CN113046069B - Method for continuously and controllably preparing nitrogen and phosphorus co-doped carbon quantum dots - Google Patents
Method for continuously and controllably preparing nitrogen and phosphorus co-doped carbon quantum dots Download PDFInfo
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Abstract
The invention discloses a method for continuously and controllably preparing nitrogen and phosphorus co-doped carbon quantum dots, and belongs to the technical field of preparation of nano functional materials. Dissolving ethanolamine in deionized water to obtain a carbon precursor solution, and adding a phosphoric acid solution while stirring to obtain a reaction solution. And injecting the reaction liquid into the tubular reactor through a plunger pump, and reacting under the heating of an oil bath to obtain the nitrogen and phosphorus co-doped carbon quantum dot solution. And cooling to room temperature, filtering and drying to obtain nitrogen and phosphorus co-doped carbon quantum dot powder. Compared with the prior art, the method has the advantages of simple raw materials, continuous and rapid reaction, safety, environmental protection, strong controllability, narrow particle size distribution and good uniformity of the synthesized nitrogen and phosphorus co-doped carbon quantum dots, and can be used in the fields of luminescent materials, metal ion detection, biological imaging and the like.
Description
Technical Field
The invention relates to a method for continuously and controllably preparing nitrogen and phosphorus co-doped carbon quantum dots, and belongs to the technical field of preparation of nano functional materials.
Background
The carbon quantum dots are also called carbon dots, are approximately spherical carbon nano materials with the particle size within 10nm, and have wide application prospects in the fields of luminescent materials, metal ion detection, biological imaging and the like due to the characteristics of good fluorescence stability, low toxicity, good biocompatibility and the like. Meanwhile, researches show that the chemical components and the structure of the carbon quantum dots can be changed by carrying out element doping on the carbon quantum dots, so that the distribution and the energy level structure of electron clouds are changed, and the optical and electronic properties of the carbon quantum dots are improved. The nitrogen and phosphorus co-doped carbon quantum dot also has the characteristics of high fluorescence quantum yield, freely-tuned blue and green (yellow) double-emission centers and the like, and has excellent and wide application prospects in the fields of trace metal ion detection, photoelectric devices, ratio sensing, biological imaging, energy storage and the like.
At present, the preparation method of nitrogen and phosphorus codoped carbon quantum dots mainly comprises a hydrothermal method and a microwave method. The hydrothermal method has low production cost, the experimental conditions can be flexibly set, but the synthesis time is long; the microwave method is simple and efficient, low in cost, safe and non-toxic, but the particle size of the carbon quantum dots is not easy to control. In addition, the above methods cannot continuously prepare carbon quantum dots, so a simple, efficient, safe, low-cost, good-continuity and strong-controllability preparation process is urgently needed to be developed.
Patent CN201810866243.1 discloses a method for obtaining double-doped nitrogen and phosphorus-carbon quantum dots by using amino acid and carbon precursors as nitrogen and carbon sources and using phosphoric acid solution as phosphorus source, and performing ultrasonic treatment, oil bath heating, centrifugation, dialysis and other steps. The method has long pretreatment time, retention time and post-treatment time, and the steps are relatively complicated.
Patent CN201610685283.7 discloses a method for preparing phosphorus-doped carbon quantum dots by using hydrotalcite and sodium methylphosphonite as raw materials. The method comprises the working procedures of screening, aging, solid-liquid separation, vacuum calcination and the like, and has the disadvantages of complicated steps and long treatment time, and simultaneously requires the conditions of high temperature of 400-600 ℃, strong acid condition of 20-40% hydrochloric acid, nitrogen protection and the like.
Patent CN201810247054.6 discloses a method for obtaining phosphorus and nitrogen co-doped carbon quantum dots by using hair and phenoxy cyclophosphazene as raw materials and carrying out the procedures of grinding, calcining, ultrasonic processing, centrifugation, dialysis, rotary evaporation and the like. The method has the advantages of complex process, long treatment time and harsh preparation conditions. In addition, the fluorescence quantum yield of the product prepared by the method is low and is only 23.5%. In contrast, the preparation method disclosed by the invention is simple in preparation process and short in treatment time, and can be used for continuously and controllably preparing the phosphorus and nitrogen co-doped carbon quantum dots with the fluorescence quantum yield of 71.80%.
Compared with the traditional kettle type reactor, the tubular reactor can realize continuous production, has the advantages of relatively large specific surface area, high heat and mass transfer rate, narrow residence time distribution and the like, and is widely applied to the fields of chemical industry, chemistry, materials and the like. At present, a tubular reactor is used for synthesis of fine chemicals and medical intermediates, but no report of preparing nitrogen and phosphorus co-doped carbon quantum dots by using the tubular reactor is available so far.
Disclosure of Invention
Based on the problems, the invention provides a method for continuously and controllably preparing nitrogen and phosphorus co-doped carbon quantum dots by using a tubular reactor in combination with the advantages of the tubular reactor.
The invention aims to provide a method for continuously and controllably preparing nitrogen and phosphorus co-doped carbon quantum dots, which comprises the following specific steps:
(1) dissolving a carbon source and a nitrogen source in water, quickly adding a phosphorus source while stirring, and stirring until the solution is clear to obtain a reaction solution;
(2) placing a feed pipe into the reaction liquid, placing the tubular reactor into an oil bath pan, and connecting a reaction device;
(3) set up suitable oil bath reaction temperature and reaction solution velocity of flow, introduce tubular reactor with the reaction solution through the inlet pipe, react under the oil bath heating and obtain nitrogen, phosphorus codope carbon quantum dot solution, collect the nitrogen, phosphorus codope carbon quantum dot solution that makes, after cooling to the room temperature, obtain nitrogen, phosphorus codope carbon quantum dot powder after filtering the product solution, drying.
In one embodiment of the present invention, in step (1), the carbon source and the nitrogen source are derived from the same substance, and the substance is any one of ethanolamine, diethanolamine, triethanolamine, ethylenediamine, and amino acids.
In one embodiment of the present invention, the phosphorus source in step (1) is any one of phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, and metaphosphoric acid.
In one embodiment of the invention, when the water in the step (1) is deionized water, and the carbon source and the nitrogen source are ethanolamine, the volume ratio of ethanolamine to deionized water is 1: 4-1: 7.
In one embodiment of the invention, when the phosphorus source in step (1) is phosphoric acid, the mass fraction of the phosphoric acid solution is 80% -90%, and the volume ratio of the ethanolamine to the phosphoric acid solution is 1: 2-1: 4.
In one embodiment of the present invention, one end of the feeding pipe in the step (2) is connected to the inlet section of the plunger pump, and the other end is placed in the reaction solution.
In one embodiment of the invention, the inlet end of the plunger pump is connected with one end of a feeding pipe, and the other end of the feeding pipe is connected with a suction nozzle and is placed under the liquid level of the reaction liquid; the outlet end of the plunger pump is connected with the discharge pipe, the tubular reactor is coiled around the column after a reaction liquid inlet pipeline and a product outlet pipeline are reserved, the coiled part is placed in an oil bath pan, the discharge pipe is connected with the inlet pipeline of the tubular reactor, and finally a product is collected through the outlet end of the outlet pipeline of the tubular reactor.
In one embodiment of the invention, the tapping pipe is connected to the pipe reactor inlet line via a flat connection.
In one embodiment of the invention, the material of the feeding pipe and the discharging pipe is polytetrafluoroethylene, the inner diameter of the pipe is 0.1-5.0 mm, and the outer diameter of the pipe is 1.2-7.0 mm.
In one embodiment of the invention, the tubular reactor inlet and outlet conduits are not separate conduits and are the non-reacting part of the tubular reactor.
In an embodiment of the present invention, in the step (2), the tubular reactor is made of a metal material which is easily heat-conductive and heat-resistant, such as a stainless steel tube, a copper tube, a nickel tube, etc., and has a length of 4 to 10 meters, an inner diameter of 0.18 to 6.0mm, and an outer diameter of 1.6 to 8.0 mm.
In one embodiment of the present invention, the flow rate of the reaction solution in step (3) is set to 0.28 to 1.7ml/min, and the residence time of the reaction solution in the tube is 10 to 60 min.
In one embodiment of the present invention, the flow rate of the reaction solution in the step (3) is set to 0.57ml/min, and the residence time of the reaction solution in the tube is 30 min.
In one embodiment of the present invention, the oil bath reaction temperature in step (3) is 100 ℃ to 250 ℃.
In one embodiment of the present invention, the oil bath reaction temperature in step (3) is 160 ℃.
In one embodiment of the present invention, the filtration in step (3) is performed using a microfiltration membrane having a pore size of 0.25 to 0.45. mu.m.
In one embodiment of the invention, the drying in the step (3) is vacuum drying, the drying time is 8-12 h, and the drying temperature is 40-80 ℃.
The second purpose of the invention is to provide the nitrogen and phosphorus co-doped carbon quantum dot prepared by the preparation method.
The invention has the beneficial effects that:
(1) according to the invention, ethanolamine is selected as a carbon source and a nitrogen source, a phosphoric acid solution is used as a phosphorus source, the raw material source is simple, the production cost is low, in addition, the amino group of ethanolamine can be used as a substitute fluorescence source for emitting fluorescence in the reaction, and the acid catalyst can help the ethanolamine to be carbonized and dehydrated.
(2) The method utilizes the tubular reactor to carry out reaction, has simple working procedures, does not need any pretreatment step, and has short retention time which is only 10-60 min; the tubular reactor has high heat transfer and mass transfer performance and continuity, can continuously and controllably prepare nitrogen and phosphorus codoped carbon quantum dots at a lower temperature, can obtain carbon quantum dot powder by only two working procedures of filtering and drying in the post-treatment, and is quick and efficient.
(3) The preparation method of the invention does not need any surface modifier, oxidant and dehydrating agent, and is safe and environment-friendly.
(4) The preparation method has strong controllability, and can flexibly adjust the doping amount of nitrogen and phosphorus in the product, the size and the particle size distribution of the product, thereby adjusting the fluorescence property of the product.
(5) The product prepared by the method has good uniformity and controllable particle size, and is easy to amplify in parallel.
Drawings
FIG. 1 is a schematic diagram of an overall device for preparing nitrogen and phosphorus co-doped carbon quantum dots in example 1; the device comprises a foam supporting plate 1, a foam supporting plate 2-1, a conical flask for containing reaction liquid 3-1, a suction nozzle 3-2, a feeding pipe 3, a plunger pump 3-3, a discharging pipe 4, a flat joint 5-1, an inlet pipeline 5, a tubular reactor 5-2, an outlet pipeline 6, an oil bath kettle 2-2 and a conical flask for collecting products.
Fig. 2 is an ultraviolet absorption spectrum of the nitrogen and phosphorus co-doped carbon quantum dot solution prepared in example 1.
Fig. 3 is a fluorescence lifetime decay diagram of the nitrogen and phosphorus co-doped carbon quantum dot solution prepared in example 3.
Fig. 4 is a TEM image of the nitrogen and phosphorus co-doped carbon quantum dot solution prepared in example 3.
Fig. 5 is a graph comparing fluorescence intensities of nitrogen and phosphorus co-doped carbon quantum dot solutions prepared in examples 1, 2 and 3.
FIG. 6 is a graph comparing fluorescence intensities of nitrogen and phosphorus co-doped carbon quantum dot solutions prepared in examples 1, 5 and 6.
Detailed Description
The present invention will be further explained with reference to the following examples and drawings, but the present invention is not limited thereto.
FIG. 1 is a schematic diagram of an overall device for preparing nitrogen and phosphorus co-doped carbon quantum dots in the following specific examples, which comprises a foam support plate 1, a conical flask 2-1 for containing reaction liquid, a suction nozzle 3-1, a feeding pipe 3-2, a plunger pump 3, a discharging pipe 3-3, a flat joint 4, an inlet pipeline 5-1, a tubular reactor 5, an outlet pipeline 5-2, an oil bath 6 and a conical flask 2-2 for collecting products.
The reaction apparatus in the following examples was connected as follows: placing a conical flask 2-1 containing reaction liquid on a foam supporting plate 1, wherein the inlet end of a plunger pump is connected with a feeding pipe 3-2 thereof; a feeding pipe 3-2 is connected with a suction nozzle 3-1 and is placed under the liquid level of a conical flask 2-1 containing reaction liquid; the outlet end of the plunger pump is connected with a discharge pipe 3-3 thereof; after the tubular reactor 5 is coiled around the column, a reaction liquid inlet pipeline 5-1 and a product outlet pipeline 5-2 are reserved, the tubular reactor 5 is placed in an oil bath pot, a discharge pipe 3-3 is connected with the inlet pipeline 5-1 of the tubular reactor 5 through a flat joint 4, and finally the outlet end of the outlet pipeline 5-2 of the tubular reactor 5 is placed in a conical flask 2-2 for collecting products so as to collect the products.
Wherein the material of the feeding pipe 3-2 and the material of the discharging pipe 3-3 is polytetrafluoroethylene, the inner diameter of the pipe diameter pipe is 0.1-5.0 mm, and the outer diameter of the pipe is 1.2-7.0 mm; the inlet pipeline 5-1 and the outlet pipeline 5-2 of the tubular reactor are not independent pipelines and are parts of the tubular reactor which do not participate in the reaction.
After the reaction temperature and the flow rate of the reaction solution were set on the oil bath and the plunger pump, the reaction was started.
Example 1
3ml of ethanolamine is dissolved in 12ml of deionized water, 6ml of phosphoric acid solution with the mass fraction of 85% is added under stirring, and after the solution is clarified, a feed pipe of a plunger pump is placed in a reaction liquid container. Placing a stainless steel tube type reactor with the length of 5.4m, the inner diameter of 2mm and the outer diameter of 4mm into an oil bath pan, connecting a reaction device, setting the flow rate of a reaction solution to be 0.57ml/min, the retention time to be 30min, setting the temperature of the oil bath pan to be 120 ℃, reacting under heating to obtain a nitrogen and phosphorus co-doped carbon quantum dot solution, collecting the nitrogen and phosphorus co-doped carbon quantum dot solution in a conical flask, cooling to room temperature, filtering the product solution by using a 0.22 mu m filter membrane, and drying under vacuum at 60 ℃ for 8 hours to obtain nitrogen and phosphorus co-doped carbon quantum dot powder.
The schematic diagram of the device for preparing nitrogen and phosphorus co-doped carbon quantum dots in the embodiment is shown in fig. 1.
0.1g of the nitrogen-phosphorus co-doped carbon quantum dot powder obtained in the embodiment is dissolved in 10ml of deionized water, an ultraviolet-visible spectrophotometer is adopted to measure the ultraviolet absorption peak of the solution, the absorption spectrum is shown in fig. 2, it can be seen from fig. 2 that the obtained carbon quantum dot solution shows obvious absorption in the range of 270-350nm, and the maximum absorption peak is at 292nm and is consistent with the ultraviolet-visible absorption spectrum of a typical carbon quantum dot, which indicates that the carbon quantum dot is successfully prepared by the method in the embodiment.
Example 2
The treatment process, the operation conditions and the equipment of the embodiment are the same as those of the embodiment 1, and the only difference is that: the temperature of the oil bath pot is set to be 140 ℃, and nitrogen and phosphorus co-doped carbon quantum dot powder is prepared for later use.
Example 3
The treatment process, the operation conditions and the equipment of the embodiment are the same as those of the embodiment 1, and the only difference is that: the temperature of the oil bath pot is set to be 160 ℃, and nitrogen and phosphorus co-doped carbon quantum dot powder is prepared for later use.
0.1g of the nitrogen and phosphorus co-doped carbon quantum dot powder obtained in the embodiment is dissolved in 10ml of deionized water, and a fluorescence lifetime test of the carbon quantum dot solution obtained by the test of the ultrafast time-resolved fluorescence lifetime spectrometer is performed, wherein a fluorescence lifetime attenuation graph of the carbon quantum dot solution is shown in fig. 3. It can be seen from fig. 3 that the fluorescence lifetime of most photons is greater than 10ns, which indicates that the nitrogen-phosphorus co-doped carbon quantum dot prepared by the invention has good fluorescence stability.
A drop of the carbon quantum dot solution is taken for transmission electron microscope detection, and the result is shown in FIG. 4. As can be seen from FIG. 4, the nitrogen and phosphorus co-doped carbon quantum dots prepared by the method have regular shapes and sizes of 3-12 nm.
Example 4
Testing of fluorescence properties:
0.1g of the nitrogen and phosphorus co-doped carbon quantum dot powder obtained in each of examples 1, 2 and 3 was dissolved in 10ml of deionized water to obtain 3 parts of carbon quantum dot solution, and the obtained solution was measured by a fluorescence spectrophotometer, and the measured fluorescence spectrum was shown in fig. 5. From FIG. 5, it can be seen that the fluorescence intensity of the carbon dot solution is increased with the increase of the reaction temperature, which indicates that the fluorescence property of the product can be changed by controlling the reaction temperature.
Testing relative fluorescence quantum yield:
the relative fluorescence quantum yield of the nitrogen and phosphorus co-doped carbon quantum dots prepared in examples 1, 2 and 3 was determined by a reference method. Selecting quinine sulfate (0.05 mol. L) -1 H of (A) 2 SO 4 ) As a standard reference substance, the fluorescence quantum yield of the product (Parker, c.a. and w.t.rees.analy) was calculated according to the following formulast,1960,85,587-600)：
Wherein 1 and 2 respectively represent carbon quantum dots and quinine sulfate, Y is fluorescence quantum yield, A represents absorbance, and S is fluorescence peak area.
The fluorescence quantum yields of the products of examples 1, 2 and 3 were measured to be 54.37%, 64.22% and 71.80%, respectively, because as the reaction temperature increased, the reaction rate and the conversion rate of ethanolamine also increased, so that the yield of nitrogen and phosphorus co-doped carbon quantum dots in the solution increased, resulting in an increase in fluorescence intensity. In addition, the electronic and structural characteristics of the carbon quantum dots are changed by doping nitrogen and phosphorus elements, so that the fluorescence quantum yield of the carbon quantum dots is improved.
Example 5
The treatment process, the operation conditions and the equipment of the embodiment are the same as those of the embodiment 1, and the only difference is that: setting the residence time of reactants to be 20min, and preparing nitrogen and phosphorus co-doped carbon quantum dot powder for later use.
Example 6
The treatment process, the operation conditions and the equipment of the embodiment are the same as those of the embodiment 1, and the only difference is that: setting the residence time of reactants to be 10min, and preparing nitrogen and phosphorus co-doped carbon quantum dot powder for later use.
Example 7
Testing of fluorescence properties:
0.1g of the carbon quantum dot powder obtained in each of examples 1, 5, and 6 was dissolved in 10ml of deionized water to obtain 3 parts of a carbon quantum dot solution, and the fluorescence intensity was measured by the method in example 4, and the measured fluorescence spectrum was shown in fig. 6. From FIG. 6, it can be seen that the fluorescence intensity of the carbon dot solution is increased with the increase of the retention time, which indicates that the invention can change the fluorescence property of the product by controlling the retention time. Likewise, this is because the yield of nitrogen and phosphorus co-doped carbon quantum dots increases with the increase of reaction time, so that the fluorescence intensity of the solution increases.
Comparative example 1
The treatment process, the operation conditions and the equipment of the embodiment are the same as those of the embodiment 1, and the only difference is that: the oil bath pan was set at 180 ℃. The prepared product is collected after the reaction, and the aggregation phenomenon is found to be serious, and obvious carbon particles are generated, so that the reactor is easy to block.
Comparative example 2
The treatment process, the operation conditions and the equipment of the embodiment are the same as those of the embodiment 1, and the only difference is that: the retention time of reactants is 50min, the prepared product is collected after the reaction, the aggregation phenomenon is also serious, and obvious carbon particles are generated, so that the reactor is easy to block.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (1)
1. A method for preparing nitrogen and phosphorus co-doped carbon quantum dots is characterized by comprising the following specific steps:
dissolving 3ml of ethanolamine in 12ml of deionized water, adding 6ml of phosphoric acid solution with the mass fraction of 85% while stirring, stirring until the solution is clear, and placing a feeding pipe of a plunger pump in a reaction solution container;
placing a stainless steel tube type reactor with the length of 5.4m, the inner diameter of 2mm and the outer diameter of 4mm into an oil bath pan, connecting a reaction device, setting the flow rate of a reaction solution to be 0.57ml/min, the retention time to be 30min, setting the temperature of the oil bath pan to be 160 ℃, reacting under heating to obtain a nitrogen and phosphorus co-doped carbon quantum dot solution, collecting the nitrogen and phosphorus co-doped carbon quantum dot solution in a conical flask, cooling to the room temperature, filtering the product solution by using a 0.22 mu m filter membrane, and drying under vacuum at 60 ℃ for 8 hours to obtain nitrogen and phosphorus co-doped carbon quantum dot powder;
the reaction apparatus was connected as follows:
placing a conical flask containing reaction liquid on a foam supporting plate, wherein the inlet end of a plunger pump is connected with a feeding pipe of the plunger pump; connecting a feed pipe with a suction nozzle, and placing the feed pipe under the liquid level of a conical flask containing reaction liquid; the outlet end of the plunger pump is connected with a discharge pipe thereof; after the tubular reactor is coiled around the column, a reaction liquid inlet pipeline and a product outlet pipeline are reserved, the tubular reactor is placed in an oil bath pan, a discharge pipe is connected with the tubular reactor inlet pipeline through a flat joint, and finally the outlet end of the tubular reactor outlet pipeline is placed in a conical flask for collecting the product to collect the product;
wherein the material of the feeding pipe and the material of the discharging pipe are polytetrafluoroethylene, the inner diameter of the pipe is 0.1-5.0 mm, and the outer diameter of the pipe is 1.2-7.0 mm; the inlet pipeline and the outlet pipeline of the tubular reactor are not independent pipelines and are parts of the tubular reactor which do not participate in the reaction.
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