CN111925793A - Preparation method of nitrogen and sulfur co-doped carbon quantum dots - Google Patents

Preparation method of nitrogen and sulfur co-doped carbon quantum dots Download PDF

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CN111925793A
CN111925793A CN202010931393.3A CN202010931393A CN111925793A CN 111925793 A CN111925793 A CN 111925793A CN 202010931393 A CN202010931393 A CN 202010931393A CN 111925793 A CN111925793 A CN 111925793A
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coal
nitrogen
sulfur
carbon quantum
quantum dots
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CN111925793B (en
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姜维佳
王玉高
薄纯辉
卫艳丽
申峻
董川
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Taiyuan University of Technology
Shanxi University
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Shanxi University
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    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract

The invention belongs to the field of carbon nano materials, and relates to a preparation method of nitrogen and sulfur co-doped carbon quantum dots. The method comprises the steps of preparing coal powder and a water solution containing chloride ions into water-coal-slurry, adding a nitrogen-sulfur dopant into the water-coal-slurry, electrifying, and carrying out electrolytic oxidation to obtain the nonmetal element co-doped solid carbon quantum dots. The invention uses cheap and easily available coal as a carbon source, uses water-coal-slurry as electrolyte, combines the synthesis of the carbon quantum dots and the non-metal doping into one step, has simple production process, is not only favorable for expanding the novel utilization mode of the coal, but also is suitable for large-scale production and application.

