A modified V2O5 nanozyme with peroxidase-like activity and a preparation method thereof

Abstract

The present invention discloses a modified V2O5 nanozyme with peroxidase-like activity and a preparation method thereof. The nanozyme is obtained by high-temperature calcination of MOFs materials. Among them, the MOFs materials use vanadium as metal ions and organic substances as ligands, and ruthenium elements are impregnated and doped. The calcination of the MOFs materials enables the metal ion vanadium to form vanadium pentoxide. The preparation method is as follows: (1) Add a vanadium compound, an organic ligand, and hydrochloric acid to a solvent, and carry out a solvothermal reaction to obtain MOFs materials; (2) Add a ruthenium salt to the solvent, then add the MOFs materials obtained in step (1), impregnate with ruthenium, and finally dry; (3) Calcinate the MOFs materials treated in step (2) at a high temperature in an air atmosphere to obtain the modified V2O5 nanozyme. By introducing Ru elements into V2O5 and obtaining the nanozyme material based on the calcination of MOFs materials, the peroxidase-like catalytic activity of V2O5 is improved.

Description

Technical Field

[0001] The present invention relates to a nanozyme, and in particular to a modified V2O5 nanozyme with peroxidase-like activity and a preparation method thereof. Background Art

[0002] Natural enzymes are highly efficient biocatalysts, but their limitations such as high cost, low stability and storage difficulties have greatly hindered their practical applications. Nanozymes are a class of nanomaterials with enzymatic activity that have the advantages of both natural enzymes and nanomaterials. They are usually low-cost, stable and easy to mass-produce, and have broad application prospects in the fields of biosensing, disease treatment and environmental protection. However, the development of nanozymes still faces some challenges. Catalytic activity and substrate selectivity are two important issues that need to be addressed in the development of nanozymes. Therefore, it is necessary to rationally design and regulate nanomaterials to develop nanozymes with efficient activity.

[0003] At present, many nanomaterials with enzyme activities such as oxidase, peroxidase, catalase, superoxide dismutase, etc. have been reported. Among them, vanadium pentoxide (V2O5) has been reported to have peroxidase-like activity among metal oxides, but its catalytic activity still has room for improvement. Summary of the invention

[0004] Purpose of the invention: The first purpose of the present invention is to provide a modified V2O5 nanozyme with peroxidase-like activity to improve the V2O5 peroxidase-like activity; the second purpose of the present invention is to provide a method for preparing the modified V2O5 nanozyme.

[0005] Technical solution: The modified V2O5 nanozyme with peroxidase-like activity described in the present invention is obtained by high-temperature calcination of MOFs material; wherein the MOFs material uses vanadium as a metal ion, organic matter as a ligand, and is impregnated and doped with ruthenium elements; the MOFs material is calcined to convert the metal ion vanadium into vanadium pentoxide.

[0006] Preferably, the organic ligand is 1,4-benzenedicarboxylic acid, trimesic acid or 1,4-naphthalene dicarboxylic acid; the mass ratio of the MOFs material to the impregnated ruthenium element is 100: 1 to 20. As the content of ruthenium increases, the peroxidase activity of the nanozyme increases.

[0007] The method for preparing the modified V2O5 nanozyme having peroxidase-like activity of the present invention comprises the following steps:

[0008] (1) adding a vanadium compound, an organic ligand, and hydrochloric acid into a solvent to perform a solvothermal reaction to obtain a MOFs material;

[0009] (2) adding ruthenium salt into a solvent, then adding the MOFs material obtained in step (1), impregnating ruthenium, and finally drying;

[0010] (3) calcining the MOFs material treated in step (2) at high temperature in an air atmosphere to obtain the modified V2O5 nanozyme.

[0011] In step (1), during the hydrothermal reaction, the metal ion vanadium combines with the organic ligand to form a metal organic framework material MOFs. Metal-organic frameworks (MOFs) constitute a class of porous materials formed by self-assembly of metal ions and organic ligands. They have an ordered porous structure, a large specific surface area and an adjustable structure.

