CN112608743B - Preparation method of coal-based fluorescent carbon quantum dots - Google Patents
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Abstract
The invention provides a preparation method of coal-based fluorescent carbon quantum dots. The method comprises the steps of taking coal as a raw material, carrying out thermal treatment at a certain temperature, carrying out hydrothermal treatment in the presence of a Fenton reagent, and filtering and dialyzing to obtain the fluorescent carbon quantum dots.
Description
Technical Field
The invention relates to a preparation method of coal-based fluorescent carbon quantum dots, belonging to the field of chemistry.
Background
Carbon Dots (CDs) have received much attention due to their low toxicity, water solubility, unique fluorescent properties, and unique structure that is easily modified. The preparation of carbon dots can be divided into a "top-down" method and a "bottom-up" method. The "top-down" method means that a carbon-containing macromolecular substance is decomposed and carbonized into carbon quantum dots of nanometer scale by a physical stripping method, a chemical oxidation method, electrochemical etching, a solvent thermal synthesis method, arc discharge, laser ablation, a thermal decomposition method, or the like. The "bottom-up" method is mainly to gradually fuse small organic molecules into carbon dots of relatively large size by pyrolysis/carbonization, hydrothermal synthesis or microwave polymerization. Carbon dots were first reported in 2004, Scrivens et al (Xu X, JACS 2004) at southern california, usa, unexpectedly discovered a new class of carbon nanoparticles with fluorescent properties when the crude single-walled carbon nanotubes were prepared by electrophoretic separation, purification, and electric arc methods, and the different components separated showed different fluorescent colors. Sun et al (Sun Y-P, JACS 2006) at the university of Cllemsen, USA, obtained fluorescent carbon dots with a particle size of about 5nm by laser etching-acid oxidation-passivation of graphite, and discovered the influence of surface passivation on the fluorescence characteristics. Thereafter, various carbonaceous macromolecules have been used to prepare carbon dots, such as petroleum coke, pitch-based carbon fibers, activated carbon, candle soot, carbon black, graphene, soy milk, food residues, and the like.
The size of the carbon dots is generally less than 10nm and is mainly composed of two parts: a carbonaceous core as a backbone of carbon dots and surface groups. The carbonaceous core is generally composed of hybridized carbon of sp2 and sp3, and has a graphite-like microcrystalline structure or amorphous carbon aggregated particles. Different preparation methods have great influence on the structure of the carbonaceous core, the crystallinity of the carbon dots obtained by a bottom-up method is lower, and the crystallinity of the carbon dots obtained by a top-down method is higher. Because the specific surface of the carbon point is larger, the coordination of surface phase atoms is insufficient, and the coordination unsaturated dangling bonds are more, the surface energy is higher, the surface energy needs to be stabilized in a mode of agglomerating and bonding surface groups, and oxygen-containing functional groups such as carboxyl, hydroxyl and the like or other groups such as amino and the like are generally introduced to the outside.
Coal is a complex carbon-containing organic mixture, the organic part is a three-dimensional reticular polymer formed by connecting crystalline carbon structural units through aliphatic hydrocarbon bonds and other bridge bonds, and the units with the structure similar to that of the carbon core of the fluorescent carbon quantum dots can be obtained after cutting. Compared with materials such as graphite, carbon black and the like, coal has a unique structure and high reactivity and is an ideal carbon dot synthetic material. The synthesis of coal-based carbon dots from top to bottom requires the breaking of bridges connecting carbon cluster units in coal under physical or chemical intervention, the segmentation into aromatic sheet layers of suitable size, and the surface treatment to make them fluorescent.
CN201710209889.8 discloses a preparation method of a coal-based carbon dot. Adding coal-based pyrolytic carbon and concentrated nitric acid into a reaction kettle, stirring and refluxing for 3-5 hours at 85-110 ℃, centrifuging filtrate, taking the precipitate as a carbon quantum dot solution, and freeze-drying to obtain the carbon quantum dot for fluorescent labeling.
