CN115043393B - Super-long phosphorescent keratin derived carbon quantum dot and preparation method thereof - Google Patents
Super-long phosphorescent keratin derived carbon quantum dot and preparation method thereof Download PDFInfo
- Publication number
- CN115043393B CN115043393B CN202210832852.1A CN202210832852A CN115043393B CN 115043393 B CN115043393 B CN 115043393B CN 202210832852 A CN202210832852 A CN 202210832852A CN 115043393 B CN115043393 B CN 115043393B
- Authority
- CN
- China
- Prior art keywords
- keratin
- carbon quantum
- quantum dot
- derived carbon
- waste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 102000011782 Keratins Human genes 0.000 title claims abstract description 124
- 108010076876 Keratins Proteins 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002699 waste material Substances 0.000 claims abstract description 57
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 21
- 230000005284 excitation Effects 0.000 claims description 18
- 210000003746 feather Anatomy 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 239000012982 microporous membrane Substances 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 244000144977 poultry Species 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 28
- 239000000463 material Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000002019 doping agent Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 238000005119 centrifugation Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 241000287828 Gallus gallus Species 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 10
- 230000006872 improvement Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 241000238424 Crustacea Species 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 210000000282 nail Anatomy 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 210000000003 hoof Anatomy 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000124008 Mammalia Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 210000000078 claw Anatomy 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000271566 Aves Species 0.000 description 1
- 101710200191 Feather keratin Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 alkalis Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides an ultralong phosphorescent keratin derived carbon quantum dot and a preparation method thereof, wherein keratin waste is crushed and then dispersed in deionized water, the temperature is raised for hydrothermal reaction, and the product of the hydrothermal reaction is subjected to centrifugation, filtration and purification treatment to obtain carbon quantum dot dispersion liquid; and freeze-drying to obtain the keratin-derived carbon quantum dot with ultra-long phosphorescence. According to the method, the keratin waste is used as a precursor, deionized water is used as a solvent, and under the condition that other chemicals such as acid, alkali, organic solvent and doping agent are not required to be added, the multi-mode luminescent carbon quantum dot material with fluorescence and ultra-long phosphorescence is prepared through simple hydrothermal process and purification treatment, so that the high-efficiency utilization of the keratin waste is realized, the multi-mode luminescent carbon quantum dot material with high added value is prepared, and the preparation method of the ultra-long phosphorescence carbon quantum dot is provided effectively, and the method has high scientific significance and practical application value.
Description
Technical Field
The invention relates to the technical field of preparation of carbon quantum dots, in particular to an ultralong phosphorescent keratin-derived carbon quantum dot and a preparation method thereof.
Background
About 860 ten thousand tons of keratin wastes are produced every year in the world, only a small part of the keratin wastes are effectively treated as rich biomass raw materials, most of the keratin wastes are buried and burned, and the keratin wastes are not effectively utilized, so that huge biomass resource waste is caused. Therefore, the development of a beneficial reuse strategy for keratin waste is the focus of current research.
Carbon quantum dots (Carbon Quantum Dots, CQDs) are novel zero-dimensional nano materials, and the particle size is generally smaller than 10nm. Compared with the traditional organic fluorescent dye, rare earth luminescent material and semiconductor quantum dot, the carbon quantum dot has the advantages of simple preparation method, good water dispersibility, wide raw material sources, low toxicity, stable optical property, good biocompatibility, high yield and the like. Therefore, in recent years, carbon quantum dots have been widely used as excellent optical materials in the fields of bioimaging, fluorescent anti-counterfeiting, drug transport, photoelectrocatalysis, inspection of heavy metal ions, and the like. If the keratin waste is used as a carbon source to prepare the carbon quantum dots, the problem of reutilization of the keratin waste can be effectively solved, and the carbon quantum dots with higher application value can be obtained, so that the method has important research significance and higher economic value.
At present, the research on the application of the keratin waste to the preparation of the carbon quantum dots is less, the emission modes of the keratin derived carbon quantum dots obtained by the research are all single, and the yield of most of the obtained carbon quantum dots is low, so that the development and the application of the keratin derived carbon quantum dots are limited to a certain extent.