[0012] Preferably, in step (1), the solvent thermal reaction temperature is 100-140°C.

[0013] Preferably, in step (1), the vanadium compound is vanadium acetylacetonate, vanadyl acetylacetonate or vanadium trichloride.

[0014] Preferably, in step (2), the ruthenium salt is ruthenium acetylacetonate, ruthenium acetate or ruthenium trichloride hydrate.

[0015] Preferably, the solvent in step (1) or (2) is methanol, ethanol or isopropanol.

[0016] In step (2), during the impregnation process, ruthenium is adsorbed on the pore surface of the MOFs material. Preferably, in step (2), the impregnation time is 10 to 15 hours.

[0017] Preferably, in step (3), the high temperature calcination temperature is 350-550°C. During the calcination process, the temperature and time will affect the phase transformation of V to V2O5 in the MOFs material, as well as the structural morphology. When calcined at low temperature, the MOF material is difficult to be transformed into vanadium pentoxide, and high temperature and long time calcination will affect the surface roughness of vanadium pentoxide, causing structural collapse.

[0018] Invention mechanism: The modified V2O5 nanozyme of the present invention introduces Ru element into V2O5, increases oxygen vacancies, promotes the electron transfer speed in the reaction process, and increases the specific surface area of ​​the nanozyme after doping with ruthenium. The ruthenium element and V2O5 synergistically catalyze to improve the peroxidase-like activity, improve the catalytic rate, and improve the peroxidase-like activity. In addition, the nanozyme is obtained by high-temperature calcination of MOFs materials. MOFs materials have an ordered porous structure and a large specific surface area, which is conducive to the adsorption of Ru during the impregnation process. In addition, the surface still has a porous structure after calcination, which increases the specific surface area of ​​the nanozyme.

[0019] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The nanoenzyme material is obtained by introducing Ru element into V2O5 and calcining the MOFs material, thereby improving the peroxidase-like catalytic activity of V2O5; (2) The preparation method is simple and the raw materials are easily available. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the SEM image of the V2O5 nanozyme prepared in Comparative Example 1;

[0021] Figure 2 This is the SEM image of the Ru-V2O5 nanozyme prepared in Example 3;

[0022] Figure 3 TEM spectrum of Ru-V2O5 nanozyme prepared in Example 3;

[0023] Figure 4 XRD patterns of the Ru-V2O5 nanozyme prepared in Example 3 and the V2O5 nanozyme prepared in Comparative Example 1;

[0024] Figure 5 This is the XPS spectrum of the Ru-V2O5 nanozyme prepared in Example 3;

[0025] Figure 6 BET spectra comparing the Ru-V2O5 nanozyme prepared in Example 3 and the V2O5 nanozyme prepared in Comparative Example 1;

[0026] Figure 7 The ultraviolet absorption spectra of the Ru-V2O5 nanozymes prepared in Examples 1 to 4 are compared with the V2O5 nanozymes prepared in Comparative Example 1;

[0027] Figure 8 The relative activity of the Ru-V2O5 nanozyme prepared in Example 3 and the V2O5 nanozyme prepared in Comparative Example 1 at different pH values;

[0028] Fig. 9 The relative activity diagram of the Ru-V2O5 nanozyme prepared in Example 3 and the V2O5 nanozyme prepared in Comparative Example 1 at different temperatures;

[0029] Fig.10 This is a comparison chart of the reaction kinetics test of the Ru-V2O5 nanozyme prepared in Example 3 and the V2O5 nanozyme prepared in Comparative Example 1 at the optimal temperature and pH. DETAILED DESCRIPTION

[0030] The technical solution of the present invention is further described below in conjunction with embodiments.

[0031] Example 1

[0032] The method for preparing the modified V2O5 nanozyme having peroxidase-like activity of the present invention comprises the following steps:

[0033] (1) Preparation of MOFs material: 4 mmol of VCl3 and 4 mmol of 1,4-benzenedicarboxylic acid were mixed evenly in 20 mL of ethanol solution, and then 4 mL of 1.0 mol / L hydrochloric acid solution was added. The mixture was placed in a reactor and reacted in an oven at 120°C for 48 hours. The mixture was washed by centrifugation and dried in vacuum at 60°C to obtain MOFs material for use.

