Hydroxystannate and method for preparing and using same

Abstract

The application discloses a hydroxyl stannate and a preparation method and application thereof, and the hydroxyl stannate has a hollow cubic structure, and the hydroxyl stannate comprises at least one of doped or undoped manganese hydroxyl stannate or copper hydroxyl stannate. The hydroxyl stannate has excellent enzyme-like catalytic performance. The acid etching method is used in the application to prepare the hydroxyl stannate with the hollow cubic structure, and the method is simple, easy to operate, high in repeatability, low in cost and suitable for industrial production.

Description

Technical Field

[0001] This invention belongs to the field of catalytic materials technology, specifically relating to a hydroxystannate, its preparation method, and its application. Background Technology

[0002] Natural enzymes are important biocatalysts due to their high catalytic activity; however, their poor biological stability, susceptibility to inactivation, and stringent storage requirements severely limit their practical catalytic applications. Therefore, researchers have been dedicated to developing artificial enzyme mimics with high catalytic activity, high stability, good biosafety, and catalytic performance comparable to natural enzymes. Nanozymes, a class of enzyme mimics that combine the unique properties of nanomaterials with catalytic functions, have attracted widespread attention in recent years and can be applied in fields such as biochemistry, pharmaceutical analysis, food processing, and environmental remediation. Nanozymes mainly include oxidase-like enzymes, catalase-like enzymes, superoxide dismutase-like enzymes, and peroxidase-like enzymes. However, the catalytic performance of traditional nanozymes remains relatively low. Summary of the Invention

[0003] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a hydroxystannate with a hollow cubic structure and excellent enzyme-like catalytic performance, which greatly expands the application scope and prospects of hydroxystannate materials.

[0004] The present invention also proposes a method for preparing hydroxystannate.

[0005] This invention also proposes the use of hydroxystannates for catalyzing the oxidation of aromatic amines.

[0006] This invention also proposes a catalytic material.

[0007] This invention also proposes the application of manganese hydroxystannate, the above-mentioned hydroxystannate, and catalytic materials.

[0008] In a first aspect, the present invention provides a hydroxystannate having a hollow cubic structure, the hydroxystannate comprising at least one of doped or undoped manganese hydroxystannate or copper hydroxystannate.

[0009] The hydroxystannate according to embodiments of the present invention has at least the following beneficial effects:

[0010] The hydroxystannate in this invention has a hollow cubic structure and excellent oxidase-like catalytic performance. For example, using MnSn(OH)6 with a hollow cubic structure to catalyze the oxidation reaction of 3,3',5,5'-tetramethylbenzidine (TMB) can rapidly oxidize and discolor TMB, demonstrating good enzyme-like performance and greatly expanding the application scope and prospects of hydroxystannate materials.

[0011] In some embodiments of the present invention, the average particle size of the hydroxystannate includes 50-800 nm, preferably 200-400 nm.

[0012] In some embodiments of the present invention, the hydroxystannate is doped or undoped manganese hydroxystannate.

[0013] Through the above embodiments, compared with solid manganese hydroxystannate, the hollow cubic structure of manganese hydroxystannate in this invention significantly improves the oxidase-like catalytic performance, greatly expanding the application scope and prospects of hydroxystannate materials.

[0014] In some preferred embodiments of the present invention, the doping elements of the manganese hydroxystannate include, but are not limited to, iron, cobalt, copper, nickel, zinc, etc.

[0015] In some preferred embodiments of the present invention, the doping element of the manganese hydroxystannate includes at least one selected from iron, cobalt, copper, nickel, or zinc.

[0016] In a second aspect, the present invention provides a method for preparing a hydroxystannate, comprising the following steps: obtaining the hydroxystannate having a hollow cubic structure by etching. Preferably, the etching is acid etching.

[0017] The method for preparing hydroxystannate according to embodiments of the present invention has at least the following beneficial effects:

[0018] This invention employs an acid etching method to prepare hydroxystannates with a hollow cubic structure. This method is simple, easy to implement, highly reproducible, and low-cost. The acid etching method effectively dissolves the hydroxystannate before etching, and the etching process avoids introducing byproducts, resulting in excellent etching performance. This method is suitable for industrial production, has good versatility, and can be used to prepare various hydroxystannates with micro / nano structures, demonstrating strong potential for widespread application.