Description

Preparation method of nitrogen and sulfur co-doped carbon quantum dots
Technical Field
The invention belongs to the technical field of carbon nano materials, and particularly relates to a preparation method of nitrogen and sulfur co-doped carbon quantum dots.
Background
The carbon quantum dots are a novel carbon nano material, and compared with the traditional nano material, the carbon quantum dots not only have good small-size characteristics, excellent optical performance and easy surface functionalization, but also keep the characteristics of low toxicity and good biocompatibility of the carbon material. Heterogeneous element doping has been used to tune the fluorescent properties and is considered to be the best approach to efficiently produce high performance carbon quantum dots, and is mostly dominated by non-metallic element doping.
China has abundant coal reserves, but is mainly used as fuel, not only causes serious environmental pollution, but also wastes the valuable fossil resources. The coal is rich in a macromolecular structure formed by condensed aromatic rings, and the component is easy to generate carbon quantum dots under the action of an oxidant, so that the expansion of non-fuel utilization of the coal is facilitated, and high-value utilization of the coal is realized. The electrochemical oxidation method is an ideal means for preparing the carbon nano material, and has the outstanding characteristics of easy control of the preparation process and mild reaction conditions. However, in the conventional electrochemical oxidation, a carbon source is often used as an electrode material, which is not favorable for the scale-up of the preparation of the carbon nano-material.
Disclosure of Invention
The invention aims to provide a preparation method of nitrogen and sulfur co-doped carbon quantum dots. The invention has the technical conception that coal is used as a carbon source, coal powder is prepared into coal water slurry by using a water solution containing chloride ions, and the coal water slurry is added with a nitrogen and sulfur source dopant to carry out electrochemical oxidation reaction to prepare the nitrogen and sulfur co-doped carbon quantum dots.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a nonmetal element co-doped carbon quantum dot comprises the following steps: 1) selecting coal as a raw material, crushing the coal to be more than 100 meshes, and then uniformly dispersing the raw material in an aqueous solution containing chloride ions by stirring to prepare coal water slurry; 2) adding a proper amount of nitrogen-sulfur dopant into the coal water slurry obtained in the step 1) by taking graphite or titanium coated with ruthenium oxide as an anode and graphite or a nickel net as a cathode, uniformly stirring, and electrifying for electrolytic oxidation; 3) after the reaction is finished, centrifuging the mixture obtained in the step 2) at a high speed, filtering unreacted residues, filling the obtained filtrate into a dialysis bag with the molecular weight cutoff of 3500Da, dialyzing for 3 days, and changing water at intervals of 12 h; 4) concentrating the solution dialyzed in the step 3) through reduced pressure distillation, and then freeze-drying to obtain the solid nitrogen and sulfur co-doped carbon quantum dots.
In a preferred technical scheme, the aqueous solution containing chloride ions can be seawater or industrial wastewater containing chloride ions.
Further accessory technical features are as follows.
The molar concentration of the chloride ions in the aqueous solution containing the chloride ions is 0.1mol/L to 2 mol/L.
In the coal water slurry, the mass concentration of the coal dust is preferably 2g/L to 30 g/L.
The selected nitrogen-sulfur dopant is preferably thiourea, and after the nitrogen-sulfur dopant is added, the concentration of the nitrogen-sulfur dopant in the mixed solution is 0.1-1 mol/L.
In the electrolytic oxidation reaction, the current density is preferably 0.1A/cm2To 1A/cm2The electrolysis time is 0.5h to 10 h.
In the technical scheme, the raw material coal is any one of lignite, subbituminous coal, bituminous coal and anthracite, and is crushed into more than 100 meshes before use.
The invention has the advantages that the raw material coal is relatively cheap and easily available, and the coal reacts in the solution instead of being used as an electrode, thereby having the advantage of easy production scale enlargement. In addition, the synthesis of the carbon quantum dots and the non-metal doping are combined into one step, so that the production process is simplified, and the production cost is effectively reduced.
Drawings
Fig. 1 is a transmission electron microscope image and a particle size distribution diagram of a nitrogen and sulfur co-doped carbon quantum dot prepared in example 1 of the present invention, in which (a) a transmission electron microscope image of a carbon quantum dot prepared using coal as a carbon source; (b) the particle size distribution histogram of the carbon quantum dots.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
(1) Selecting Zhaotong lignite as a raw material, crushing the Zhaotong lignite to be more than 100 meshes, weighing 0.2g of coal powder, and uniformly dispersing the coal powder in 0.1L of aqueous solution with the chloride ion concentration of 1.7mol/L by stirring to prepare the coal water slurry with the concentration of 2 g/L.
