CN116121769A - Preparation method of two-dimensional layered sulfur nanomaterial - Google Patents
Preparation method of two-dimensional layered sulfur nanomaterial Download PDFInfo
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Abstract
The invention belongs to the technical field of nano sulfur preparation, and relates to a preparation method of a two-dimensional lamellar sulfur nano material, which comprises the following steps: 1) Preparing a sulfur source and a corresponding electrolyte respectively; the sulfur source is thiourea or sublimed sulfur; 2) Uniformly mixing a sulfur source with an electrolyte to obtain a mixture; continuously adding a stabilizer into the mixture, and stirring to obtain a mixed electrolyte, wherein the electrolyte is solid or liquid, and the stabilizer is solid or liquid; 3) And (3) electrolyzing the mixed electrolyte in the step (2) to obtain the two-dimensional lamellar sulfur nanomaterial. The invention prepares the two-dimensional lamellar sulfur nanomaterial by using sublimed sulfur or thiourea as a sulfur source and BSA or PEDOT: PSS as a stabilizer through an electrolytic method, and the synthesized lamellar sulfur nanomaterial has short synthesis time and high yield and shows good photoelectrochemical property in aqueous solution.
Description
Technical Field
The invention belongs to the technical field of nano sulfur preparation, and relates to a preparation method of a two-dimensional lamellar sulfur nano material.
Background
The sulfur nanomaterial comprises sulfur nanoparticles, sulfur quantum dots and two-dimensional lamellar sulfur nanomaterial. The sulfur nano material does not contain heavy metal elements, has the advantages of low cytotoxicity, excellent water dispersibility, light stability, good biocompatibility, tunable luminescence and the like, and has potential application in the fields of biological detection, gas sensing, photoelectrocatalysis and photoelectric devices.
In recent years, lamellar sulfur nano-sheets (S-NSs) are presented as a novel two-dimensional lamellar sulfur nano-material, and compared with other two-dimensional nano-materials, the lamellar sulfur nano-sheets have unique semiconductor performance, excellent stability, excellent photoelectric conversion and photocatalytic performance, and potential gas sensitivity and photoelectric catalytic activity. Heretofore, there have been methods of solid mechanical ball milling sublimated sulfur, mechanical ultrasonic stripping sublimated sulfur, self-assembly of sulfur quantum dots to form layered sulfur, etc., and although layered sulfur nanomaterial can be obtained, the following problems still remain: (1) In the existing preparation method, the dopamine ball milling commercial sulfur is adopted to produce S-NSs, and the S-NSs are applied to the anode of a lithium sulfur battery to show high electrochemical activity, but the solid mechanical preparation method is not suitable for exploring the photoelectrochemical property in aqueous solution, so that the application of lamellar sulfur nano materials is greatly limited; (2) In the existing method, bovine Serum Albumin (BSA) is also used as a dispersion stabilizer, and S-NSs are successfully obtained by directly sublimating sulfur through ultrasonic treatment. Or the self-assembly of sulfur quantum dots can also be reported to form S-NSs nano materials, but the methods have the defect of long synthesis time, require 3-5 days, and have low yield which cannot reach milligram level.
Disclosure of Invention
Aiming at the technical problems of long synthesis time, low yield and limited use in the existing preparation of the two-dimensional lamellar sulfur nanomaterial, the invention provides a preparation method of the two-dimensional lamellar sulfur nanomaterial, which is characterized in that sublimed sulfur or thiourea is used as a sulfur source, BSA or PEDOT: PSS is used as a stabilizer, and the two-dimensional lamellar sulfur nanomaterial is prepared by adopting an electrolytic method, so that the synthesis time is short, the yield is high, and the nanomaterial shows good photoelectrochemical properties in aqueous solution.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the two-dimensional lamellar sulfur nanomaterial comprises the following steps of:
1) Preparing a sulfur source and a corresponding electrolyte respectively; the sulfur source is thiourea or sublimed sulfur;
2) Uniformly mixing a sulfur source with an electrolyte to obtain a mixture; continuously adding a stabilizer into the mixture, and stirring to obtain a mixed electrolyte; the electrolyte is solid or liquid, and the stabilizer is solid or liquid;
3) And (3) electrolyzing the mixed electrolyte in the step (2) to obtain the two-dimensional lamellar sulfur nanomaterial.
Further, in the step 2), the sulfur source is thiourea, the stabilizer is a mixture of bovine serum albumin BSA and water, and the electrolyte is NaCl solid, KCl solid or Na 2 CO 3 Solid, na 2 SO 4 Solids or K 2 SO 4 The dosage ratio of the sulfur source, the electrolyte, the water and the stabilizer is 0.2 g-1.5 g:0.5g:40mL:10 mg-90 mg.
Further, in the step 2), the sulfur source is thiourea, the stabilizer is 3, 4-ethylenedioxythiophene/styrene sulfonate solution, and the electrolyte is NaCl solid, KCl solid or Na 2 CO 3 Solid, na 2 SO 4 Solids or K 2 SO 4 The dosage ratio of the sulfur source, the electrolyte and the stabilizer is 0.2 g-1.5 g:0.5g:40mL; the concentration of the stabilizer is 0.005 g/mL-0.05 g/mL.
Further, in the step 2), the stirring temperature is 20-30 ℃ and the stirring time is 0.5-2 h.
Further, in the step 3), constant current electrolysis is adopted for electrolysis, and the electrolysis current is 0.1-0.2A; the electrolysis time is 30 min-90 min.
Further, in the step 3), electrolysis is constant voltage electrolysis, naOH solid is further added into the mixed electrolyte, and the usage ratio of the mixed electrolyte to the NaOH solid is 40mL:0.4 g-4 g; the constant voltage is 0.6V-0.7V, and the electrolysis time is 30 min-300 min.
Further, in the step 2), the sulfur source is sublimed sulfur, the electrolyte is a NaOH solution, the stabilizer is bovine serum albumin BSA, and the dosage ratio of the sulfur source to the electrolyte is 0.2 g-1.4 g:80mL; the concentration of the electrolyte is 0.1 mol/L-2 mol/L; the ratio of the mixture to bovine serum albumin BSA was 40mL: 10-90 mg.
