CN111117607A - Preparation method and application of graphene quantum dots with blue fluorescence characteristics - Google Patents

Preparation method and application of graphene quantum dots with blue fluorescence characteristics Download PDF

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CN111117607A
CN111117607A CN201911218623.5A CN201911218623A CN111117607A CN 111117607 A CN111117607 A CN 111117607A CN 201911218623 A CN201911218623 A CN 201911218623A CN 111117607 A CN111117607 A CN 111117607A
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graphene quantum
gqds
quantum dots
blue fluorescence
preparation
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计亚军
邓亚磊
陈飞
任富勇
王兆琦
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University of Shanghai for Science and Technology
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    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching

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Abstract

The invention provides a preparation method and application of graphene quantum dots with blue fluorescence characteristics, wherein the method comprises the following steps: dispersing residual starch in the sweet potato residue in water to form a suspension; transferring the suspension into a reaction kettle to hydrolyze starch to obtain glucose, maltose and aldehydes; glucose is hydrolyzed under hydrothermal conditions to give C ═ C bonds, and under hydrothermal conditions to give GQDs. The invention has the advantages that: the preparation method is simple in preparation process, low in cost and environment-friendly, and has great potential in the aspect of large-scale preparation of the graphene quantum dots. Prepared graphene quantum dot toolHas blue fluorescence characteristics and good hydrophilicity, and is suitable for Hg in aqueous solution2+Selective quenching can occur. Is expected to be applied in the fields of biological imaging, optical sensing, energy storage conversion and the like.