[0034] (2) Ru impregnation: Weigh 100 mg of the MOFs material dried in step (1), stir it with 5 mg of RuCl3·xH2O (containing 1.85 mg of Ru) in an ethanol solution, impregnate it for 12 hours, and then centrifuge and dry it;

[0035] (3) Preparation of Ru-V2O5: The material obtained after centrifugal drying in step (2) was calcined in an air atmosphere at a temperature of 5°C / min to 400°C and maintained at this temperature for 4 h to finally obtain the product Ru-V2O5 nanozyme.

[0036] Example 2

[0037] On the basis of Example 1, in step (2), 100 mg of MOFs material and 10 mg of RuCl3·xH2O (containing 3.7 mg of Ru) were added, and the other conditions remained unchanged.

[0038] Example 3

[0039] On the basis of Example 1, in step (2), 100 mg of MOFs material and 20 mg of RuCl3·xH2O (containing 7.4 mg of Ru) were added, and the other conditions remained unchanged.

[0040] Example 4

[0041] On the basis of Example 1, in step (2), 100 mg of MOFs material and 50 mg of RuCl3·xH2O (containing 18.5 mg of Ru) were added, and the other conditions remained unchanged.

[0042] Example 5

[0043] The method for preparing the modified V2O5 nanozyme having peroxidase-like activity of the present invention comprises the following steps:

[0044] (1) Preparation of MOFs material: 4 mmol of VCl3 and 4 mmol of 1,4-benzenedicarboxylic acid were mixed evenly in 20 mL of ethanol solution, and then 4 mL of 1.0 mol / L hydrochloric acid solution was added. The mixture was placed in a reactor and reacted in an oven at 120°C for 48 hours. The mixture was washed by centrifugation and dried in vacuum at 60°C to obtain MOFs material for use.

[0045] (2) Ru impregnation: Weigh 100 mg of the MOFs material dried in step (1), stir it with 5 mg of ruthenium acetylacetonate (containing 1.23 mg of Ru) in an ethanol solution, impregnate it for 12 hours, and then centrifuge and dry it;

[0046] (3) Preparation of Ru-V2O5: The material obtained after centrifugal drying in step (2) was calcined in an air atmosphere at a temperature of 5°C / min to 400°C and maintained at this temperature for 4 h to finally obtain the product Ru-V2O5 nanozyme.

[0047] Example 6

[0048] The method for preparing the modified V2O5 nanozyme having peroxidase-like activity of the present invention comprises the following steps:

[0049] (1) Preparation of MOFs material: 4 mmol of VCl3 and 4 mmol of 1,4-benzenedicarboxylic acid were mixed evenly in 20 mL of ethanol solution, and then 4 mL of 1.0 mol / L hydrochloric acid solution was added. The mixture was placed in a reactor and reacted in an oven at 120°C for 48 hours. The mixture was washed by centrifugation and dried in vacuum at 60°C to obtain MOFs material for use.

[0050] (2) Ru impregnation: Weigh 100 mg of the MOFs material dried in step (1), stir it with 5 mg of ruthenium acetate (containing 2.06 mg of Ru) in an ethanol solution, impregnate it for 12 hours, and then centrifuge and dry it;

[0051] (3) Preparation of Ru-V2O5: The material obtained after centrifugal drying in step (2) was calcined in an air atmosphere at a temperature of 5°C / min to 400°C and maintained at this temperature for 4 h to finally obtain the product Ru-V2O5 nanozyme.

[0052] Example 7

[0053] The method for preparing the modified V2O5 nanozyme having peroxidase-like activity of the present invention comprises the following steps:

[0054] (1) Preparation of MOFs material: 4 mmol of VCl3 and 4 mmol of 1,4-naphthalene dicarboxylic acid were mixed evenly in 20 mL of ethanol solution, and then 4 mL of 1.0 mol / L hydrochloric acid solution was added. The mixture was placed in a reactor and reacted in an oven at 120°C for 48 hours. The mixture was washed by centrifugation and dried in vacuum at 60°C to obtain MOFs material for use.