The patent with publication number CN111573652A provides a preparation method of chicken feather nitrogen doped carbon quantum dots, which comprises the steps of mixing chicken feather material with deionized water, adding a nitrogen-containing chemical as a doping agent for hydrothermal reaction, and centrifuging and filtering a hydrothermal reaction product to obtain chicken feather nitrogen doped carbon quantum dot dispersion liquid. Although the method provided by the patent can utilize chicken feather to prepare the carbon quantum dots, the chicken feather used by the method is the stem removing part of the chicken feather, complex stem removing treatment is required to be added in the practical application process, the removed stem part cannot be effectively utilized, and the utilization rate of keratin waste and the yield of the carbon quantum dots are low. Meanwhile, the carbon quantum dot prepared by the method provided by the patent only has single fluorescence characteristic, the fluorescence characteristic is required to depend on the doping effect of the nitrogenous chemical, and the carbon quantum dot prepared by chicken feather only under the undoped condition is difficult to reach effective fluorescence intensity, so that the requirement of practical application cannot be met.
In view of the above, there is a need to design an improved method for preparing keratin-derived carbon quantum dots, which can improve the utilization rate of keratin waste and simultaneously prepare high-yield multi-mode luminescent carbon quantum dots by a simple and environment-friendly process, so as to solve the above problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an ultralong phosphorescent keratin-derived carbon quantum dot and a preparation method thereof. According to the invention, keratin waste is used as a precursor, deionized water is used as a solvent, and under the condition that other chemical reagents such as acid, alkali, organic solvent, doping agent and the like are not required to be additionally added, the multi-mode luminescent carbon quantum dot with fluorescence and ultra-long phosphorescence is prepared through a simple hydrothermal process and purification treatment. The invention not only realizes the high-efficiency utilization of the keratin waste and prepares the multimode luminescent carbon quantum dot material with high added value, but also effectively provides a preparation method of the ultra-long phosphorescent carbon quantum dot, and has higher scientific significance and practical application value.
In order to achieve the above purpose, the invention provides a preparation method of an ultralong phosphorescent keratin-derived carbon quantum dot, comprising the following steps:
s1, crushing keratin waste to obtain keratin waste powder;
s2, dispersing the keratin waste powder obtained in the step S1 in deionized water to obtain precursor dispersion liquid;
s3, placing the precursor dispersion liquid obtained in the step S2 into a reaction kettle, and performing hydrothermal reaction at a preset temperature; after the reaction is finished, centrifuging and filtering a product of the hydrothermal reaction, and purifying to obtain a carbon quantum dot dispersion liquid;
and S4, freeze-drying the carbon quantum dot dispersion liquid obtained in the step S3 to obtain the solid keratin derived carbon quantum dot.
As a further improvement of the present invention, in step S3, the purification treatment is performed by column chromatography using a 200-300 mesh silica gel column.
As a further improvement of the present invention, in step S1, the keratin waste is one or more of mammalian hair, fowl feather, crustacean; preferably, the crustacean comprises nails, hooves and claws.
As a further improvement of the invention, in the step S2, the mass-volume ratio of the keratin waste powder to the deionized water is (0.2-1) g/50 mL.
As a further improvement of the invention, in the step S3, the reaction temperature of the hydrothermal reaction is 140-220 ℃ and the reaction time is not less than 4 hours.
As a further improvement of the present invention, in step S3, the filtration is performed using a microporous membrane.
In order to achieve the above purpose, the invention also provides an ultra-long phosphorescent keratin-derived carbon quantum dot, which is obtained according to the preparation method provided by the technical scheme and can emit fluorescence and phosphorescence.
As a further improvement of the invention, the room temperature phosphorescent lifetime of the keratin-derived carbon quantum dots is > 0.49s.
As a further improvement of the invention, when the excitation wavelength is 250-450 nm, the fluorescence emission wavelength of the keratin derived carbon quantum dot is 400-480 nm, and the phosphorescence emission wavelength is 430-510 nm.
