Two-dimensional high-entropy oxide and preparation method and application thereof
Preparing two-dimensional high-entropy oxides by calcining hydrotalcite nanosheets solves the complex and cost-effective problems of existing methods, realizes structural uniformity and stability of the material, and improves its performance in chemical dynamic therapy and sound sensitivity applications.
Patent Information
- Application Number
- CN202311496162.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-11-10
- Publication Date
- 2025-05-13
AI Technical Summary
The existing high entropy oxide preparation methods are complex and costly, and it is difficult to form uniform two-dimensional high entropy oxides, affecting their performance in chemodynamic therapy and sound sensitizer applications.
Hydral talc nanosheets are used as the precursor to prepare two-dimensional high-entropy oxides by calcining method, and the calcination temperature and time are controlled to ensure the structural uniformity and stability of the material. This method is simple in process, has low equipment requirements, and can be prepared in large quantities.
The prepared two-dimensional high-entropy oxide has good catalytic activity, can produce a large amount of ROS, and is well responsive to ultrasound. It can effectively kill tumor cells in drug preparation and has good nuclear magnetic imaging functions.
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Figure CN119976995A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of preparation of anticancer drugs, and more specifically, to a two-dimensional high entropy oxide and a preparation method and application thereof. Background Art
[0002] Cancer is one of the most lethal diseases in the world. Traditional cancer treatments (chemotherapy, surgery, radiation) have disadvantages such as strong side effects and great damage to normal tissues. Nanozymes are an emerging class of nanomaterials with properties similar to enzymes. Due to their inherent advantages, such as low cost, high stability and durability, they are considered to be an ideal substitute for natural enzymes.
[0003] Nanozymes, especially those that produce reactive oxygen species, have been developed into therapeutic drugs with broad application prospects due to their specific spatiotemporal selectivity and minimal invasiveness, which avoid the nonspecific accumulation and drug resistance caused by conventional high-dose chemotherapy. The mimetic enzyme activity of nanozymes is closely related to the type, substrate, concentration, pH value and reaction temperature of the nanozyme.
[0004] The constituent elements of different valence states and valence ratios will lead to changes in the catalytic type and activity of nanozymes. High entropy oxides are oxides composed of five or more metals in equal or approximately equal amounts. The interaction of multiple elements helps to form a stable unidirectional solid solution structure and provide multiple element active sites. Therefore, the electronic structure and geometric structure of high entropy oxides can be adjusted to a large extent. Nanozymes with rich catalytic active centers and excellent performance were constructed. High entropy oxides break the immiscible gaps between elements through internal synergy and promote the optimization of enzyme catalytic performance. Compared with traditional nanozymes, the multi-element arrangement of high entropy oxide nanomaterials gives them multiple characteristics such as lattice distortion, heterogeneity, strain effect and coordination effect. Obviously, fine-tuning high entropy oxides can maximize the catalytic performance of enzymes and achieve ideal reaction kinetic rates.
[0005] NADH and NAD+ are important redox cofactors at the core of metabolism. They not only provide the proton motive force required for the mitochondrial electron transport chain (ETC), but are also required for the step of producing adenosine triphosphate (ATP) in tumor glycolysis. + The balanced state can effectively kill tumor cells.
[0006] The degree of uniform and random dispersion of multiple cations is an important indicator for evaluating HEOs. However, due to the introduction of multiple metal elements with different atomic radii, the formation of high entropy oxides often leads to the precipitation of certain elements. Taking Cu as an example, four short and two long copper-oxygen bonds will lead to Cu with disordered oxygen sublattice regulation. 2+Local Jahn-Teller type distortions are unfavorable for the formation of uniform HEOs. In addition, the current direct / indirect preparation methods are often complicated and costly. Summary of the invention
[0007] Based on the above facts, the purpose of the present invention is to provide a two-dimensional high entropy oxide and its preparation method and application. The two-dimensional high entropy oxide can be applied to chemodynamic therapy drugs and can also have sonosensitizer effects.