[0055] (2) Ru impregnation: Weigh 100 mg of the MOFs material dried in step (1), stir it with 5 mg of RuCl3·xH2O (containing 1.85 mg of Ru) in an ethanol solution, impregnate it for 12 hours, and then centrifuge and dry it;

[0056] (3) Preparation of Ru-V2O5: The material obtained after centrifugal drying in step (2) was calcined in an air atmosphere at a temperature of 5°C / min to 400°C and maintained at this temperature for 4 h to finally obtain the product Ru-V2O5 nanozyme.

[0057] Example 8

[0058] The method for preparing the modified V2O5 nanozyme having peroxidase-like activity of the present invention comprises the following steps:

[0059] (1) Preparation of MOFs material: 4 mmol of VCl3 and 4 mmol of trimesic acid were mixed evenly in 20 mL of ethanol solution, and then 4 mL of 1.0 mol / L hydrochloric acid solution was added. The mixture was placed in a reactor and reacted in an oven at 120°C for 48 hours. The mixture was washed by centrifugation and dried in vacuum at 60°C to obtain MOFs material for use.

[0060] (2) Ru impregnation: Weigh 100 mg of the MOFs material dried in step (1), stir it with 5 mg of RuCl3·xH2O (containing 1.85 mg of Ru) in an ethanol solution, impregnate it for 12 hours, and then centrifuge and dry it;

[0061] (3) Preparation of Ru-V2O5: The material obtained after centrifugal drying in step (2) was calcined in an air atmosphere at a temperature of 5°C / min to 400°C and maintained at this temperature for 4 h to finally obtain the product Ru-V2O5 nanozyme.

[0062] Example 9

[0063] The method for preparing the modified V2O5 nanozyme having peroxidase-like activity of the present invention comprises the following steps:

[0064] (1) Preparation of MOFs material: 4 mmol of vanadium acetylacetonate and 4 mmol of 1,4-benzenedicarboxylic acid were mixed evenly in 20 mL of ethanol solution, and then 4 mL of 1.0 mol / L hydrochloric acid solution was added. The mixture was placed in a reactor and reacted in an oven at 120°C for 48 hours. The mixture was washed by centrifugation and dried in vacuum at 60°C to obtain MOFs material for use.

[0065] (2) Ru impregnation: Weigh 100 mg of the MOFs material dried in step (1), stir it with 5 mg of RuCl3·xH2O (containing 1.85 mg of Ru) in an ethanol solution, impregnate it for 12 hours, and then centrifuge and dry it;

[0066] (3) Preparation of Ru-V2O5: The material obtained after centrifugal drying in step (2) was calcined in an air atmosphere at a temperature of 5°C / min to 400°C and maintained at this temperature for 4 h to finally obtain the product Ru-V2O5 nanozyme.

[0067] Example 10

[0068] The method for preparing the modified V2O5 nanozyme having peroxidase-like activity of the present invention comprises the following steps:

[0069] (1) Preparation of MOFs material: 4 mmol of vanadium acetylacetonate and 4 mmol of 1,4-benzenedicarboxylic acid were mixed evenly in 20 mL of ethanol solution, and then 4 mL of 1.0 mol / L hydrochloric acid solution was added. The mixture was placed in a reactor and reacted in an oven at 120°C for 48 hours, centrifuged and washed, and vacuum dried at 60°C to obtain MOFs material for use;

[0070] (2) Ru impregnation: Weigh 100 mg of the MOFs material dried in step (1), stir it with 5 mg of RuCl3·xH2O (containing 1.85 mg of Ru) in an ethanol solution, impregnate it for 12 hours, and then centrifuge and dry it;

[0071] (3) Preparation of Ru-V2O5: The material obtained after centrifugal drying in step (2) was calcined in an air atmosphere at a temperature of 5°C / min to 400°C and maintained at this temperature for 4 h to finally obtain the product Ru-V2O5 nanozyme.