CN201811247616.3 discloses a method for preparing carbon quantum dots with good water solubility and high fluorescence intensity by using coal as a raw material through ferrate pre-oxidation and hydrogen peroxide step-by-step oxidation, and controlling the energy band of the carbon quantum dots by controlling reaction conditions.
CN201610939905.4 discloses a preparation method of carbon quantum dots based on coal tar pitch. Putting coal tar pitch into deionized water, performing ball milling and ultrasonic dispersion treatment to obtain carbon quantum dot dispersion, oxidizing by H2O2, centrifuging at high speed and drying in vacuum to obtain carbon quantum dot powder with average size of about 3nm, and realizing selective detection of HCHO.
The preparation method of the coal-based carbon dots disclosed in the patent uses strong acid and other substances, and can cause the problems of high corrosivity, high pollution, energy consumption, complex process and the like. When the hydrogen peroxide is used for oxidation, the product is water, no external pollution is introduced, but the hydrogen peroxide is decomposed more by itself during direct oxidation treatment, and the utilization rate of the oxidant is low. The hydrothermal synthesis method has simple process, the surface of the synthesized carbon quantum dot contains rich oxygen-containing functional groups, the water solubility is excellent, and the surface of the carbon quantum dot can be subjected to surface functional modification in the preparation process. The coal is subjected to hydrothermal treatment by using the hydrogen peroxide, and the advantages of two methods of hydrogen peroxide oxidation and hydrothermal synthesis can be combined, so that the reaction in a closed environment can inhibit the ineffective decomposition of the hydrogen peroxide from the chemical balance, the temperature of the hydrogen peroxide oxidation treatment is further increased, and the oxidation treatment capacity and the utilization efficiency of the hydrogen peroxide are improved.
In addition, the Fenton reagent formed by adding Fe ions into hydrogen peroxide has strong oxidizing property which is second to that of potassium permanganate, other pollutants are not generated after decomposition, ineffective decomposition of coal can be further inhibited after sealing treatment under the Fe ions and hydrothermal conditions, and the oxidation treatment capacity and the effective utilization rate of hydrogen peroxide are improved. However, the literature indicates that the fluorescence of the carbon quantum dots is inhibited by adding the Fe ions, so that how to balance the catalytic effect of the Fe ions and the relationship between the catalytic effect and the fluorescence quenching are very critical. In addition, the oxidizing 'cutting' capacity of the coal molecules by the hydrogen peroxide is also accurately regulated and controlled, so that the fluorescence of the carbon points is optimal.
Disclosure of Invention
The invention discloses a preparation method of a coal-based fluorescent carbon quantum dot, which is characterized by comprising the following steps of taking coal as a raw material, carrying out heat treatment at a certain temperature, carrying out hydrothermal treatment in the presence of a Fenton reagent, and filtering and dialyzing to obtain the fluorescent carbon quantum dot.
According to a preferred embodiment, wherein the coal is one or more of lignite, gas coal, fat coal or coking coal.
According to a preferred embodiment, wherein the heat treatment conditions are between room temperature and 900 ℃, preferably between room temperature and 650 ℃.
According to a preferred embodiment, the concentration of Fe ions in the Fenton reagent is 0.0025 to 0.1mol/L, preferably 0.005 to 0.025 mol/L.
According to a preferred embodiment, the ratio of iron: hydrogen peroxide: the ratio of coal (coke) is 1: 5: 1-1: 40: 4.
according to a preferred embodiment, the hydrothermal temperature is between room temperature and 150 ℃, preferably between 100 and 150 ℃.
According to a preferred embodiment, the hydrothermal treatment time is 0.2 to 24 hours, preferably 0.5 to 4 hours.
The method can effectively accelerate the oxidative decomposition of coal and inhibit the ineffective decomposition of hydrogen peroxide so as to improve the utilization efficiency of the coal, and more importantly, the hydrothermal oxidation method can simultaneously combine the double effects of the oxidative decomposition and the hydrothermal synthesis, so that the fluorescent carbon quantum dots with controllable structures and properties can be quickly and conveniently synthesized in one step. Although the literature indicates that the Fe ions can inhibit the generation of fluorescence under the conventional conditions, the invention still exerts the favorable catalytic action under the innovative process technology to effectively inhibit the disadvantages.
