Preparation method of transition metal disulfide nano material

Abstract

The invention discloses a preparation method of a transition metal disulfide nano material, and belongs to the technical field of novel catalytic materials.The preparation method comprises the following steps that L-cysteine or thioacetamide serves as a sulfur-containing precursor and a modifier, polyhydric alcohol serves as a solvent and a reducing agent, transition metal salt is added after dissolution, and the transition metal disulfide nano material is obtained; after stirring and dissolving, heating in a stainless steel high-pressure reaction kettle, and centrifuging, washing and drying the heated mixed solution to obtain the transition metal disulfide nano material. The preparation method of the transition metal disulfide nano material is simple, efficient, green and economical, and the prepared transition metal disulfide nano material is high in purity, high in biocompatibility, good in dispersity in water and excellent in photo-thermal performance, peroxidase activity and antioxidant activity.

Description

Technical Field

[0001] The present invention relates to the technical field of novel catalytic material preparation, and in particular to a method for preparing a transition metal disulfide nanomaterial. Background Art

[0002] As efficient and specific biocatalysts, enzymes can participate in the regulation of key biological processes such as signal transduction, metabolism, and digestion and absorption. However, natural enzymes have high production costs, are prone to variability and inactivation, and have low yields, making them difficult to use widely. Therefore, researchers have gradually developed nanozymes with enzyme-mimicking capabilities and nanometer sizes. Nanozymes refer to functional nanomaterials that follow the kinetics of enzymatic reactions under physiological conditions and efficiently catalyze enzyme-substrate conversions. Compared with traditional enzymes, nanozymes have higher catalytic activity, good stability, lower production costs, and simpler preparation / purification steps. Currently, a large number of nanomaterials, such as metal nanoparticles, metal oxide nanoparticles, carbon-based nanomaterials, and metal-organic frameworks, have been shown to function like natural enzymes.

[0003] In recent years, researchers have discovered that transition metal disulfides, such as iron disulfide, cobalt disulfide, and nickel disulfide, possess exceptional peroxidase-like activity. These compounds also possess excellent reducibility, effectively scavenging reactive oxygen species (ROS) in organisms. Furthermore, they biodegrade under acidic conditions to produce trace metal elements and the bioactive gas molecule H2S, offering promising applications in biomedicine.

[0004] Currently, the preparation of transition metal disulfide nanomaterials primarily involves preparing precursor nanomaterials such as transition metal oxides, then reacting these with sulfur powder at high temperatures under an inert gas atmosphere. This method is complex, energy-intensive, and hazardous. Furthermore, the resulting materials suffer from poor water dispersibility and low biocompatibility. Summary of the Invention

[0005] The present invention aims to provide a method for preparing a transition metal disulfide nanomaterial. The preparation method is simple, efficient, green and economical. The prepared transition metal disulfide nanomaterial has high purity, high biocompatibility, good dispersibility in water, and excellent photothermal performance, peroxidase activity, and antioxidant activity.

[0006] To achieve the above object, the present invention provides a method for preparing a transition metal disulfide nanomaterial, comprising the following steps:

[0007] S1. Adding a sulfur-containing precursor to a polyol and sonicating until all solids are dissolved to obtain a first solution;

[0008] S2, adding the transition metal salt to the first solution and stirring until all the solids are dissolved to obtain a second solution;

[0009] S3, transferring the second solution to a stainless steel autoclave and heating it to obtain a third solution;

[0010] S4. Centrifuging, washing, and drying the third solution to obtain transition metal disulfide nanomaterials.

[0011] Preferably, in S1, the sulfur-containing precursor is one or both of thioacetamide and L-cysteine.

[0012] Preferably, in S1, the polyol is one of ethylene glycol and glycerol.

[0013] Preferably, in S1, the ratio of the sulfur-containing precursor to the polyol is 5-10 mL of polyol to 1 mmol of the sulfur-containing precursor.

[0014] Preferably, in S2, the transition metal salt is one of ferric chloride, cobalt chloride, nickel chloride, ferric nitrate, cobalt nitrate, and nickel nitrate.

[0015] Preferably, the molar ratio of the sulfur-containing precursor to the transition metal salt is (5-10):1.

[0016] Preferably, in S3, the heating temperature is 180-220° C., and the heating time is 12-24 h.