Description

Preparation method and application of graphene quantum dots with blue fluorescence characteristics
Technical Field
The invention relates to the technical field of heavy metal ion detection, in particular to a preparation method and application of graphene quantum dots with blue fluorescence characteristics.
Background
GQDs, a typical 0D material, attracts great interest of broad scholars due to their outstanding boundary effect and quantum confinement effect. At present, the method is widely applied to the fields of biological imaging, optical sensing, energy storage and conversion and the like.
The current mature preparation method is mainly a top-down method, and generally takes graphene, carbon nanotubes, carbon fibers and the like as raw materials. However, these raw materials have the disadvantages of long synthesis period and harsh synthesis conditions (strong acid and strong oxidant) during the preparation process, resulting in high raw material cost. In addition, the adoption of the raw materials still needs to add strong acid during the synthesis of GQDs, which means that the method causes secondary pollution to the environment. The disadvantages of high cost and high contamination make GQDs difficult to manufacture in large quantities. In contrast, there is an advantage in that the bottom-up method, in which glucose, citric acid, starch, and the like can be used as raw materials, is used. The raw materials have the characteristics of nature, reproducibility, low price and the like, and the GQDs synthesized by taking the raw materials as the raw materials have the advantages of small demand for strong acid, easy adjustment of the size of the GQDs and the like, and are one of the hot spots of the current research.
Therefore, how to develop a green synthesis technology for preparing GQDs in large scale by using biomass has extremely important practical value.
Disclosure of Invention
The invention aims to provide a preparation method and application of graphene quantum dots with blue fluorescence characteristics, sweet potato residues are used as raw materials, the preparation method of GQDs has the advantages of simple process, low cost and environmental friendliness, and the obtained GQDs are used for Hg2+Has selective detection function.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a green preparation method for preparing graphene quantum dots with blue fluorescence characteristics comprises the following steps:
dispersing residual starch in the sweet potato residue in water to form a suspension;
transferring the suspension into a reaction kettle to hydrolyze starch to obtain glucose, maltose and aldehydes;
glucose is hydrolyzed under hydrothermal conditions to give C ═ C bonds, and under hydrothermal conditions to give GQDs.
Further, the sweet potato residue is dispersed in deionized water in a powder form and stirred to obtain a suspension.
Further, the mixture of the sweet potato residue and the deionized water is heated to 60 ℃ and then is magnetically stirred for 14min to obtain a suspension.
Further, the reaction kettle is a Teflon reaction kettle with a stainless steel shell.
Further, the temperature for carrying out the reaction in the reaction kettle is 200 ℃, and the reaction time is 12 hours.
Further, the reactant obtained under the hydrothermal method condition is separated by a centrifugal mode to obtain supernatant containing GQDs.
A graphene quantum dot prepared by the green preparation method described above.
The application of GQDs prepared by the aforementioned green preparation method in the field of heavy metal ion detection in water.
Compared with the prior art, the invention has the advantages that: the preparation method is simple in preparation process, low in cost and environment-friendly, and has great potential in the aspect of large-scale preparation of the graphene quantum dots.
The graphene quantum dot prepared by the method has blue fluorescence characteristics and good hydrophilicity, and can be used for treating Hg in an aqueous solution2+Selective quenching can occur. Is expected to be applied in the fields of biological imaging, optical sensing, energy storage conversion and the like.
Drawings
FIG. 1 is an HRTEM image and a crystal diffraction pattern of GQDs in example 1, wherein (a) a high-power transmission electron micrograph of the GQDs is shown with an inset of their size distribution; (b) the crystal spacing of the GQDs under a high power electron microscope corresponds to the crystal diffraction patterns in the insets, the crystal spacing is 0.238nm and 0.333nm, and respectively corresponds to the 100 crystal face and the 002 crystal face of the graphite type carbon, which indicates that the GQDs can be successfully prepared according to the method.
FIG. 2 is a Fourier transform infrared spectrum of GQDs in example 1.
FIG. 3 is a UV-Vis spectrum of GQDs in example 1.
FIG. 4 is the fluorescence spectrum of GQDs in example 1 excited by different wavelengths in the visible region.
FIG. 5 is a graph showing the recognition performance of GQDs for heavy metal ions in example 2.
FIG. 6 shows the addition of different concentrations of Hg in example 22+Fluorescence spectra of post-GQDs.
FIG. 7 is a plot of fluorescence quenching efficiency of GQDs versus mercury ion concentration as fitted to example 2.
FIG. 8 shows the primary fluorescence of GQDs and the fluorescence when Hg in example 22+Digital photo contrast graph of complete quenching of GQDs fluorescence when the concentration reaches a certain amount.
Detailed Description
The technical solution adopted by the present invention will be further explained with reference to the schematic drawings.
Example 1: preparation of GQDs
2g of the sweet potato residue powder was first weighed and dispersed in 50mL of deionized water, heated to 60 ℃ and magnetically stirred for 15min, and then the resulting suspension was transferred to a Teflon reaction kettle with a stainless steel shell and reacted at 200 ℃ for 12 hours. Finally, the resulting brown solution was centrifuged to obtain a supernatant containing GQDs.
HRTEM analysis of example 1 (combined with fig. 1): the size of the obtained GQDs is less than 5nm, the crystal spacing is 0.238nm and 0.333nm, and the obtained GQDs respectively correspond to 100 crystal faces and 002 crystal faces of the graphite type carbon, which indicates that the GQDs can be successfully prepared according to the method.
FT-IR analysis of example 1: from FIG. 2, it is found that the peak value is 1656cm-1And 1415cm-1The two characteristic peaks in (a) correspond to the stretching vibration of C ═ C, which is consistent with the results of HRTEM. And at 1328cm-1And 2906cm-1The two absorption peak positions of (A) correspond to those of C-HStretching vibration, C-O vibration at 1073cm-1Has response at 3411cm-1The absorption peaks at (A) are then due to O-H and N-H stretching vibrations. The presence of oxygen-containing functional groups and amino groups will increase the hydrophilicity of the material and thus enable it to be well dispersed in water.
FIG. 3 is a UV-VISIBLE spectrogram of GQDs; FIG. 4 shows the fluorescence spectrum of GQDs excited by different wavelengths in the visible region.
UV-vis analysis of example 1, the weak peak at 226nm is due to п → п of C ═ C bonds, and the strong peak at 286nm is associated with C ═ O bonds n → п.
PL analysis of example 1: as the excitation wavelength increased from 340nm to 540nm, the emission peak was red-shifted from 441nm to 546nm, with the excitation wavelength corresponding to the strongest fluorescence peak being 440 nm. This phenomenon is related to the surface state of the material.
Example 2: detection research of GQDs on heavy metal ions in aqueous solution
Configuration 2.5 × 10-4mol·L-1And (2) adding a certain amount of metal ion solution into 10mL of GQDs (gallium-zinc-selenium-doped cadmium-doped cobalt-doped chromium-doped mercury-doped potassium) solution, and measuring the fluorescence intensity of the GQDs before and after the addition of the metal ions under the excitation wavelength of 440nm and the slit width of 2.5 nm.
Configurations 0.75, 1.0, 1.5, 2.0, 2.5 × 10-4mol·L-1Hg of2+Aqueous solution, taking out quantitative volume of Hg2+The solution was added to 10mL GQDs solution, and the addition of different volumes of Hg was measured at 440nm excitation wavelength and 2.5nm slit width2+Change in fluorescence intensity of post-GQDs solutions. To get a more intuitive and in-depth understanding of the detection effect, the fluorescence quenching efficiency and the corresponding Hg were plotted2+Concentration dependence graph.
Analysis of recognition performance of GQDs for heavy metal ions (see FIG. 5): hg is a mercury vapor2+Can obviously quench the fluorescence of the GQDs. In contrast, the influence of other metal ions on the fluorescence intensity of GQDs is not obvious, which indicates that the GQDs prepared by the method have no obvious effect on Hg in water body2+Has selective detection effect.
Adding Hg with different concentrations2+Fluorescence spectrogram analysis of post-GQDs (see fig. 6): when different concentrations of Hg are used2+After being added to the GQDs solution, the fluorescence intensity gradually decreases.
Fluorescence quenching efficiency of GQDs and Hg2+Fitted curve analysis of concentration (see fig. 7): quenching efficiency in a certain range ((F)0-F)/F0) And Hg2+Exhibits a good linear relationship (R)20.986), which shows that the GQDs prepared by the method can quantify the heavy metal Hg in the water body within a certain range2+The concentration of (c).
Primary fluorescence of GQDs and Hg when2+Digital photo-contrast analysis of complete quenching of the fluorescence of GQDs at concentrations up to certain amounts (see fig. 8): heavy metal Hg2+Can completely quench the fluorescence of the GQDs, which shows that the GQDs prepared by the method are applied to Hg in water2+The detection aspect has important value.
The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any way. It will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