The fluorescent coal-based carbon quantum dots prepared by the method have wide raw material sources and easily adjustable light absorption and luminescence. Through screening the fluorescence intensity and wavelength, the carbon dot structure and the properties, the final part of the carbon dot solution shows very good effect of degrading organic pollutants through photocatalysis and very good biocompatibility.
Drawings
FIG. 1 shows the fluorescence spectrum of a part of the sample under 320nm UV light;
FIG. 2 TEM image of example 4 sample;
FIG. 3 shows the photocatalytic effect of the carbon dots obtained in example 2 and example 7 in the ultraviolet light to catalyze and degrade methylene blue;
FIG. 4 is a graph showing the cytotoxicity results of a part of the samples.
Detailed Description
The terms referred to in the present invention are all terms of general meaning in the art and are words of common usage in the art. The substances and reactions involved in the present invention are those which are commonly known in the art or which are commercially available, unless otherwise specified.
According to the characteristics of carbon core and surface group in the fluorescent carbon dots, the molecular structure of coal also has a macromolecular structure which takes condensed aromatic rings as cores and is connected by a bridge bond. The Fenton reagent is used for matching with hydroxyl free radicals generated by a hydrothermal method to selectively decompose and self-assemble macromolecules of coal according to different reactivities of aromatic ring C-C bonds and bridge bonds in the coal, so that the coal-based fluorescent carbon dots with high fluorescence intensity and adjustable particle size are obtained, and the coal-based fluorescent carbon dots can be used for biological labeling or fluorescent labeling of porous substance permeable pores. The preparation process is optimized by adjusting the proportion of Fe3+, H2O2 and the coal, and a new idea is provided for high-value utilization of the coal. The method is simple to operate, mild in condition, green and clean, and wide in application, and has good implementability.
The present inventors have completed the present invention through intensive studies based on the existing research bases relating to coal chemistry, coal chemical industry and catalysis. The method comprises the following steps:
a) preparing ferric chloride, ferric sulfate or ferric nitrate into aqueous solution with a certain concentration according to an optimized proportion;
b) carrying out heat treatment on lignite, fat coal, coking coal or anthracite for a period of time under an inert atmosphere at a certain temperature according to different reaction characteristics of the lignite, the fat coal, the coking coal or the anthracite;
c) adding a certain amount of iron ion solution into the sample to slowly pump a certain volume of hydrogen peroxide;
d) placing the mixed solution in a hydrothermal kettle, and carrying out hydrothermal treatment for a certain time in a drying oven at a certain temperature;
e) after the hydrothermal treatment, filtering the sample by using a microporous filter membrane at room temperature, dialyzing by using a dialysis bag with a certain molecular interception amount, and removing small molecular salts to obtain a fluorescent carbon dot solution with a certain size.
The method can effectively accelerate the oxidative decomposition of coal, inhibit the ineffective decomposition of hydrogen peroxide to improve the utilization efficiency of the coal, and more importantly, the hydrothermal oxidation method can simultaneously combine the double effects of the oxidative decomposition and the hydrothermal synthesis, so that the fluorescent carbon quantum dots with controllable structures and properties can be quickly and conveniently synthesized in one step. Although the literature indicates that the Fe ion can inhibit the generation of fluorescence under the conventional conditions, the invention still exerts the favorable catalytic action under the innovative process technology so as to effectively inhibit the disadvantages.
The fluorescent coal-based carbon quantum dots prepared by the method have wide raw material sources and easily adjustable light absorption and luminescence. Through screening the fluorescence intensity and wavelength, the carbon dot structure and the properties, the final part of the carbon dot solution shows very good effect of degrading organic pollutants through photocatalysis and very good biocompatibility.