[0017] Therefore, the present invention adopts the above-mentioned method for preparing a transition metal disulfide nanomaterial, which has the following beneficial effects:

[0018] (1) The present invention uses polyols as solvents and reducing agents, and L-cysteine or thioacetamide as sulfur-containing precursors and modifiers, which is green, economical, and has high biocompatibility;

[0019] (2) The preparation method of the present invention is simple and efficient, and the prepared transition metal disulfide nanomaterial has high purity and good dispersibility in water;

[0020] (3) The transition metal disulfide nanomaterial prepared by the present invention has high catalytic activity and good antioxidant effect as a nanozyme.

[0021] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is an XRD pattern of the iron disulfide nanomaterial prepared in Example 1 of the method for preparing a transition metal disulfide nanomaterial of the present invention;

[0023] Figure 2This is a SEM image of the iron disulfide nanomaterial prepared in Example 1 of the method for preparing a transition metal disulfide nanomaterial of the present invention;

[0024] Figure 3 This is an XRD pattern of nickel disulfide nanomaterial prepared in Example 2 of the method for preparing a transition metal disulfide nanomaterial of the present invention;

[0025] Figure 4 This is a SEM image of a nickel disulfide nanomaterial prepared in Example 2 of a method for preparing a transition metal disulfide nanomaterial of the present invention;

[0026] Figure 5 This is a SEM image of a cobalt disulfide nanomaterial prepared in Example 3 of the method for preparing a transition metal disulfide nanomaterial of the present invention;

[0027] Figure 6 This is a photothermal performance test result diagram of an iron disulfide nanomaterial prepared in Example 1 of a method for preparing a transition metal disulfide nanomaterial of the present invention;

[0028] Figure 7 This is a graph showing the peroxidase activity test results of the iron disulfide nanomaterial prepared in Example 1 of the method for preparing a transition metal disulfide nanomaterial of the present invention;

[0029] Figure 8 This is a graph showing the antioxidant activity test results of the iron disulfide nanomaterial prepared in Example 1 of the method for preparing a transition metal disulfide nanomaterial of the present invention. DETAILED DESCRIPTION

[0030] The technical solution of the present invention is further described below with reference to the accompanying drawings and embodiments.

[0031] Unless otherwise defined, technical or scientific terms used in this invention shall have the same ordinary meaning as those generally understood by persons of ordinary skill in the art to which this invention pertains. The terms "first," "second," and similar terms used in this invention do not denote any order, quantity, or importance, but are merely used to distinguish different components.

[0032] Example 1

[0033] A method for preparing an iron disulfide nanomaterial comprises the following steps:

[0034] S1. Add 5 mmol of L-cysteine to 30 mL of ethylene glycol and sonicate until the solid is completely dissolved to obtain a first solution;

[0035] S2, adding 0.5 mmol of ferric chloride to the first solution, stirring until all the solids are dissolved, to obtain a second solution;

[0036] S3, transferring the second solution to a 50 mL stainless steel autoclave and heating at 200° C. for 24 h to obtain a third solution;

[0037] S4. Centrifuge the third solution at 6000 rpm for 5 min, discard the supernatant, wash the precipitate with deionized water three times, and dry it naturally at room temperature to obtain black iron disulfide nanopowder.

[0038] Example 2

[0039] A method for preparing a nickel disulfide nanomaterial comprises the following steps:

[0040] S1. Add 5 mmol of thioacetamide to 30 mL of ethylene glycol, and sonicate until all the solids are dissolved to obtain a first solution;

[0041] S2, adding 0.5 mmol nickel chloride to the first solution, stirring until the solid is completely dissolved to obtain a second solution;

[0042] S3, transferring the second solution to a 50 mL stainless steel autoclave and heating at 200° C. for 24 h to obtain a third solution;

[0043] S4. Centrifuge the third solution at 6000 rpm for 5 min, discard the supernatant, wash the precipitate with deionized water three times, and dry it naturally at room temperature to obtain black nickel disulfide nanopowder.

[0044] Example 3

[0045] A method for preparing a cobalt disulfide nanomaterial comprises the following steps:

[0046] S1. Add 5 mmol of L-cysteine to 30 mL of ethylene glycol and sonicate until all the solid is dissolved to obtain a first solution;

[0047] S2, adding 0.5 mmol of cobalt nitrate to the first solution, stirring until the solid is completely dissolved to obtain a second solution;

[0048] S3, transferring the second solution to a 50 mL stainless steel autoclave and heating at 200° C. for 24 h to obtain a third solution;

[0049] S4. Centrifuge the third solution at 6000 rpm for 5 min, discard the supernatant, wash the precipitate with deionized water three times, and dry it naturally at room temperature to obtain black cobalt disulfide nanopowder.