As a further improvement of the invention, the particle size of the keratin derived carbon quantum dots is 1.5-5.5 nm.
The beneficial effects of the invention are as follows:
(1) The preparation method of the invention uses keratin waste as a precursor and deionized water as a solvent to prepare precursor dispersion liquid, and then successfully prepares the multi-mode luminescent carbon quantum dot with fluorescence and ultra-long phosphorescence through simple hydrothermal process and purification treatment. On the basis of the method provided by the invention, on one hand, the keratin waste can be prepared into the carbon quantum dots, the utilization rate and the added value of the keratin waste are improved, waste is turned into wealth, and an effective way is provided for reutilization of the keratin waste; on the other hand, the method provided by the invention can also effectively improve the optical performance of the prepared carbon quantum dots, so that the carbon quantum dots can emit fluorescence and phosphorescence, and have ultra-long room temperature phosphorescence life.
(2) According to the preparation method of the super-long phosphorescent keratin-derived carbon quantum dot, keratin waste is subjected to hydrothermal reaction under specific conditions, and after the hydrothermal reaction product is subjected to centrifugation and filtration treatment, the keratin-derived carbon quantum dot is further subjected to purification treatment, so that the surface of the keratin-derived carbon quantum dot has enough hydrogen bonds, and the optical performance of the keratin-derived carbon quantum dot can be effectively improved through freeze-drying treatment, the prepared solid carbon quantum dot can emit fluorescence and phosphorescence, the phosphorescence service life can reach 0.493s, long afterglow phenomenon of 15s can be observed by naked eyes, and the problems of poor optical performance and single luminous mode of the conventional keratin-derived carbon quantum dot are effectively solved, so that the preparation method has higher scientific significance and practical value.
(3) According to the preparation method of the super-long phosphorescent keratin derived carbon quantum dot, keratin waste serving as a precursor is environment-friendly and renewable, the source of raw materials is wide, the adopted solvent is deionized water, and chemical reagents such as other acids, alkalis, organic solvents and doping agents are not required to be added in the preparation process, so that the cost is reduced, and the environment-friendly requirement is met. Meanwhile, based on the method provided by the invention, all the feather keratin waste after being crushed can be used for preparing the carbon quantum dots, the stems do not need to be removed, the treatment procedure of the keratin waste is simplified, the full utilization of the keratin waste is realized, and the yield and the optical performance of the carbon quantum dots are also improved. In addition, the preparation method of the carbon quantum dot provided by the invention only needs to carry out the processes of crushing, hydrothermal reaction, purification, freeze drying and the like, the required equipment is conventional equipment, the reaction conditions are easy to control, the requirement of actual industrialized mass production can be met, and the method has higher practical application value.
Drawings
Fig. 1 is a transmission electron microscope image of the carbon quantum dots prepared in example 1.
Fig. 2 is a high resolution transmission electron microscope image of the carbon quantum dots prepared in example 1.
Fig. 3 is a particle size distribution diagram of the carbon quantum dots prepared in example 1.
Fig. 4 is a graph showing a comparison of the carbon quantum dot solution prepared in example 1 under the irradiation of a fluorescent lamp and an ultraviolet lamp at 365 nm.
Fig. 5 is a graph of fluorescence emission spectra of the carbon quantum dots prepared in example 1 at different excitation wavelengths.
Fig. 6 is a graph showing phosphorescence emission spectra of the carbon quantum dots prepared in example 1 at different excitation wavelengths.
Fig. 7 is a phosphorescent lifetime spectrum of the carbon quantum dot prepared in example 1.
Fig. 8 is a graph of fluorescence emission spectra of the carbon quantum dots prepared in example 2 at different excitation wavelengths.
Fig. 9 is a physical picture of the carbon quantum dot powder prepared in example 1.