[0019] In some embodiments of the present invention, the preparation method includes the following steps:

[0020] S1, solid hydroxystannate was prepared by precipitation method;

[0021] S2, acid etching is performed on the hydroxystannate obtained in step S1 to obtain a hydroxystannate with a hollow cubic structure.

[0022] The method for preparing hydroxystannate according to embodiments of the present invention has at least the following beneficial effects:

[0023] In this invention, solid hydroxystannates prepared by precipitation are etched with acid to obtain hydroxystannates with a hollow cubic structure. The etched hydroxystannates exhibit superior enzyme-like catalytic performance. For example, when used to catalyze the oxidation reaction of TMB, they can rapidly oxidize and discolor TMB, demonstrating excellent enzyme-like properties. This greatly expands the application range and prospects of hydroxystannate materials. Furthermore, the entire preparation process is simple and easy to operate, low in cost, with mild and easily controllable reaction conditions, high reproducibility, and meets practical production needs, making it suitable for industrial production. This method also has good versatility and can be used to prepare various hydroxystannates with micro / nano structures, demonstrating strong potential for widespread application.

[0024] In some preferred embodiments of the present invention, step S1 includes the following operation: mixing a sodium hydroxystannate precursor solution with a salt solution and reacting to obtain a solid hydroxystannate.

[0025] In some preferred embodiments of the present invention, the salt solution includes at least one of a soluble manganese salt solution or a soluble copper salt solution.

[0026] In some more preferred embodiments of the present invention, the salt solution may further include a soluble iron, cobalt, nickel or zinc salt solution.

[0027] In some preferred embodiments of the present invention, the manganese salt includes at least one of manganese sulfate, manganese nitrate, or manganese chloride; and the copper salt includes at least one of copper sulfate, copper chloride, or copper nitrate.

[0028] In some more preferred embodiments of the present invention, the sodium hydroxystannate precursor solution contains sodium hydroxystannate, and the concentration of sodium hydroxystannate is 0.01-3 mol / L, preferably 0.02-1 mol / L.

[0029] In some more preferred embodiments of the present invention, the cation concentration in the salt solution is 0.01-3 mol / L, preferably 0.02-1 mol / L.

[0030] In some more preferred embodiments of the present invention, the volume ratio of the sodium hydroxystannate precursor solution to the salt solution is (0.2-2):(0.2-2).

[0031] In some more preferred embodiments of the present invention, step S1 includes the following operation: mixing the salt solution with ammonia water, and then mixing it with the sodium hydroxystannate precursor solution to react and obtain solid hydroxystannate.

[0032] Through the above implementation methods, the addition of ammonia water is beneficial to the formation of the cubic structure of hydroxystannate.

[0033] In some preferred embodiments of the present invention, the ammonia water contains NH 3· The concentration of H2O ranges from 12 to 16 mol / L.

[0034] In some more preferred embodiments of the present invention, the volume ratio of the salt solution to the ammonia water includes (4-6):1.

[0035] In some more preferred embodiments of the present invention, step S1 further includes preparing the sodium hydroxystannate precursor solution, specifically including the following operations: mixing tin salt, sodium-containing alkaline substance and solvent I to obtain the sodium hydroxystannate precursor solution.

[0036] In some more preferred embodiments of the present invention, the tin salt comprises tin tetrachloride, and optionally, the tin tetrachloride comprises crystalline tin tetrachloride.

[0037] In some more preferred embodiments of the present invention, the sodium-containing alkaline substance includes sodium hydroxide.

[0038] In some preferred embodiments of the present invention, solvent I comprises water.

[0039] In some more preferred embodiments of the present invention, the molar ratio of tin tetrachloride to sodium hydroxide is (0.01-0.5):(0.5-5).

[0040] In some preferred embodiments of the present invention, step S1 includes the following operation: mixing the salt solution with ammonia and sodium hydroxystannate precursor solution, and stirring at 50-80°C for 2-6 hours to obtain hydroxystannate.