[0008] In order to achieve the above object, the present invention adopts the following technical solutions:
[0009] In one aspect, the present invention provides a two-dimensional high entropy oxide having a macroscopic morphology of hydrotalcite; and
[0010] The metal elements in the high entropy oxide are selected from five or more of iron, cobalt, nickel, copper, zinc, aluminum and manganese.
[0011] The two-dimensional high entropy oxide (HEO) material has a typical macroscopic hexagonal structure of two-dimensional hydrotalcite, but does not have the microscopic fine structure of hydrotalcite. The two-dimensional high entropy compound material has a two-dimensional sheet structure.
[0012] Furthermore, the metal elements in the high entropy oxide are selected from six of iron, cobalt, nickel, copper, zinc, aluminum and manganese. In this case, the obtained two-dimensional high entropy oxide has better properties.
[0013] Furthermore, in the high entropy oxide, the molar ratio between the metals is 1:1.
[0014] Furthermore, in the high entropy oxide, the molar ratio of six of iron, cobalt, nickel, copper, zinc, aluminum and manganese is 1:1:1:1:1:1.
[0015] Furthermore, the diameter of the two-dimensional high entropy oxide is 90-150nm.
[0016] Furthermore, the diameter of the two-dimensional high entropy oxide is 80-120 nm.
[0017] Furthermore, the diameter of the two-dimensional high entropy oxide is 90-110 nm.
[0018] Furthermore, the diameter of the two-dimensional high entropy oxide is 100 nm.
[0019] In the technical solution of the present invention, the diameter and size of the two-dimensional high entropy oxide refer to the maximum opposite side length of its hexagonal structure.
[0020] Furthermore, the high entropy oxide is obtained by calcining hydrotalcite nanosheets. The two-dimensional high entropy oxide obtained by this method has a uniform and stable structure.
[0021] Further, the calcination temperature is 300-900°C, and the time is 3-24h. In some examples, the calcination temperature is 300-700°C, 300-500°C, 500-700°C, 500-900°C, 300°C, 500°C, 700°C, 900°C, etc. By controlling the calcination temperature, the obtained two-dimensional high entropy oxide has uniform size and stable structure.
[0022] Further, the temperature is increased to the calcination temperature at a heating rate of 2-5°C / min.
[0023] In another aspect, the present invention provides a method for preparing the two-dimensional high entropy oxide as described above, comprising the following steps:
[0024] A mixed solution of soluble salts of five or more metals selected from iron, cobalt, nickel, copper, zinc, aluminum and manganese in an equal molar ratio of the metal elements and an alkaline solution are respectively added dropwise to an aqueous solution containing polyethylene glycol and sodium nitrate, mixed at 80° C. under alkaline conditions, centrifuged and dried after the reaction, to obtain hydrotalcite nanosheets;
[0025] The hexahydrotalcite nanosheets are placed in a tubular furnace and calcined in an air atmosphere to obtain the two-dimensional high entropy oxide.
[0026] Furthermore, the calcination temperature is 300-900°C and the calcination time is 3-24h.
[0027] Further, the temperature is increased to the calcination temperature at a heating rate of 2-5°C / min.
[0028] Furthermore, the soluble metal salt is selected from soluble inorganic metal salts.
[0029] Furthermore, the soluble metal salt is selected from one of metal nitrates and metal chlorides.
[0030] The preparation method has simple process, low requirements on equipment, strong controllability, can be prepared in large quantities, and is environmentally friendly.
[0031] Furthermore, the alkali solution is selected from sodium hydroxide, sodium carbonate or a mixture of the two.
[0032] Furthermore, the alkali solution is selected from sodium hydroxide and sodium carbonate mixed in a mass ratio of 2:(0.5-1.5) (preferably 2:1).
[0033] Furthermore, the alkaline condition is a pH of 8-10, preferably 9.
[0034] Furthermore, the reaction time is more than 8 hours.
[0035] Furthermore, the calcination is not limited to being carried out in a tubular furnace, but may also be carried out in an open heating system such as a muffle furnace.