[0050] Experimental Test 1

[0051] The product prepared in Example 1-2 was characterized by X-ray powder diffractometer, and the results were as follows: Figure 1 and Figure 3 As shown, the product of Example 1 is high-purity orthorhombic iron disulfide, and the product of Example 2 is high-purity cubic nickel disulfide.

[0052] The products prepared in Examples 1-3 were characterized and analyzed by scanning electron microscopy. Figure 2 、 Figure 4 、 Figure 5 As shown, the iron disulfide nanomaterial prepared in Example 1 is a micron-sized flaky structure; the nickel disulfide nanomaterial prepared in Example 2 is a spherical particle with a diameter of about 500 nm, which is slightly agglomerated; and the cobalt disulfide nanomaterial prepared in Example 3 is a spherical particle with a diameter of about 70 nm.

[0053] Experimental Test 2

[0054] like Figure 6 As shown, before the addition of iron disulfide nanomaterials, the temperature of deionized water was stable at around 22°C under 808nm near-infrared light with a power of 1 W. After adding 0.1 mg / mL of the iron disulfide nanomaterial prepared in Example 1, the temperature of the deionized water rose rapidly from 22°C to 68°C under 808nm near-infrared light with a power of 1 W, demonstrating that the iron disulfide nanomaterials have excellent photothermal properties.

[0055] The peroxidase activity of the iron disulfide nanomaterial prepared in Example 1 was determined by colorimetry. Figure 7 As shown, under the catalysis of iron disulfide nanomaterials, hydrogen peroxide converted colorless tetramethylbenzidine (TMB) into blue oxidized TMB (TMBox), and the absorbance changed at 652nm, which proved that iron disulfide nanomaterials had excellent peroxidase nanozyme activity.

[0056] The antioxidant properties of the iron disulfide nanomaterial prepared in Example 1 were judged by its ability to scavenge the typical nitrogen free radical active substance, 2,2-biphenyl-1-picrylhydrazyl (DPPH). Figure 8 It can be seen that iron disulfide nanomaterials with a concentration of 0.1 mg / mL can scavenge 75% of DPPH free radicals within 5 min, which proves that iron disulfide nanomaterials have strong antioxidant properties.

[0057] Therefore, the present invention adopts the above-mentioned preparation method of transition metal disulfide nanomaterial, which is simple, efficient, green and economical. The prepared transition metal disulfide nanomaterial has high purity, high biocompatibility, good dispersibility in water, and excellent photothermal performance, peroxidase activity, and antioxidant activity.

[0058] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solutions of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a transition metal disulfide nanomaterial, characterized in that: The following steps are involved: S1. Adding a sulfur-containing precursor to a polyol and sonicating until all solids are dissolved to obtain a first solution; S2, adding the transition metal salt to the first solution and stirring until all the solids are dissolved to obtain a second solution; S3, transferring the second solution to a stainless steel autoclave and heating it to obtain a third solution; S4. Centrifuging, washing, and drying the third solution to obtain transition metal disulfide nanomaterials.

2. The method for preparing a transition metal disulfide nanomaterial according to claim 1, characterized in that: In S1, the sulfur-containing precursor is one or both of thioacetamide and L-cysteine.

3. The method for preparing a transition metal disulfide nanomaterial according to claim 1, characterized in that: In S1, the polyol is one of ethylene glycol and glycerol.

4. The method for preparing a transition metal disulfide nanomaterial according to claim 1, characterized in that: In S1, the ratio of sulfur-containing precursor to polyol is 5-10 mL polyol to 1 mmol sulfur-containing precursor.

5. The method for preparing a transition metal disulfide nanomaterial according to claim 1, characterized in that: In S2, the transition metal salt is one of ferric chloride, cobalt chloride, nickel chloride, ferric nitrate, cobalt nitrate, and nickel nitrate.

6. The method for preparing a transition metal disulfide nanomaterial according to claim 1, characterized in that: The molar ratio of the sulfur-containing precursor to the transition metal salt is (5-10):

1.

7. The method for preparing a transition metal disulfide nanomaterial according to claim 1, characterized in that: In S3, the heating temperature is 180-220° C., and the heating time is 12-24 h.

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