Preparation method and application of blue fluorescent deuterated graphene quantum dots
Blue fluorescent deuterated graphene quantum dots were prepared by hydrothermal method, which solved the stability and toxicity problems of existing blue light graphene quantum dot materials, achieved high yield and stable fluorescence performance at high temperature, and expanded its application in biological imaging, optoelectronic devices and energy catalysis.
Patent Information
- Application Number
- CN202510927638.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-07
- Publication Date
- 2025-09-26
AI Technical Summary
The existing technology lacks stable and efficient blue light graphene quantum dots, especially in applications in the fields of bioimaging, optoelectronic devices and energy catalysis. Traditional materials have problems of high toxicity and poor photostability.
Blue fluorescent deuterated graphene quantum dots were prepared by a hydrothermal method. Sodium deuterium oxide was added to a graphene oxide dispersion to adjust the pH value to 8-10, a hydrothermal reaction was carried out, and then the dispersion was frozen and freeze-dried to obtain blue fluorescent deuterated graphene quantum dots with bright blue light emission.
The prepared blue fluorescent deuterated graphene quantum dot material has good stability and high yield, and can maintain stable fluorescence properties at high temperatures. It is suitable for fields such as biological imaging, optoelectronic devices and energy catalysis.
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Figure CN120698447A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of fluorescent materials, and in particular relates to a preparation method and application of blue fluorescent deuterated graphene quantum dots. Background Art
[0002] In recent years, the rapid development of nanomaterials science has spawned a series of novel functional materials with unique optoelectronic properties. Among them, graphene quantum dots (GQDs) have become a research hotspot due to their excellent physicochemical properties. GQDs not only inherit graphene's high conductivity, large surface area, and outstanding mechanical strength, but also exhibit tunable fluorescence properties due to quantum confinement and edge effects. These properties have broadened the application prospects of GQDs in fields such as nanotechnology, optoelectronics, and biomedicine. Blue-light GQDs, in particular, have attracted considerable attention due to their stable and efficient luminescence in the 400nm-480nm wavelength range. They show broad application prospects in bioimaging, optoelectronic devices, environmental monitoring, and energy catalysis. In bioimaging, blue-light GQDs can effectively label cells and tissues, providing high-resolution imaging. Their low toxicity and high biocompatibility make them safe for use in in vivo experiments. In addition, the application of blue light GQDs in optoelectronic devices also shows good performance. It can be used as a luminescent material in light-emitting diodes and lasers to improve the luminous efficiency and stability of the devices.
[0003] Compared to traditional semiconductor quantum dots and organic fluorescent dyes, blue-light GQDs have low toxicity, high biocompatibility, excellent photostability, and tunable surface chemical properties, making them ideal candidates for the next generation of green nanomaterials. Traditional semiconductor quantum dots may release harmful substances during use, while the non-toxic properties of blue-light GQDs make their application in the biomedical field safer and more reliable. In addition, the photostability of blue-light GQDs is superior to that of many organic fluorescent dyes, and they can maintain stable luminescence properties under long-term excitation, making them suitable for experiments that require long-term observation. As a new type of nanomaterial, blue-light GQDs have shown broad application prospects in bioimaging, optoelectronic devices, environmental monitoring, and energy catalysis due to their unique optoelectronic properties and excellent physicochemical properties. Summary of the Invention
[0004] In response to the problem that graphene quantum dots lack blue light, the purpose of the present invention is to provide a preparation method and application of blue fluorescent deuterated graphene quantum dots.