Fig. 10 is a physical picture of the carbon quantum dot powder prepared in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of an ultralong phosphorescent keratin-derived carbon quantum dot, which comprises the following steps:
s1, crushing keratin waste to obtain keratin waste powder;
s2, dispersing the keratin waste powder obtained in the step S1 in deionized water to obtain precursor dispersion liquid;
s3, placing the precursor dispersion liquid obtained in the step S2 into a reaction kettle, and performing hydrothermal reaction at a preset temperature; after the reaction is finished, centrifuging and filtering a product of the hydrothermal reaction, and purifying to obtain a carbon quantum dot dispersion liquid;
and S4, freeze-drying the carbon quantum dot dispersion liquid obtained in the step S3 to obtain the keratin derived carbon quantum dot.
In the step S1, the keratin waste is one or more of mammal hair, poultry feather and crustacean; preferably, the hair species include hair, beard and bird feathers, and the crustacean species include nails, hooves and claws.
In the step S2, the mass volume ratio of the keratin waste powder to the deionized water is (0.2-1) g/50 mL.
In the step S3, the reaction temperature of the hydrothermal reaction is 140-220 ℃, and the reaction time is not less than 4 hours; filtering by using a microporous membrane; the purification treatment adopts a 200-300 mesh silica gel column for column chromatography.
The invention also provides an ultralong phosphorescent keratin-derived carbon quantum dot, which is prepared by the preparation method provided by the technical scheme and can emit fluorescence and phosphorescence.
When the excitation wavelength is 250-450 nm, the fluorescence emission wavelength of the keratin derived carbon quantum dot is 400-480 nm, and the phosphorescence emission wavelength is 430-510 nm; the room temperature phosphorescence lifetime of the keratin derived carbon quantum dots is more than 0.49s; the particle size of the keratin derived carbon quantum dots is 1.5-5.5 nm.
The ultra-long phosphorescent keratin-derived carbon quantum dot and the preparation method thereof provided by the invention are described below with reference to specific examples, comparative examples and drawings.
Example 1
The embodiment provides a preparation method of an ultralong phosphorescent keratin-derived carbon quantum dot, which comprises the following steps:
s1, taking chicken feathers as keratin waste, cleaning and drying the keratin waste, and fully crushing the keratin waste into powder by a crusher to obtain keratin waste powder;
s2, weighing 0.4g of dried keratin waste powder, and dispersing the keratin waste powder in 50mL of deionized water to obtain a precursor solution;
s3, placing the precursor solution obtained in the step S2 into a 100mL reaction kettle, sealing, performing hydrothermal reaction at 220 ℃, stopping heating after the reaction is performed for 10 hours, cooling the mixed solution after the reaction to room temperature, performing centrifugal treatment, filtering the supernatant after the centrifugation by using a microporous membrane, and performing column chromatography on the filtrate by using a 200-300-mesh silica gel column to obtain a purified solution, namely a carbon quantum dot solution;
and S4, freeze-drying the carbon quantum dot solution obtained in the step S3 by adopting a freeze dryer to obtain the keratin derived carbon quantum dot.
Through tests, the yield of the keratin-derived carbon quantum dots prepared by the embodiment is as high as 85%, and the problem that the yield of the keratin-based carbon quantum dots is too low in the prior art is effectively solved.
In order to characterize the keratin-derived carbon quantum dots prepared in the embodiment, transmission electron microscopy tests are carried out on the keratin-derived carbon quantum dots, and transmission electron microscopy images under different resolutions are measured, wherein the transmission electron microscopy images are respectively shown in fig. 1 and fig. 2. As can be seen from fig. 1 and 2, the particle size of the keratin-derived carbon quantum dots prepared in this embodiment is smaller, the lattice spacing is about 0.21nm, and the (100) crystal face of graphite is reflected, so that the keratin-derived carbon quantum dots have a good crystal structure. The particle size distribution of the keratin-derived carbon quantum dots prepared in this example was further counted, and the results are shown in fig. 3. As can be seen from fig. 3, the particle size distribution of the keratin-derived carbon quantum dots prepared in this example was in the range of 1.5 to 5.5nm, and the average particle size was 3.43nm.