(2) Titanium coated with ruthenium oxide is taken as an anode, a nickel net is taken as a cathode, 0.1mol of thiourea is added into the coal water slurry prepared in the step (1), and the current density is 0.5A/cm2And (3) electrifying the coal water slurry obtained in the step (1) for electrolytic oxidation for 1.5 h.
(3) After the reaction is finished, centrifuging the mixture obtained in the step (2) at a high speed, filtering unreacted residues, filling the obtained filtrate into a dialysis bag with the molecular weight cutoff of 3500Da, dialyzing for 3 days, and changing water at intervals of 12 h;
(4) the solution in the dialysis bag is concentrated by reduced pressure distillation, and then the sulfur and nitrogen co-doped solid carbon quantum dots can be obtained by freeze drying, wherein the quantum yield of the carbon quantum dots is 1.6%.
Fig. 1 is a transmission electron microscope image and a particle size distribution diagram of the nitrogen and sulfur co-doped carbon quantum dot prepared in example 1. As is obvious from FIG. 1, the particle size of the nitrogen and sulfur co-doped carbon quantum dot prepared by the method is 0.5-3 nm.
Table 1 shows XPS test results of the nitrogen and sulfur co-doped carbon quantum dots prepared by the method of the present invention, and it can be seen from the data in table 1 that in the elements on the surface of the nitrogen and sulfur co-doped carbon quantum dots prepared by the method of the present invention, the N element is 6.29%, and the S element is 5.40%; table 2 shows XPS test results of carbon quantum dots prepared without adding a dopant during the preparation of carbon quantum dots under the same conditions, and comparing the data in tables 1 and 2, it is obvious that N, S element in thiourea is well doped on the surface of the carbon quantum dots by the preparation method of the present invention.
Table 1 XPS test data of nitrogen and sulfur co-doped carbon quantum dots
Figure BDA0002670359730000041
Table 2 XPS test data for undoped carbon quantum dots
Figure BDA0002670359730000042
Example 2
(1) Selecting Yining bituminous coal as a raw material, crushing the raw material to more than 100 meshes, weighing 3g of coal powder, and uniformly dispersing the coal powder in 0.1L of water solution with the concentration of 0.1mol/L by stirring to prepare the coal water slurry with the concentration of 30 g/L.
(2) Adding 1mol of thiourea into the coal water slurry prepared in the step (1) by taking titanium coated with ruthenium oxide as an anode and a nickel net as a cathode, and controlling the current density to be 1A/cm2And (3) electrifying the coal water slurry obtained in the step (1) for electrolytic oxidation for 0.5 h.
(3) After the reaction is finished, centrifuging the mixture obtained in the step (2) at a high speed, filtering unreacted residues, filling the obtained filtrate into a dialysis bag with the molecular weight cutoff of 3500Da, dialyzing for 3 days, and changing water at intervals of 12 h;
(4) and concentrating the solution in the dialysis bag through reduced pressure distillation, and then freeze-drying to obtain the sulfur-nitrogen co-doped solid carbon quantum dots, wherein the quantum yield of the carbon quantum dots is 1.5%.
Example 3
(1) The method comprises the steps of selecting Luliang bituminous coal as a raw material, crushing the raw material into more than 100 meshes, weighing 1g of coal powder, and uniformly dispersing the coal powder into 0.1L of aqueous solution with the chloride ion concentration of 0.5mol/L by stirring to prepare the coal water slurry with the concentration of 10 g/L.
(2) Adding 0.3mol of thiourea into the coal water slurry prepared in the step (1) by taking titanium coated with ruthenium oxide as an anode and a nickel net as a cathode, wherein the current density is 0.1A/cm2And (3) electrifying the coal water slurry obtained in the step (1) for electrolytic oxidation for 3.0 h.
(3) After the reaction is finished, centrifuging the mixture obtained in the step (2) at a high speed, filtering unreacted residues, filling the obtained filtrate into a dialysis bag with the molecular weight cutoff of 3500Da, dialyzing for 3 days, and changing water at intervals of 12 h;
(4) the solution in the dialysis bag is concentrated by reduced pressure distillation, and then the nitrogen and sulfur co-doped solid carbon quantum dots can be obtained by freeze drying, wherein the quantum yield of the carbon quantum dots is 1.35%.
Example 4
(1) Selecting Jincheng anthracite as a raw material, crushing the anthracite into more than 100 meshes, weighing 1g of coal powder, and uniformly dispersing the coal powder into 0.1L of aqueous solution with 1mol/L of chloride ion concentration to prepare the coal water slurry with 10g/L of chloride ion concentration.
(2) Respectively taking graphite sheets as anode and cathode materials, adding 0.8mol of thiourea into the coal water slurry prepared in the step (1) to ensure that the current density is 1.0A/cm2And (3) electrifying the coal water slurry obtained in the step (1) for electrolytic oxidation for 10 h.
(3) After the reaction is finished, centrifuging the mixture obtained in the step (2) at a high speed, filtering unreacted residues, filling the obtained filtrate into a dialysis bag with the molecular weight cutoff of 3500Da, dialyzing for 3 days, and changing water at intervals of 12 h;
(4) the solution in the dialysis bag is concentrated by reduced pressure distillation, and then the nitrogen and sulfur co-doped solid carbon quantum dots can be obtained by freeze drying, wherein the quantum yield of the carbon quantum dots is 1.45%.