[0036] On the other hand, the present invention provides a sonosensitizer prepared from the two-dimensional high entropy oxide as described above.
[0037] Furthermore, the sonosensitizer is a sonosensitizer for tumor treatment.
[0038] In another aspect, the present invention provides use of the two-dimensional high entropy oxide material as described above in the preparation of a nuclear magnetic resonance imaging agent.
[0039] Unless otherwise specified, various raw materials used in the present invention can be purchased commercially or obtained by conventional means in the art.
[0040] The beneficial effects of the present invention are as follows:
[0041] The two-dimensional high entropy oxide (HEO) of the present invention has good responsiveness to ultrasound while generating a large amount of ROS, and can also destroy NADH / NAD + Balanced state, it is used in the preparation of drugs, can effectively kill tumor cells, and has a good effect on cancer treatment. At the same time, because it contains Fe and Mn elements, it has good nuclear magnetic resonance imaging function.
[0042] The preparation method provided by the present invention has universal applicability. The method uses hydrotalcite as a precursor and fully combines the advantages of simple synthesis steps, easy mass preparation and uniform dispersion of metal ions. The process is simple and has low equipment requirements, strong controllability, can be prepared in large quantities, and is environmentally friendly, forming a high-quality and low-cost synthesis scheme. BRIEF DESCRIPTION OF THE DRAWINGS
[0043] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings.
[0044] Figure 1 A transmission electron micrograph of the two-dimensional high entropy oxide (HEO-300) prepared in Example 1 is shown.
[0045] Figure 2 The AFM image of the two-dimensional high entropy oxide (HEO-300) prepared in Example 1 is shown.
[0046] Figure 3 The XRD patterns of the two-dimensional high entropy oxide (HEO) materials prepared at different calcination temperatures in Example 1 are shown.
[0047] Figure 4 The catalytic activity results of the two-dimensional high entropy oxide (HEO-300) using TMB as a model developer in Example 1 are shown.
[0048] Figure 5 The electron spin resonance graph of the oxide obtained in Example 1 is shown.
[0049] Figure 6 The UV-visible spectrum of the oxidation of NADH by the two-dimensional high entropy oxide (HEO-300) in Example 1 is shown. DETAILED DESCRIPTION
[0050] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.
[0051] Example 1
[0052] A two-dimensional high entropy oxide (HEO) is prepared in the following steps:
[0053] 1) Dissolve 1.14g of manganese nitrate hexahydrate, 1.62g of iron nitrate nonahydrate, 1.16g of cobalt nitrate hexahydrate, 1.16g of nickel nitrate hexahydrate, 1.5g of aluminum nitrate nonahydrate and 0.97g of copper nitrate trihydrate in 100mL of water and mix them evenly to obtain liquid A; dissolve 1.70g of sodium nitrate in 25ml of polyethylene glycol 400 and 75ml of water and mix them evenly to obtain liquid B; dissolve 2.0g of sodium hydroxide in 100ml of water and mix them evenly to obtain liquid C; under stirring in a water bath at 80°C, slowly add liquid A and liquid C to liquid B at the same time, adjust the pH to 9, react for 8h, centrifuge, wash, freeze-dry, and then disperse in water to obtain high entropy hydrotalcite nanosheet colloid.
[0054] 2) The hexahydrotalcite nanosheets obtained in step 1) are placed in a tubular furnace and calcined at 300° C. for 3 h in air at a heating rate of 5° C. / min to obtain a two-dimensional high entropy oxide (HEO-300).
[0055] In this example, the transmission electron micrograph of the prepared two-dimensional high entropy oxide (HEO-300) is as follows: Figure 1 As shown. Figure 1 It can be seen that the two-dimensional high entropy oxide has a typical hexagonal structure. The maximum opposite side length of the hexagon is about 100-150nm.
[0056] The AFM image of the two-dimensional high entropy oxide is shown in Figure 2 As shown in the figure, it can also be seen that the two-dimensional high entropy oxide has a typical hexagonal structure and is a sheet structure. It should be noted here that since the prepared sheet-like high entropy oxides are stacked, Figure 2In the size diagram, the surface length and thickness are the data sizes obtained after stacking multiple sheets of high entropy oxide.