To examine the fluorescence properties of the keratin-derived carbon quantum dots prepared in this example, the carbon quantum dot solution prepared in step S3 was respectively exposed to natural sunlight and ultraviolet lamp (365 nm), and the results are shown in fig. 4. In fig. 4, the left side is in natural sunlight, and it can be seen that the carbon quantum dot solution is yellow; the right side is irradiated by an ultraviolet lamp, so that the carbon quantum dot solution can be seen to emit obvious blue fluorescence.
In order to analyze the fluorescence and phosphorescence properties of the keratin-derived carbon quantum dots prepared in this example, the carbon quantum dot solution obtained in step S3 was diluted 10 times with deionized water, and its optical properties were tested with a hitachi fluorescence spectrophotometer F-4700 at different excitation wavelengths, so as to obtain a fluorescence emission spectrum and a phosphorescence emission spectrum at different excitation wavelengths, which are shown in fig. 5 and 6, respectively.
As can be seen from fig. 5, when the excitation wavelength is 300 to 400nm, the fluorescence emission wavelength of the keratin-derived carbon quantum dot is 400 to 450nm. When the excitation wavelength is 350nm, the intensity of the fluorescence emission peak is highest, and the corresponding fluorescence emission wavelength is 430nm.
As can be seen from fig. 6, the phosphorescent emission wavelength of the keratin-derived carbon quantum dots is 447 to 503nm when the excitation wavelength is 250 to 450nm. Wherein, when the excitation wavelength is 370nm, the intensity of the phosphorescence emission peak is the highest, and the corresponding phosphorescence emission wavelength is 444nm.
To further examine the phosphorescence properties of the keratin-derived carbon quantum dots prepared in this example, the phosphorescence lifetime thereof was tested, and the results are shown in fig. 7. As can be seen from fig. 7, the room temperature phosphorescent lifetime of the keratin-derived carbon quantum dot prepared in this example reaches 0.493s, and has an ultra-long room temperature phosphorescent lifetime. And after the excitation light source is turned off, the long afterglow phenomenon of 15 seconds can still be observed by naked eyes.
Therefore, the method provided by the embodiment takes the keratin waste chicken feather as a precursor and takes deionized water as a solvent, does not need stem removal operation on the chicken feather, only successfully prepares the multi-mode luminescent carbon quantum dot with fluorescence and ultra-long phosphorescence through a simple hydrothermal process and purification treatment, and effectively improves the optical performance of the prepared keratin-derived carbon quantum dot while fully utilizing the keratin waste, and solves the problems of poor optical performance and single luminescent mode of the conventional keratin-derived carbon quantum dot.
Comparative example 1
The present comparative example provides a method for preparing keratin-derived carbon quantum dots, which is different from example 1 in that the purification treatment in step S3 is not performed, and the remaining steps are the same as example 1, and are not repeated here.
The results of comparing the present comparative example with the carbon quantum dot powder prepared in example 1 are shown in fig. 9 and 10, respectively. In fig. 9, from left to right, the carbon quantum dot powder prepared in example 1 is subjected to irradiation by a fluorescent lamp, irradiation by an ultraviolet lamp at 365nm, and irradiation by an ultraviolet lamp turned off; in FIG. 10, the carbon quantum dot powder prepared in comparative example 1 is shown in a real image under irradiation of a fluorescent lamp and under irradiation of an ultraviolet lamp at 365nm in order from left to right. As can be seen from comparing fig. 9 and fig. 10, the purified keratin-derived carbon quantum dot prepared in example 1 can emit obvious blue fluorescence under the irradiation of an ultraviolet lamp, can still present a green room temperature phosphorescence phenomenon after the ultraviolet lamp is turned off, and has obvious long afterglow phenomenon; the non-purified keratin-derived carbon quantum dots prepared in comparative example 1 were relatively weak in fluorescence under irradiation of an ultraviolet lamp, and did not have room temperature phosphorescence properties, and no afterglow phenomenon was observed to the naked eye. Compared with the carbon quantum dot powder after purification, the carbon quantum dot powder before purification has the advantages of deeper color, large particles, serious agglomeration phenomenon, easy moisture absorption, low fluorescence intensity and no observation of phosphorescence phenomenon, and causes transfer of electrons or energy of the carbon quantum dot.
