Medium-entropy metal oxide and preparation method and application thereof

Abstract

The invention belongs to the technical field of photocatalytic antibiosis and antifouling. The medium-entropy metal oxide is provided, the chemical general formula of the medium-entropy metal oxide is Cu2-x-yGaxZnyO, and x and y are numerical values meeting the requirements that x is larger than 0 and smaller than 1, and y is larger than 0 and smaller than 1; the oxide is a polyhedral irregular cubic nano particle; according to the oxide, Ga and Zn are used as dispersion phases, Cu2O is used as a matrix phase, and Ga and Zn form coordinate bonds with Cu2O crystal lattices through oxygen atoms and are randomly and uniformly distributed in the matrix phase Cu2O. The invention also provides a preparation method of the medium-entropy metal oxide and application of the medium-entropy metal oxide as or used for preparing a photocatalytic antibacterial antifouling material. A unique entropy state structure is obtained through bimetal doping in a specific proportion, so that the medium-entropy metal oxide has a lasting, stable and efficient antibacterial inhibition effect in a wide temperature range of 0-50 DEG C.

Description

Technical Field

[0001] This invention belongs to the field of photocatalytic antibacterial and antifouling technology, and provides a medium-entropy metal oxide and its preparation method, as well as its application in photocatalytic antibacterial and antifouling materials. Background Technology

[0002] Marine engineering equipment is highly susceptible to biofilm formation due to bacterial and other microbial adhesion during service, gradually leading to marine biofouling. To prevent biofilm formation, photocatalytic antibacterial treatment and antifouling technology are effective means of preventing and controlling microbial contamination. Nanoscale photocatalytic antibacterial materials with cuprous oxide (Cu2O) as the main component are currently the mainstream antibacterial and antifouling products. In practical applications, Cu2O nanoscale photocatalytic antibacterial materials suffer from problems such as easy recombination of photogenerated carriers, easy corrosion over a wide temperature range, and excessive release of copper ions. Methods to improve the stability and efficiency of Cu2O nanoscale photocatalytic antibacterial materials include ion doping strategies, defect engineering, heterostructures, and crystal plane engineering. Existing research mainly focuses on promoting the separation and extraction of photogenerated carriers. However, binary metal oxides (Cu2O) are difficult to control precisely due to their inherent structural and compositional limitations. Compared to binary metal oxides, medium-entropy metal oxides (MEMOs) are typically composed of three or more but fewer than five elements. Its highly uniform and random elemental distribution, increased mixing entropy, and unique combination of multiple metal elements endow it with extraordinary structural and functional properties, thus attracting widespread attention.

[0003] Existing research has applied the medium-entropy strategy to the design and synthesis of photoelectrocatalytic materials, electrode materials, and specialty materials. Notably, this medium-entropy strategy generates a multi-metal synergistic effect, significantly modulating the electronic structure of the materials. Of particular interest is the crucial impact of adjusting the electronic structure of photocatalytic materials on their photocatalytic activity and stability over a wide temperature range. Modifying photocatalytic materials using the medium-entropy strategy can significantly enhance their photocatalytic activity. However, how to easily and stably prepare medium-entropy materials while ensuring uniform elemental stoichiometry and maintaining a stable single-phase structure remains a pressing challenge. Therefore, it is essential to achieve the controllable preparation of medium-entropy metal oxides and enhance their photocatalytic activity and stability over a wide temperature range.

[0004] Therefore, the field of photocatalytic antibacterial and antifouling technology urgently needs a high-efficiency and stable photocatalytic antibacterial material that can adapt to a wide temperature range. Summary of the Invention

[0005] The purpose of this invention is to prepare a medium-entropy metal oxide photocatalytic antibacterial and antifouling material that can adapt to a wide temperature range environment, and is highly efficient and stable. By changing the content of the dispersed phase in MEMOs, a multi-metal synergistic effect can be generated, thereby significantly regulating the electronic structure of the material and improving its photocatalytic antibacterial ability.

[0006] To achieve the above objectives, in a first aspect, the present invention provides a medium-entropy metal oxide with the general chemical formula Cu. 2-x-y Ga x Zn y O, where x and y are numerical values ​​satisfying 0 < x < 1 and 0 < y < 1; the medium-entropy metal oxide is an irregular cubic nanoparticle; the medium-entropy metal oxide has Ga and Zn as dispersed phases and Cu2O as matrix phase, and Ga and Zn are randomly and uniformly distributed in the matrix phase Cu2O through coordination bonds formed by oxygen atoms with the Cu2O lattice.

