CN115044368B - Method for synthesizing sulfur quantum dots by photocatalytic oxidation - Google Patents
Method for synthesizing sulfur quantum dots by photocatalytic oxidation Download PDFInfo
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- CN115044368B CN115044368B CN202210708975.4A CN202210708975A CN115044368B CN 115044368 B CN115044368 B CN 115044368B CN 202210708975 A CN202210708975 A CN 202210708975A CN 115044368 B CN115044368 B CN 115044368B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
A method for synthesizing sulfur quantum dots by photocatalytic oxidation mainly uses ultraviolet light irradiation energy to enable nano TiO 2 Generating photo-generated electrons e after absorbing energy ‑ And electron holes h + The electron holes h generated + Can be used for dissolving O in solution 2 And H 2 Oxidation of O molecules to reactive oxygen species followed by reaction with S in solution 2‑ The sulfur quantum dots with fluorescence property are generated under the action of polyethylene glycol. The method has the advantages of strong controllability, simple synthesis steps, mild reaction conditions and the like. The synthesized sulfur quantum dot has adjustable light wavelength, excellent and stable light-emitting performance and unique chemical property, and has good application prospect in the fields of analytical sensing, life science and the like.
Description
Technical Field
A process for preparing sulfur quantum dot by photo-catalytic oxidation mainly uses nano TiO 2 Is a photocatalyst, na 2 S is a sulfur source, polyethylene glycol-400 is a passivating agent and ultraviolet irradiation is a main reaction condition, and belongs to the field of material preparation.
Background
Sulfur quantum dots (Sulfur quantum dots, SQDs) are an inorganic quantum dot material which is emerging in recent years, have excellent and stable luminescence properties and unique chemical properties, and have attracted a great deal of attention in the fields of analytical sensing, life sciences and the like. Currently, sulfur quantum dots are synthesized primarily based on thermal reaction synthesis methods (j.am. Chem. Soc., 2018, 140:7878-7884). However, the sulfur quantum dots synthesized by this method have low fluorescence quantum yield, long reaction time and low synthesis yield, which limit the development of SQDs. To overcome such drawbacks, improvements have been made to date including hydrogen peroxide etching (Angew. Chem. Int. Ed.,2019, 58, 7040-7044.), microwave assist (RSCAdv., 2020, 10, 17266-17269.), pure oxygen atmosphere reaction (chem. Sci.,2020, 11:772-777.), copper ion etching (ACS Omega,2020, 5, 5407-5411.), and the like. Although the improved thermal synthesis method has obvious progress in the aspects of fluorescence quantum yield, reaction time, operation steps and the like of the SQDs, the current synthesis method of the SQDs is still insufficient, and besides a thermal synthesis route, only a nitric acid stripping method and a chemical mechanical polishing method can synthesize the SQDs without depending on water bath heating conditions. However, these two methods have low synthesis yields and poor controllability, so that new synthetic routes for SQDs are also required to be developed. Therefore, the invention starts from the photocatalytic synthesis technology and synthesizes the SQDs by utilizing a photocatalytic oxidation mode.
Disclosure of Invention
The invention aims to utilize nano TiO 2 Is a photocatalyst, na 2 S is a sulfur source, polyethylene glycol (PEG-400) is a passivating agent, and ultraviolet LED lights are illuminated and stirred to serve as main reaction conditions. First, with sulfur source Na 2 S is based, under the condition of ultraviolet illumination, nano TiO 2 Absorbing ultraviolet light with energy greater than the band gap energy, and then transferring electrons on the valence band into the conduction band to generate photo-generated electrons e - And electron holes h + . Wherein h is + Can be combined with O in solution 2 And H 2 O molecules act and oxidize them to reactive oxygen species ROS, e.g. ∙ OH, ∙ O 2- Etc., followed by S 2- React with ROS and are oxidized to S x 2- Oxidized to sulfur simple substance, and aggregated and cracked with the help of PEG-400 to form SQDs, and the SQDs with fluorescence property are synthesized by photocatalysis.
The technical scheme of the invention is as follows:
(1) Na is treated with ultrapure water 2 S∙9H 2 O is dissolved, and then nano TiO is added 2 Aqueous dispersion and 1-3 mL of polyethylene glycol (PEG-400). After stirring uniformly, transferring the mixed solution into a non-cover glass tank, and irradiating and stirring the solution by using a purple LED lamp to react for 4-15 hours.
(2) After the illumination is finished, removing the solid nano TiO by centrifugation 2 And taking supernatant, and adding hydrogen peroxide for etching.
(3) Removing most of the water solvent in the etched solution by using a vacuum rotary evaporator, transferring into a dialysis bag, and putting into ultrapure water for dialysis treatment.
(4) The dialyzed solution is firstly distilled to remove most of the water solvent, and then transferred to a test tube and dried in vacuum to obtain the sulfur quantum dot solid material.
Effects of the invention
Compared with the prior art, the invention has the following advantages:
(1) The preparation process and the reaction time are short.
(2) The reaction condition is mild, photocatalysis is utilized, and the reaction controllability is strong.
(3) The wavelength of the synthesized sulfur quantum dot light can be adjusted.