Example 2
The embodiment provides a method for preparing a keratin-derived carbon quantum dot, which is different from embodiment 1 in that keratin waste is changed from chicken feathers to beards, and other steps and corresponding parameters are consistent with embodiment 1 and are not repeated herein.
The carbon quantum dot solution prepared in this example was diluted 10 times with deionized water, and its optical properties were tested with a hitachi fluorescence spectrophotometer F-4700 at different excitation wavelengths, and fluorescence emission spectra at different excitation wavelengths were measured, as shown in fig. 8.
As can be seen from fig. 8, the emission wavelength of the keratin-derived carbon quantum dot has an excitation wavelength dependence, and when the excitation wavelength is 290 to 430nm, the fluorescence emission wavelength of the keratin-derived carbon quantum dot is 400 to 480nm. When the excitation wavelength is 370nm, the intensity of the fluorescence emission peak is highest, and the corresponding fluorescence emission wavelength is 433nm.
Examples 3 to 8 and comparative example 2
Examples 3 to 8 and comparative example 2 respectively provide a preparation method of ultra-long phosphorescent keratin-derived carbon quantum dots, which is different from example 1 in that the amount of keratin waste and the conditions of hydrothermal reaction are adjusted, and the preparation parameters corresponding to each example and comparative example are shown in table 1.
Table 1 preparation parameters of examples 3 to 8 and comparative example 2
The performances of the ultralong phosphorescent keratin-derived carbon quantum dots prepared in examples 3 to 7 and comparative examples 2 to 3 were tested, and as a result, it was found that: the keratin-derived carbon quantum dots prepared by adopting different processes have room temperature phosphorescence phenomena with different service lives, and the change of process parameters can influence the yield of the carbon quantum dots and the luminous intensity of the carbon quantum dots, and the yield, the luminous intensity and the phosphorescence service life data of the carbon quantum dots prepared by each example and the comparative example are shown in table 2.
TABLE 2 partial Performance parameters of carbon Quantum dots prepared in examples 3-8 and comparative example 2
As can be seen from Table 2, although the adjustment of the process parameters had a certain effect on the performance of the carbon quantum dots, the yield of the carbon quantum dots prepared in examples 3 to 8 could reach 80% or more, and the carbon quantum dots had relatively high luminous intensity and relatively long room temperature phosphorescence lifetime. Comparing examples 3 to 4 with comparative example 2, it can be seen that too high a concentration of keratin waste in the precursor dispersion liquid may affect the luminescence intensity of the prepared carbon quantum dots; as can be seen from comparative examples 5 to 8, the temperature of the hydrothermal reaction is properly increased within a certain range, and the reaction time is prolonged, which is advantageous for improving the performance of the carbon quantum dots. However, if the reaction temperature is further increased in this way, carbonization is facilitated, and the carbon quantum dot size becomes large, but the light emission intensity of the carbon quantum dot is affected.
Based on the method, the mass volume ratio of the keratin waste powder to the deionized water in the precursor dispersion liquid is preferably (0.2-1) g/50 mL, the hydrothermal reaction temperature is preferably 140-220 ℃, and the reaction time is controlled to be not less than 4 hours, so that the preparation of the super-long phosphorescent keratin derived carbon quantum dot with excellent performance can be ensured.
It should be noted that, the keratin waste used in the preparation process of the super-long phosphorescent keratin-derived carbon quantum dot provided by the invention is not limited to the feathers and beards used in the above embodiments, and may be the feathers of mammals, flying birds or crustaceans such as nails, hooves and nails, and can achieve similar effects, which belong to the protection scope of the invention.