[0007] Preferably, the Cu 2-x-y Ga x Zn y The entropy of O-type metal oxide nanoparticles is 80-90 nm in diameter.

[0008] In a second aspect, the present invention provides a method for preparing the above-mentioned medium-entropy metal oxide, wherein Ga and Zn are uniformly dispersed and in situ doped into Cu2O by liquid-phase reduction-in-situ doping, and the doping concentration is controlled to obtain an ideal morphology and a mixed entropy value, while ensuring structural stability.

[0009] Specifically, the preparation method includes the following steps: (1) Dissolve citrate in deionized water and stir to obtain solution A; the amount of deionized water added is the amount that can completely dissolve the citrate; (2) Add copper salt to solution A, stir to dissolve, and then obtain solution B; (3) Add gallium salt and zinc salt to solution B in sequence, stir to dissolve, and then obtain solution C; (4) Sodium hydroxide is added to deionized water and dissolved to obtain solution D; the amount of deionized water added is the amount that allows the sodium hydroxide to dissolve completely; (5) Stir solution C, then slowly pour solution D into solution C while continuing to stir to obtain solution E; (6) Add ascorbic acid to deionized water and dissolve to obtain solution F; ascorbic acid can reduce divalent copper ions to monovalent copper ions; the amount of deionized water added is the amount that allows the ascorbic acid to be completely dissolved; (7) Stir solution E, then slowly add solution F dropwise into solution E to obtain solution G. Continue stirring, collect the precipitate, wash it, and dry the washed sample to obtain Cu. 2-x-y Ga x Zn y O is a medium-entropy metal oxide, where 0 < x < 1 and 0 < y < 1. Applying gallium and zinc salts with different contents to step (3) yields Cu with different contents of Ga and Zn substitution. 2-x-y Gax Zn y O-type entropy-medium metal oxides.

[0010] Further, the citrate in step (1) is citrate dihydrate, that is, a salt formed by citrate ion and metal ions, including but not limited to sodium, potassium, calcium, magnesium, iron ions, such as sodium citrate dihydrate (Na3C6H5O7·2H2O) and potassium citrate dihydrate (K3C6H5O7·2H2O).

[0011] Further, the copper salt mentioned in step (2) is copper sulfate pentahydrate (CuSO4·5H2O).

[0012] Further, the gallium salt and zinc salt mentioned in step (3) are gallium nitrate trihydrate (Ga(NO3)3·3H2O) and zinc acetate dihydrate ((CH3COO)2Zn·2H2O), respectively.

[0013] Further, the stirring time in step (1) is 5 min-10 min; the stirring time in step (2) is 5 min-10 min; the stirring time for gallium salt and zinc salt in step (3) is 5 min-10 min respectively; the time for pouring solution D into solution C in step (5) is 20 s-1 min, and the stirring time is 5 min-10 min; the time for pouring solution F into solution E in step (7) is 20 s-1 min, and the stirring time is 30 min-60 min.

[0014] Further, in step (7), the precipitate is collected by centrifugation, and then washed with deionized water and acetone in sequence. The number of times the deionized water is washed is 3, and the number of times the acetone is washed is 1. The washed sample is dried in a vacuum environment for 6 h-8 h. It is preferred to dry the obtained material at about 60°C. Those skilled in the art will understand that the drying temperature can be adjusted as needed, as long as the purpose of removing the solvent can be achieved.

[0015] Furthermore, the mass ratio of citrate to copper salt, gallium salt, zinc salt, sodium hydroxide and ascorbic acid is (50~55):(25~30):(3~11):(3~9):(19~20):(20~22), preferably 53:30:(3~11):(3~9):19:21.

[0016] In a third aspect, the present invention provides the application of the aforementioned medium-entropy metal oxide as or in the preparation of photocatalytic antibacterial and antifouling materials. The medium-entropy metal oxide can be used directly as a photocatalytic antibacterial and antifouling material, or added as a functional material to a photocatalytic antibacterial and antifouling coating or composite structure.