Further, in the step 2), the sulfur source is sublimed sulfur, the electrolyte is a NaOH solution, the stabilizer is a 3, 4-ethylenedioxythiophene/styrene sulfonate solution, and the dosage ratio of the sulfur source to the electrolyte is 0.2 g-1.4 g:80mL; the concentration of the electrolyte is 0.1 mol/L-2 mol/L; the dosage ratio of the mixture to the stabilizer is 40mL: 0.027-2.1 mL, and the concentration of the stabilizing agent in the mixed electrolyte is 0.001-0.08 g/mL.
Further, in the step 2), the uniform mixing temperature is 70-120 ℃ and the uniform mixing time is 1-5 h.
Further, in the step 3), the electrolysis is constant current electrolysis, the constant current is 0.1A-0.2A, and the electrolysis time is 30 min-120 min.
The beneficial effects of the invention are as follows:
1. the invention synthesizes the nano material S-NSs with a two-dimensional layered structure by adopting sublimed sulfur or thiourea as a sulfur source and adopting BSA or PEDOT: PSS as a stabilizer through an electrolytic method, the preparation method is simple, the electrolytic time is 30-300 min, the preferable time is less than 3h, the synthesis time is short, the yield of the generated S-NSs is high, the milligram grade can be reached, the weighing is convenient, the industrialization is easy, and a novel method is provided for synthesizing the layered S-NSs nano material.
2. The invention uses sublimed sulfur or thiourea as a sulfur source, the raw materials are easy to obtain, the time consumption is short, the cost is greatly saved, the economic benefit is higher, and the invention has great commercial application prospect.
3. The invention prepares the two-dimensional S-NSS material by direct current electrolysis, shows unique multiband PL luminescence characteristic, and the prepared S-NSS has better aqueous solution dispersibility and electrochemical property, thereby providing reference for developing potential application of the S-NSS material.
Drawings
FIG. 1 is a PL spectrum of two-dimensional layered sulfur nanomaterial S-NSs prepared in examples 1-10 using sublimed sulfur as a sulfur source, BSA or PEDOT: PSS as a stabilizer;
FIG. 2 is a PL spectrum and a physical diagram of S-NSs prepared under different electrolysis time by sublimating sulfur and BSA as a stabilizer;
FIG. 3 is a graph of UV-Vis absorption spectra and a graph of physical objects before and after electrolysis of sublimed sulfur and different stabilizers;
FIG. 4 is a SEM of sublimed sulfur, different stabilizers to make S-NSs;
FIG. 5 shows PL spectra of S-NSs prepared by using BSA as a stabilizer and different thiourea dosages under 1h of electrolysis;
FIG. 6 is a PL spectrum of S-NSs prepared with thiourea as a raw material and BSA as a stabilizer at different electrolysis times;
FIG. 7 is a PL spectrum of S-NSs prepared from thiourea as a raw material and a stabilizer PEDOT: PSS at different concentrations;
FIG. 8 is a UV-Vis absorption spectrum of S-NSs prepared with thiourea, BSA or PEDOT: PSS as a stabilizer;
FIG. 9 is an atomic force microscope image of S-NSs prepared from thiourea as a starting material and BSA as a stabilizer;
FIG. 10 is an atomic force microscope image of S-NSs prepared from thiourea as a starting material and stabilizer PEDOT: PSS;
FIG. 11 is a transmission electron microscope image of S-NSs prepared with thiourea as the sulfur source;
FIG. 12 is an X-ray photoelectron spectrum of thiourea as a sulfur source to produce S-NSs;
FIG. 13 is an X-ray diffraction spectrum of S-NSs prepared by using thiourea as a sulfur source.
Detailed Description
For a further understanding of the present invention, the present invention is described below in connection with the following examples, but the description is merely to further illustrate the features and advantages of the present invention and is not intended to limit the claims of the present invention.
The invention adopts an electrolytic method to prepare two-dimensional lamellar sulfur nano material S-NSs, specifically uses sublimed sulfur or thiourea as a sulfur source, adds the sulfur source into electrolyte water, then adds a stabilizer, and finally electrolyzes to prepare the S-NSs.
As the stabilizer is selected to directly influence the morphology of a synthesized product in the synthesis of the nano material, the stabilizer is bovine serum albumin or 3, 4-ethylenedioxythiophene/styrene sulfonate (PEDOT: PSS).
(1) Bovine Serum Albumin (BSA): is an albumin in bovine serum. BSA can be used as an effective stripping agent and also can be used as a strong stabilizer to prevent the reagglomeration of single-layer nano-sheets, and the biocompatibility of the synthesized nano-material is greatly improved due to the excellent biocompatibility of BSA of the nano-material coated by BSA; in addition, due to the good hydrogen bonding effect between BSA, the BSA-coated nano particles can be further assembled through the hydrogen bonding effect between BSA, so that nano materials with different morphologies are formed.
(2) The 3, 4-ethylenedioxythiophene/polystyrene sulfonate solution (PEDOT: PSS) is an aqueous solution of a high molecular polymer consisting of two substances of PEDOT and PSS, and has high conductivity. PEDOT is a polymer of DOT (3, 4-ethylenedioxythiophene monomer), PSS is polystyrene sulfonate; the two substances together greatly improve the solubility of PEDOT, and the PEDOT-PSS conductive polymer has high conductivity (41000S/cm) and high stability, and is usually used as a stabilizer and is easy to process. PEDOT, PSS, adopted in the embodiment of the invention is purchased from Shanghai Luo Enpai reagent 155090-83-8, and the molecular formula is C 14 H 14 O 5 S 2 PEDOT/PSS concentration was 1.5g/mL.
Different sulfur sources are used for explaining the preparation process of the two-dimensional lamellar sulfur nanomaterial.
When sublimed sulfur is used as a sulfur source, the sublimed sulfur generates S through chemical reaction 2- Formed sulfide ion S 2- Adsorbed on the surface of sulfur to form polysulfide, so that the sulfur is gradually dissolved. When a voltage is applied to an aqueous solution of an alkaline medium, low-valence sulfur ions S can be generated 2- And oxidized to form new zero-valent sulfur S (0). The formed zero-valent sulfur S (0) is coated by a stabilizer BSA or PEDOT:PSS, and the stabilizer BSA or PEDOT:PSS has better hydrogen bonding effect, so that the zero-valent sulfur S (0) is further self-assembled to form lamellar S-NSs, and meanwhile, the BSA or PEDOT: PSS is used as an effective stabilizer and is adsorbed on the surface of formed S-NSs, so that the layered nano-sheets can be prevented from being aggregated again.