[0057] In this embodiment, the XRD pattern of the prepared two-dimensional high entropy oxide (HEO-300) material is as follows: Figure 3 shown.
[0058] At the same time, the same preparation method as above is adopted, but the calcination temperature in step 2) is different, namely 500°C, 700°C and 900°C. The XRD patterns of the obtained two-dimensional high entropy oxides (HEO-500, HEO-700 and HEO-900) are as follows: Figure 3 shown.
[0059] Figure 3 In the PDF#82-1039 is the PDF card of spinel structure. Figure 3 It can be seen that the structure changes with the calcination temperature, and the most ideal effect is achieved when the calcination temperature is 300℃.
[0060] The two-dimensional high entropy oxide (HEO-300) obtained when the calcination temperature is 300°C is dispersed in PBS at a concentration of 1 mg / ml to obtain a dispersion, and hydrogen peroxide is added to the dispersion to simulate the tumor microenvironment, which can make TMB color. The UV-visible spectra of the catalytic activity (catalyzing the oxidation of NADH to NAD+) when the concentrations of hydrogen peroxide are 0.2mM, 0.4mM, 0.6mM, 0.8mM, and 1.0mM are as follows: Figure 4 As shown. Figure 4 It can be seen that the two-dimensional high-entropy oxide is concentration-dependent on hydrogen peroxide and can play a better role in the tumor microenvironment (because there is very little hydrogen peroxide in normal cells, but there is an excess of hydrogen peroxide in tumors).
[0061] At the same time, if Figure 5 Electron spin resonance imaging was used to further verify the type of ROS produced. Figure 4 A in the middle is the control group, and the specific electron spin resonance results are HEO (0.1 mg / mL) + H2O2 (1.0 mM) + DMPO (100 μM) aqueous solution, HEO (0.1 mg / mL) + DMPO (100 μM) aqueous solution, H2O2 (1.0 mM) + DMPO (100 μM) aqueous solution and DMPO alone. It can be seen from the results that HEO does not produce ROS when it exists alone, but produces ROS when H2O2 exists; Figure 5B is the electron spin resonance result of HEM prepared at different calcination temperatures (water solution of HEO (1 mg / mL) + H2O2 (1.0 mM) + DMPO (100 μM)). The comparative test proves that when HEO or hydrogen peroxide exists alone, it basically does not produce a 1:2:2:1 peak, while when HEO and hydrogen peroxide exist at the same time, an obvious 1:2:2:1 peak is produced, proving that ·OH is produced. Figure 5 Figure B proves that under the same external test conditions, the maximum amount of hydroxyl radicals is produced when the final calcination temperature is 300°C, and its performance is the best.
[0062] at last, Figure 6 The UV-visible spectrum of NADH oxidation by two-dimensional high entropy oxide (HEO-300) is shown. It can be seen from the figure that the oxidation of NADH can be monitored by UV-visible absorption spectrum. After adding HEO and hydrogen peroxide, the NADH absorption peak centered at 340nm is significantly weakened over time, while the NAD absorption peak centered at 260nm is significantly weakened. + The absorption peak is enhanced. This conversion involves the conversion of NADH to NAD + The changes in , indicating that HEO can stimulate NADH oxidation through NADH oxidase mimicking activity.
[0063] Example 2
[0064] A two-dimensional high entropy oxide (HEO) is prepared in the following steps:
[0065] 1) Dissolve 0.79g of manganese chloride tetrahydrate, 1.08g of ferric chloride hexahydrate, 0.95g of cobalt chloride hexahydrate, 0.95g of nickel chloride hexahydrate, 0.97g of aluminum chloride hexahydrate and 0.38g of cupric chloride dihydrate in 100mL of water and mix them evenly to obtain liquid A; dissolve 1.70g of sodium nitrate in 25mL of polyethylene glycol 400 and 75mL of water and mix them evenly to obtain liquid B; dissolve 2.0g of sodium hydroxide in 100mL of water and mix them evenly to obtain liquid C; under stirring in a water bath at 80°C, slowly add liquid A and liquid C to liquid B at the same time, adjust the pH to 9, react for 8h, centrifuge, wash, freeze-dry, and disperse in water to obtain high entropy hydrotalcite nanosheet colloid.