[0041] In some preferred embodiments of the present invention, step S1 includes the following operations: mixing the salt solution with ammonia and sodium hydroxystannate precursor solution, reacting, centrifuging and washing, and drying to obtain the hydroxystannate.

[0042] In some preferred embodiments of the present invention, in step S1, water and ethanol are used for centrifugal washing.

[0043] In some preferred embodiments of the present invention, in step S1, the rotation speed of the centrifugal washing is 8000-15000 rpm / min.

[0044] In some more preferred embodiments of the present invention, the drying temperature in step S1 is 50-80°C.

[0045] In some preferred embodiments of the present invention, step S2 includes the following operation: acid etching of the hydroxystannate obtained in step S1 using inorganic acid and / or organic acid.

[0046] In some preferred embodiments of the present invention, the inorganic acid includes at least one of hydrochloric acid, nitric acid or sulfuric acid; and the organic acid includes trifluoromethanesulfonic acid.

[0047] In some preferred embodiments of the present invention, step S2 includes the following operations: dispersing the hydroxystannate obtained in step S1 in water to obtain an aqueous dispersion of hydroxystannate, adding an inorganic acid, stirring, and obtaining a hydroxystannate with a hollow cubic structure.

[0048] In some more preferred embodiments of the present invention, the inorganic acid includes hydrochloric acid, and optionally, the concentration of the hydrochloric acid is 0.1-1.0 mol / L.

[0049] In some more preferred embodiments of the present invention, the ratio of the amount of the inorganic acid to the hydroxystannate obtained in step S1 is (10-20) mL:(40-60) mg.

[0050] In some more preferred embodiments of the present invention, in step S2, the mass ratio of the hydroxystannate obtained in step S1 to water is 1:(200-400).

[0051] In some more preferred embodiments of the present invention, the hydroxystannate is preferably dispersed by ultrasonic dispersion.

[0052] In some more preferred embodiments of the present invention, the inorganic acid is preferably added dropwise.

[0053] In some more preferred embodiments of the present invention, in step S2, after stirring, the mixture is centrifuged, washed, and dried to obtain a hydroxystannate with a hollow cubic structure.

[0054] In some more preferred embodiments of the present invention, in step S2, water and ethanol are used for centrifugal washing, respectively.

[0055] In some more preferred embodiments of the present invention, the drying temperature in step S2 is 50-80°C.

[0056] In a third aspect, the present invention proposes the use of the above-mentioned hydroxystannate having a hollow cubic structure for catalyzing the oxidation reaction of aromatic amines.

[0057] In some preferred embodiments of the present invention, the aromatic amine includes at least one of 3,3',5,5'-tetramethylbenzidine (TMB), benzidine, o-toluidine, or o-phenylenediamine.

[0058] In a fourth aspect, the present invention provides a catalytic material comprising the aforementioned hydroxystannate having a hollow cubic structure.

[0059] In some embodiments of the present invention, the catalytic material is an enzyme-like catalyst. Preferably, the enzyme-like catalyst is an oxidase-like catalyst.

[0060] In a fifth aspect, the invention proposes the application of manganese hydroxystannate, the aforementioned hydroxystannate having a hollow cubic structure, and catalytic materials in enzyme-like catalysis.

[0061] Through the above embodiments, manganese hydroxystannate exhibits oxidase-like catalytic performance, which expands the application scope and prospects of hydroxystannate materials to a certain extent. The hydroxystannate with a hollow cubic structure in this invention possesses excellent oxidase-like catalytic performance. For example, compared to solid manganese hydroxystannate, the oxidase-like catalytic performance of manganese hydroxystannate with a hollow cubic structure in this invention is significantly improved, greatly expanding the application scope and prospects of hydroxystannate materials.

[0062] In some embodiments of the present invention, the enzyme-like catalysis includes enzyme-like catalysis of the oxidation reaction of aromatic amines; preferably, the aromatic amines include at least one of TMB, benzidine, o-toluidine, or o-phenylenediamine.

[0063] In some embodiments of the present invention, manganese hydroxystannate, the above-mentioned hydroxystannate having a hollow cubic structure, and catalytic materials are used in the preparation of enzyme-like catalysts.

[0064] The beneficial effects of this invention include:

[0065] (1) The hydroxystannate in this invention has a hollow cubic structure and excellent enzyme-like catalytic performance. For example, MnSn(OH)6 with a hollow cubic structure can rapidly oxidize and discolor TMB, and has good oxidase-like catalytic performance.

[0066] (2) The hollow cubic structure of doped or undoped manganese hydroxystannate in this invention has significantly improved oxidase-like catalytic performance compared with solid manganese hydroxystannate, which greatly expands the application scope and prospects of hydroxystannate materials.

[0067] (3) The preparation method of hydroxystannate in this invention is a simple, inexpensive, and highly reproducible method. The preparation process is simple, requiring no subsequent purification steps such as impurity removal. The entire preparation process is easy to operate, the reaction process is easy to control, highly reproducible, and low in cost, meeting the needs of actual production. Furthermore, this method does not use any organic substances as solvents, giving it significant advantages from both economic and environmental perspectives. Attached Figure Description

[0068] The present invention will be further described below with reference to the accompanying drawings and embodiments, wherein:

[0069] Figure 1 The image shows a scanning electron microscope image of the manganese hydroxystannate prepared in Comparative Example 2.

[0070] Figure 2 This is a scanning electron microscope image of MHS-1 in Embodiment 1 of the present invention;

[0071] Figure 3 The image shown is a scanning electron microscope image of MHS-2 in Embodiment 1 of the present invention.

[0072] Figure 4 The X-ray powder diffraction pattern of MHS-1 in Example 1 of this invention;

[0073] Figure 5 The X-ray powder diffraction pattern of MHS-2 in Example 1 of this invention;

[0074] Figure 6 The image shows a scanning electron microscope image of zinc hydroxystannate in Comparative Example 1.

[0075] Figure 7 The adsorption spectra of the colorimetric reaction measured in the enzyme-like catalytic performance test of MHS-1 and MHS-2 in Example 1 of this invention are shown.

[0076] Figure 8 These are comparative photographs of the TMB solution containing zinc hydroxystannate (Comparative Example 1) after prolonged standing and the TMB solution without zinc hydroxystannate, as shown in the experimental examples of this invention. Detailed Implementation

[0077] The following will describe the concept and technical effects of the present invention clearly and completely with reference to embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0078] Unless otherwise specified, the experimental methods described in the following examples are generally performed under conventional conditions in the art or as recommended by the manufacturer; the raw materials and reagents used are all commercially available from the conventional market unless otherwise specified.

[0079] Example 1

[0080] This embodiment discloses a hydroxystannate, specifically manganese hydroxystannate with a hollow cubic structure, and its preparation process includes:

[0081] (I) Solid MnSn(OH)6 is prepared by precipitation method, including:

[0082] Weigh 0.52 mol of NaOH solid and 0.05 mol of SnCl4·5H2O solid and add them sequentially to a 200 mL beaker. Add 100 mL of deionized water and stir with a glass rod until completely dissolved. Pour the resulting mixture into a 500 mL volumetric flask and dilute to the mark with distilled water to prepare precursor solution (A). Weigh 0.005 mol of MnSO4·H2O solid and add it to a 100 mL beaker. Add 100 mL of deionized water to prepare manganese sulfate solution (B). 2+ The concentration was 0.05 mol / L. Equal volumes of solution A and solution B (30 mL each) were measured. Under stirring conditions, 6 mL of concentrated ammonia (ammonia concentration approximately 14 mol / L) was added dropwise to solution B and stirred for 15 min. Then, the measured solution A was added dropwise. After stirring for 10 min, the solution was transferred to a round-bottom flask and stirred at a constant temperature of 70 °C for 4 h. Finally, the solution was washed three times by centrifugation with 35 mL of deionized water and 35 mL of anhydrous ethanol at a speed of 11000 rpm / min. The product was removed and dried overnight (more than 10 hours) in a 70 °C oven. After thorough grinding, solid sample I was obtained, which is solid MnSn(OH)6, named MHS-1. The preparation process is as follows (1) and (2):