In summary, the invention provides an ultralong phosphorescent keratin-derived carbon quantum dot and a preparation method thereof. According to the invention, the keratin waste is crushed and then dispersed in deionized water, the hydrothermal reaction is carried out, and the product of the hydrothermal reaction is subjected to centrifugation, filtration and purification treatment to obtain a carbon quantum dot solution; after freeze drying, the keratin derived carbon quantum dot with ultra-long phosphorescence is obtained. According to the method, the keratin waste is used as a precursor, deionized water is used as a solvent, and under the condition that other chemical reagents such as acid, alkali, organic solvent and doping agent are not required to be added, the multi-mode luminescent carbon quantum dot with fluorescence and ultra-long phosphorescence is prepared through a simple hydrothermal process and purification treatment, so that the high-efficiency utilization of the keratin waste is realized, the luminescent mode of the carbon quantum dot is effectively expanded, and the method has higher research significance and practical application value.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (5)
1. The preparation method of the keratin-derived carbon quantum dot is characterized by comprising the following steps of:
s1, crushing keratin waste to obtain keratin waste powder; the keratin waste is one or two of mammalian hair and poultry feathers;
s2, dispersing the keratin waste powder obtained in the step S1 in deionized water to obtain precursor dispersion liquid; the mass volume ratio of the keratin waste powder to the deionized water is (0.2-1) g, 50 and mL;
s3, placing the precursor dispersion liquid obtained in the step S2 into a reaction kettle, and performing hydrothermal reaction at a preset temperature; the reaction temperature of the hydrothermal reaction is 140-220 ℃, and the reaction time is not less than 4 hours; after the reaction is finished, centrifuging and filtering a product of the hydrothermal reaction, and purifying to obtain a carbon quantum dot dispersion liquid; the purification treatment comprises the steps of filtering by adopting a microporous membrane, and performing column chromatography by adopting a 200-300-mesh silica gel column;
s4, freeze-drying the carbon quantum dot dispersion liquid obtained in the step S3 to obtain solid keratin derived carbon quantum dots; the solid state keratin-derived carbon quantum dots are capable of emitting fluorescence and phosphorescence.
2. A keratin-derived carbon quantum dot, characterized in that: the keratin-derived carbon quantum dot is prepared by the preparation method of claim 1, and can emit fluorescence and phosphorescence.
3. The keratin-derived carbon quantum dot of claim 2, wherein: when the excitation wavelength is 250-450 nm, the fluorescence emission wavelength of the keratin derived carbon quantum dot is 400-480 nm, and the phosphorescence emission wavelength is 430-510 nm.
4. The keratin-derived carbon quantum dot of claim 2, wherein: the room temperature phosphorescent lifetime of the keratin-derived carbon quantum dots is > 0.49s.
5. The keratin-derived carbon quantum dot of claim 2, wherein: the particle size of the keratin derived carbon quantum dots is 1.5-5.5 nm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210832852.1A CN115043393B (en) | 2022-07-15 | 2022-07-15 | Super-long phosphorescent keratin derived carbon quantum dot and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210832852.1A CN115043393B (en) | 2022-07-15 | 2022-07-15 | Super-long phosphorescent keratin derived carbon quantum dot and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115043393A CN115043393A (en) | 2022-09-13 |
CN115043393B true CN115043393B (en) | 2023-11-10 |
Family
ID=83165181
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210832852.1A Active CN115043393B (en) | 2022-07-15 | 2022-07-15 | Super-long phosphorescent keratin derived carbon quantum dot and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115043393B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109957398A (en) * | 2017-12-26 | 2019-07-02 | Tcl集团股份有限公司 | Nitrogen-doped carbon quantum dot and preparation method thereof |
CN110079309A (en) * | 2019-04-28 | 2019-08-02 | 新乡医学院 | A kind of green synthesis method of blue-light-emitting carbon quantum dot |