The invention relates to a preparation method of a two-dimensional lamellar sulfur nanomaterial, which comprises the following steps:
1) Preparing a sulfur source and a corresponding electrolyte respectively; the sulfur source is thiourea.
2) Uniformly mixing a sulfur source with an electrolyte to obtain a mixture; continuously adding a stabilizer into the mixture, and stirring to obtain a mixed electrolyte; the electrolyte is solid or liquid, and the stabilizer is solid or liquid;
3) And (3) electrolyzing the mixed electrolyte in the step (2) to obtain the two-dimensional lamellar sulfur nanomaterial.
In the step 2), the sulfur source is thiourea, the stabilizer is the mixture of bovine serum albumin BSA and water, and the electrolyte is NaCl solid, KCl solid and Na 2 CO 3 Solid, na 2 SO 4 Solids or K 2 SO 4 The dosage ratio of the solid, the sulfur source, the electrolyte, the water and the stabilizer is 0.2 g-1.5 g:0.5g:40mL:10 mg-90 mg.
In the step 2), the sulfur source is thiourea, the stabilizer is 3, 4-ethylenedioxythiophene/styrene sulfonate solution, and the electrolyte is NaCl solid, KCl solid and Na 2 CO 3 Solid, na 2 SO 4 Solids or K 2 SO 4 Solid, sulfurThe dosage ratio of the source, the electrolyte and the stabilizer is 0.2 g-1.5 g:0.5g:40mL; the concentration of the stabilizer is 0.005 g/mL-0.05 g/mL.
In the step 2), the stirring temperature is 20-30 ℃ and the stirring time is 0.5-2 h.
In the step 3), constant current electrolysis is adopted for electrolysis, and the electrolysis current is 0.1-0.2A; the electrolysis time is 30 min-90 min.
In the step 3), the electrolysis is constant voltage electrolysis, naOH solid is also added into the mixed electrolyte, and the dosage ratio of the mixed electrolyte to the NaOH solid is 40mL:0.4 g-4 g; the constant voltage is 0.6V-0.7V, and the electrolysis time is 30 min-300 min.
When sublimed sulfur is used as a sulfur source, thiourea is hydrolyzed to generate S 2- Ions, S 2- The ions are oxidized at the anode to generate zero-valent S (0), the generated zero-valent S (0) is coated by a stabilizer BSA or PEDOT: PSS, and the formed zero-valent S (0) is self-assembled to form lamellar sulfur through the hydrogen bond between the BSA or PEDOT: PSS.
The invention relates to a preparation method of a two-dimensional lamellar sulfur nanomaterial, which comprises the following steps:
1) Preparing a sulfur source and a corresponding electrolyte respectively; the sulfur source is sublimed sulfur.
2) Uniformly mixing a sulfur source with an electrolyte to obtain a mixture; continuously adding a stabilizer into the mixture, and stirring to obtain a mixed electrolyte;
3) And (3) electrolyzing the mixed electrolyte in the step (2) to obtain the two-dimensional lamellar sulfur nanomaterial.
In the step 2), the sulfur source is sublimed sulfur, the electrolyte is NaOH solution, the stabilizer is 3, 4-ethylenedioxythiophene/styrene sulfonate solution, and the dosage ratio of the sulfur source to the electrolyte is 0.2 g-1.4 g:80mL; the concentration of the electrolyte is 0.1mol/L to 2mol/L; the ratio of the mixture to the stabilizer was 40mL: 0.027-2.1 mL, and the concentration of the stabilizing agent in the mixed electrolyte is 0.001-0.08 g/mL.
In the step 2), the sulfur source is sublimed sulfur, the electrolyte is NaOH solution, the stabilizer is bovine serum albumin BSA, and the dosage ratio of the sulfur source to the electrolyte is 0.2 g-1.4 g:80mL; the concentration of the electrolyte is 0.1mol/L to 2mol/L; the ratio of the mixture to bovine serum albumin BSA was 40mL: 10-90 mg.
In the step 2), the uniform mixing temperature is 70-120 ℃ and the uniform mixing time is 1-5 h.
In the step 3), the electrolysis is constant current electrolysis, the constant current is 0.1A-0.2A, and the electrolysis time is 30-120 min.
In the preparation process, when constant current electrolysis is adopted, the designed electrolysis system is as follows: two Pt wires are adopted as electrodes, the distance between the two Pt wire electrodes is 2cm, and the depth of the electrodes inserted into the electrolyte aqueous solution is 2.5cm. However, other electrolysis systems can also be designed, with the aim of obtaining two-dimensional layered sulfur nanomaterials by electrolysis.
In the preparation process, when constant voltage electrolysis is adopted, the designed electrolysis system is as follows: two Pt wires are adopted as electrodes, the distance between the two Pt wire electrodes is 2cm, and the depth of the electrodes inserted into the electrolyte aqueous solution is 2.5cm. While the reference electrode Vs is a saturated calomel electrode.
The electrode system adopted in the specific implementation of the embodiment is the above, but other electrolytic systems can be designed, so that the two-dimensional lamellar sulfur nanomaterial can be obtained through electrolysis.
The preparation method of the two-dimensional lamellar sulfur nanomaterial S-NSs provided by the invention is described in a specific example.
Example 1
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 0.8g of sublimed sulfur is weighed, added into a round bottom flask containing 80mL of 1mol/LNaOH solution, heated and stirred at 100 ℃ for reaction for 1h until the sublimed sulfur is completely dissolved, and the color of the mixed solution is changed from yellow suspension solution to orange transparent solution.
2) Taking 40mL of the orange transparent mixed solution obtained in the step 1), adding 50mg of BSA as a stabilizer, controlling constant current to be 0.2A, and carrying out direct current electrolysis for 1.5h to obtain a dispersion liquid containing the two-dimensional lamellar sulfur nanomaterial S-NSs, wherein the dispersion liquid can be dialyzed or centrifuged as required to obtain the S-NSs dispersion liquid or solid with small molecular impurities removed.