[0017] This invention employs a wet chemical reduction-in-situ doping method. By adjusting the doping ratio, unique defects or electronic structures are formed, along with specific core-shell or gradient distributions. Furthermore, by controlling the position or valence state of the doped atoms within the crystal lattice through conditions such as pH, temperature, and reduction rate, Cu atoms are randomly and uniformly distributed in the Cu₂O matrix phase through coordination bonds formed by oxygen atoms with the Cu₂O lattice. 2-x-y Ga x Zn y O-type medium-entropy metal oxides. Using Cu₂O as the substrate provides a suitable semiconductor bandgap energy, laying the foundation for photocatalytic reactions. Introducing Zn as one of the doping metals, whose atomic radius is very close to that of copper, allows for morphological control during doping by adjusting the doping amounts of gallium and zinc salts within a specific range, thus maintaining the stability of the Cu₂O phase. Simultaneously, an appropriate amount of Zn as a dopant can both provide impurity energy level regulation to adjust the material's band structure and enhance light absorption performance, and regulate the binding energy of intermediates to enhance catalytic activity. Introducing an appropriate amount of Ga can effectively achieve synergistic control of the electronic structure by multiple metal elements. Its largest unfilled Ga 4p orbital is close to the Fermi level and has significant ps / d electron orbital coupling, serving as a new electron donor active center and inducing internal charge redistribution. On the one hand, the 4p electron orbital energy level of Ga is higher than that of Cu 3d and Zn 3d orbitals, which can generate a strong "ps / d" orbital coupling effect, effectively stabilizing the Cu material within the main lattice. On the other hand, the low mixing enthalpy among Ga, Zn, and Cu can maintain the stability of the Cu2O phase during the double doping process, making Cu... 2-x-y Ga x Zn y O-type medium-entropy metal oxides exhibit efficient and stable photocatalytic activity adaptable to a wide temperature range.

[0018] The present invention has the following beneficial effects: This preparation method synthesizes medium-entropy metal oxides with precisely tunable compositions under ambient temperature and pressure. Through entropy-state structure design, gallium and zinc, which have low enthalpy of mixing with copper, were selected to obtain single-phase stable Cu. 2-x-y Ga x Zn y OMEMOs. The preparation method involves few steps, short time, high yield, is simple and environmentally friendly, and is suitable for large-scale preparation.

[0019] Prepared Cu 2-x-y Ga x Zn y OMEMOs possess multiple metal active sites. Through the "ps / d" orbital coupling effect, they promote electronic structure modulation, which alters the band structure, thereby enhancing light absorption performance and improving photocatalytic activity.

[0020] Prepared Cu 2-x-y Ga x Zn y The enhanced light absorption properties of O MEMOs endow it with excellent self-heating characteristics, enabling stable and long-lasting photocatalytic sterilization effects over a wide temperature range. Low-temperature self-heating accelerates the redox reaction kinetics between seawater and dissolved oxygen on the material surface; at high temperatures, its unique entropy structure maintains long-lasting sterilization performance. Attached Figure Description

[0021] Figure 1 (a) is a scanning electron microscope image of Cu₂O nanomaterials prepared in Comparative Example 1; (b) is a scanning electron microscope image of Cu₂O nanomaterials prepared in Example 1. 1.6 Ga 0.2 Zn 0.2 Scanning electron microscope image of O MEMO nanomaterials.

[0022] Figure 2 Cu prepared in Example 1 1.6 Ga 0.2 Zn 0.2 Transmission electron microscopy (TEM) images and energy dispersive spectroscopy (EDS) scans of O2 MEMO nanomaterials.

[0023] Figure 3 It is the prepared Cu 2-x-y Ga x Zn y X-ray diffraction patterns of O MEMO nanomaterials and Cu2O nanomaterials prepared in Comparative Example 1.

[0024] Figure 4 Cu₂O prepared in Comparative Example 1 and Cu with different dispersed phase contents 2-x-y Ga x Zn y Photocatalytic performance of O MEMO nanomaterials: light absorption performance (a) and photogenerated carrier separation capability (b).

[0025] Figure 5 Cu₂O prepared in Comparative Example 1 and Cu with different dispersed phase contents 2-x-y Ga x Zn y Detection of ROS-active substances in O MEMO nanomaterials (a, b).