Some embodiments of the invention process are as follows:
example 1: crushing lignite, sieving with a 100-mesh sieve, taking 2g of lignite powder, pumping 20ml of hydrogen peroxide at a speed of 1ml/min, mixing, placing a reaction kettle filled with a sample in an oven at 150 ℃ for reaction for 1 hour, cooling, performing suction filtration by using a 0.22-micron polytetrafluoroethylene filter membrane, and dialyzing by using a dialysis bag with the molecular weight cutoff of 1000Da (water is changed every 8 hours and is changed for 3 times) to obtain a light yellow transparent carbon dot aqueous solution. The carbon dot aqueous solution was measured without further treatment to have a fluorescence intensity of 693917 using a transient-steady state fluorescence spectrometer (Edinburgh FLS9800) with an excitation wavelength of 320 nm.
Example 2: crushing lignite, sieving with a 100-mesh sieve, taking 2g lignite powder, adding 1ml of 1g/L FeCl3 solution, pumping 20ml of hydrogen peroxide at the speed of 1ml/min, mixing, placing a reaction kettle containing a sample in a 150 ℃ oven for reacting for 1 hour, cooling, performing suction filtration by using a 0.22-micron polytetrafluoroethylene filter membrane, and dialyzing by using a dialysis bag with the molecular weight cutoff of 1000Da (changing water every 8 hours, changing for 3 times) to obtain a light yellow transparent carbon dot aqueous solution. The carbon dot aqueous solution was measured without further treatment to have a fluorescence intensity of 990502 using a transient-steady state fluorescence spectrometer (Edinburgh FLS9800) with an excitation wavelength of 320 nm.
Example 3: crushing lignite, sieving with a 100-mesh sieve, taking 2g lignite powder, adding 1ml of 1g/L FeCl3 solution, pumping 20ml of hydrogen peroxide at the speed of 1ml/min, mixing, placing a reaction kettle containing a sample in an oven at 150 ℃ for 2 hours, cooling, performing suction filtration by using a 0.22-micron polytetrafluoroethylene filter membrane, and dialyzing by using a dialysis bag with the molecular weight cutoff of 1000Da (water is changed every 8 hours, and the water is changed for 3 times) to obtain a light yellow transparent carbon dot aqueous solution. The carbon dot aqueous solution was measured without further treatment to have a fluorescence intensity of 1018392 using a transient-steady state fluorescence spectrometer (Edinburgh FLS9800) with an excitation wavelength of 320 nm.
Example 4: taking 2g of lignite powder, adding 1ml of 1g/L FeCl3 solution, pumping 20ml of hydrogen peroxide at the speed of 1ml/min, mixing, placing the reaction kettle containing the sample in a drying oven at 150 ℃ for 24 hours, cooling, performing suction filtration by using a 0.22 mu m polytetrafluoroethylene filter membrane, and dialyzing by using a dialysis bag with the molecular weight cutoff of 1000Da (changing water every 8 hours and changing for 3 times) to obtain a light yellow transparent carbon dot aqueous solution. The carbon dot solution was measured without further treatment for fluorescence intensity of 812704 using a transient-steady state fluorescence spectrometer (Edinburgh FLS9800) with an excitation wavelength of 320 nm.
Example 5: the brown coal is crushed and sieved by a 100-mesh sieve, 2g of brown coal powder is taken, 4ml of FeCl3 solution with the concentration of 1g/L is added, 20ml of hydrogen peroxide is pumped in at the speed of 1ml/min, the reaction kettle containing the sample is placed in an oven with the temperature of 150 ℃ for reaction for 1h after mixing, a polytetrafluoroethylene filter membrane with the diameter of 0.22 mu m is used for suction filtration after cooling, and dialysis is carried out by a dialysis bag with the cut-off molecular weight of 1000Da (water is changed every 8h for 3 times) to obtain the light yellow transparent carbon dot aqueous solution. The carbon dot aqueous solution was measured without further treatment to have a fluorescence intensity of 669229 using a transient-steady state fluorescence spectrometer (Edinburgh FLS9800) with an excitation wavelength of 320 nm.