[0066] 2) The hexahydrotalcite nanosheets obtained in step 1) are placed in a tubular furnace, and calcined at 300° C. for 3 h in an air atmosphere at a heating rate of 5° C. / min to obtain a two-dimensional high entropy oxide (HEO) material.
[0067] The obtained material is a flaky hexagonal structure, and the maximum opposite side length of the hexagon is between 90-150nm. It is dispersed in PBS to simulate the tumor microenvironment, and the ultraviolet-visible spectrum shows that TMB can be used to show the generation of ROS. At the same time, the electron spin resonance image is used to further verify that the ROS generated is ·OH, etc., and the ultraviolet-visible spectrum shows that it has an oxidative effect on NADH.
[0068] Example 3
[0069] Example 1 was repeated, except that in step 1), one of the nitrates in “1.14 g manganese nitrate hexahydrate, 1.62 g iron nitrate nonahydrate, 1.16 g cobalt nitrate hexahydrate, 1.16 g nickel nitrate hexahydrate, 1.5 g aluminum nitrate nonahydrate, and 0.97 g copper nitrate trihydrate” was randomly replaced with “1.19 g zinc nitrate hexahydrate”. The other conditions remained unchanged, and a two-dimensional high entropy oxide (HEO) material was prepared.
[0070] The obtained material is a flaky hexagonal structure, and the maximum opposite side length of the hexagon is between 90-150nm. It is dispersed in PBS to simulate the tumor microenvironment, and the ultraviolet-visible spectrum shows that TMB can be used to show the generation of ROS. At the same time, the electron spin resonance image is used to further verify that the ROS generated is ·OH, etc., and the ultraviolet-visible spectrum shows that it has an oxidative effect on NADH.
[0071] Example 4
[0072] Example 1 was repeated, except that "polyethylene glycol" was replaced with "Tween" in step 1). Other conditions remained unchanged, and a two-dimensional high entropy oxide (HEO) material was prepared.
[0073] The obtained material is a flaky hexagonal structure, and the maximum opposite side length of the hexagon is between 90-150nm. It is dispersed in PBS to simulate the tumor microenvironment, and the ultraviolet-visible spectrum shows that TMB can be used to show the generation of ROS. At the same time, the electron spin resonance image is used to further verify that the ROS generated is ·OH, etc., and the ultraviolet-visible spectrum shows that it has an oxidative effect on NADH.
[0074] Example 5
[0075] Example 1 was repeated, except that in step 2), "high temperature calcination for 3 h" was replaced with "high temperature calcination for 5 h, 8 h, 12 h, 16 h, 20 h or 24 h". The other conditions remained unchanged, and a two-dimensional high entropy oxide (HEO) material was prepared.
[0076] The obtained material is a flaky hexagonal structure, and the maximum opposite side length of the hexagon is between 90-150nm. It is dispersed in PBS to simulate the tumor microenvironment, and the ultraviolet-visible spectrum shows that TMB can be used to show the generation of ROS. At the same time, the electron spin resonance image is used to further verify that the ROS generated is ·OH, etc., and the ultraviolet-visible spectrum shows that it has an oxidative effect on NADH.
[0077] Example 6
[0078] Example 1 was repeated, except that the "high temperature calcination temperature of 300° C." in step 2) was replaced with "500° C., 700° C. or 900° C." The other conditions remained unchanged, and a two-dimensional high entropy oxide (HEO) material was prepared.
[0079] The obtained material is a flaky hexagonal structure, and the maximum opposite side length of the hexagon is between 90-150nm. It is dispersed in PBS to simulate the tumor microenvironment, and the ultraviolet-visible spectrum shows that TMB can be used to show the generation of ROS. At the same time, the electron spin resonance image is used to further verify that the ROS generated is ·OH, etc., and the ultraviolet-visible spectrum shows that it has an oxidative effect on NADH.