Example 2
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 0.8g of sublimed sulfur is weighed, added into a round bottom flask containing 80mL of 1mol/LNaOH solution, heated and stirred at 100 ℃ for reaction for 1h until the sublimed sulfur is completely dissolved, and the color of the mixed solution is changed from yellow suspension solution to orange transparent solution.
2) Taking 40mL of the orange transparent mixed solution obtained in the step 1), adding 10mg of BSA as a stabilizer, controlling constant current to be 0.2A, and carrying out direct current electrolysis for 1.5h to obtain a dispersion liquid containing the two-dimensional lamellar sulfur nanomaterial S-NSs, wherein the dispersion liquid can be dialyzed or centrifuged as required to obtain the S-NSs dispersion liquid or solid with small molecular impurities removed.
Example 3
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 0.8g of sublimed sulfur is weighed, added into a round bottom flask containing 80mL of 1mol/LNaOH solution, heated and stirred at 100 ℃ for reaction for 1h until the sublimed sulfur is completely dissolved, and the color of the mixed solution is changed from yellow suspension solution to orange transparent solution.
2) Taking 40mL of the orange transparent mixed solution obtained in the step 1), adding 30mg of BSA as a stabilizer, controlling constant current to be 0.2A, and carrying out direct current electrolysis for 1.5h to obtain a dispersion liquid containing the two-dimensional lamellar sulfur nanomaterial S-NSs, wherein the dispersion liquid can be dialyzed or centrifuged as required to obtain the S-NSs dispersion liquid or solid with small molecular impurities removed.
Example 4
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 0.8g of sublimed sulfur is weighed, added into a round bottom flask containing 80mL of 1mol/LNaOH solution, heated and stirred at 100 ℃ for reaction for 1h until the sublimed sulfur is completely dissolved, and the color of the mixed solution is changed from yellow suspension solution to orange transparent solution.
2) Taking 40mL of the orange transparent mixed solution obtained in the step 1), adding 70mg of BSA as a stabilizer, controlling constant current to be 0.2A, and carrying out direct current electrolysis for 1.5h to obtain a dispersion liquid containing the two-dimensional lamellar sulfur nanomaterial S-NSs, wherein the dispersion liquid can be dialyzed or centrifuged as required to obtain the S-NSs dispersion liquid or solid with small molecular impurities removed.
Example 5
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 0.8g of sublimed sulfur is weighed, added into a round bottom flask containing 80mL of 1mol/LNaOH solution, heated and stirred at 100 ℃ for reaction for 1h until the sublimed sulfur is completely dissolved, and the color of the mixed solution is changed from yellow suspension solution to orange transparent solution.
2) Taking 40mL of the orange transparent mixed solution obtained in the step 1), adding 90mg of BSA as a stabilizer, controlling constant current to be 0.2A, and carrying out direct current electrolysis for 1.5h to obtain a dispersion liquid containing the two-dimensional lamellar sulfur nanomaterial S-NSs, wherein the dispersion liquid can be dialyzed or centrifuged as required to obtain the S-NSs dispersion liquid or solid with small molecular impurities removed.
Example 6
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 0.8g of sublimed sulfur is weighed, added into a round bottom flask containing 80mL of 1mol/L NaOH, heated and stirred at 100 ℃ for reaction for 1h until the sublimed sulfur is completely dissolved, and the color of the mixed solution is changed from yellow suspension solution to orange transparent solution.
2) Taking 40mL of the orange transparent mixed solution obtained in the step 1), adding 270 mu L (0.27 mL) of PEDOT: PSS as a stabilizer, mixing, controlling the concentration of the stabilizer in the mixed electrolyte to be 0.01g/mL, controlling constant current to be 0.2A, and carrying out direct current electrolysis for 1.5h to obtain the two-dimensional lamellar sulfur nanomaterial S-NSs.
Example 7
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 0.8g of sublimed sulfur is weighed, 80mL of 1mol/L NaOH solution is added into a round bottom flask, and the mixture is heated and stirred at 100 ℃ for reaction for 1h until the sublimed sulfur is completely dissolved, and the color of the mixed solution is changed from yellow suspension solution to orange transparent solution.
2) And (3) taking 40mL of the orange transparent mixed solution obtained in the step (1), adding 27 mu L (0.027 mL) of PEDOT: PSS as a stabilizer, mixing, controlling the concentration of the stabilizer in the mixed electrolyte to be 0.001g/mL, controlling constant current to be 0.2A, and carrying out direct current electrolysis for 1.5h to obtain the two-dimensional lamellar sulfur nanomaterial S-NSs.
Example 8
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 0.8g of sublimed sulfur is weighed, added into a round bottom flask containing 80mL of 1mol/LNaOH solution, heated and stirred at 100 ℃ for reaction for 1h until the sublimed sulfur is completely dissolved, and the color of the mixed solution is changed from yellow suspension solution to orange transparent solution.
2) Taking 40mL of the orange transparent mixed solution obtained in the step 1), adding 135 mu L (0.135 mL) of PEDOT: PSS as a stabilizer, mixing, controlling the concentration of the stabilizer in the mixed electrolyte to be 0.005g/mL, controlling constant current to be 0.2A, and carrying out direct current electrolysis for 1.5h to obtain the two-dimensional lamellar sulfur nanomaterial S-NSs.
Example 9
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 0.8g of sublimed sulfur is weighed, added into a round bottom flask containing 80mL of 1mol/LNaOH solution, heated and stirred at 100 ℃ for reaction for 1h until the sublimed sulfur is completely dissolved, and the color of the mixed solution is changed from yellow suspension solution to orange transparent solution.
2) Taking 40mL of the orange transparent mixed solution obtained in the step 1), adding 1.35mL of PEDOT/PSS as a stabilizer, mixing, controlling the concentration of the stabilizer in the mixed electrolyte to be 0.05g/mL, controlling constant current to be 0.2A, and carrying out direct current electrolysis for 1.5h to obtain the two-dimensional lamellar sulfur nanomaterial S-NSs.
Example 10
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 0.8g of sublimed sulfur is weighed, added into a round bottom flask containing 80mL of 1mol/LNaOH solution, heated and stirred at 100 ℃ for reaction for 1h until the sublimed sulfur is completely dissolved, and the color of the mixed solution is changed from yellow suspension solution to orange transparent solution.
2) Taking 40mL of the orange transparent mixed solution obtained in the step 1), adding 2.1mL of PEDOT: PSS as a stabilizer, mixing, controlling the concentration of the stabilizer in the mixed electrolyte to be 0.08g/mL, controlling constant current to be 0.2A, and carrying out direct current electrolysis for 1.5h to obtain the two-dimensional lamellar sulfur nanomaterial S-NSs.
Example 11
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 1g of thiourea is weighed as a sulfur source, 0.5g of sodium chloride is used as an electrolyte, and 40mL of ultrapure water is added to obtain a mixed solution;
2) To 40ml of the mixed solution, 50mg of BSA as a stabilizer was added, and the mixture was stirred for 30 minutes, and electrolyzed at constant current (0.2A) for 1 hour to obtain an S-NSS dispersion.
Example 12
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 0.2g of thiourea is weighed as a sulfur source, 0.5g of sodium chloride is used as an electrolyte, and 40mL of ultrapure water is added to obtain a mixed solution;
2) To 40ml of the mixed solution, 50mg of BSA as a stabilizer was added, and the mixture was stirred for 30 minutes, and electrolyzed at constant current (0.2A) for 1 hour to obtain an S-NSS dispersion.
Example 13
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 0.5g of thiourea is weighed as a sulfur source, 0.5g of sodium chloride is used as an electrolyte, and 40mL of ultrapure water is added to obtain a mixed solution;
2) To 40ml of the mixed solution, 50mg of BSA as a stabilizer was added, and the mixture was stirred for 30 minutes, and electrolyzed at constant current (0.2A) for 1 hour to obtain an S-NSS dispersion.
Example 14
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 1.5g of thiourea is weighed as a sulfur source, 0.5g of sodium chloride is used as an electrolyte, and 40mL of ultrapure water is added to obtain a mixed solution;
2) To 40ml of the mixed solution, 50mg of BSA as a stabilizer was added, and the mixture was stirred for 30 minutes, and electrolyzed at constant current (0.2A) for 1 hour to obtain an S-NSS dispersion.
Example 15
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 1g of thiourea is weighed as a sulfur source, 0.5g of sodium chloride is used as an electrolyte, and 40mL of ultrapure water is added to obtain a mixed solution;
2) To 40ml of the mixed solution, 50mg of BSA as a stabilizer was added, and the mixture was stirred for 30 minutes, and electrolyzed at constant current (0.2A) for 30 minutes to obtain an S-NSS dispersion.
Example 16
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 1g of thiourea is weighed as a sulfur source, 0.5g of sodium chloride is used as an electrolyte, and 40mL of ultrapure water is added to obtain a mixed solution;
2) To 40ml of the mixed solution, 50mg of BSA as a stabilizer was added, and the mixture was stirred for 30 minutes, and electrolyzed at constant current (0.2A) for 40 minutes to obtain an S-NSS dispersion.
Example 17
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1) 1g of thiourea is weighed as a sulfur source, 0.5g of sodium chloride is used as an electrolyte, and 40mL of ultrapure water is added to obtain a mixed solution;
2) To 40ml of the mixed solution, 50mg of BSA as a stabilizer was added, and the mixture was stirred for 30 minutes, and electrolyzed at constant current (0.2A) for 80 minutes to obtain an S-NSS dispersion.
Example 18
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1g of thiourea is weighed as a sulfur source, 0.5g of sodium chloride is taken as an electrolyte, 40mL of PEDOT/PSS which is 0.01g/mL is added as a stabilizer, the mixture is stirred for 30min, and electrolysis is carried out for 1h under constant current (0.2A), so as to obtain S-NSs dispersion liquid.
Example 19
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1g of thiourea is weighed as a sulfur source, 0.5g of sodium chloride is taken as an electrolyte, 40mL of PEDOT/PSS which is 0.005g/mL is added as a stabilizer, and the mixture is stirred for 30min and electrolyzed for 1h under constant current (0.2A) to obtain an S-NSs dispersion.
Example 20
In this embodiment, the preparation method of the two-dimensional layered sulfur nanomaterial includes the following steps:
1g of thiourea is weighed as a sulfur source, 0.5g of sodium chloride is taken as an electrolyte, 40mL of PEDOT/PSS which is 0.05g/mL is added as a stabilizer, the mixture is stirred for 30min, and electrolysis is carried out for 1h under constant current (0.2A), so that S-NSs dispersion liquid is obtained.
The specific embodiments of the invention are listed above, and the two-dimensional lamellar sulfur nanomaterial S-NSs can be obtained by using sublimed sulfur or thiourea as a sulfur source, adding the sulfur source into electrolyte water, then adding a stabilizer, and finally adopting an electrolytic method.
The performance of the two-dimensional lamellar sulfur nanomaterial prepared in the above embodiment is verified by experiments to illustrate the technical advantages of the preparation method of the invention.
The test is mainly to verify that PL behavior of S-NSs is prepared when sublimated sulfur is used as a sulfur source and stabilizer is BSA or PEDOT: PSS respectively.
The samples are: two-dimensional layered sulfur nanomaterial prepared in examples 1 to 10.
The PL spectrum of the nanomaterial S-NSs was measured at an excitation wavelength of 300nm for the above sample, and the result is shown in FIG. 1. Wherein: FIG. 1A shows the PL spectra of the nanomaterial at different amounts of BSA, and FIG. 1B shows the PL spectra of the nanomaterial at different concentrations of PEDOT: PSS.
It can be seen from 1 that S-NSs prepared with PEDOT: PSS as stabilizer and BSA as stabilizer exhibit multi-band PL emission characteristics when the excitation wavelength is in the range of 280nm to 380 nm. This is similar to the PL characteristics of the previously reported S-NSs. The multiband emission characteristics of S-NSs have never been reported in black phosphorus and graphene, which may be due to the anisotropic or complex bandgap structure of S-NSs; it was also demonstrated that it is possible to synthesize S-NSs with both stabilizers separately, with little difference in PL behavior of the synthesized S-NSs.
Also, as can be seen from FIG. 1A, the PL intensity of the synthesized S-NSs was maximized when BSA was 50 mg; as can be seen from FIG. 1B, the PL intensity of the synthesized S-NSs was best at a PEDOT: PSS concentration of 0.01 g/mL.
The test is mainly to verify that PL behaviors of S-NSs are prepared under different electrolysis time when sublimated sulfur is used as a sulfur source and stabilizers are BSA respectively.
Sample: the S-NSs nanomaterial prepared in example 1 was synthesized.
Meanwhile, referring to the synthesis conditions of example 1, the S-NSs nano materials were synthesized under conditions of 60min, 80min, 100min and 120min, respectively, by changing the electrolysis time. S-NSs nano material is synthesized under 5 groups of different electrolysis time.
The PL spectra of the S-NSs formed under different electrolysis times are measured under different excitation wavelengths, the color and pH change physical image results of the dispersion liquid in the electrolysis process are shown in figure 2, wherein figures 2A-2E are respectively photoluminescence spectra of the S-NSs prepared by sublimating sulfur under different electrolysis times by taking BSA as a stabilizer (50 mg), and figure 2F is a color change physical image of the dispersion liquid with the electrolysis times of 0min, 30min, 60min, 80min and 90min.
Referring to FIGS. 2A to 2E, it can be seen from the intensities of peaks in the spectrograms that the electrolysis time is 60min, the fluorescence intensity of the obtained S-NSs is weak, and the PL intensity of the prepared S-NSs is maximum when the electrolysis time is 90min, so that the electrolysis time optimization time is 90min.
Referring to fig. 2F, a yellow transparent solution was used before electrolysis, and the yellow transparent solution gradually became a pale yellow turbid state with increasing electrolysis time during the electrolysis after adding BSA, and after electrolysis for 90min or longer, the solution disappeared yellow to become a white milk-like dispersion, indicating the formation of S-NSs; moreover, as the electrolysis time increases, the alkalinity of the electrolytic solution gradually decreases, which means that the reaction of the NaOH etching sublimed sulfur in the dispersion liquid gradually completes, and the consumption of the NaOH dispersed in the solution is gradually consumed.
The test is mainly to verify that when sublimed sulfur is used as a sulfur source and the stabilizer is BSA or PEDOT: PSS respectively, the ultraviolet visible absorption spectrum characteristics of the solution before and after electrolysis are achieved.
Sample: in example 1, BSA was used as a stabilizer, and a solution before the start of electrolysis and a solution after 90 minutes of electrolysis were used to obtain UV-Vis absorption spectra before and after electrolysis.
In example 6, PEDOT: PSS was used as a stabilizer, and the solution before the start of electrolysis and the solution after the electrolysis for 90 minutes were used to obtain UV-Vis absorption spectra before and after the electrolysis.
UV-Vis absorption spectra, the results are shown in FIG. 3. Wherein: FIG. 3A is a UV-Vis absorption spectrum and physical image before and after electrolysis of S-NSs prepared from sublimed sulfur in the presence of stabilizer BSA; FIG. 3B is a graph showing UV-Vis absorption spectra and a physical image before and after electrolysis of the S-NSs prepared from sublimed sulfur in the presence of PEDOT: PSS.
As can be seen from fig. 3A, the pre-electrolysis dispersion solution was a transparent yellow solution with UV-Vis absorption peaks at 220nm, attributable to the light absorption of the dissolved polysulfide; in addition, the heteroatom (S, O) contains non-bonded electrons, and the n→σ transition may occur in the 150-250nm range, with absorption bands at 220nm and 218nm also possibly resulting from the n→σ transition. After electrolysis of the dispersion solution, the dispersion became milky white, and the dispersion had new absorption bands at 301nm and 380nm, which were similar to the published shoulder peaks of S-NSs at 310nm and 380nm, indicating that the successful synthesis of S-NSs with BSA as stabilizer was possible. In addition, due to S 2 2- The species has an absorption band centered at 305nm in DMF, so the 301nm absorption band may appear to be S 2 2- Evidence of species presence indicates S 2 2- More likely to adsorb on the S-NSs surface.
As can be seen from fig. 3B, the color of the dispersion before and after electrolysis changed significantly, since PEDOT: PSS itself had a blue color and polysulfide had a yellow color, the dispersion with PEDOT: PSS as the stabilizer was grayish green before electrolysis, and the absorption band occurring at 218nm indicated the presence of polysulfide; the pale green color is significantly reduced after electrolysis of the dispersion, mainly due to the formation of milky S-NSs, and likewise, a new absorption band centered at 301nm and 380nm appears after electrolysis of the dispersion, which also indicates that PEDOT: PSS as a stabilizer can also successfully synthesize S-NSs.
Test 4
The test is mainly to verify that when sublimated sulfur is used as a sulfur source and a stabilizer is BSA or PEDOT: PSS respectively, scanning electron microscope analysis of S-NSs is prepared.
Sample: S-NSs prepared in example 1 and S-NSs prepared in example 6.
SEM images of the samples were measured, and the results are shown in fig. 4. Wherein: (a) And (b) is an SEM image of S-NSs synthesized under BSA using sublimed sulfur as a sulfur source; (c) And (d) is an SEM image of S-NSs synthesized at PEDOT: PSS with sublimed sulfur as a sulfur source.
As can be seen from FIG. 4, the prepared S-NSs have a distinct lamellar structure, and a layer-by-layer stacking phenomenon is observed, regardless of whether the stabilizer is BSA or PEDOT: PSS, and the prepared S-NSs have a micron-sized. It is known that the two-dimensional lamellar sulfur nanomaterial S-NSs can be prepared by using sublimed sulfur as a sulfur source and BSA or PEDOT: PSS as a stabilizer.
Test 5
The test is mainly to verify that when thiourea is used as a sulfur source and a stabilizer is BSA, PL behaviors of S-NSs are prepared by using different thiourea dosages.
Sample: S-NSs prepared in examples 11 to 14.