Example 6: the lignite is crushed and sieved by a 100-mesh sieve, the lignite is pyrolyzed for 2 hours at 300 ℃ under the nitrogen atmosphere (the temperature rising speed is 5 ℃/min), 2g of lignite semi-coke powder is taken, 1ml of 1g/L FeCl3 solution is added, 20ml of hydrogen peroxide is pumped in at the speed of 1ml/min, the reaction kettle with the sample is placed in a 150 ℃ oven for reaction for 1 hour after mixing, the reaction kettle is filtered by a 0.22 mu m polytetrafluoroethylene filter membrane after cooling, and a light yellow transparent carbon dot aqueous solution is obtained after dialysis by a dialysis bag with the molecular weight cutoff of 1000Da (water is changed every 8 hours and 3 times). The carbon dot aqueous solution was measured without further treatment to have a fluorescence intensity of 1174379 using a transient-steady state fluorescence spectrometer (Edinburgh FLS9800) with an excitation wavelength of 320 nm.
Example 7: the lignite is crushed and sieved by a 100-mesh sieve, the lignite is pyrolyzed for 2 hours at 600 ℃ under the nitrogen atmosphere (the temperature rising speed is 5 ℃/min), 2g of lignite semi-coke powder is taken, 1ml of 1g/L FeCl3 solution is added, 20ml of hydrogen peroxide is pumped in at the speed of 1ml/min, the reaction kettle containing the sample is placed in a 150 ℃ oven to react for 1 hour after mixing, the reaction kettle is filtered by a 0.22 mu m polytetrafluoroethylene filter membrane after cooling, and a light yellow transparent carbon dot aqueous solution is obtained after dialysis by a dialysis bag with the molecular weight cutoff of 1000Da (water is changed every 8 hours and is changed for 3 times). The carbon dot aqueous solution was measured without further treatment to have a fluorescence intensity of 3594805 using a transient-steady state fluorescence spectrometer (Edinburgh FLS9800) with an excitation wavelength of 320 nm.
Example 8: the lignite is crushed and sieved by a 100-mesh sieve, the lignite is pyrolyzed for 2 hours at 900 ℃ under the nitrogen atmosphere (the temperature rising speed is 5 ℃/min), 2g of lignite semi-coke powder is taken, 1ml of 1g/L FeCl3 solution is added, 20ml of hydrogen peroxide is pumped in at the speed of 1ml/min, the reaction kettle with the sample is placed in a 150 ℃ oven to react for 1 hour after mixing, the reaction kettle is filtered by a 0.22 mu m polytetrafluoroethylene filter membrane after cooling, and dialyzed by a dialysis bag with the molecular weight cutoff of 1000Da (water is changed every 8 hours and water is changed for 3 times) to obtain an aqueous solution, and almost no fluorescence exists under an ultraviolet lamp.
Example 9: crushing fat coal, sieving with a 100-mesh sieve, pyrolyzing at 300 ℃ for 2h (the temperature rising speed is 5 ℃/min) in a nitrogen atmosphere, taking 2g of lignite semicoke powder, adding 1ml of 1g/L FeCl3 solution, pumping 20ml of hydrogen peroxide at the speed of 1ml/min, mixing, placing a reaction kettle containing a sample in a 150 ℃ oven for reaction for 1h, cooling, performing suction filtration by using a 0.22 mu m polytetrafluoroethylene filter membrane, and dialyzing by using a dialysis bag with the molecular weight cutoff of 1000Da (changing water every 8h for 3 times) to obtain a light yellow transparent carbon dot water solution. The carbon dot aqueous solution was measured without further treatment to have a fluorescence intensity of 1174936 using a transient-steady state fluorescence spectrometer (Edinburgh FLS9800) with an excitation wavelength of 320 nm.