[0005] To achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is as follows: a method for preparing blue fluorescent deuterated graphene quantum dots, wherein the blue fluorescent deuterated graphene quantum dots are blue fluorescent deuterated graphene quantum dots that emit bright blue light with a wavelength of 330nm-600nm and an emission center located at 430nm-435nm when the excitation wavelength is 310nm, and the preparation method comprises: ultrasonically dispersing graphene oxide in heavy water to obtain a graphene oxide dispersion; Alkali is added to the dispersion to adjust the pH value; after stirring at room temperature, the dispersion is placed in a polytetrafluoroethylene-lined stainless steel autoclave and placed in a blast drying oven for hydrothermal reaction; after the reaction is completed, the autoclave is cooled to room temperature, taken out, and centrifuged to obtain a supernatant; the supernatant is placed in a refrigerator and frozen, taken out, and filtered with a membrane injection filter after melting to obtain a deuterated graphene quantum dot solution; the deuterated graphene quantum dot solution is placed in a refrigerator and frozen again, and then the frozen product is placed in a freeze dryer and freeze-dried to obtain blue fluorescent deuterated graphene quantum dots.
[0006] Furthermore, in the graphene oxide dispersion, the concentration of graphene oxide is 1 mg / mL-2 mg / mL.
[0007] Furthermore, the base is sodium deuterium oxide.
[0008] Furthermore, the pH is adjusted to 8-10.
[0009] Furthermore, the stirring at room temperature has a stirring time of 6 hours to 12 hours.
[0010] Furthermore, the hydrothermal reaction temperature is 80° C.-150° C., and the hydrothermal reaction time is 8 h-12 h.
[0011] Furthermore, the membrane injection filter has a pore size of 0.22 μm.
[0012] The invention provides applications of blue fluorescent deuterated graphene quantum dots in biological imaging, optoelectronic devices, environmental monitoring and energy catalysis.
[0013] The beneficial effects of the present invention are:
[0014] 1. The blue fluorescent deuterated graphene quantum dot material provided by the present invention has a simple preparation method, readily available raw materials, and the material is stable.
[0015] 2. The blue fluorescent deuterated graphene quantum dot material provided by the present invention can produce bright blue light emission.
[0016] 3. The blue fluorescent deuterated graphene quantum dot material provided by the present invention can be successfully prepared without dialysis, with short preparation time, high yield and large output. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 TEM image of GQDs prepared in Comparative Example 1.
[0018] Figure 2 XRD patterns of GQDs prepared in Comparative Example 1 and DGQDs prepared in Example 1.
[0019] Figure 3 These are the emission spectra of the GQDs prepared in Comparative Example 1 and the DGQDs prepared in Example 1.
[0020] Figure 4 This is the CIE coordinate diagram of GQDs prepared in Comparative Example 1.
[0021] Figure 5 This is the CIE coordinate diagram of DGQDs prepared in Example 1.
[0022] Figure 6 This is the temperature-dependent spectrum of GQDs prepared in Comparative Example 1.
[0023] Figure 7 This is the temperature-dependent spectrum of DGQDs prepared in Example 1. DETAILED DESCRIPTION
[0024] Comparative Example 1 Blue Fluorescent Graphene Quantum Dots (GQDs)
[0025] 1. The preparation method is as follows:
[0026] 0.08 g of graphene oxide (GO) powder was weighed into 40 mL of deionized water to a concentration of 2 mg / mL. The GO solution was then ultrasonically dispersed for 20 minutes to obtain a graphene oxide dispersion. An appropriate amount of sodium hydroxide was then added to the graphene oxide dispersion to adjust the pH to 9.5. After stirring at room temperature for 12 hours, the resulting mixture was placed in a 50 mL polytetrafluoroethylene-lined stainless steel autoclave and placed in a forced air drying oven at 100°C for a hydrothermal reaction for 10 hours. After the reaction, the autoclave was cooled to room temperature, removed from the autoclave, and centrifuged at 8000 rpm for 30 minutes to obtain a supernatant. The supernatant was then refrigerated for 5 hours, removed, and, after thawing, filtered through a 0.22 μm membrane syringe filter to obtain a graphene quantum dot (GQD) solution. The obtained GQDs solution was placed in a refrigerator and frozen again, and then the frozen product was placed in a freeze dryer and frozen for 24 hours to obtain blue fluorescent graphene quantum dots (GQDs) powder.