For the four samples, PL spectra of the material at different wavelengths are obtained, the PL spectra of the four samples are shown in fig. 5, and fig. 5A to 5D are PL spectra corresponding to thiourea contents of 0.2g, 0.5g, 1.0g and 1.5g, respectively.
As can be seen from FIG. 5, the PL intensity of the product solution obtained under this condition was weak with the amount of 0.2g of thiourea, and the prepared product solution exhibited remarkable S-NSs multiband photoluminescence characteristics when the amount of thiourea was 0.5g and 1g, and the PL intensity of the prepared S-NSs was maximum when the amount of thiourea was 1g, and the PL of the prepared S-NSs was rather weak when the amount of thiourea was 1.5g, indicating that a large amount of thiourea in this system was unfavorable for the formation of S-NSs.
Test 6
The test is mainly to verify that PL behaviors of S-NSs are prepared at different electrolysis times when thiourea is used as a sulfur source and stabilizers are BSA respectively.
Sample: S-NSs prepared in example 11 and S-NSs prepared in examples 15 to 17.
For the four samples, PL spectra of the material under different wavelengths are obtained, the PL spectra of the four samples are shown in fig. 6, and fig. 6A to 6D are PL spectra corresponding to electrolysis times of 30min, 40min, 60min and 80min, respectively.
As can be seen from FIG. 6, when the electrolysis time was 30min, PL of the resulting solution had no significant multiple emission PL characteristics; the PL of the resulting solution exhibits significant multiband PL emission characteristics with increasing electrolysis time. When the electrolysis time was increased to 60min, the PL intensity of the prepared S-NSs was strongest, indicating an optimal electrolysis time of 60min.
Test 7
The test mainly verifies that the PL behavior of S-NSs is prepared by taking thiourea as a sulfur source and PEDOT-PSS as a stabilizer at different stabilizer concentrations.
Sample: S-NSs prepared in examples 18 to 20.
For the three samples, PL spectra of the material at different wavelengths were obtained, and the PL spectra of the third group of samples are shown in fig. 7, and fig. 7A to 7C are PL spectra corresponding to stabilizer (PEDOT: PSS) concentrations of 0.005g/mL, 0.01g/mL, and 0.05g/mL, respectively.
As can be seen from FIG. 7, the S-NSs prepared under the experimental conditions exhibit multi-wavelength PL emission characteristics consistent with the multi-wavelength PL emission exhibited by the S-NSs prepared by sublimating sulfur as a sulfur source and the S-NSs prepared by using BSA as a stabilizer, which indicates that the S-NSs can be successfully prepared by using PEDOT: PSS as a stabilizer, and it can be seen that the concentration of PEDOT: PSS has a great influence on the PL forming the S-NSs, and the PL intensity exhibited at the concentration of PEDOT: PSS of 0.01g/mL is the strongest.
Experiment 8
The test mainly verifies that when thiourea is used as a sulfur source and the stabilizer is BSA or PEDOT: PSS respectively, the ultraviolet-visible absorption spectrum characteristics of the solution before and after electrolysis are achieved.
Sample: S-NSs prepared in example 11 and S-NSs prepared in example 18.
The UV-Vis absorption spectra of the above samples were measured, and the results are shown in FIG. 8. Wherein: (a) An ultraviolet visible absorption spectrum corresponding to S-NSs prepared for example 11; (b) UV-visible absorption spectrum corresponding to S-NSs prepared for example 18.
Referring to FIG. 8, S-NSs prepared with BSA as a stabilizer had absorption bands at 235nm and 270nm, and S-NSs prepared with PEDOT: PSS as a stabilizer had absorption bands at 216.5nm and 267.0 nm. The heteroatom (S, O) contains non-bonded electrons and the transition of n→σ can occur in the range of 150-250nm, so the absorption bands at 235m and 216.5nm can result from the transition of n→σ. The absorption bands at 270nm and 267nm are similar to the shoulder peaks reported for S-NSs at 280nm, thus demonstrating that S-NSs can be successfully prepared with thiourea as the sulfur source, BSA or PEDOT: PSS as the stabilizer.
Test 9
The test is mainly to verify that when thiourea is used as a sulfur source and the stabilizer is BSA or PEDOT: PSS respectively, the prepared S-NSS material is characterized by an atomic force microscope.
Sample: S-NSs prepared in example 11 and S-NSs prepared in example 18.
The AFM results of the respective S-NSs were measured on the above samples and are shown in FIGS. 9 and 10. FIG. 9 is an AFM image of S-NSs prepared with BSA as stabilizer and thiourea as sulfur source; FIG. 10 is an AFM image of S-NSs prepared with PEDOT: PSS as stabilizer and thiourea as sulfur source.
The laminated structure is clearly seen in fig. 9, and the stacked S-NSs is seen at the edge portions thereof, the multi-layered S-NSs is not monodisperse, the S-NSs layers have a lateral height of about 3-6nm, the stacking of S-NSs is seen at the edge portions, and the S-NSs layers have a lateral height of about 5-8nm, as is clear from fig. 10. It is illustrated that the preparation of S-NS with BSA as stabilizer or PEDOT: PSS as stabilizer is feasible.
The test is mainly to verify that when thiourea is used as a sulfur source and the stabilizer is PEDOT to PSS, the prepared S-NSS material is characterized by a transmission electron microscope.
Transmission electron microscope TEM images were obtained using the S-NSs prepared in example 18 as a sample, and the results are shown in FIG. 11. Wherein, (a) is a TEM image at 50 nm; (b) is a TEM image at 20 nm; (c) is a TEM image at 100 nm.
As can be seen from FIG. 11, S-NSs have a distinct lamellar structure, and S-NSs are prepared with micron-sized dimensions and are of different sizes.
Test 11
The test is mainly to verify that when thiourea is used as a sulfur source and the stabilizer is PEDOT to PSS, the X-ray photoelectron spectrum of the prepared S-NSS material is characterized.
In order to analyze the functional groups and elemental composition of the material surface, XPS tests were performed.
XPS test was performed using the S-NSs prepared in example 18 as a sample, and the results are shown in FIG. 12. Wherein, (a) is XPS energy spectrum; (b) Is S 2P High resolution XPS energy spectrum.
