Chiral metal sulfide nano material and preparation method thereof
A one-step hydrothermal method using chiral-inducing agents synthesizes chiral metal sulfide nanoparticles with tunable optical activity and high stability, addressing inefficiencies in existing methods and enabling scalable production.
Patent Information
- Application Number
- CN202510360545.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-26
- Publication Date
- 2025-07-15
AI Technical Summary
The prior art is difficult to efficiently prepare chiral metal sulfides, resulting in limited application in areas where chirality has specific requirements. The traditional methods are costly, complex processes, poor repetition, and difficult to achieve large-scale production.
Chiral metal sulfide nanomaterials are prepared by one-step hydrothermal method. Nanomaterials with asymmetric structures are prepared by introducing chiral structure inducers during crystal growth and controlling reaction conditions such as temperature and pH.
The prepared chiral metal sulfide nanomaterials show good chiral optical activity in the visible light zone, have high stability and photoresponsiveness, uniform morphology, good repeatability, and are suitable for large-scale production.
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Figure CN120309002A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of nanomaterials, and particularly to a chiral metal sulfide nanomaterial and a preparation method thereof. Background Art
[0002] Due to their unique asymmetric structures, chiral materials exhibit great application potential in the fields of optics, catalysis, biomedicine, etc. As an important class of semiconductor materials, metal sulfides have suitable bandgaps, good optoelectronic properties and chemical stability, and have been widely studied in optoelectronic devices, photocatalysis, etc. However, traditional chiral metal sulfides mostly have non-chiral structures, which limits their applications in some fields with specific requirements for chirality.
[0003] Currently, there are various methods for preparing chiral materials, such as the template method, self-assembly method, etc. However, these methods have many problems when preparing chiral metal sulfides. The template method often requires a complex template preparation process, with high costs and difficult template removal, and it is easy to leave impurities that affect the material properties; the self-assembly method has extremely strict requirements for the control of reaction conditions, and the synthesis process is difficult to repeat, resulting in low preparation efficiency and unstable quality of chiral metal sulfides, and it is difficult to achieve large-scale production applications. Summary of the Invention
[0004] The purpose of the present invention is to provide a chiral metal sulfide nanomaterial and a preparation method thereof. The synthesized different chiral metal sulfides exhibit good chiral optical activity in the visible light region, have adjustable optical activity, and at the same time have high photochemical stability and light responsiveness.
[0005] To achieve the above purpose, the present invention provides the following technical solutions:
[0006] A preparation method of a chiral metal sulfide nanomaterial, comprising the following steps:
[0007] Step 1: Dissolve 0.5 - 3 mol of metal salt in 10 - 30 mL of deionized water to prepare solution A, and add a sulfur source and a chiral structure inducer to solution A and dissolve them fully to form solution B, where the molar ratio of the metal salt, sulfur source and chiral structure inducer is 1:1.5:1.5;
[0008] Step 2: Slowly add a 0.1 - 2 mol / L alkaline solution to solution B to adjust the pH of the solution to 6 - 11;
[0009] Step 3: Place the solution B with adjusted pH in a hydrothermal autoclave at 120 - 200 °C for hydrothermal reaction for 1 h - 24 h;
[0010] Step 4: After the reaction is completed, centrifuge, wash ultrasonically, and vacuum dry at 30 - 80 °C to obtain the chiral metal sulfide nanomaterial.
[0011] Further, the metal cation in the metal salt in Step 1 is one or more of silver, copper, zinc, iron, cadmium, and indium, and the anion is one or more of sulfate, nitrate, chloride, and acetate.
[0012] Further, the sulfur source in Step 1 is one or more of thiourea, cysteine, thioacetamide, methionine, and penicillamine.
[0013] Further, the chiral structure inducer in Step 1 is one or more of cysteine, methionine, and penicillamine.
[0014] Further, the alkaline solution in Step 2 is one or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, and aqueous ammonia solution.
[0015] Further, the rotation speed of centrifugation in Step 4 is 4000 rpm - 10000 rpm, the time is 5 min - 10 min, and the number of times is 1 - 3 times.
[0016] Further, the power of ultrasonic washing in Step 4 is 20 W - 100 W, and the time is 5 - 30 min.
[0017] Further, the time of vacuum drying in Step 4 is 2 - 12 h.
[0018] The chiral metal sulfide nanomaterials prepared by the above method have a particle size of 100 - 2000 nm and have adjustable optical activity.
[0019] Compared with the prior art, the present invention has the following beneficial effects:
[0020] The method for preparing chiral metal sulfides by chiral ligand-induced one-step hydrothermal method adopted in the present invention has a simpler chiral induction mechanism, that is, introducing asymmetric elements during crystal growth to promote the asymmetric growth trend of crystals. At the same time, due to the introduction of chiral ligands during the hydrothermal process, the chiral ligands participate in the reaction under high temperature and high pressure, so that the product no longer contains chiral ligands, and the chiral signal originates from the chiral nanoparticles themselves, rather than being provided by chiral ligands, having a more stable structure and excellent repeatability. The prepared samples have uniform morphology and stable structure, and the hydrothermal method can prepare a large amount of samples with high repeatability, making the chiral metal sulfide nanomaterials prepared by the present invention have broad application prospects.
[0021] By regulating the types of metal sources, temperature, pH, and types of chiral ligands, etc., the present invention obtains different types of chiral metal sulfide nanomaterials. The synthesized different chiral metal sulfides have good chiral optical activity in the visible light region, have adjustable optical activity, and at the same time have high photochemical stability and light responsiveness. Brief Description of the Drawings
[0022] Figure 1 It is the CD spectrogram of the In2S3 nanomaterial prepared in Example 1 of the present invention;
[0023] Figure 2 It is the CD spectrogram of the In2S3 nanomaterial prepared in Example 2 of the present invention;
[0024] Figure 3 It is the CD spectrogram of the ZnIn2S4 nanomaterial prepared in Example 3 of the present invention;
[0025] Figure 4 It is the CD spectrogram of the ZnIn2S4 nanomaterial prepared in Example 4 of the present invention;
[0026] Figure 5 It is the SEM image of the In2S3 nanomaterial prepared in Example 1 of the present invention;
[0027] Figure 6 It is the SEM image of the In2S3 nanomaterial prepared in Example 2 of the present invention;
[0028] Figure 7 It is the SEM image of the ZnIn2S4 nanomaterial prepared in Example 3 of the present invention;
[0029] Figure 8 It is the SEM image of the ZnIn2S4 nanomaterial prepared in Example 4 of the present invention;
[0030] Figure 9 It is the SEM-Mapping image of the ZnIn2S4 nanomaterial prepared in Example 3 of the present invention. Detailed Embodiments
[0031] To make the above objects, features and advantages of the present invention more obvious and understandable, the present invention will be described in detail below with reference to the drawings and specific embodiments.
[0032] Example 1: A preparation method of a chiral In2S3 nanomaterial, comprising the following steps:
[0033] Step 1: Dissolve 1 mol of indium nitrate in 10 mL of deionized water to prepare solution A, add a sulfur source and a chiral structure inducer to solution A and dissolve them fully to form solution B, wherein both the sulfur source and the chiral structure inducer are cysteine, and the molar ratio of indium nitrate, the sulfur source and the chiral structure inducer is 1:1.5:1.5;
[0034] Step 2: Slowly drop 1 mol / L NaOH solution into solution B to adjust the pH of the solution to 8;
[0035] Step 3: Place the solution B with adjusted pH into a hydrothermal autoclave at 180 °C for hydrothermal reaction for 12 h;
[0036] Step 4: After the reaction is completed, centrifuge 3 times, each time at a rate of 6000 rpm for 8 min, then ultrasonically wash for 30 min at a power of 20 W, and vacuum dry at 60 °C for 6 h to obtain In2S3 nanoparticles.
[0037] Example 2:
[0038] This example is the same as Example 1, except that in Step 2, an alkali NaOH solution is added to adjust the pH of solution B to 6.
[0039] Example 3: A preparation method of chiral ZnIn2S4 nanomaterial, comprising the following steps:
[0040] Dissolve a mixture of 0.375 mol indium nitrate and 0.75 mol zinc nitrate in 30 mL deionized water to prepare solution A, add a sulfur source and a chiral structure inducer to solution A and dissolve them fully to form solution B, where both the sulfur source and the chiral structure inducer are cysteine, and the molar ratio of the mixed metal salts of indium nitrate and zinc nitrate, the sulfur source and the chiral structure inducer is 1:1.5:1.5;
[0041] Step 2: Slowly drop 2 mol / L ammonia water solution into solution B to adjust the solution pH to 9;
[0042] Step 3: Place the solution B with adjusted pH into a hydrothermal autoclave at 120 °C for hydrothermal reaction for 24 h;
[0043] Step 4: After the reaction is completed, centrifuge 2 times, each time at a rate of 4000 rpm for 10 min, then ultrasonically wash for 5 min at a power of 100 W, and vacuum dry at 30 °C for 12 h to obtain chiral ZnIn2S4 nanoparticles.
[0044] Example 4:
[0045] This example is the same as Example 3, except that in Step 2, an ammonia water solution is added to adjust the pH of solution B to 11.
[0046] The chiral optical activity of the chiral metal sulfide nanomaterials prepared in Examples 1-4 was evaluated using a circular dichroism spectrometer, as Figures 1-4 shown, it can be seen that the nanomaterials prepared by using the chiral structure inducer have excellent circular dichroism signals. Comparing Figure 1 and Figure 2It can be seen that adjusting the pH value causes the double-peak inversion CD signal of the nanomaterial in the visible light region of 400-700nm to transform into a broad negative peak of 400-700nm. Figure 3 and Figure 4 It can also be seen that adjusting the pH value causes the CD signal peak of the nanomaterial in the visible light region to move to a wide band, and the peak value of the CD peak becomes larger. Therefore, it can be seen that adjusting the pH value causes the circular dichroism (CD) signal of the nanomaterial in the visible light region to change. Figure 1 and Figure 3 It can be seen that the circular dichroism signal in the visible light region changes by adjusting the type of metal source. This is because the introduction of zinc changes the chiral optical activity of the product.
[0047] The chiral metal sulfide nanomaterials prepared in Examples 1-4 were analyzed by field emission scanning electron microscopy (FE-SEM) to determine their morphological characteristics. Figures 5-8 As shown, it can be seen that the particle size of the chiral indium sulfide nanoparticles prepared in Example 1 is 500-600nm, and it is observed that the chiral indium sulfide nanoparticles are assembled from nanosheets. The chiral indium sulfide nanomaterial prepared in Example 2 is a sheet structure, and the chiral indium sulfide nanomaterial prepared in Example 3 is a spiral pancake structure with a particle size of 500-700nm. The chiral indium sulfide nanomaterial prepared in Example 4 is a spherical structure with a particle size of 600-800nm. It can be seen that the change in pH value has an effect on the morphology of the product, resulting in a change in the chiral optical activity of the product.
[0048] Mapping was performed on the chiral metal sulfide nanomaterial prepared in Example 3 to collect element signals, such as Figure 9 As shown, it can be seen that the Zn, In, and S elements in the D-ZnIn2S4 nanoparticles are evenly distributed on the surface, and no impurity phase is precipitated, indicating that the indium zinc sulfide solid solution is successfully synthesized.
[0049] Embodiment 5: A method for preparing a chiral silver sulfide nanomaterial, comprising the following steps:
[0050] Step 1: dissolving 0.5 mol of silver nitrate in 15 mL of deionized water to prepare solution A, adding a sulfur source and a chiral structure inducer to solution A and fully dissolving them to form solution B, wherein the sulfur source is thioacetamide and penicillamine, the chiral structure inducer is methionine, and the molar ratio of silver nitrate, sulfur source and chiral structure inducer is 1:1.5:1.5;
[0051] Step 2: Slowly add a 0.1 mol / L mixed solution of sodium hydroxide and calcium hydroxide into solution B to adjust the pH of the solution to 6;
[0052] Step 3: Place the solution B with adjusted pH value into a hydrothermal autoclave at 200 °C for hydrothermal reaction for 1 h;
[0053] Step 4: After the reaction is completed, centrifuge at a rate of 10,000 rpm for 5 min, then ultrasonically wash at a power of 50 W for 15 min, and vacuum dry at 80 °C for 2 h to obtain chiral silver sulfide nanoparticles.
[0054] Example 6: A preparation method of a chiral copper sulfide nanomaterial, comprising the following steps:
[0055] Step 1: Dissolve 3 mol of copper acetate in 30 mL of deionized water to prepare solution A, add a sulfur source and a chiral structure inducer to solution A and dissolve them fully to form solution B, wherein the sulfur source is thioacetamide, the chiral structure inducer is penicillamine, and the molar ratio of copper acetate, the sulfur source and the chiral structure inducer is 1:1.5:1.5;
[0056] Step 2: Slowly drop 2 mol / L ammonia water solution into solution B to adjust the pH value of the solution to 11;
[0057] Step 3: Place the solution B with adjusted pH value into a hydrothermal autoclave at 160 °C for hydrothermal reaction for 15 h;
[0058] Step 4: After the reaction is completed, centrifuge 3 times, each time at a rate of 8,000 rpm for 6 min, then ultrasonically wash at a power of 100 W for 5 min, and vacuum dry at 80 °C for 12 h to obtain a chiral metal sulfide nanomaterial.
[0059] Example 7: A preparation method of a chiral zinc cadmium sulfide nanomaterial, comprising the following steps:
[0060] Step 1: Dissolve a mixture of 1.5 mol of cadmium nitrate and 0.5 mol of zinc sulfate in 20 mL of deionized water to prepare solution A, add a sulfur source and a chiral structure inducer to solution A and dissolve them fully to form solution B, wherein the sulfur source is a mixture of thiourea and thioacetamide, the chiral structure inducer is a mixture of cysteine, methionine and penicillamine, and the molar ratio of the mixed metal salt of cadmium nitrate and zinc sulfate, the sulfur source and the chiral structure inducer is 1:1.5:1.5;
[0061] Step 2: Slowly drop 0.5 mol / L potassium hydroxide solution into solution B to adjust the pH value of the solution to 10;
[0062] Step 3: Place the solution B with adjusted pH value into a hydrothermal autoclave at 150 °C for hydrothermal reaction for 18 h;
[0063] Step 4: After the reaction is completed, centrifuge for 3 times, each time at a speed of 4000 rpm for 10 minutes, then ultrasonically wash for 5 minutes at a power of 100 W, and vacuum dry at 50° C. for 8 hours to obtain chiral zinc cadmium sulfide nanomaterials.
[0064] Embodiment 8: A method for preparing a chiral zinc cadmium sulfide nanomaterial, comprising the following steps:
[0065] Step 1: dissolving a mixture of 0.8 mol of ferrous chloride and 1.6 mol of indium nitrate in 25 mL of deionized water to prepare solution A, adding a sulfur source and a chiral structure inducer to solution A and fully dissolving them to form solution B, wherein the sulfur source is a mixture of thiourea, cysteine and methionine, the chiral structure inducer is a mixture of cysteine and penicillamine, and the molar ratio of the mixed metal salt of ferrous chloride and indium nitrate, the sulfur source and the chiral structure inducer is 1:1.5:1.5;
[0066] Step 2: Slowly add 1.5 mol / L potassium hydroxide solution to solution B to adjust the pH of the solution to 11;
[0067] Step 3: Place the pH-adjusted solution B in a hydrothermal reactor at 190°C for 4 hours;
[0068] Step 4: After the reaction is completed, centrifuge at a speed of 8000 rpm for 5 minutes, then ultrasonically wash at a power of 60 W for 20 minutes, and vacuum dry at 70° C. for 4 hours to obtain chiral zinc cadmium sulfide nanomaterials.
Claims
1. A preparation method of a chiral metal sulfide nanomaterial, characterized in that, It includes the following steps: Step 1: Dissolve 0.5 - 3 mol of metal salt in 10 - 30 mL of deionized water to prepare solution A, and add a sulfur source and a chiral structure inducer to solution A and dissolve them fully to form solution B, where the molar ratio of the metal salt, the sulfur source, and the chiral structure inducer is 1:1.5:1.5; Step 2: Slowly add a 0.1 - 2 mol / L alkaline solution to solution B to adjust the pH of the solution to 6 - 11; Step 3: Place the solution B with adjusted pH in a hydrothermal autoclave at 120 - 200 °C for hydrothermal reaction for 1 h - 24 h; Step 4: After the reaction is completed, centrifuge, wash by ultrasound, and vacuum dry at 30 - 80 °C to obtain a chiral metal sulfide nanomaterial.
2. The preparation method of a defect-rich carbon-supported transition metal / metal oxide according to claim 1, characterized in that, The metal cation in the metal salt described in Step 1 is one or more of silver, copper, zinc, iron, cadmium, and indium, and the anion is one or more of sulfate, nitrate, chloride, and acetate.
3. The preparation method of a chiral metal sulfide nanomaterial according to claim 1, characterized in that, The sulfur source described in Step 1 is one or more of thiourea, cysteine, thioacetamide, methionine, and penicillamine.
4. The preparation method of a chiral metal sulfide nanomaterial according to claim 1, wherein, The chiral structure inducer described in Step 1 is one or more of cysteine, methionine, and penicillamine.
5. The preparation method of a chiral metal sulfide nanomaterial according to claim 1, characterized in that, The alkaline solution described in Step 2 is one or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, and ammonia water solution.
6. The preparation method of a chiral metal sulfide nanomaterial according to claim 1, characterized in that, The rotation speed of the centrifuge in Step 4 is 4000 rpm - 10000 rpm, the time is 5 min - 10 min, and the number of times is 1 - 3 times.
7. The preparation method of a chiral metal sulfide nanomaterial according to claim 1, characterized in that, The power of the ultrasonic washing in Step 4 is 20 W - 100 W, and the time is 5 - 30 min.
8. The preparation method of a chiral metal sulfide nanomaterial according to claim 1, characterized in that The time of the vacuum drying in Step 4 is 2 - 12 h.
9. The chiral metal sulfide nanomaterial prepared by the preparation method according to any one of claims 1-8, characterized in that, The particle size of the chiral metal sulfide nanomaterial is 100 - 2000 nm, and it has adjustable optical activity.