[0027] 2. Testing
[0028] Transmission electron microscopy images of the prepared GQDs are shown in Figure 2. Figure 1 , Figure 1It shows that the size of the prepared GQDs is about 2nm, and an obvious lattice spacing of 0.22nm can be observed.
[0029] The XRD patterns of the prepared GQDs are shown in Figure 2 , Figure 2 It shows an obvious peak near 21°, indicating the presence of graphene structure inside it.
[0030] The emission spectra of the prepared GQDs are shown in Figure 3 , Figure 3 It was shown that when the excitation wavelength was 310 nm, GQDs exhibited emission ranging from 330 nm to 600 nm, with the emission center located at 430 nm.
[0031] The CIE coordinates of the prepared GQDs are shown in Figure 2. Figure 4 , Figure 4 The display shows that the color coordinates are (0.158, 0.089), which is located in the blue light area.
[0032] Example 1 Blue Fluorescent Deuterated Graphene Quantum Dots (DGQDs)
[0033] 1. The preparation method is as follows:
[0034] 0.08 g of graphene oxide (GO) powder was weighed into 40 mL of heavy water to a concentration of 2 mg / mL. The GO solution was then ultrasonically dispersed for 20 minutes to obtain a GO dispersion. An appropriate amount of sodium deuterium oxide was then added to the GO dispersion to adjust the pH to 9.5. After stirring at room temperature for 12 hours, the resulting mixture was placed in a 50 mL Teflon-lined stainless steel autoclave and placed in a forced air drying oven at 100°C for a hydrothermal reaction for 10 hours. After the reaction, the autoclave was cooled to room temperature, removed from the autoclave, and centrifuged at 8000 rpm for 30 minutes to obtain a supernatant. The supernatant was then refrigerated for 5 hours, removed, and, after thawing, filtered through a 0.22 μm membrane syringe filter to obtain a deuterated graphene quantum dot (DGQD) solution. The obtained DGQDs solution was placed in a refrigerator and frozen again, and then the frozen product was placed in a freeze dryer and frozen for 24 hours to obtain blue fluorescent deuterated graphene quantum dots (DGQDs) powder.
[0035] 2. Testing
[0036] The XRD patterns of the prepared DGQDs are shown in Figure 2. Figure 2 , Figure 2 It shows an obvious peak near 21°, indicating the presence of graphene structure inside it.
[0037] The emission spectra of the prepared DGQDs are shown in Figure 3 , Figure 3It was shown that when the excitation wavelength was 310 nm, DGQDs exhibited luminescence ranging from 330 nm to 600 nm, with the emission center located at 435 nm.
[0038] The CIE coordinates of the prepared DGQDs are shown in Figure 2. Figure 5 , Figure 5 The display shows that the color coordinates are (0.156, 0.094), which is located in the blue light area.
[0039] 3. Effect of pH on Blue Fluorescent Deuterated Graphene Quantum Dots
[0040] 0.08 g of graphene oxide (GO) powder was weighed into 40 mL of heavy water to a concentration of 2 mg / mL. The GO solution was then ultrasonically dispersed for 20 minutes to obtain a graphene oxide dispersion. The pH of the graphene oxide dispersion was adjusted to 6, 7, 8, 9, and 10 using sodium deuterium oxide. After stirring at room temperature for 12 hours, the resulting mixed solution was placed in a 50 mL polytetrafluoroethylene-lined stainless steel autoclave and placed in a forced air drying oven at 100°C for a hydrothermal reaction for 10 hours. After the reaction, the autoclave was cooled to room temperature, removed from the autoclave, and centrifuged at 8000 rpm for 30 minutes to obtain a supernatant. The supernatant was refrigerated for 5 hours, removed, and, after thawing, filtered through a 0.22 μm membrane syringe filter to obtain a deuterated graphene quantum dot (DGQD) solution. The obtained DGQDs solution was placed in a refrigerator and frozen again. The frozen product was then placed in a freeze dryer and frozen for 24 hours to obtain deuterated graphene quantum dot (DGQDs) powders adjusted to different pH values. The test results are shown in Table 1.
[0041] Table 1
[0042]
[0043] As shown in Table 1, when the pH value of the graphene oxide dispersion is adjusted to 6, DGQDs can hardly emit light. When the pH value of the graphene oxide dispersion is adjusted to 7, 8, 9, and 10, DGQDs show blue light emission.
[0044] Example 2 Quantum Yield and Luminescence Thermal Quenching Performance of Blue Fluorescent Graphene Quantum Dots (GQDs) and Blue Fluorescent Deuterated Graphene Quantum Dots (DGQDs)
[0045] After testing, the quantum yields of GQDs and DGQDs were 0.4% and 6.2% respectively, and DGQDs increased by about 15.5 times.
[0046] Test of the luminescence thermal quenching performance of GQDs and DGQDs: weigh 0.2g GQDs and 0.2g DGQDs respectively, and then disperse them in 2mL water. After ultrasonic dispersion, heat to boiling, and then test their emission spectra at 20℃, 40℃, 60℃, and 80℃ respectively. Figure 6 and Figure 7 The temperature-dependent spectra of GQDs and DGQDs are shown. GQDs exhibit almost no luminescence at 80°C, indicating temperature quenching. DGQDs, on the other hand, still exhibit strong luminescence at 80°C. DGQDs, with their excellent thermal stability, maintain stable fluorescence and structural integrity at high temperatures. This gives them unique advantages in applications requiring high-temperature stability, such as bioimaging, optoelectronic devices, environmental monitoring, and energy catalysis.
Claims
1. A method for preparing blue fluorescent deuterated graphene quantum dots, characterized in that: The blue fluorescent deuterated graphene quantum dots are blue fluorescent deuterated graphene quantum dots that, when the excitation wavelength is 310 nm, exhibit luminescence within the range of 330 nm to 600 nm, with an emission center located at 430 nm to 435 nm, and have bright blue light emission. The preparation method comprises: ultrasonically dispersing graphene oxide in heavy water to obtain a graphene oxide dispersion; adding alkali to the graphene oxide dispersion to adjust the pH; stirring at room temperature, placing the dispersion into a stainless steel autoclave lined with polytetrafluoroethylene, and placing the dispersion in a blast drying oven for hydrothermal reaction; after the reaction is completed, cooling the autoclave to room temperature, removing the autoclave, and centrifuging to obtain a supernatant; freezing the supernatant in a refrigerator, removing the supernatant, and filtering the supernatant with a membrane syringe filter after melting to obtain a deuterated graphene quantum dot solution; freezing the deuterated graphene quantum dot solution in a refrigerator again, and then freeze-drying the frozen product in a freeze dryer to obtain blue fluorescent deuterated graphene quantum dots.
2. The method for preparing blue fluorescent deuterated graphene quantum dots according to claim 1, wherein: In the graphene oxide dispersion, the concentration of graphene oxide is 1 mg / mL-2 mg / mL.
3. The method for preparing blue fluorescent deuterated graphene quantum dots according to claim 1, wherein: The base is sodium deuteride.
4. The method for preparing blue fluorescent deuterated graphene quantum dots according to claim 1, wherein: The pH is adjusted to 8-10.
5. The method for preparing blue fluorescent deuterated graphene quantum dots according to claim 1, wherein: The stirring at room temperature has a stirring time of 6h-12h.
6. The method for preparing blue fluorescent deuterated graphene quantum dots according to claim 1, wherein: The hydrothermal reaction temperature is 80° C.-150° C., and the hydrothermal reaction time is 8 h-12 h.
7. The method for preparing blue fluorescent deuterated graphene quantum dots according to claim 1, wherein: The membrane injection filter has a pore size of 0.22 μm.
8. Application of blue fluorescent deuterated graphene quantum dots prepared by the method according to any one of claims 1 to 7 in biological imaging, optoelectronic devices, environmental monitoring and energy catalysis.