As can be seen from FIG. 12, S-NSs prepared from thiourea with PEDOT: PSS as stabilizer, comprising S 2p 、C 1s 、N 1s And O 1s Four elements, C, N, O from thiourea as raw material. S is S 2P The high resolution XPS spectra included 160.9eV, 163.9eV, 164.9eV and 167.7eV. Binding energy is ascribed to S at 163.9eV 2- . The binding energy of 164.9eV is zero-valent sulfur, similar to sublimed sulfur. The binding energy of 167.7eV is attributed to-SO 2 . Thus, S-NSs consist essentially of atomic sulfur and surface-abundant sulfonyl/sulfonate/S 2- Composition is prepared.
Test 12
The test is mainly to verify that when thiourea is used as a sulfur source and the stabilizer is PEDOT to PSS, the X-ray diffraction spectrum of the prepared S-NSS material is characterized.
XRD analysis was performed using the S-NSs prepared in example 18 as a sample, to obtain a spectrum; and is combined with S 8 Standard XRD comparison results are shown in figure 13.
Referring to FIG. 13, the prepared S-NSs have distinct diffraction peaks at 23.0 °, 26.0 °, 27.8 °, 31.8 °, etc., the peak positions of which coincide with diffraction peaks of sublimed sulfur (JCPCDS card No. 83-2285), wherein the diffraction peaks at 23 ° and 27.8 ° correspond to the (222) and (313) crystal planes of sublimed sulfur crystals, indicating that the prepared S-NSs have a structure similar to that of rhombic sublimed sulfur.
The experiment shows that the method is feasible by adopting sublimated sulfur or thiourea as a sulfur source, BSA or PEDOT: PSS as a stabilizer and adopting an electrolytic method to prepare the two-dimensional lamellar sulfur nanomaterial S-NSs; and the SEM of the synthesized S-NSs material observes a distinct lamellar structure, and the synthesized S-NSs all exhibit unique multiband PL luminescence characteristics. The preparation method of the S-NSs is simple to operate, short in time consumption, less than 3 hours, high in yield and up to milligram level; the prepared S-NSs have good aqueous solution dispersibility and provide references for developing potential applications thereof.
Claims (10)
1. The preparation method of the two-dimensional lamellar sulfur nanomaterial is characterized by comprising the following steps of:
1) Preparing a sulfur source and a corresponding electrolyte respectively; the sulfur source is thiourea or sublimed sulfur;
2) Uniformly mixing a sulfur source with an electrolyte to obtain a mixture; continuously adding a stabilizer into the mixture, and stirring to obtain a mixed electrolyte, wherein the electrolyte is solid or liquid, and the stabilizer is solid or liquid;
3) And (3) electrolyzing the mixed electrolyte in the step (2) to obtain the two-dimensional lamellar sulfur nanomaterial.
2. The method for preparing two-dimensional lamellar sulfur nanomaterial according to claim 1, wherein in the step 2), sulfur source is thiourea, the stabilizer is a mixture of bovine serum albumin BSA and water, and the electrolyte is NaCl solid, KCl solid, na 2 CO 3 Solid, na 2 SO 4 Solids or K 2 SO 4 The dosage ratio of the sulfur source, the electrolyte, the water and the stabilizer is 0.2 g-1.5 g:0.5g:40mL:10 mg-90 mg.
3. The method for preparing two-dimensional lamellar sulfur nanomaterial according to claim 1, wherein in the step 2), sulfur source is thiourea, the stabilizer is 3, 4-ethylenedioxythiophene/styrene sulfonate solution, and the stabilizer isThe electrolyte is NaCl solid, KCl solid, na 2 CO 3 Solid, na 2 SO 4 Solids or K 2 SO 4 The dosage ratio of the sulfur source, the electrolyte and the stabilizer is 0.2 g-1.5 g:0.5g:40mL; the concentration of the stabilizer is 0.005 g/mL-0.05 g/mL.
4. The method for preparing a two-dimensional layered sulfur nanomaterial according to claim 2 or 3, wherein in the step 2), the stirring temperature is 20 to 30 ℃, and the stirring time is 0.5 to 2 hours.
5. The method for preparing a two-dimensional layered sulfur nanomaterial according to claim 4, wherein in the step 3), constant current electrolysis is used for electrolysis, and the electrolysis current is 0.1-0.2A; the electrolysis time is 30 min-90 min.
6. The method for preparing a two-dimensional layered sulfur nanomaterial according to claim 4, wherein in the step 3), electrolysis is constant voltage electrolysis, naOH solid is further added into the mixed electrolyte, and the usage ratio of the mixed electrolyte to the NaOH solid is 40mL:0.4 g-4 g; the constant voltage is 0.6V-0.7V, and the electrolysis time is 30 min-300 min.
7. The method for preparing the two-dimensional lamellar sulfur nanomaterial according to claim 1, wherein in the step 2), a sulfur source is sublimed sulfur, the electrolyte is a NaOH solution, the stabilizer is bovine serum albumin BSA, and the usage ratio of the sulfur source to the electrolyte is 0.2 g-1.4 g:80mL; the concentration of the electrolyte is 0.1 mol/L-2 mol/L; the ratio of the mixture to bovine serum albumin BSA was 40mL: 10-90 mg.
8. The method for preparing two-dimensional lamellar sulfur nanomaterial according to claim 1, wherein in the step 2), a sulfur source is sublimed sulfur, the electrolyte is a NaOH solution, the stabilizer is a 3, 4-ethylenedioxythiophene/styrene sulfonate solution, and the dosage ratio of the sulfur source to the electrolyte is 0.2 g-1.4 g:80mL; the concentration of the electrolyte is 0.1 mol/L-2 mol/L; the dosage ratio of the mixture to the stabilizer is 40mL: 0.027-2.1 mL, and the concentration of the stabilizing agent in the mixed electrolyte is 0.001-0.08 g/mL.
9. The method for preparing a two-dimensional layered sulfur nanomaterial according to claim 7 or 8, wherein in the step 2), the mixing temperature is 70-120 ℃, and the mixing time is 1-5 hours.
10. The method for preparing a two-dimensional layered sulfur nanomaterial according to claim 9, wherein in the step 3), the electrolysis is constant current electrolysis, the constant current is 0.1A to 0.2A, and the electrolysis time is 30min to 120min.
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