[0083] 6OH - + Sn 4+ → Sn(OH)6 2- (1)

[0084] Mn 2+ + Sn(OH)6 2- → MnSn(OH)6 (2);

[0085] (II) Acid etching step, including:

[0086] Weigh 50 mg of solid sample I obtained in step (Ⅰ), ultrasonically disperse it in 15 mL of deionized water, then add 15 mL of 0.5 mol / L hydrochloric acid dropwise, and stir for 15 min with a magnetic stirrer. Finally, wash the sample three times by centrifugation with 35 mL of deionized water and 35 mL of anhydrous ethanol, respectively. Take out the product, dry it overnight (more than 10 hours) in a 70℃ oven, and grind it thoroughly to obtain solid sample II. MnSn(OH)6 with a hollow cubic structure is obtained and named MHS-2.

[0087] This embodiment also discloses a catalytic material, including the hollow cubic structure MnSn(OH)6 prepared in this embodiment.

[0088] Comparative Example 1

[0089] This comparative example discloses a zinc hydroxystannate with a hollow structure. The difference between its preparation process and that of Example 1 is that in step (Ⅰ), 0.05 mol of ZnSO4·7H2O is used instead of 0.05 mol of MnSO4·H2O in Example 1.

[0090] Comparative Example 2

[0091] This comparative example discloses a manganese hydroxystannate, the preparation process of which differs from that of Example 1 in that concentrated ammonia was not added to solution B in step (Ⅰ).

[0092] Test case

[0093] This test example evaluated the performance of the hydroxystannate in the examples and comparative examples. The specific test methods included:

[0094] (1) Structural characterization:

[0095] a) The microstructure of manganese hydroxystannate obtained in Comparative Example 2, MHS-1 and MHS-2 in Example 1 were characterized respectively, and the resulting scanning electron microscope (SEM) images are shown below. Figure 1-3 As shown. By Figure 3 It can be seen that the manganese hydroxystannate prepared in Example 1 has a hollow cubic structure and an average particle size of 200-400 nm.

[0096] b) The X-ray powder diffraction (XRD) patterns of MHS-1 and MHS-2 in Example 1 were measured as follows: Figure 4-5 As shown. By Figure 4-5 It can be seen that MnSn(OH)6 was successfully prepared in Example 1.

[0097] c) The microstructure of zinc hydroxystannate prepared in Comparative Example 1 was characterized, and the resulting scanning electron microscope (SEM) images are shown below. Figure 6 As shown. By Figure 6 It can be seen that when solid ZnSn(OH)6 is prepared using zinc salt and then acid etched, the resulting material has a messy and irregular shape and does not form a hollow cubic structure.

[0098] (2) The oxidase-like catalytic performance of MHS-1, MHS-2 prepared in Example 1 and zinc hydroxystannate prepared in Comparative Example 1 was tested:

[0099] The oxidase-like catalytic activity of materials MnSn(OH)6 and zinc hydroxystannate was evaluated using 3,3',5,5'-tetramethylbenzidine (TMB) as a substrate. The absorbance of different samples was measured using a UV-Vis-NIR Spectrophotometer (Agilent Cray 5000) to evaluate the catalytic activity of the samples.

[0100] The enzyme-like catalytic performance test specifically included: preparing 0.5 mg / mL catalyst aqueous solutions (i.e., aqueous solutions of MHS-1, MHS-2, and zinc hydroxystannate prepared in Comparative Example 1, respectively); adding 3 mL of deionized water and 20 μL of TMB solution to a test tube; stirring thoroughly; measuring 150 μL of catalyst solution with a pipette; capping the tube; shaking thoroughly; recording the time; and observing and recording the color change of the solution. It was found that the TMB solution containing MHS-1 turned blue in approximately 15 seconds, while the TMB solution containing MHS-2 turned blue within only 5 seconds, and the color change of the solution containing MHS-2 was significantly deeper than that of the solution containing MHS-1; however, the TMB solution containing zinc hydroxystannate from Comparative Example 1 did not change color at all (it remained unchanged even after prolonged standing, such as after 2 hours).

[0101] The adsorption spectra of the colorimetric reaction measured in the enzyme-like catalytic performance test of MHS-1 and MHS-2 in Example 1 are shown below. Figure 7 As shown in the figure. Combined with the results of the enzyme-like catalytic performance test, it can be seen that MnSn(OH)6 can rapidly oxidize and change the color of TMB, indicating that its enzyme-like catalytic performance is good. MnSn(OH)6 with a hollow cubic structure has better enzyme-like catalytic performance than the unetched solid cubic MnSn(OH)6.

[0102] The enzyme-like performance of zinc hydroxystannate in Comparative Example 1 is shown in the following image. Figure 8 As shown, when the zinc hydroxystannate solution prepared in Comparative Example 1 was used to catalyze the oxidation of TMB solution, the solution did not change color, indicating that hollow ZnSn(OH)6 does not have enzyme-like properties.

[0103] In summary, the specific type of hydroxystannate in this invention—MnSn(OH)6 with a hollow cubic structure—can rapidly oxidize and discolor TMB, achieving oxidation and discoloration within 5 seconds or even 2 seconds. It exhibits excellent oxidase-like catalytic performance, significantly improving upon solid manganese hydroxystannate, thus greatly expanding the application scope and prospects of hydroxystannate materials.

[0104] Furthermore, the preparation method of hydroxystannate in this invention is simple, inexpensive, and highly reproducible. The preparation process is simple, requiring no subsequent purification steps such as impurity removal. The entire preparation process is easy to operate, the reaction process is easy to control, highly reproducible, and low-cost, meeting the needs of actual production. At the same time, this method does not use any organic substances as solvents, which gives it significant advantages from both economic and environmental perspectives.

[0105] It should be noted that, unless otherwise specified, "room temperature" or "normal temperature" in this article refers to approximately 30°C; and the word "approximately" in numerical values ​​in this article means an error of ±2%.

[0106] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments, and various changes can be made within the scope of knowledge possessed by those skilled in the art without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features thereof can be combined with each other unless otherwise specified.

Claims

1. A hydroxystannate for use in a pseudo-oxidase catalyst, characterized in that, The hydroxystannate has a hollow cubic structure, and is doped or undoped manganese hydroxystannate; the average particle size of the hydroxystannate is 50-400 nm; the hydroxystannate is prepared by a method comprising the following steps: S1, mixing a salt solution with ammonia water, and then mixing with a sodium hydroxystannate precursor solution, stirring and reacting at 50-80°C for 2-6 h to obtain a solid hydroxystannate; the salt solution comprises a soluble manganese salt solution, the concentration of NH3·H2O in the ammonia water comprises 12-16 mol / L, and the volume ratio of the salt solution to ammonia water comprises (4-6):1; S2, using an inorganic acid to perform acid etching on the hydroxystannate obtained in step S1 to obtain a hydroxystannate having a hollow cubic structure; wherein the inorganic acid comprises hydrochloric acid, the concentration of the hydrochloric acid is 0.1-1.0 mol / L, and the ratio of the amount of the hydrochloric acid to the hydroxystannate obtained in step S1 is (10-20) mL:(40-60) mg.

2. The hydroxystannate salt according to claim 1, characterized in that, The average particle size of the hydroxystannate comprises 200-400 nm.

3. The hydroxystannate salt according to claim 1, characterized in that, The doping element of the doped manganese hydroxystannate comprises at least one of iron, cobalt, copper, nickel or zinc.

4. The hydroxystannate salt of claim 1, wherein, Step S1 further comprises preparing the sodium hydroxystannate precursor solution, specifically comprising the following operation: mixing a tin salt, a sodium-containing alkaline substance and a solvent I to obtain the sodium hydroxystannate precursor solution.

5. The hydroxystannate salt of claim 1, wherein, Step S2 comprises the following operation: dispersing the hydroxystannate obtained in step S1 in water to obtain a water dispersion of the hydroxystannate, adding an inorganic acid, stirring to obtain a hydroxystannate having a hollow cubic structure.

6. The hydroxystannate of any one of claims 1-5 for catalyzing an oxidation reaction of an aromatic amine.

7. A catalytic material, characterized by The hydroxystannate of any one of claims 1-5.

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