[0080] Example 7
[0081] Example 2 was repeated, except that "polyethylene glycol" was replaced with "cellulose" in step 1). Other conditions remained unchanged, and a two-dimensional high entropy oxide (HEO) material was prepared.
[0082] The obtained material is a flaky hexagonal structure, and the maximum opposite side length of the hexagon is between 90-150nm. It is dispersed in PBS to simulate the tumor microenvironment, and the ultraviolet-visible spectrum shows that TMB can be used to show the generation of ROS. At the same time, the electron spin resonance image is used to further verify that the ROS generated is ·OH, etc., and the ultraviolet-visible spectrum shows that it has an oxidative effect on NADH.
[0083] Example 8
[0084] Example 2 was repeated, except that in step 1), "reacting for 8 hours" was replaced with "reacting for 4 hours, 6 hours, 10 hours or 12 hours". Other conditions remained unchanged, and a two-dimensional high entropy oxide (HEO) material was prepared.
[0085] The obtained material is a flaky hexagonal structure, and the maximum opposite side length of the hexagon is between 90-150nm. It is dispersed in PBS to simulate the tumor microenvironment, and the ultraviolet-visible spectrum shows that TMB can be used to show the generation of ROS. At the same time, the electron spin resonance image is used to further verify that the ROS generated is ·OH, etc., and the ultraviolet-visible spectrum shows that it has an oxidative effect on NADH.
[0086] Example 9
[0087] Example 2 was repeated, except that the "heating rate of 5°C / min" in step 2) was replaced with "heating rate of 2°C / min". The other conditions remained unchanged, and a two-dimensional high entropy oxide (HEO) material was prepared.
[0088] The obtained material is a flaky hexagonal structure, and the maximum opposite side length of the hexagon is between 90-150nm. It is dispersed in PBS to simulate the tumor microenvironment, and the ultraviolet-visible spectrum shows that TMB can be used to show the generation of ROS. At the same time, the electron spin resonance image is used to further verify that the ROS generated is ·OH, etc., and the ultraviolet-visible spectrum shows that it has an oxidative effect on NADH.
[0089] Example 10
[0090] Example 2 was repeated, except that the step 1) of "stirring in a water bath at 80°C for 8 h" was replaced with "stirring in a water bath at 60°C for 12 h", and other conditions remained unchanged, to prepare a two-dimensional high entropy oxide (HEO) material.
[0091] The obtained material is a flaky hexagonal structure, and the maximum opposite side length of the hexagon is between 90-150nm. It is dispersed in PBS to simulate the tumor microenvironment, and the ultraviolet-visible spectrum shows that TMB can be used to show the generation of ROS. At the same time, the electron spin resonance image is used to further verify that the ROS generated is ·OH, etc., and the ultraviolet-visible spectrum shows that it has an oxidative effect on NADH.
[0092] Embodiment 11
[0093] The preparation method is basically the same as that in Example 1, except that the step 1) of "dissolving 1.14 g of manganese nitrate hexahydrate, 1.62 g of ferric nitrate nonahydrate, 1.16 g of cobalt nitrate hexahydrate, 1.16 g of nickel nitrate hexahydrate, 1.5 g of aluminum nitrate nonahydrate and 0.97 g of copper nitrate trihydrate in 100 mL of water and mixing them uniformly to form liquid A" is replaced with "dissolving five random transition metal nitrates selected from 1.14 g of manganese nitrate hexahydrate, 1.62 g of ferric nitrate nonahydrate, 1.16 g of cobalt nitrate hexahydrate, 1.16 g of nickel nitrate hexahydrate, 1.5 g of aluminum nitrate nonahydrate and 0.97 g of copper nitrate trihydrate in 100 mL of water and mixing them uniformly to form liquid A". The other conditions remain unchanged, and the two-dimensional high entropy oxide (HEO) material can still be prepared.
[0094] The obtained material is a flaky hexagonal structure, and the maximum opposite side length of the hexagon is between 90-150nm. It is dispersed in PBS to simulate the tumor microenvironment, and the ultraviolet-visible spectrum shows that TMB can be used to show the generation of ROS. At the same time, the electron spin resonance image is used to further verify that the ROS generated is ·OH, etc., and the ultraviolet-visible spectrum shows that it has an oxidative effect on NADH.
[0095] Comparative Example 1
[0096] The preparation method is basically the same as that in Example 1, except that "pH = 9" is replaced by "pH = 7" in step 1). The other conditions remain unchanged, and the two-dimensional high entropy oxide (HEO) material cannot be obtained.
[0097] The obtained material has a disordered size and no typical hexagonal structure. It is dispersed in PBS to simulate the tumor microenvironment and cannot make TMB color. At the same time, electron spin resonance images are used to further verify that it does not produce ROS and does not oxidize NADH.
[0098] Comparative Example 2
[0099] The preparation method is basically the same as that of Example 1, except that in step 2), "calcined at 300°C for 3h in air with a heating rate of 5°C / min" is replaced with "calcined at 100°C for 3h in air with a heating rate of 5°C / min". The other conditions remain unchanged, and the two-dimensional high entropy oxide (HEO) material cannot be prepared.
[0100] Comparative Example 3
[0101] The preparation method is basically the same as that of Example 1, except that in step 2), "calcined at 300°C for 3h under air gas with a heating rate of 5°C / min" is replaced with "calcined at 300°C for 3h under inert gas with a heating rate of 5°C / min." The other conditions remain unchanged, and the two-dimensional high entropy oxide (HEO) material cannot be prepared.
[0102] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made on the basis of the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.
Claims
1. A two-dimensional high entropy oxide, characterized in that: The high entropy oxide has a macroscopic morphology of hydrotalcite; and The metal elements in the high entropy oxide are selected from five or more of iron, cobalt, nickel, copper, zinc, aluminum and manganese.
2. The two-dimensional high entropy oxide according to claim 1, characterized in that: In the high entropy oxide, the molar ratio of any two of iron, cobalt, nickel, copper, zinc, aluminum and manganese is 1:
1.
3. The two-dimensional high entropy oxide according to claim 1, characterized in that The diameter of the high entropy oxide is 90-150nm.
4. The two-dimensional high entropy oxide according to claim 1, characterized in that The high entropy oxide is obtained by calcining hydrotalcite nanosheets; Preferably, the calcination temperature is 300-900° C. and the calcination time is 3-24 h.
5. The method for preparing a two-dimensional high entropy oxide according to any one of claims 1 to 4, characterized in that: The steps include: A mixed solution of soluble salts of five or more metals selected from iron, cobalt, nickel, copper, zinc, aluminum and manganese in an equal molar ratio of the metal elements and an alkaline solution are respectively added dropwise to an aqueous solution containing polyethylene glycol and sodium nitrate, mixed at 80° C. under alkaline conditions, centrifuged and dried after the reaction, to obtain hydrotalcite nanosheets; The hydrotalcite nanosheets are placed in a tubular furnace and calcined in an air atmosphere to obtain the two-dimensional high entropy oxide.
6. The preparation method according to claim 5, characterized in that: The calcination temperature is 300-900°C and the calcination time is 3-24h; and / or The temperature was raised to the calcination temperature at a heating rate of 2-5°C / min.
7. The preparation method according to claim 5, characterized in that: The soluble salt of the metal is selected from soluble inorganic salts of the metal; and / or The soluble metal salt is selected from one of metal nitrates and metal chlorides.
8. A sonosensitizer, characterized in that: Prepared from the two-dimensional high entropy oxide as described in any one of claims 1 to 4.
9. The sonosensitizer according to claim 8, characterized in that: The sonosensitizer is a sonosensitizer for tumor treatment.
10. Use of the two-dimensional high entropy oxide material according to any one of claims 1 to 3 in the preparation of a nuclear magnetic resonance imaging agent.