CN110371949A (en) * | 2019-08-09 | 2019-10-25 | 华南师范大学 | A kind of method, carbon quantum dot and its application of green rapid synthesis carbon quantum dot |
CN112591747A (en) * | 2020-12-15 | 2021-04-02 | 吉林大学 | Preparation method of artiodactyla animal hoof nail derived carbon quantum dots |
CN114591737A (en) * | 2022-03-16 | 2022-06-07 | 北京化工大学 | Multicolor fluorescent carbon dots, and preparation method and application thereof |
-
2022
- 2022-07-15 CN CN202210832852.1A patent/CN115043393B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109957398A (en) * | 2017-12-26 | 2019-07-02 | Tcl集团股份有限公司 | Nitrogen-doped carbon quantum dot and preparation method thereof |
CN110079309A (en) * | 2019-04-28 | 2019-08-02 | 新乡医学院 | A kind of green synthesis method of blue-light-emitting carbon quantum dot |
CN110371949A (en) * | 2019-08-09 | 2019-10-25 | 华南师范大学 | A kind of method, carbon quantum dot and its application of green rapid synthesis carbon quantum dot |
CN112591747A (en) * | 2020-12-15 | 2021-04-02 | 吉林大学 | Preparation method of artiodactyla animal hoof nail derived carbon quantum dots |
CN114591737A (en) * | 2022-03-16 | 2022-06-07 | 北京化工大学 | Multicolor fluorescent carbon dots, and preparation method and application thereof |
Non-Patent Citations (1)
Title |
---|
One-step fabrication of high quantum yield sulfurand nitrogen-doped carbon dots for sensitive andselective detection of Cr(VI);Saihua Wang etc.;《RSC Advances》;第107717~107722页 * |
Also Published As
Publication number | Publication date |
---|---|
CN115043393A (en) | 2022-09-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102583307B (en) | Fluorescent carbon quantum dot extracted from eggs, preparation method and application thereof | |
CN109135738B (en) | Waste tobacco stem-based nitrogen-doped carbon dots and synthesis method and application thereof | |
CN110294471A (en) | A kind of synthetic method of the nitrogen co-doped graphene quantum dot of boron | |
CN113148979B (en) | Method for preparing carbon dots with different colors under same wavelength by using tobacco waste and application | |
CN109054825B (en) | Fluorescent carbon quantum dot and efficient preparation method thereof | |
CN106497561B (en) | Method for preparing graphene quantum dot yellow fluorescent powder or mixture thereof and method for preparing white light LED device | |
CN111635758A (en) | Preparation method of silica-coated fluorescent carbon quantum dot composite microspheres | |
CN110922967A (en) | Method for synthesizing high-fluorescence boron-nitrogen co-doped graphene quantum dots by one-pot hydrothermal method | |
CN115043393B (en) | Super-long phosphorescent keratin derived carbon quantum dot and preparation method thereof | |
CN109588375A (en) | Fluorescent natural silk preparation method based on Spanish mackerel internal organ and the compound carbon dots of mulberry leaf | |
CN114410299B (en) | Carbon dot and preparation method of carbon dot-based composite material | |
CN110041923B (en) | Preparation method and application of fluorescent carbon quantum dots Phe-CDs | |
CN114736676B (en) | Algae-based carbon quantum dot and preparation method thereof | |
CN107722974B (en) | Preparation method of biomass tar derived carbon quantum dots | |
CN109502569B (en) | Method for synthesizing green fluorescent biomass carbon dots by microwave and application | |
CN109294570B (en) | Preparation method of yellow oil phase carbon dots | |
CN111977632A (en) | Green preparation method of spinach-based multicolor luminescent carbon quantum dots | |
CN110272738A (en) | A kind of preparation method of secondary color fluorescent carbon quantum dot | |
CN110171806B (en) | Preparation method of water-soluble red light sulfur quantum dots | |
CN114262610B (en) | Preparation method of green carbon dot-based fluorescent powder | |
CN111662713B (en) | Preparation method of double-carbon-source double-nitrogen-source multicolor fluorescent carbon dots | |
CN110724528B (en) | Rosin-based carbon dot material and preparation method and application thereof | |
CN105586038B (en) | A kind of red or green rare-earth phosphate phosphor material and preparation method thereof | |
CN114806553B (en) | Preparation method of matrix-free phosphorescent carbon quantum dot | |
CN108251106B (en) | Preparation method of red fluorescent carbon dot powder |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |