 3, adding CMC, and stirring evenly;

[0081] Step 5: Add carbon nanotubes (0.13 g to 0.17 g) to the product obtained in step 4 to form a slurry;

[0082] Step 6: Evenly brush the slurry obtained in step 5 onto carbon paper to prepare a battery cathode.

[0083] It is expected that iron-chromium nanoalloy (Fe2Cr) cathode can also be prepared by a similar preparation method.

[0084] Example 4

[0085] The zinc-hydrogen battery is prepared by stacking a zinc sheet, a glass fiber separator, and the iron-based nano-alloy cathode prepared in Example 1 in sequence, and then bonding them with a binder (PTFE) to form a package. The hydrogen production of the zinc-hydrogen battery in an in vitro simulated tumor environment (pH 6.0) is characterized as follows. Figure 2 As shown, it can be seen that the zinc-hydrogen battery has a good hydrogen evolution effect.

[0086] Example 5

[0087] The zinc-hydrogen battery of Example 4 was subjected to a cytotoxicity test on tumor cells. The results are as follows: Figure 3 As shown, in the simulated body fluid environment, after 24 hours, the apoptosis characteristics of tumor cells were obvious.

[0088] The same batch of tumor-bearing mice were randomly divided into a control group and an experimental group. Several tumor-bearing mice in the experimental group were anesthetized; the zinc-hydrogen battery of Example 4 was surgically implanted into the tumor tissue area of the tumor-bearing mice in the experimental group. The zinc-hydrogen battery performed well in the body fluid environment, had a long therapeutic effect, and had a good therapeutic effect. Figure 4The results show that zinc-hydrogen batteries can significantly reduce tumor size in tumor-bearing mice and ultimately cure the tumor. When zinc-hydrogen batteries are precisely implanted near tumor tissue, the generated hydrogen gas can directly act on tumor cells in situ, triggering a series of biochemical effects. Tiny hydrogen molecules can penetrate into tumor cells, disrupting their mitochondrial function and leading to impaired energy metabolism. Hydrogen can also cause lysosome rupture, further exacerbating cell damage. Furthermore, hydrogen can destroy key cellular components such as cytochromes, ultimately leading to tumor cell death. The localized release of hydrogen gas not only minimizes damage to normal tissue but also ensures its effective killing of tumor cells.

[0089] Comparative Example 1

[0090] The same batch of tumor-bearing mice were randomly divided into a control group and an experimental group.

[0091] Several tumor-bearing mice in the experimental groups were anesthetized; and the Fe-based nano-alloy cathode of the zinc-hydrogen battery of Example 1 was surgically implanted into the tumor tissue area of the tumor-bearing mice in the experimental groups.

[0092] Comparative Example 2

[0093] The same batch of tumor-bearing mice were randomly divided into a control group and an experimental group.

[0094] Several tumor-bearing mice in the experimental groups were anesthetized; the batteries assembled in Example 4 were implanted into the tumor tissue areas of the tumor-bearing mice in the experimental groups, with the cathode and anode separated and the batteries not working.

[0095] from Figure 4 It can be seen that there was no significant change in the tumors of mice implanted with a single positive electrode (Comparative Example 1) and a non-working battery (Comparative Example 2), indicating that the Fe-based nano-alloy cathode has good biocompatibility, but has no tumor treatment effect itself. However, after implanting the working battery in Example 5, the tumors of mice were significantly reduced, reflecting a good tumor treatment effect.

[0096] In summary, the present invention provides a zinc-hydrogen battery Fe-based nano-alloy cathode, a preparation method thereof, and its application in tumor treatment. The Fe-based nano-alloy cathode not only has good biosafety, but also exhibits high stability. This innovative nano-alloy material has huge application potential in the field of tumor treatment and can be used as a potential tumor treatment product. The battery composed of the nano-alloy and metallic zinc performed well in animal experiments, and was able to significantly reduce the tumor size of tumor-bearing mice, and ultimately achieve tumor cure. This discovery not only proves the effectiveness of the nano-alloy in tumor treatment, but also once again verifies its high biosafety, providing strong support for future clinical applications. Compared with other hydrogen treatment methods, the present invention uses an implanted battery to generate hydrogen in situ in the tumor tissue, so it is more effective than other reported treatment options.

[0097] Those skilled in the art should understand that they can implement variations by combining the prior art with the above embodiments, which will not be described in detail here. Such variations do not affect the essence of the present invention and will not be described in detail here.

[0098] The above describes the preferred embodiments of the present invention. It should be understood that the present invention is not limited to the above-mentioned specific embodiments, and the devices and structures that are not described in detail should be understood to be implemented in a common manner in the art; any technician familiar with the art can use the above-mentioned disclosed methods and technical contents to make many possible changes and modifications to the technical solutions of the present invention without departing from the scope of the technical solutions of the present invention, or modify them into equivalent embodiments of equivalent changes, which does not affect the essential content of the present invention. Therefore, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention that do not depart from the content of the technical solutions of the present invention are still within the scope of protection of the technical solutions of the present invention.

Claims

1. A zinc-hydrogen battery iron-based nano alloy cathode, characterized by: The invention relates to an iron-based nano alloy made by alloying iron with another metal element as a cathode active material; the other metal element is at least one of chromium, aluminum, platinum and nickel; and the atomic ratio of iron to the other metal element is 1 to 3:

1.

2. The iron-based nano alloy cathode for zinc-hydrogen battery according to claim 1, characterized in that: The iron-based nano alloy cathode comprises a mixture of an iron-based nano alloy, a binder and a conductive agent.

3. A method for preparing an iron-based nano alloy cathode for a zinc-hydrogen battery, characterized in that: The following steps are involved: S1. Dissolving an iron source precursor, wherein the iron source precursor is at least one of ferric sulfate and ferric acetylacetonate; then adding another metal element precursor and stirring evenly; the other metal element precursor is at least one of platinum, aluminum, chromium, and nickel; and the atomic ratio of iron to the other metal element is 1 to 3:1; S2. Centrifugally filter the product obtained in step S1, add a polymer compound, and stir evenly; the polymer compound is at least one of PE, PVC, PVE, and PVP; S3, adding a strong reducing agent to the product obtained in step S2, stirring, collecting the product by centrifugation, and drying to obtain an iron-based nano alloy; S1 to S3 were performed in an inert gas environment; S4, dispersing the Fe-based nano alloy material using a solvent, then adding a binder and stirring evenly; S5. Adding a conductive agent to the product obtained in step S4 to prepare a slurry; S6. Evenly brush the slurry obtained in step S5 onto carbon paper to prepare an iron-based nano alloy cathode for a zinc-hydrogen battery.

4. The method for preparing an iron-based nano alloy cathode for a zinc-hydrogen battery according to claim 3, wherein: The strong reducing agent is at least one of benzenesulfonic acid, potassium iodide, potassium bisulfite, and sodium borohydride.

5. The method for preparing an iron-based nano alloy cathode for a zinc-hydrogen battery according to claim 3, characterized in that: The drying is freeze-drying.

6. The method for preparing an iron-based nano alloy cathode for a zinc-hydrogen battery according to claim 3, characterized in that: The binder is at least one of PAN, PAA, CMC, and PTFE; the conductive agent is at least one of Ketjen black, carbon nanotubes, graphene, and acetylene black.

7. A zinc-hydrogen battery iron-based nano alloy cathode, characterized in that: It is prepared by the preparation method according to any one of claims 3 to 6.

8. A zinc-hydrogen battery, characterized in that: The invention comprises a zinc anode, a glass fiber separator and the zinc-hydrogen battery iron-based nano alloy cathode according to any one of claims 1, 2 and 7, which are stacked in sequence.

9. An application of the zinc-hydrogen battery for in situ tumor treatment as claimed in claim 8, characterized in that: Body fluid serves as the electrolyte of the zinc-hydrogen battery.

10. An application of the zinc-hydrogen battery for in situ tumor treatment according to claim 9, characterized in that: The zinc-hydrogen battery according to claim 8 is implanted into the tumor tissue area through surgery or interventional means.

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