Example 10: the method comprises the following steps of crushing coke coal, sieving the crushed coke coal with a 100-mesh sieve, pyrolyzing the crushed coke coal at 300 ℃ for 2 hours (the temperature rising speed is 5 ℃/min) in a nitrogen atmosphere, taking 2g of lignite semicoke powder, adding 1ml of 1g/L FeCl3 solution, pumping 20ml of hydrogen peroxide at the speed of 1ml/min, mixing, placing a reaction kettle containing a sample in a 150-DEG C oven for reaction for 1 hour, cooling, performing suction filtration by using a 0.22-mu m polytetrafluoroethylene filter membrane, and dialyzing by using a dialysis bag with the molecular weight cutoff of 1000Da (changing water every 8 hours and changing for 3 times) to obtain a transparent carbon dot water solution. The carbon dot solution was measured without further treatment for fluorescence intensity of 665294 using a transient-steady state fluorescence spectrometer (Edinburgh FLS9800) with an excitation wavelength of 320 nm.
Example 11: the anthracite is crushed and sieved by a 100-mesh sieve, the powder is pyrolyzed for 2h at 300 ℃ under the nitrogen atmosphere (the temperature rising speed is 5 ℃/min), 2g of lignite semicoke powder is taken, 1ml of 1g/L FeCl3 solution is added, 20ml of hydrogen peroxide is pumped in at the speed of 1ml/min, the mixture is mixed, a reaction kettle containing a sample is placed in a 150 ℃ oven for reaction for 1h, the reaction kettle is cooled and filtered by a 0.22 mu m polytetrafluoroethylene filter membrane, and dialysis is carried out by a dialysis bag with the molecular weight cutoff of 1000Da (water is changed every 8h and is changed for 3 times) to obtain a transparent carbon dot water solution. The carbon dot solution was measured without further treatment for fluorescence intensity of 1443560 using a transient-steady state fluorescence spectrometer (Edinburgh FLS9800) with an excitation wavelength of 320 nm.
The fluorescence spectrum of some of the example samples under 320nm UV is shown in FIG. 1. Examples 2, 3, 7, and 11, in which the emission wavelength was around 430nm, had blue-violet fluorescence under the ultraviolet light, examples 1, 5, and 9, in which the emission wavelength was around 450nm, and examples 6, in which the emission wavelength was around 460nm, had blue-green fluorescence under the ultraviolet light.
The TEM image of the sample of example 4 is shown in fig. 2, in which the carbon dot particles are small spheres of about 5 to 10nm, and the lattice fringes of different orientations are visible after amplification, and it can be judged that the carbon dot particles are formed by aggregation of a plurality of smaller nano carbon crystals.
FIG. 3 is a graph showing the photocatalytic effect of the carbon dots obtained in examples 2 and 7 in the ultraviolet light for catalyzing and degrading methylene blue, and the degradation rate can reach 50% within 3.2 h.
The cytotoxicity results of a portion of the samples are shown in figure 4. It can be seen that the results of cytotoxicity show low toxicity of the fluorescent quantum dots.
The specific examples given in this detailed description of the invention are intended to be illustrative of the invention and are not intended to be limiting.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (8)
1. A preparation method of a coal-based fluorescent carbon quantum dot is characterized by comprising the following steps of taking coal as a raw material, carrying out thermal treatment at a certain temperature, carrying out hydrothermal treatment in the presence of a Fenton reagent, and filtering and dialyzing to obtain the fluorescent carbon quantum dot;
wherein the Fenton reagent is formed by adding Fe ions into hydrogen peroxide;
the concentration of Fe ions in the Fenton reagent is 0.0025-0.1 mol/L;
the Fe: hydrogen peroxide: the coal proportion is 1: 5: 1-1: 40: 4.
2. the method of claim 1, wherein the coal is one or more of lignite, gas coal, fat coal, or coking coal.
3. The method of claim 1, wherein the heat treatment conditions are room temperature to 900 ℃.
4. The method of claim 1, wherein the heat treatment conditions are room temperature to 650 ℃.
5. The method according to claim 1, wherein the concentration of Fe ions in the Fenton reagent is 0.005-0.025 mol/L.
6. The method according to claim 1, wherein the hydrothermal temperature is 100 to 150 ℃.
7. The method according to claim 1, wherein the hydrothermal treatment time is 0.2 to 24 hours.
8. The method according to claim 1, wherein the hydrothermal treatment time is 0.5 to 4 hours.
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