CN114350355B - Single-peak-emission vinasse-based green light carbon quantum dot and preparation method thereof - Google Patents
Single-peak-emission vinasse-based green light carbon quantum dot and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of fluorescent luminescent materials, and particularly relates to a single-peak-emission vinasse-based green light carbon quantum dot and a preparation method thereof. And preparing the single-peak-emission vinasse-based green light carbon quantum dot, wherein the carbon source of the single-peak-emission vinasse-based green light carbon quantum dot is sorghum vinasse, and performing hydrothermal reaction on the sorghum vinasse to obtain the single-peak-emission vinasse-based green light carbon quantum dot. The preparation method of the single-peak-emission vinasse-based green light carbon quantum dot is simple, and can effectively solve the problems of resource waste/environmental pollution and the like caused by sorghum vinasse.
Description
Technical Field
The invention belongs to the technical field of fluorescent luminescent materials, and particularly relates to a single-peak-emission vinasse-based green light carbon quantum dot and a preparation method thereof.
Background
The carbon quantum dot is a novel fluorescent carbon nanomaterial, one of the most important members in the family of carbon nanomaterials, and is found by Xu et al in 2004 and then named by Sun et al in 2006. In general, the carbon dots are spherical carbon nanoparticles having a particle diameter of less than 10nm and excellent dispersion. Besides the advantages of high quantum yield and adjustable emission wavelength of the traditional semiconductor quantum dot, the carbon dot has the advantages of good light stability, low cytotoxicity, good biocompatibility, easy surface modification, high chemical inertness and the like. Therefore, the carbon quantum dot can be widely used as a high-grade fluorescent nano material in the fields of cell imaging, in-vivo imaging, drug delivery, fluorescence sensing, photocatalysis, multicolor light-emitting diode (LED) production, energy conversion and storage and the like. Carbon dots are becoming research hotspots in the fields, are potential substitutes for traditional semiconductor quantum dots, have huge application potential and wide prospect, and are concerned by academia and industry.
At present, due to the wide application of the carbon quantum dots in the fields of biological imaging and the like, the green and safe synthesis of the carbon quantum dots is of great concern. Methods for preparing carbon quantum dots can be generally classified into top-down and bottom-up methods according to the selection of carbon sources. The top-down method mainly comprises the steps of stripping large-particle carbon to obtain small-particle carbon nano particles by a physical or chemical method, and generally adopts graphite, graphite oxide, carbon nano tubes and the like as carbon sources, so that the method has high raw material cost, complex preparation process and post-treatment process, and is difficult to realize the large-scale production of the carbon quantum dots. The bottom-up method is to directly synthesize the carbon quantum dots by taking certain organic compounds as carbon sources, and common methods include a hydrothermal method, a solvothermal method, a pyrolysis method, a microwave method and the like. The surface of the carbon quantum dot prepared by the method often has a large number of defects and functional groups, and the fluorescence property of the carbon quantum dot is often influenced by factors such as the surface state, the edge state, doping elements and the like of the carbon dot, so that the carbon quantum dot generates a large number of fluorescence emission centers. However, at present, no method for precisely regulating surface defects and edge functional groups exists, and carbon sources of carbon quantum dots prepared by the prior art are often aromatic chemical substances, so that the problem of environmental protection is generally existed.
The sorghum distillers 'grains are byproducts generated after the sorghum is used for brewing wine in a winery, and include grain residues and certain insoluble substances generated in the brewing or fermentation process, and the sorghum distillers' grains have large yield, complex components and difficult storage. Currently, most enterprises basically use the dried materials as feed or fertilizer after simple drying treatment. However, if the sorghum distillers' grains are directly applied to soil as fertilizer, not only serious resource waste is caused, but also serious environmental pollution is caused.
Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a single-peak-emission vinasse-based green light carbon quantum dot and a preparation method thereof. The preparation method of the single-peak-emission vinasse-based green light carbon quantum dot takes the sorghum vinasse as a raw material, is prepared by a hydrothermal method, is simple, and can effectively solve the problems of resource waste/environmental pollution and the like caused by the sorghum vinasse.
In order to achieve the above object, the present invention provides the following technical solutions: a preparation method of a single-peak-emission vinasse-based green light carbon quantum dot comprises the steps of preparing a carbon source of the single-peak-emission vinasse-based green light carbon quantum dot as sorghum vinasse, and performing hydrothermal reaction on the sorghum vinasse to obtain the single-peak-emission vinasse-based green light carbon quantum dot.