Claims (7)

1. A preparation method of nitrogen and sulfur co-doped carbon quantum dots is characterized in that coal powder and an aqueous solution containing a certain amount of chloride ions are prepared into water-coal-slurry, graphite or titanium coated with ruthenium oxide is used as an anode, graphite or a nickel net is used as a cathode, and the water-coal-slurry is added with a proper amount of nitrogen and sulfur doping agent and then is electrified for electrolysis; and after the reaction is finished, performing high-speed centrifugal separation on the obtained mixture, filtering supernatant obtained by centrifugal separation, filling the obtained filtrate into a dialysis bag with the molecular weight cutoff of 3500Da, dialyzing for 3 days, changing water every 12h, concentrating the solution in the dialysis bag by reduced pressure distillation, and then freeze-drying to obtain the solid nitrogen and sulfur co-doped carbon quantum dots.
2. The preparation method of the nitrogen and sulfur co-doped carbon quantum dot according to claim 1, wherein the raw materials for preparing the coal water slurry are coal and the aqueous solution containing the chloride ions, and the coal water slurry is prepared by crushing the coal into coal powder and then uniformly dispersing the coal powder in the aqueous solution containing the chloride ions.
3. The method for preparing nitrogen and sulfur co-doped carbon quantum dots according to claim 2, wherein the molar concentration of chloride ions in the aqueous solution containing chloride ions is 0.1mol/L to 2 mol/L.
4. The method for preparing the carbon quantum dot according to claim 1, wherein the concentration of the pulverized coal in the coal water slurry is 2g/L to 30 g/L.
5. The preparation method of the nitrogen and sulfur co-doped carbon quantum dot according to claim 1, wherein the nitrogen and sulfur dopant is thiourea, and after the nitrogen and sulfur dopant is added, the concentration of the nitrogen and sulfur dopant in the mixed solution is 0.1-1 mol/L.
6. The preparation method of the nitrogen and sulfur co-doped carbon quantum dot as claimed in claim 1, wherein the current density is 0.1A/cm in the electrolytic oxidation reaction process2To 1A/cm2The electrolysis time is 0.5h to 10 h.
7. The method for preparing nitrogen and sulfur co-doped carbon quantum dots according to any one of the preceding claims, wherein the raw material coal of the coal water slurry is any one of lignite, subbituminous coal, bituminous coal and anthracite, and the raw material coal is pulverized to be more than 100 meshes before use.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104028291A (en) * 2014-06-12 2014-09-10 大连理工大学 Nitrogen-doped fluorescent carbon-dot and carbon-dot graphene composite as well as production method and application thereof
CN104449693A (en) * 2014-11-12 2015-03-25 南昌大学 Method for preparing nitrogen and sulfur-doped fluorescent carbon quantum dots
CN107384394A (en) * 2017-07-26 2017-11-24 广西师范学院 The preparation method of water-soluble nitrogen sulphur phosphor codoping carbon quantum dot
CN107955601A (en) * 2017-11-13 2018-04-24 东华大学 Iron ion detection nitrogen sulphur codope carbon quantum dot and preparation method thereof
CN110217792A (en) * 2019-06-06 2019-09-10 中山大学 A kind of multi-stage porous Carbon Materials of nitrogen sulfur doping and its preparation method and application
CN111573653A (en) * 2020-05-19 2020-08-25 山西大学 Nitrogen-sulfur self-doped fluorescent carbon quantum dot and preparation method and application thereof
CN112095113A (en) * 2020-09-07 2020-12-18 太原理工大学 Method for preparing carbon quantum dots by taking coal as raw material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104028291A (en) * 2014-06-12 2014-09-10 大连理工大学 Nitrogen-doped fluorescent carbon-dot and carbon-dot graphene composite as well as production method and application thereof
CN104449693A (en) * 2014-11-12 2015-03-25 南昌大学 Method for preparing nitrogen and sulfur-doped fluorescent carbon quantum dots
CN107384394A (en) * 2017-07-26 2017-11-24 广西师范学院 The preparation method of water-soluble nitrogen sulphur phosphor codoping carbon quantum dot
CN107955601A (en) * 2017-11-13 2018-04-24 东华大学 Iron ion detection nitrogen sulphur codope carbon quantum dot and preparation method thereof
CN110217792A (en) * 2019-06-06 2019-09-10 中山大学 A kind of multi-stage porous Carbon Materials of nitrogen sulfur doping and its preparation method and application
CN111573653A (en) * 2020-05-19 2020-08-25 山西大学 Nitrogen-sulfur self-doped fluorescent carbon quantum dot and preparation method and application thereof
CN112095113A (en) * 2020-09-07 2020-12-18 太原理工大学 Method for preparing carbon quantum dots by taking coal as raw material

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