[0026] Figure 6 Cu₂O prepared in Comparative Example 1 and Cu with different dispersed phase contents 2-x-y Ga x Zn y Photocatalytic wide-temperature-range long-lasting antibacterial effect of O MEMO nanomaterials (a, b). Detailed Implementation

[0027] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0028] The following embodiments are merely exemplary and can only be used to explain and illustrate the technical solutions of the present invention, and should not be construed as limiting the technical solutions of the present invention.

[0029] Comparative Example 1: Preparation of Cu2O Nanomaterials (1) Dissolve 0.529 g of sodium citrate dihydrate in 150 mL of deionized water and stir magnetically for 5 min to obtain solution A. Add 0.299 g of copper sulfate pentahydrate to solution A and stir for 10 min to dissolve to obtain solution B.

[0030] (2) Add 0.192 g of sodium hydroxide to 1 mL of deionized water and dissolve to obtain solution C. Stir solution B, then slowly pour solution C into solution B over 30 s and continue stirring for 10 min to obtain solution D; (3) 0.211 g of ascorbic acid was added to 1 mL of deionized water and dissolved to obtain solution E. Solution D was stirred, and then solution E was slowly added dropwise to solution D to obtain solution F. The mixture was stirred for 45 min, and the precipitate was collected by centrifugation and washed with deionized water and acetone in sequence. The sample was dried in a vacuum environment to obtain Cu2O nanomaterials at a drying temperature of 60℃ for 6 hours.

[0031] Comparative Example 2: Preparation of Cu 1.6 Zn 0.4 O nanomaterials (1) Dissolve 0.529 g of sodium citrate dihydrate in 150 mL of deionized water and stir magnetically for 5 min to obtain solution A. Add 0.299 g of copper sulfate pentahydrate to solution A and stir for 10 min to dissolve to obtain solution B.

[0032] (2) Add 0.033 g of zinc acetate dihydrate to solution B, stir for 10 min to dissolve and obtain solution C.

[0033] (3) Add 0.192 g of sodium hydroxide to 1 mL of deionized water and dissolve to obtain solution D. Stir solution C, then slowly pour solution D into solution C over 30 s and continue stirring for 10 min to obtain solution E; (4) 0.211 g of ascorbic acid was added to 1 mL of deionized water and dissolved to obtain solution F. Solution E was stirred, and then solution F was slowly added dropwise to solution E to obtain solution G. The mixture was stirred for 45 min, and the precipitate was collected by centrifugation and washed sequentially with deionized water and acetone. The sample was dried under vacuum to obtain Cu. 1.6Zn 0.4 O nanomaterials were dried at 60℃ for 6 hours.

[0034] Comparative Example 3: Preparation of Cu 1.6 Ga 0.4 O nanomaterials (1) Dissolve 0.529 g of sodium citrate dihydrate in 150 mL of deionized water and stir magnetically for 5 min to obtain solution A. Add 0.299 g of copper sulfate pentahydrate to solution A and stir for 10 min to dissolve to obtain solution B.

[0035] (2) 0.038 g of gallium nitrate trihydrate was added to solution B and stirred for 10 min to dissolve, resulting in solution C.

[0036] (3) Add 0.192 g of sodium hydroxide to 1 mL of deionized water and dissolve to obtain solution D. Stir solution C, then slowly pour solution D into solution C over 30 s and continue stirring for 10 min to obtain solution E; (4) 0.211 g of ascorbic acid was added to 1 mL of deionized water and dissolved to obtain solution F. Solution E was stirred, and then solution F was slowly added dropwise to solution E to obtain solution G. The mixture was stirred for 45 min, and the precipitate was collected by centrifugation and washed sequentially with deionized water and acetone. The sample was dried under vacuum to obtain Cu. 1.6 Ga 0.4 O nanomaterials were dried at 60℃ for 6 hours.

[0037] Example 1: Preparation of Cu 1.6 Ga 0.2 Zn 0.2 O nanomaterials (1) Dissolve 0.529 g of sodium citrate dihydrate in 150 mL of deionized water and stir magnetically for 5 min to obtain solution A. Add 0.299 g of copper sulfate pentahydrate to solution A and stir for 10 min to dissolve to obtain solution B.

[0038] (2) Add 0.038 g gallium nitrate trihydrate to solution B and stir magnetically for 10 min to obtain solution C; add 0.033 g zinc acetate dihydrate to solution C and stir for 10 min to dissolve to obtain solution D.