Preferably, the method comprises the following steps:
(1) Dissolving the sorghum vinasse in deionized water, and placing the solution in a reaction container for preheating to obtain a reaction solution A;
(2) Filtering the reaction solution A obtained by the treatment in the step (1) to obtain a reaction solution B;
(3) Carrying out a hydrothermal reaction on the reaction solution B obtained by the treatment in the step (2) until the organic matters are dehydrated, dehydrogenated, carbonized and discolored to obtain a reaction product C;
(4) And (3) filtering and dialyzing the reaction product C after the hydrothermal reaction in the step (3) to obtain the single-peak-emission vinasse-based green light carbon quantum dot.
Preferably, in the step (1), the preheating temperature is 150-220 ℃ and the heat preservation time is 0.5-1h.
Preferably, in the step (2), the reaction solution a is cooled to room temperature, and then the particulate matter is trapped and filtered by a filter screen.
Preferably, in the step (2), the reaction solution a is cooled to room temperature, and then the particulate matter is trapped and filtered by adopting a 100-mesh filter screen.
Preferably, in the step (3), the temperature of the hydrothermal reaction is 150-220 ℃ and the reaction time is 6-12h.
Preferably, in step (3), the temperature of the hydrothermal reaction is 150 ℃ and the reaction time is 6 hours.
Preferably, in the step (3), the filtration membrane used in the filtration is a 0.22 μm microporous filtration membrane.
Preferably, in the step (3), the dialysis membrane is a 1000-3500Da dialysis membrane, and the dialysis time is 24-72 hours.
The invention also provides a single-peak-emission vinasse-based green light carbon quantum dot, which adopts the following technical scheme: the single-peak-emission vinasse-based green light carbon quantum dot is prepared by adopting the preparation method.
Preferably, the optimal excitation wavelength of the single-peak-emitted vinasse-based green light carbon quantum dot is 370nm, and the emission peak of the single-peak-emitted vinasse-based green light carbon quantum dot is not changed along with the change of the excitation wavelength under the irradiation of 280-500nm excitation light.
The beneficial effects are that:
the single-peak-emission vinasse-based green light carbon quantum dot is prepared from sorghum vinasse serving as a raw material through a hydrothermal method, is simple in preparation method, and can effectively solve the problems of resource waste/environmental pollution and the like caused by the sorghum vinasse.
The invention solves the problem that byproducts generated in the white spirit brewing process cannot be recycled, can effectively utilize sorghum distilled grains, and extends the industrial chain of the white spirit manufacturing industry.
The method selects the sorghum distillers' grains as a carbon source, has the advantages of readily available raw materials, abundant resources, environmental protection, simple process, low cost and mild reaction conditions, and is suitable for large-scale production.
The optimal excitation wavelength of the single-peak-emitted vinasse-based green light carbon quantum dot is 370nm, and the emission light peak position cannot change along with the change of the incident light peak under the irradiation of 280-500nm excitation light.
The single-peak-emission vinasse-based green light carbon quantum dot can be applied to various fields such as cell labeling, biological imaging, fluorescent probes, photoluminescence and electroluminescent films, devices and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. Wherein:
FIG. 1 is a photograph of a single peak emitted aqueous solution of distiller's grains-based green light carbon quantum dots according to example 1 under irradiation of fluorescent lamps (left) and 365nm ultraviolet lamps (right);
FIG. 2 is an XRD pattern of a single-peak-emission distillers' grains-based green carbon quantum dot provided in example 1 of the present invention;
fig. 3 is a comparison of the infrared spectrum (lower) of the single-peak-emission distillers 'grains-based green light carbon quantum dots and the infrared spectrum (upper) of the carbon source (sorghum distillers' grains) provided in example 1 of the present invention;
FIG. 4 is a fluorescence emission spectrum of the single-peak emission distillers' grains-based green carbon quantum dot solution provided in example 1 of the present invention under the optimal excitation wavelength;
FIG. 5 is a 3D fluorescence emission spectrum of the single-peak emission distillers' grains-based green light carbon quantum dot solution provided in example 1 of the present invention;
FIG. 6 is a graph showing the comparison of fluorescence intensity of single-peak-emission distillers' grains-based green carbon quantum dots according to examples 1 and 2 of the present invention;
FIG. 7 is a 3D fluorescence emission spectrum of a single-peak-emission distiller's grain-based cyan light carbon quantum dot provided by example 2 of the present invention;
FIG. 8 is a fluorescence emission spectrum of the single-peak emission distillers' grains-based green light carbon quantum dot solution according to example 3 of the present invention under the optimal excitation wavelength;
FIG. 9 is a fluorescence emission spectrum of the single-peak emission distillers' grains-based green carbon quantum dot solution according to example 4 of the present invention under the optimal excitation wavelength;
FIG. 10 is a fluorescence emission spectrum of the single-peak emission distillers' grains-based green carbon quantum dot solution according to example 5 of the present invention under the optimal excitation wavelength;
fig. 11 is a graph showing the comparison of fluorescence intensity of the single-peak-emission distillers' grains-based green light carbon quantum dot solution according to example 1 of the present invention after being modified with NaOH modifier and ethanol modifier without modifier.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
The present invention will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Aiming at the problem that a large number of fluorescence emission centers are easy to generate for the carbon quantum dots in the prior art (the carbon quantum dots prepared by the prior art are multi-peak emission), the invention provides a preparation method of a single-peak emission vinasse-based green light carbon quantum dot. According to the preparation method provided by the embodiment of the invention, the carbon source for preparing the single-peak-emission vinasse-based green light carbon quantum dot is sorghum vinasse, and the single-peak-emission vinasse-based green light carbon quantum dot can be prepared by performing hydrothermal reaction on the sorghum vinasse.
According to the invention, the distilled grain of sorghum is selected as a carbon source, and carbonyl groups on the surface of distilled grain of sorghum are interacted through hydrothermal reaction, so that the carbonyl groups are converted into carboxyl groups, and the distilled grain-based green light carbon quantum dots with single peak emission are prepared.
In a preferred embodiment of the invention, the method comprises the following steps: (1) Dissolving the sorghum vinasse in deionized water, and placing the solution in a reaction container for preheating to obtain a reaction solution A; (2) Filtering the reaction solution A obtained by the treatment in the step (1) to obtain a reaction solution B; (3) Carrying out a hydrothermal reaction on the reaction solution B obtained by the treatment in the step (2) until the organic matters are dehydrated, dehydrogenated, carbonized and discolored to obtain a reaction product C; (4) And (3) filtering and dialyzing the reaction product C after the hydrothermal reaction in the step (3) to obtain the single-peak-emission vinasse-based green light carbon quantum dot. The single-peak-emission vinasse-based green light carbon quantum dot is dissolved in an aqueous solution to form a yellowish carbon quantum dot solution.
In a preferred embodiment of the invention, in step (1), the preheating is carried out at a temperature of 150-220 ℃ (e.g. 150 ℃, 180 ℃, 200 ℃ or 220 ℃) and the incubation time is 0.5-1h (e.g. 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1 h).
In the preferred embodiment of the present invention, in step (2), the reaction solution a is cooled to room temperature, and then the particulate matter is trapped and filtered by a filter screen.
In the preferred embodiment of the present invention, in step (2), the reaction solution a is cooled to room temperature, and then the particulate matter is trapped and filtered by using a 100 mesh filter screen.
In a preferred embodiment of the invention, in step (3), the temperature of the hydrothermal reaction is 150-220 ℃ (e.g. 150 ℃, 180 ℃, 200 ℃ or 220 ℃) and the reaction time is 6-12 hours (e.g. 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours).
In a preferred embodiment of the invention, in the step (3), the temperature of the hydrothermal reaction is 150 ℃ and the reaction time is 6 hours.
In a preferred embodiment of the present invention, in the step (3), the filtration membrane used in the filtration is a 0.22 μm microporous membrane.
In a preferred embodiment of the present invention, in step (3), the step of centrifuging the reaction product C is further included before the filtering; after centrifugation, the supernatant was filtered.
In a preferred embodiment of the present invention, in the step (3), the dialysis (dialysis is performed by placing the dialysis bag in pure water) is performed by using a dialysis membrane of 1000-3500Da (for example, 1000Da or 3500 Da) for a dialysis time of 24-72 hours (for example, 24 hours, 36 hours, 48 hours, 60 hours or 72 hours).
The invention also provides a single-peak-emission vinasse-based green light carbon quantum dot, which adopts the following technical scheme: the single-peak-emission vinasse-based green light carbon quantum dot is prepared by adopting the preparation method.
In the preferred embodiment of the invention, the optimal excitation wavelength of the single-peak-emitted vinasse-based green light carbon quantum dot is 370nm, and the emission peak of the single-peak-emitted vinasse-based green light carbon quantum dot is not changed along with the change of the excitation wavelength under the irradiation of 280-500nm excitation light.
The vinasse-based green light carbon quantum dot capable of unimodal emission and the preparation method thereof are described in detail below through specific examples.
Example 1
The single-peak-emission vinasse-based green light carbon quantum dot is prepared by the following method:
(1) Crushing sorghum vinasse by using a crusher, sieving by using a 50-mesh screen, adding 2.5g of vinasse powder into 15mL of deionized water, placing into a 25mL stainless steel high-pressure reaction kettle with a tetrafluoroethylene lining, heating to 150 ℃ at a constant speed in an oven, and heating at a constant temperature for 0.5h to obtain a reaction solution A;
(2) Cooling the reaction solution A obtained by the treatment in the step (1) to room temperature, and intercepting and filtering by adopting a filter screen with the aperture of 100 meshes to obtain a reaction solution B;
(3) Placing the reaction solution B obtained by the treatment in the step (2) into a stainless steel high-pressure reaction kettle with a tetrafluoroethylene lining, heating to 150 ℃ at a constant speed, heating at the constant temperature of 150 ℃ for 6 hours, and cooling to room temperature to obtain a reaction product C;
(4) And (3) filtering the reaction product C obtained in the step (3) by using a 0.22 mu m microporous filter membrane, performing vacuum suction filtration, and dialyzing with a 3500Da dialysis membrane for 72 hours to obtain the single-peak-emission vinasse-based green light carbon quantum dot (dissolved in the solution) of the embodiment.
The yield of the single-peak-emitted vinasse-based green light carbon quantum dots in the embodiment is about 40%. Wherein, the yield is calculated according to the following method: after the carbon quantum dot solution prepared in this example was freeze-dried, the mass M of the solid powder obtained was weighed, the mass of distillers' grains was weighed before the reaction, and the yield calculation method was Φ=m/m×%.
FIG. 1 is a photograph of a single-peak-emitted distillers' grains-based green carbon quantum dot (solution) under irradiation of a fluorescent lamp (left) and a 365nm ultraviolet lamp (right); it can be seen that the single-peak-emission vinasse-based cyan carbon quantum dot solution in this embodiment is a yellowish liquid (left) under sunlight irradiation, and has bright cyan emission (right) under 365nm ultraviolet lamp irradiation.
Fig. 2 is an X-ray diffraction spectrum (XRD) of the single-peak-emitted distillers 'grains-based green carbon quantum dots of the present embodiment, and as can be seen from fig. 2, the X-ray diffraction spectrum of the single-peak-emitted distillers' grains-based green carbon quantum dots of the present embodiment is a single broad spectrum, and the peak position is at 24.3 ° at 2θ, corresponding to the diffraction of the (002) plane of the graphite grains. The XRD pattern has no impurity peak, which indicates that the crystallinity of the prepared carbon quantum dots is higher.
Fig. 3 is a graph of infrared spectra of the single-peak-emitted distillers ' grains-based cyan light carbon quantum dots (lower) and the sorghum distillers ' grains (upper), and as can be seen from fig. 3, the sorghum distillers ' grains contain a large amount of carbonyl groups, and after the single-peak-emitted distillers ' grains-based cyan light carbon quantum dots are prepared by the reaction, the stretching vibration peak of the carbonyl groups is weakened, which illustrates that the formation of the single-peak-emitted distillers ' grains-based cyan light carbon quantum dots in the embodiment mainly depends on the mutual reaction between the carbonyl groups; and as can be seen from fig. 3, the prepared single-peak-emission vinasse-based green light carbon quantum dot has rich surface functional groups, and is favorable for further modification.
Fig. 4 is a fluorescence emission spectrum of the single-peak-emission distillers 'grains-based cyan light carbon quantum dot solution prepared in this example at an optimal excitation wavelength (370 nm), and it can be seen from the graph that the single-peak-emission distillers' grains-based cyan light carbon quantum dot solution prepared in this example has stronger single-peak blue to cyan fluorescence emission.
Fig. 5 is a 3D fluorescence emission spectrum of the single-peak-emission distillers 'grains-based green light carbon quantum dot solution prepared in this example, and it can be seen from the figure that the fluorescence emission peak position of the single-peak-emission distillers' grains-based green light carbon quantum dot solution prepared in this example does not change with the change of the excitation wavelength, and the optical property is stable.
Example 2
The single-peak-emission vinasse-based green light carbon quantum dot is prepared by the following method:
(1) Crushing sorghum vinasse by using a crusher, sieving by using a 50-mesh screen, adding 2.5g of vinasse powder into 15mL of deionized water, placing into a 25mL stainless steel high-pressure reaction kettle with a tetrafluoroethylene lining, heating to 150 ℃ at a constant speed in an oven, and heating at a constant temperature for 0.5h to obtain a reaction solution A;
(2) Cooling the reaction solution A obtained by the treatment in the step (1) to room temperature, and intercepting and filtering by adopting a filter screen with the aperture of 100 meshes to obtain a reaction solution B;
(3) Placing the reaction solution B obtained by the treatment in the step (2) into a stainless steel high-pressure reaction kettle with a tetrafluoroethylene lining, heating to 220 ℃ at a constant speed, heating at the constant temperature of 220 ℃ for 6 hours, and cooling to room temperature to obtain a reaction product C;
(4) And (3) filtering the reaction product C obtained in the step (3) by using a 0.22 mu m microporous filter membrane, performing vacuum suction filtration, and dialyzing with a 3500Da dialysis membrane for 72 hours to obtain the single-peak-emission vinasse-based green light carbon quantum dot (dissolved in the solution) of the embodiment.
The yield of the single-peak-emitted vinasse-based green light carbon quantum dots in the embodiment is about 2%. Wherein, the yield is calculated according to the following method: after the carbon quantum dot solution prepared in this example was freeze-dried, the mass M of the solid powder obtained was weighed, the mass of distillers' grains was weighed before the reaction, and the yield calculation method was Φ=m/m×%.
FIG. 6 is a graph showing the comparison of fluorescence intensity of single-peak-emission distillers' grains-based green carbon quantum dots according to examples 1 and 2 of the present invention; as can be seen from fig. 6, when the temperature of the reaction in step (3) was adjusted to 220 ℃, the fluorescence spectrum of the prepared single-peak-emission distillers' grains-based green carbon quantum dots was substantially identical to that of example 1.
FIG. 7 is a 3D fluorescence emission spectrum of a single-peak-emission distiller's grain-based cyan light carbon quantum dot provided by example 2 of the present invention; as can be seen from fig. 7, when the temperature of the reaction in the step (3) is adjusted to 220 ℃, the 3D fluorescence emission spectrum of the prepared single-peak-emission distillers' grains-based green carbon quantum dots is substantially identical to that of example 1.
Example 3
The single-peak-emission vinasse-based green light carbon quantum dot is prepared by the following method:
(1) Crushing sorghum vinasse by using a crusher, sieving by using a 50-mesh screen, adding 2.5g of vinasse powder into 15mL of deionized water, placing into a 25mL stainless steel high-pressure reaction kettle with a tetrafluoroethylene lining, heating to 220 ℃ at a constant speed in an oven, and heating at a constant temperature for 1h to obtain a reaction solution A;
(2) Cooling the reaction solution A obtained by the treatment in the step (1) to room temperature, and intercepting and filtering by adopting a filter screen with the aperture of 100 meshes to obtain a reaction solution B;
(3) Placing the reaction solution B obtained by the treatment in the step (2) into a stainless steel high-pressure reaction kettle with a tetrafluoroethylene lining, heating to 220 ℃ at a constant speed, heating at the constant temperature of 220 ℃ for 9 hours, and cooling to room temperature to obtain a reaction product C;
(4) And (3) filtering the reaction product C obtained in the step (3) by using a 0.22 mu m microporous filter membrane, performing vacuum suction filtration, and dialyzing with a 3500Da dialysis membrane for 72 hours to obtain the single-peak-emission vinasse-based green light carbon quantum dot (dissolved in the solution) of the embodiment.
The yield of the single-peak-emitted vinasse-based green light carbon quantum dots in the embodiment is about 2%. Wherein, the yield is calculated according to the following method: after the carbon quantum dot solution prepared in this example was freeze-dried, the mass M of the solid powder obtained was weighed, the mass of distillers' grains was weighed before the reaction, and the yield calculation method was Φ=m/m×%.
The fluorescence emission spectrum of the single-peak-emission vinasse-based green light carbon quantum dot solution prepared in the embodiment under the optimal excitation wavelength (370 nm) is shown in fig. 8.
Example 4
The single-peak-emission vinasse-based green light carbon quantum dot is prepared by the following method:
(1) Crushing sorghum vinasse by using a crusher, sieving by using a 50-mesh screen, adding 2.5g of vinasse powder into 15mL of deionized water, placing into a 25mL stainless steel high-pressure reaction kettle with a tetrafluoroethylene lining, heating to 220 ℃ at a constant speed in an oven, and heating at a constant temperature for 1h to obtain a reaction solution A;
(2) Cooling the reaction solution A obtained by the treatment in the step (1) to room temperature, and intercepting and filtering by adopting a filter screen with the aperture of 100 meshes to obtain a reaction solution B;
(3) Placing the reaction solution B obtained by the treatment in the step (2) into a stainless steel high-pressure reaction kettle with a tetrafluoroethylene lining, heating to 220 ℃ at a constant speed, heating at the constant temperature of 220 ℃ for 12 hours, and cooling to room temperature to obtain a reaction product C;
(4) And (3) filtering the reaction product C obtained in the step (3) by using a 0.22 mu m microporous filter membrane, performing vacuum suction filtration, and dialyzing with a 3500Da dialysis membrane for 72 hours to obtain the single-peak-emission vinasse-based green light carbon quantum dot (dissolved in the solution) of the embodiment.
The yield of the single-peak-emitted vinasse-based green light carbon quantum dots in the embodiment is about 2%. Wherein, the yield is calculated according to the following method: after the carbon quantum dot solution prepared in this example was freeze-dried, the mass M of the solid powder obtained was weighed, the mass of distillers' grains was weighed before the reaction, and the yield calculation method was Φ=m/m×%.
The fluorescence emission spectrum of the single-peak-emission vinasse-based green light carbon quantum dot solution prepared in the embodiment under the optimal excitation wavelength (370 nm) is shown in fig. 9.
Example 5
The single-peak-emission vinasse-based green light carbon quantum dot is prepared by the following method:
(1) Crushing sorghum vinasse by using a crusher, sieving by using a 50-mesh screen, adding 2.5g of vinasse powder into 15mL of deionized water, placing into a 25mL stainless steel high-pressure reaction kettle with a tetrafluoroethylene lining, heating to 150 ℃ at a constant speed in an oven, and heating at a constant temperature for 1h to obtain a reaction solution A;
(2) Cooling the reaction solution A obtained by the treatment in the step (1) to room temperature, and intercepting and filtering by adopting a filter screen with the aperture of 100 meshes to obtain a reaction solution B;
(3) Placing the reaction solution B obtained by the treatment in the step (2) into a stainless steel high-pressure reaction kettle with a tetrafluoroethylene lining, heating to 150 ℃ at a constant speed, heating at the constant temperature of 150 ℃ for 6 hours, and cooling to room temperature to obtain a reaction product C;
(4) And (3) filtering the reaction product C obtained in the step (3) by using a 0.22 mu m microporous filter membrane, performing vacuum suction filtration, and dialyzing with a 3500Da dialysis membrane for 72 hours to obtain the single-peak-emission vinasse-based green light carbon quantum dot (dissolved in the solution) of the embodiment.
The yield of the single-peak-emitted vinasse-based green light carbon quantum dots in the embodiment is about 37%. Wherein, the yield is calculated according to the following method: after the carbon quantum dot solution prepared in this example was freeze-dried, the mass M of the solid powder obtained was weighed, the mass of distillers' grains was weighed before the reaction, and the yield calculation method was Φ=m/m×%.
The fluorescence emission spectrum of the single-peak-emission vinasse-based green light carbon quantum dot solution prepared in the embodiment under the optimal excitation wavelength (370 nm) is shown in fig. 10.