[0072] Embodiment 11

[0073] The method for preparing the modified V2O5 nanozyme having peroxidase-like activity of the present invention comprises the following steps:

[0074] (1) Preparation of MOFs material: 4 mmol of VCl3 and 4 mmol of 1,4-benzenedicarboxylic acid were mixed evenly in 20 mL of methanol solution, and then 4 mL of 1.0 mol / L hydrochloric acid solution was added. The mixture was placed in a reactor and reacted in an oven at 120°C for 48 hours. The mixture was centrifuged and washed, and vacuum dried at 60°C to obtain MOFs material for use.

[0075] (2) Ru impregnation: Weigh 100 mg of the MOFs material dried in step (1), stir it with 5 mg of RuCl3·xH2O (containing 1.85 mg of Ru) in a methanol solution, impregnate it for 12 hours, and then centrifuge and dry it;

[0076] (3) Preparation of Ru-V2O5: The material obtained after centrifugal drying in step (2) was calcined in an air atmosphere at a temperature of 5°C / min to 400°C and maintained at this temperature for 4 h to finally obtain the product Ru-V2O5 nanozyme.

[0077] Example 12

[0078] The method for preparing the modified V2O5 nanozyme having peroxidase-like activity of the present invention comprises the following steps:

[0079] (1) Preparation of MOFs material: 4 mmol of VCl3 and 4 mmol of 1,4-benzenedicarboxylic acid were mixed evenly in 20 mL of isopropanol solution, and then 4 mL of 1.0 mol / L hydrochloric acid solution was added. The mixture was placed in a reactor and reacted in an oven at 120°C for 48 hours. The mixture was washed by centrifugation and dried in vacuum at 60°C to obtain MOFs material for use.

[0080] (2) Ru impregnation: Weigh 100 mg of the MOFs material dried in step (1), stir it with 5 mg of RuCl3·xH2O (containing 1.85 mg of Ru) in an isopropanol solution, impregnate it for 12 hours, and then centrifuge and dry it;

[0081] (3) Preparation of Ru-V2O5: The material obtained after centrifugal drying in step (2) was calcined in an air atmosphere at a temperature of 5°C / min to 400°C and maintained at this temperature for 4 h to finally obtain the product Ru-V2O5 nanozyme.

[0082] Example 13

[0083] The method for preparing the modified V2O5 nanozyme having peroxidase-like activity of the present invention comprises the following steps:

[0084] (1) Preparation of MOFs material: 4 mmol of VCl3 and 4 mmol of 1,4-benzenedicarboxylic acid were mixed evenly in 20 mL of ethanol solution, and then 4 mL of 1.0 mol / L hydrochloric acid solution was added. The mixture was placed in a reactor and reacted in an oven at 120°C for 48 hours. The mixture was washed by centrifugation and dried in vacuum at 60°C to obtain MOFs material for use.

[0085] (2) Ru impregnation: Weigh 100 mg of the MOFs material dried in step (1), stir it with 5 mg of RuCl3·xH2O (containing 1.85 mg of Ru) in an ethanol solution, impregnate it for 14 hours, and then centrifuge and dry it;

[0086] (3) Preparation of Ru-V2O5: The material obtained after centrifugal drying in step (2) was calcined in an air atmosphere at a temperature of 5°C / min to 400°C and maintained at this temperature for 4 h to finally obtain the product Ru-V2O5 nanozyme.

[0087] Embodiment 14

[0088] The method for preparing the modified V2O5 nanozyme having peroxidase-like activity of the present invention comprises the following steps:

[0089] (1) Preparation of MOFs material: 4 mmol of VCl3 and 4 mmol of 1,4-benzenedicarboxylic acid were mixed evenly in 20 mL of ethanol solution, and then 4 mL of 1.0 mol / L hydrochloric acid solution was added. The mixture was placed in a reactor and reacted in an oven at 120°C for 48 hours. The mixture was washed by centrifugation and dried in vacuum at 60°C to obtain MOFs material for use.

[0090] (2) Ru impregnation: Weigh 100 mg of the MOFs material dried in step (1), stir it with 5 mg of RuCl3·xH2O (containing 1.85 mg of Ru) in an ethanol solution, impregnate it for 12 hours, and then centrifuge and dry it;

[0091] (3) Preparation of Ru-V2O5: The material obtained after centrifugal drying in step (2) was calcined in an air atmosphere at a temperature of 5°C / min to 500°C and maintained at this temperature for 4 h to obtain the product Ru-V2O5 nanozyme.

[0092] Embodiment 15

[0093] The method for preparing the modified V2O5 nanozyme having peroxidase-like activity of the present invention comprises the following steps:

[0094] (1) Preparation of MOFs material: 4 mmol of VCl3 and 4 mmol of 1,4-benzenedicarboxylic acid were mixed evenly in 20 mL of ethanol solution, and then 4 mL of 1.0 mol / L hydrochloric acid solution was added. The mixture was placed in a reactor and reacted in an oven at 130°C for 48 hours. The mixture was washed by centrifugation and dried in vacuum at 60°C to obtain MOFs material for use.

[0095] (2) Ru impregnation: Weigh 100 mg of the MOFs material dried in step (1), stir it with 5 mg of RuCl3·xH2O (containing 1.85 mg of Ru) in an ethanol solution, impregnate it for 12 hours, and then centrifuge and dry it;

[0096] (3) Preparation of Ru-V2O5: The material obtained after centrifugal drying in step (2) was calcined in an air atmosphere at a temperature of 5°C / min to 400°C and maintained at this temperature for 4 h to finally obtain the product Ru-V2O5 nanozyme.

[0097] Comparative Example 1

[0098] Based on Example 3, step (2) is not performed to obtain V2O5 nanozyme.

[0099] Structural characterization

[0100] The nanozymes prepared in Example 3 and Comparative Example 1 were physically characterized by SEM, TEM, and XRD.

[0101] By SEM Figure 1 It can be seen that the calcined V2O5 nanozyme exhibits a spindle-like morphology.

[0102] By SEM Figure 2 It can be obtained that the Ru-doped nanozyme has the same morphology as the calcined V2O5 nanozyme, and after calcination, it shows a rough surface and a porous structure.

[0103] By TEM Figure 3 It can be seen that the morphology of V2O5 after doping with ruthenium is a shuttle-shaped structure.

[0104] From XRD pattern Figure 4 It can be seen that there is no obvious change in the peaks in the figure after doping with ruthenium, indicating that the structure of V2O5 remains unchanged after doping with ruthenium.

[0105] XPS spectrum Figure 5 It can be obtained that V, O, and Ru in Ru-V2O5 nanozyme mainly exist in valence states, and it is confirmed that Ru is successfully doped into V2O5.

[0106] Tested by BET Figure 6 It can be seen that the incorporation of Ru increases the specific surface area of ​​Ru-V2O5 nanozyme.

[0107] Performance Characterization

[0108] (1) Peroxidase activity test

[0109] In a buffer solution of pH = 4.0, H2O2 and TMB were added, and then equal amounts of the Ru-V2O5 nanozymes prepared in Examples 1 to 4 and the V2O5 nanozyme solutions prepared in Comparative Example 1 were added, respectively. After reacting for 2 minutes, the UV-visible absorption spectrum was measured. The test results are as follows: Figure 7 shown.

[0110] Depend on Figure 7 It can be seen that the characteristic absorption peak of Ru-V2O5 prepared in Examples 1 to 4 at 652 nm is significantly higher than the characteristic absorption peak of V2O5 prepared in Comparative Example 1, indicating that Ru doping significantly improves the peroxidase-like activity of V2O5.

[0111] (2) Effect of pH on the activity of Ru-V2O5 nanozymes

[0112] The absorbance at 652 nm of the Ru-V2O5 nanozyme solution prepared in Example 3 and the V2O5 nanozyme solution prepared in Comparative Example 1 in phosphate buffer solutions with pH values ​​of 2, 3, 4, 5, 6, and 7 was compared, and the relative activity was calculated compared with the blank control group. The test results are shown in FIG. Figure 8 shown.

[0113] Depend on Figure 8 It can be obtained that the optimal pH of Ru-V2O5 and V2O5 nanozymes is 4.0.

[0114] (3) Effect of temperature on the activity of Ru-V2O5 nanozymes

[0115] Comparison of the absorbance at 652 nm of the Ru-V2O5 nanozyme solution prepared in Example 3 and the V2O5 nanozyme solution prepared in Comparative Example 1 in a phosphate buffer solution of pH = 4.0 at different temperatures (15°C, 25°C, 35°C, 45°C, 55°C, 65°C) was performed, and the relative activity was calculated compared with that of the blank control group. The test results are shown in FIG. Fig. 9 shown.

[0116] Depend on Fig. 9 It can be obtained that the optimum temperature of Ru-V2O5 and V2O5 nanozymes is 35℃.

[0117] (4) Kinetic comparison of Ru-V2O5 nanozyme and V2O5 nanozyme activities

[0118] Take the Ru-V2O5 nanozyme solution prepared in Example 3 and the V2O5 nanozyme solution prepared in Comparative Example 1 with the same concentration, add TMB and H2O2 solution to a phosphate buffer solution with pH = 4.0 at 35°C, and perform kinetic monitoring at 652nm. The test results are as follows: Fig.10 shown.

[0119] Depend on Fig.10 It can be seen that the absorbance change of Ru-V2O5 is significantly higher than that of V2O5, indicating that Ru-V2O5 nanozyme has better peroxidase-like activity.

Claims

1. A modified V2O5 nanozyme having peroxidase-like activity, characterized in that: The nanozyme is obtained by high-temperature calcination of MOFs material; wherein the MOFs material uses vanadium as metal ion, organic matter as ligand, and is impregnated with ruthenium element; the MOFs material is calcined to convert the metal ion vanadium into vanadium pentoxide.

2. The modified V2O5 nanozyme having peroxidase-like activity according to claim 1, characterized in that: The organic ligand is 1,4-benzenedicarboxylic acid, trimesic acid or 1,4-naphthalene dicarboxylic acid.

3. The modified V2O5 nanozyme with peroxidase-like activity according to claim 2, characterized in that: The mass ratio of the MOFs material to the impregnated ruthenium element is 100:1-20.

4. A method for preparing the modified V2O5 nanozyme having peroxidase-like activity according to claim 1, characterized in that: The following steps are involved: (1) adding a vanadium compound, an organic ligand, and hydrochloric acid into a solvent to perform a solvothermal reaction to obtain a MOFs material; (2) adding ruthenium salt into a solvent, then adding the MOFs material obtained in step (1), impregnating ruthenium, and finally drying; (3) calcining the MOFs material treated in step (2) at high temperature in an air atmosphere to obtain the modified V2O5 nanozyme.

5. The method for preparing the modified V2O5 nanozyme having peroxidase-like activity according to claim 4, characterized in that: In step (1), the solvent thermal reaction temperature is 100-140°C.

6. The method for preparing the modified V2O5 nanozyme having peroxidase-like activity according to claim 4, characterized in that: In step (3), the high temperature calcination temperature is 350-550°C.

7. The method for preparing the modified V2O5 nanozyme having peroxidase-like activity according to claim 4, characterized in that: In step (1), the vanadium compound is vanadium acetylacetonate, vanadyl acetylacetonate or vanadium trichloride.

8. The method for preparing the modified V2O5 nanozyme having peroxidase-like activity according to claim 4, characterized in that: In step (2), the ruthenium salt is ruthenium acetylacetonate, ruthenium acetate or ruthenium trichloride hydrate.

9. The method for preparing the modified V2O5 nanozyme having peroxidase-like activity according to claim 4, characterized in that: The solvent described in step (1) or (2) is methanol, ethanol or isopropanol.

10. The method for preparing the modified V2O5 nanozyme having peroxidase-like activity according to claim 4, characterized in that: In step (2), the immersion time is 10 to 15 hours.

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