[0039] (3) Add 0.192 g of sodium hydroxide to 1 mL of deionized water and dissolve to obtain solution E. Stir solution D, then slowly pour solution E into solution D over 30 s and continue stirring for 10 min to obtain solution F; (4) 0.211 g of ascorbic acid was added to 1 mL of deionized water and dissolved to obtain solution G. Solution F was stirred, and then solution G was slowly added dropwise to solution F over 30 s to obtain solution H. The mixture was stirred continuously for 45 min, and the precipitate was collected by centrifugation. The precipitate was washed three times with deionized water and once with acetone. The sample was dried under vacuum to obtain Cu. 1.6 Ga 0.2 Zn 0.2 O nanomaterials were dried at 60℃ for 6 hours.

[0040] Example 2: Preparation of Cu 1.4 Ga 0.3 Zn 0.3 O nanomaterials (1) Dissolve 0.529 g of sodium citrate dihydrate in 150 mL of deionized water and stir magnetically for 5 min to obtain solution A. Add 0.299 g of copper sulfate pentahydrate to solution A and stir for 10 min to dissolve to obtain solution B.

[0041] (2) 0.066 g gallium nitrate trihydrate solution B was magnetically stirred for 10 min to obtain solution C. 0.056 g zinc acetate dihydrate was added to solution C and stirred for 10 min to dissolve, thus obtaining solution D.

[0042] (3) Add 0.192 g of sodium hydroxide to 1 mL of deionized water and dissolve to obtain solution E. Stir solution D, then slowly pour solution E into solution D over 20 s and continue stirring for 10 min to obtain solution F; (4) 0.211 g of ascorbic acid was added to 1 mL of deionized water and dissolved to obtain solution G. Solution F was stirred, and then solution G was slowly added dropwise to solution F over 20 s to obtain solution H. The mixture was stirred continuously for 30 min, and the precipitate was collected by centrifugation. The precipitate was washed three times with deionized water and once with acetone. The sample was dried under vacuum to obtain Cu. 1.4 Ga 0.3 Zn 0.3 O nanomaterials were dried at 60℃ for 7 hours.

[0043] Example 3: Preparation of Cu 1.2 Ga 0.4 Zn 0.4 O nanomaterials (1) Dissolve 0.529 g of sodium citrate dihydrate in 150 mL of deionized water and stir magnetically for 10 min to obtain solution A. Add 0.299 g of copper sulfate pentahydrate to solution A and stir for 5 min to dissolve to obtain solution B.

[0044] (2) 0.102 g gallium nitrate trihydrate solution B was magnetically stirred for 5 min to obtain solution C. 0.087 g zinc acetate dihydrate was added to solution C and stirred for 5 min to dissolve, thus obtaining solution D.

[0045] (3) Add 0.192 g of sodium hydroxide to 1 mL of deionized water and dissolve to obtain solution E. Stir solution D, then slowly pour solution E into solution D over 60 s and continue stirring for 5 min to obtain solution F; (4) 0.211 g of ascorbic acid was added to 1 mL of deionized water and dissolved to obtain solution G. Solution F was stirred, and then solution G was slowly added dropwise to solution F over 60 s to obtain solution H. The mixture was stirred continuously for 60 min, and the precipitate was collected by centrifugation. The precipitate was washed three times with deionized water and once with acetone. The sample was dried under vacuum to obtain Cu. 1.2 Ga 0.4 Zn 0.4 O nanomaterials were dried at 60℃ for 8 hours. Example 4: Effect Example

[0046] Cu 2-x-y Ga x Zn y Structural characterization and performance testing of O MEMO nanomaterials: (1) Characterization of composite material structure: The morphology of Cu2O nanomaterials is as follows: Figure 1 As shown in figure a, it is a uniform, rounded-corner cubic structure with a diameter of approximately 100 nm. The Cu after doping treatment... 1.6 Ga 0.2 Zn 0.2 The morphology of O MEMO nanomaterials Figure 1 b shows that Cu 1.6 Ga 0.2 Zn 0.2 OMEMOs have a multifaceted, irregular cubic nanoparticle shape with a particle size of 80-90 nm. This is due to the lattice distortion caused by the displacement of Cu elements in the matrix phase Cu2O by the dispersed phase metal elements Ga and Zn. Ga and Zn form coordination bonds with the Cu2O lattice through oxygen atoms and are randomly and uniformly distributed in the matrix phase Cu2O. The formed Ga-O-Cu and Zn-O-Cu chemical bonds are beneficial for the regulation of electronic structure and the stabilization of Cu materials.

[0047] To characterize Cu₂O, Cu 2-x-y Ga x Zn y The crystal structure and composition of O MEMOs were determined, and the prepared samples were scanned using energy dispersive spectroscopy. Figure 2 Cu can be seen 2-x-y Ga x Zn y Elemental composition of O MEMOs (Cu 1.6 Ga 0.2 Zn 0.2 (O), proving that the dispersed phase metallic elements Ga and Zn are randomly and uniformly dispersed in Cu2O. X-ray diffraction analysis as follows: Figure 3 As shown, the crystal structure reflects the trend of entropy mixing, confirming the successful doping of Ga and Zn ions. Cu 2-x-y Ga x Zn y The diffraction peak of O MEMOs at 29.6° corresponds to the (110) crystal plane of Cu₂O. 2-x-y Ga x Zn y The diffraction peak of O MEMOs at 36.4° corresponds to the (111) crystal plane. Comparing this to the Cu2O spectrum, no diffraction peaks of other oxides were found, indicating that Ga and Zn are uniformly dispersed in Cu2O. 1.6 Ga 0.2 Zn 0.2 The diffraction peak (111) of OMEMOs shifts relative to the original Cu₂O (111)₂θ value, indicating that the incorporation of Ga and Zn ions affects the cell parameters. This suggests that single-phase stable Cu 2-x-y Ga x Zn y Successful preparation of O MEMOs.

[0048] (2) Performance characterization: like Figure 4 As shown in figure a, Cu was studied by photoluminescence spectroscopy. 2-x-y Ga x Zn y Separation of photogenerated carriers in OMEMOs. Cu 1.6 Ga 0.2 Zn 0.2 O MEMOs exhibit the lowest peak intensity, indicating that carrier recombination is effectively suppressed. This is likely because oxygen vacancies generated at this doping ratio act as electron trapping sites, capturing photogenerated electrons and reducing electron-vacancy recombination. 2-x-y Ga x Zn y The entropy structure of O MEMOs overcomes the limitations of binary and ternary metal oxides in electronic structure regulation. Absorption performance was characterized by UV-Vis spectroscopy in the 300-800 nm wavelength range. Cu₂O and Cu 2-x-y Ga x Zn yThe absorption spectra of O MEMOs are as follows: Figure 4 As shown in b. Compared to Cu₂O, Cu 2-x-y Ga x Zn y The absorption edge of O MEMOs undergoes a red shift, enhancing light absorption and improving photocatalytic activity.

[0049] like Figure 5 As shown in ab, Cu₂O and Cu are used. 2-x-y Ga x Zn y O MEMOs under simulated sunlight irradiation, respectively using Cu2O and Cu 2-x-y Ga x Zn y The minimum antibacterial concentration of O MEMOs was subjected to a 45-day sustained photocatalytic antibacterial experiment to compare the long-term stability of photocatalytic bactericidal activity of various materials. For example... Figure 5 a represents the inhibition rate of the above material against Gram-positive bacteria (Staphylococcus aureus). Figure 5 b represents the inhibition rate against Gram-negative bacteria (Pseudomonas aeruginosa). Cu 1.6 Ga 0.2 Zn 0.2 O MEMOs were 99.9% and 99.6% respectively on day 1, and remained at 84.7% and 86.6% by day 45. This indicates that Cu 2-x-y Ga x Zn y O MEMOs exhibit long-lasting and stable photocatalytic performance. Cu 2-x-y Ga x Zn y O MEMOs can be used directly as photocatalytic antibacterial and antifouling materials, generating bactericidal substances through photocatalysis to achieve synergistic antibacterial and antifouling functions; they can also be added as functional materials to photocatalytic antibacterial and antifouling coatings or composite structures, Cu 2-x-y Ga x Zn y O MEMOs, as a nano-dispersion system, can improve the overall antifouling performance of dispersed coatings and composite structures.

[0050] like Figure 6 As shown in ab, a long-term antibacterial experiment was conducted for 60 days under simulated sunlight exposure and a temperature range of 0°C-50°C. The antibacterial results on day 60 show that MEMOs Cu... 1.6 Ga 0.2 Zn 0.2O2 MEMOs maintained inhibition rates of 82.93% and 80.33% against Staphylococcus aureus and Pseudomonas aeruginosa, respectively. This indicates that MEMOs possess durable, stable, and highly effective antibacterial inhibitory effects over a wide temperature range (0°C–50°C). This property is attributed to Cu 2-x-y Ga x Zn y O MEMOs possess unique entropy-state structures obtained through bimetallic doping at specific ratios.

[0051] The above describes the preparation of Cu using a simple wet chemical reduction-in-situ doping method and a high-temperature pyrolysis method. 2-x-y Ga x Zn y A detailed explanation of several types of O photocatalytic nanomaterials.

[0052] It should be noted that the present invention is not limited to the above embodiments; for those skilled in the art, modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions claimed by the present invention.

Claims

1. A medium-entropy metal oxide, characterized in that, The general chemical formula of the medium-entropy metal oxide is Cu. 2-x- y Ga x Zn y O, where x and y are numerical values ​​satisfying 0 < x < 1 and 0 < y < 1; the medium-entropy metal oxide is a multifaceted, irregular cubic nanoparticle; the medium-entropy metal oxide has Ga and Zn as dispersed phases and Cu2O as matrix phase, with Ga and Zn randomly and uniformly distributed in the matrix phase Cu2O through coordination bonds formed by oxygen atoms with the Cu2O lattice.

2. The medium-entropy metal oxide according to claim 1, characterized in that, The nanoparticles have a particle size of 80-90 nm.

3. A method for preparing a medium-entropy metal oxide, characterized in that, Includes the following steps: (1) Dissolve citrate in deionized water and stir to obtain solution A; (2) Add copper salt to solution A, stir to dissolve, and then obtain solution B; (3) Add gallium salt and zinc salt to solution B in sequence, stir to dissolve, and then obtain solution C; (4) Sodium hydroxide is added to deionized water and dissolved to obtain solution D; (5) Stir solution C, then slowly pour solution D into solution C while continuing to stir to obtain solution E; (6) Add ascorbic acid to deionized water, dissolve, and obtain solution F; (7) Stir solution E, then slowly add solution F dropwise into solution E to obtain solution G. Continue stirring, collect the precipitate, wash, and dry to obtain Cu. 2-x-y Ga x Zn y O is a medium-entropy metal oxide, where 0 < x < 1 and 0 < y < 1.

4. The preparation method according to claim 3, characterized in that, The citrate in step (1) is sodium citrate dihydrate; the copper salt in step (2) is copper sulfate pentahydrate; the gallium salt and zinc salt in step (3) are gallium nitrate trihydrate and zinc acetate dihydrate, respectively.

5. The preparation method according to claim 3, characterized in that, The stirring time in step (1) is 5 min-10 min; the stirring time in step (2) is 5 min-10 min; the stirring time for gallium salt and zinc salt in step (3) is 5 min-10 min respectively; the time for pouring solution D into solution C in step (5) is 20 s-1 min, and the stirring time is 5 min-10 min; the time for pouring solution F into solution E in step (7) is 20 s-1 min, and the stirring time is 30 min-60 min.

6. The preparation method according to claim 3, characterized in that, In step (7), the washing method is to wash with deionized water and acetone in sequence, with the number of times of washing with deionized water being 3 times and the number of times of washing with acetone being 1 time; the washed sample is dried in a vacuum environment at a drying temperature of 60 ℃ and a drying time of 6 h-8 h.

7. The preparation method according to claim 3, characterized in that, The mass ratio of the citrate to the copper salt, gallium salt, zinc salt, sodium hydroxide and ascorbic acid is (50~55):(25~30):(3~11):(3~9):(19~20):(20~22).

8. The preparation method according to claim 3, characterized in that, The mass ratio of the citrate to the copper salt, gallium salt, zinc salt, sodium hydroxide and ascorbic acid is 53:30:(3-11):(3-9):19:

21.

9. The application of the medium-entropy metal oxide as described in claim 1 or 2, or the medium-entropy metal oxide prepared by the preparation method according to any one of claims 3-8, as or for the preparation of photocatalytic antibacterial and antifouling materials.

Images