Detailed Description
Example 1
7.0 g of Na was treated with 45. 45 mL of ultrapure water 2 S∙9H 2 O is dissolved, and then 2mL of nano TiO with the concentration of 10mg/mL is added 2 Aqueous dispersion and 1mL of polyethylene glycol (PEG-400). After stirring well, the mixture was transferred to a coverless glass jar, and the solution was irradiated with a violet LED lamp (20W, 365 nm) to react 4. 4 h. After the illumination is completed, removing the solid nano TiO by centrifugation (8000 r/min,10 min) 2 And taking the supernatant, and adding hydrogen peroxide (the final concentration is 3%, and the volume of the supernatant is 3:4). Most of the aqueous solvent in the etched solution was removed by a vacuum rotary evaporator, transferred to a dialysis bag with a retention of 1000D, and dialyzed in ultrapure water for 3 days. The dialyzed solution is firstly distilled to remove most of the water solvent, then transferred to a test tube and dried overnight at 60 ℃ in vacuum, thus obtaining the sulfur quantum dot solid material.
Example 2
7.0 g of Na was treated with 45. 45 mL of ultrapure water 2 S∙9H 2 O is dissolved, and then 2mL of nano TiO with the concentration of 10mg/mL is added 2 Aqueous dispersion and 3mL of polyethylene glycol (PEG-400). After stirring well, the mixture was transferred to a coverless glass jar, and the solution was irradiated with a violet LED lamp (20W, 365 nm) to react 15 h. After the illumination is completed, removing the solid nano TiO by centrifugation (8000 r/min,10 min) 2 And taking the supernatant, and adding hydrogen peroxide (the final concentration is 3%, and the volume of the supernatant is 3:4).
Most of the aqueous solvent in the etched solution was removed by a vacuum rotary evaporator, transferred to a dialysis bag with a retention of 1000D, and dialyzed in ultrapure water for 3 days. The dialyzed solution is firstly distilled to remove most of the water solvent, then transferred to a test tube and dried overnight at 60 ℃ in vacuum, thus obtaining the sulfur quantum dot solid material.
The quantum efficiency of the sulfur quantum dots prepared in the examples 1 and 2 can reach 27.8%, and the sulfur quantum dots can be used for imaging analysis of cells due to good biocompatibility and biotoxicity.
Claims (4)
1. A method for synthesizing sulfur quantum dots by utilizing photocatalytic oxidation mainly uses nano TiO 2 Is a photocatalyst, na 2 S is a sulfur source, polyethylene glycol-400 is a passivating agent and ultraviolet irradiation is a main reaction condition, and is characterized by comprising the following steps:
na is treated with ultrapure water 2 S∙9H 2 O is dissolved, and then nano TiO is added 2 Aqueous dispersion and 1-3 mL of polyethylene glycol (PEG-400); after stirring uniformly, transferring the mixed solution into a non-cover glass tank, irradiating with a purple LED lamp, and stirring the solution to react for 4-15 h; after the illumination is finished, removing the solid nano TiO by centrifugation 2 Taking supernatant, and adding hydrogen peroxide for etching; removing most of the water solvent in the etched solution by using a vacuum rotary evaporator, transferring into a dialysis bag, and putting into ultrapure water for dialysis treatment; the dialyzed solution is firstly distilled to remove most of the water solvent, and then transferred to a test tube and dried in vacuum to obtain the sulfur quantum dot solid material.
2. The method as claimed in claim 1, wherein the sulfur quantum dots are synthesized by photocatalysis using nano TiO as the photocatalyst 2。
3. The method of claim 1, wherein the light source is a violet LED lamp and the illumination time is 4-15 hours.
4. The process of claim 1, wherein in step (1), the sulfur source is Na 2 S∙9H 2 O。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012663A (en) * | 2018-07-27 | 2018-12-18 | 范唯凌 | A kind of nano silver/carbon composite photocatalyst material and its preparation method and application |
| CN111420678A (en) * | 2020-01-19 | 2020-07-17 | 西安科技大学 | Based on H2O2Method for preparing nano sulfur materials with different shapes by regulation and control |
| CN111978954A (en) * | 2020-08-11 | 2020-11-24 | 山东理工大学 | Preparation method of sulfur quantum dots with blue fluorescence characteristic |
| CN112852412A (en) * | 2021-01-19 | 2021-05-28 | 中南大学 | Method for rapidly synthesizing high-fluorescence sulfur quantum dots |
| CN113025314A (en) * | 2021-03-18 | 2021-06-25 | 中国科学院合肥物质科学研究院 | Simple method for rapidly preparing sulfur quantum dots |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012663A (en) * | 2018-07-27 | 2018-12-18 | 范唯凌 | A kind of nano silver/carbon composite photocatalyst material and its preparation method and application |
| CN111420678A (en) * | 2020-01-19 | 2020-07-17 | 西安科技大学 | Based on H2O2Method for preparing nano sulfur materials with different shapes by regulation and control |
| CN111978954A (en) * | 2020-08-11 | 2020-11-24 | 山东理工大学 | Preparation method of sulfur quantum dots with blue fluorescence characteristic |
| CN112852412A (en) * | 2021-01-19 | 2021-05-28 | 中南大学 | Method for rapidly synthesizing high-fluorescence sulfur quantum dots |
| CN113025314A (en) * | 2021-03-18 | 2021-06-25 | 中国科学院合肥物质科学研究院 | Simple method for rapidly preparing sulfur quantum dots |
Non-Patent Citations (2)
| Title |
|---|
| Henggang Wang et al..Hydrogen Peroxide Assisted Synthesis of Highly Luminescent Sulfur Quantum Dots.Angew. Chem. Int. Ed..2019,第58卷7040-7044. * |
| Lihua Shen et al..One‑Step Hydrothermal Synthesis of Sulfur Quantum Dots for Photoelectrochemical Catalysis for Dye Degradation.Journal of Electronic Materials.2022,第51卷3092–3100. * |
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