Experimental example
NaOH and ethanol are respectively adopted as modifier, the single-peak-emission vinasse-based green light carbon quantum dots prepared in the embodiment 1 are modified, and the fluorescence intensity before and after modification is measured:
weighing 0.4g of the green light carbon quantum dot powder prepared in the example (the single-peak emission vinasse-based green light carbon quantum dot prepared in the example 1 is obtained after freeze-drying), dissolving in 1mL of deionized water to obtain a carbon quantum dot solution A, mixing with 10mL of deionized water, 10mL of ethanol and 10mL of 1.8g/L NaOH solution respectively, magnetically stirring for 10min, and performing ultrasonic treatment for 5min to obtain modifier treated solutions B, C, D respectively; the fluorescence intensities of the solutions B (deionized water), C (ethanol modification) and D (NaOH modification) after the modifier treatment were measured respectively.
The experimental results are shown in FIG. 11. As can be seen from fig. 11, the results modified by NaOH and ethanol can help prove that: the single-peak-emission vinasse-based green light carbon quantum dot is mainly due to the fact that the surface of the single-peak-emission vinasse-based green light carbon quantum dot contains a large amount of carboxyl. As can be seen from fig. 3 and 11, the single-peak emission distillers' grains-based green light carbon quantum dots of the present invention are prepared by converting carbonyl groups on the surface of sorghum distillers grains into carboxyl groups.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the single-peak-emission vinasse-based green light carbon quantum dot is characterized by comprising the following steps of:
(1) Dissolving sorghum vinasse in deionized water, and placing the solution in a reaction container for preheating to obtain a reaction solution A;
(2) Filtering the reaction solution A obtained by the treatment in the step (1) to obtain a reaction solution B;
(3) Carrying out a hydrothermal reaction on the reaction solution B obtained by the treatment in the step (2) until the organic matters are dehydrated, dehydrogenated, carbonized and discolored to obtain a reaction product C;
(4) Filtering and dialyzing the reaction product C after the hydrothermal reaction in the step (3) to obtain the single-peak-emitted vinasse-based green light carbon quantum dots;
in the step (1), the preheating temperature is 150 ℃, and the heat preservation time is 0.5-1h;
in the step (3), the temperature of the hydrothermal reaction is 150 ℃ and the reaction time is 6 hours;
in the step (2), the reaction solution A is cooled to room temperature, and then a filter screen is adopted to intercept and filter the particulate matters of the reaction solution A.
2. The method for preparing the single-peak-emission vinasse-based green light carbon quantum dot according to claim 1, wherein in the step (2), the reaction solution A is cooled to room temperature, and then a 100-mesh filter screen is adopted to intercept and filter particulate matters in the reaction solution A.
3. The method for preparing the single-peak-emission vinasse-based green light carbon quantum dot according to claim 1, wherein in the step (4), a filter membrane adopted in the filtering is a 0.22 μm microporous filter membrane.
4. The method for preparing the single-peak-emission vinasse-based green light carbon quantum dot according to claim 1, wherein in the step (4), a dialysis membrane of 1000-3500Da is adopted in the dialysis, and the dialysis time is 24-72 hours.
5. The single-peak-emission vinasse-based green light carbon quantum dot is characterized in that the single-peak-emission vinasse-based green light carbon quantum dot is prepared by the preparation method according to any one of claims 1-4.
6. The single-peak-emitted vinasse-based cyan light carbon quantum dot of claim 5, wherein the single-peak-emitted vinasse-based cyan light carbon quantum dot has an optimal excitation wavelength of 370nm, and the single-peak-emitted vinasse-based cyan light carbon quantum dot has an emission peak that does not change with the change of the excitation wavelength under the irradiation of 280-500nm excitation light.
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| CN109943325A (en) * | 2019-04-17 | 2019-06-28 | 云南大学 | A method of feux rouges carbon quantum dot is prepared with grape vinasse |
| CN110451488A (en) * | 2019-07-24 | 2019-11-15 | 桂林理工大学 | A kind of method of Passivation modified cane molasses graphene quantum dot |
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| CN109943325A (en) * | 2019-04-17 | 2019-06-28 | 云南大学 | A method of feux rouges carbon quantum dot is prepared with grape vinasse |
| CN110451488A (en) * | 2019-07-24 | 2019-11-15 | 桂林理工大学 | A kind of method of Passivation modified cane molasses graphene quantum dot |
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| Yun Man等.Starch fermentation wastewater as a precursor to prepare S,N-doped carbon dots for selective Fe(III) detection and carbon microspheres for solution decolorization.Microchemical Journal.2020,第第159卷卷第105338页. * |
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