1. A green preparation method for preparing graphene quantum dots with blue fluorescence characteristics is characterized by comprising the following steps:
dispersing residual starch in the sweet potato residue in water to form a suspension;
transferring the suspension into a reaction kettle to hydrolyze starch to obtain glucose, maltose and aldehydes;
glucose is hydrolyzed under hydrothermal conditions to give C ═ C bonds, and under hydrothermal conditions to give GQDs.
2. The green preparation method of graphene quantum dots with blue fluorescence characteristics according to claim 1, wherein the sweet potato residue is dispersed in deionized water in a powder form and stirred to obtain a suspension.
3. The green preparation method of graphene quantum dots with blue fluorescence characteristics according to claim 2, wherein the mixture of sweet potato residue and deionized water is heated to 60 ℃ and then magnetically stirred for 14min to obtain a suspension.
4. The green preparation method of graphene quantum dots with blue fluorescence characteristics according to claim 1, wherein the reaction kettle is a teflon reaction kettle with a stainless steel shell.
5. The green preparation method of graphene quantum dots with blue fluorescence characteristics according to claim 4, wherein the reaction temperature in the reaction kettle is 200 ℃ and the reaction time is 12 hours.
6. The green preparation method for preparing the graphene quantum dots with the blue fluorescence characteristic according to claim 1, wherein the reactant obtained under the hydrothermal method condition is separated by a centrifugal method to obtain a supernatant containing GQDs.
7. A graphene quantum dot prepared by the green preparation method of any one of claims 1 to 6.
8. The use of GQDs obtained by the green preparation method according to any one of claims 1 to 6 in the field of heavy metal ion detection in water.
CN201911218623.5A 2019-12-03 2019-12-03 Preparation method and application of graphene quantum dots with blue fluorescence characteristics Pending CN111117607A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112794297A (en) * 2021-01-08 2021-05-14 上海理工大学 Synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108455581A (en) * 2018-04-04 2018-08-28 三峡大学 Prepare the green synthesis method of graphene and graphene quantum dot simultaneously using starch

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108455581A (en) * 2018-04-04 2018-08-28 三峡大学 Prepare the green synthesis method of graphene and graphene quantum dot simultaneously using starch

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LU WENBO: "Green synthesis of carbon nanodots as an effective fluorescent probe for sensitive and selective detection of mercury(II) ions", 《JOURNAL OF NANOPARTICLE RESEARCH》 *
SHEN JIE: "Facile synthesis of fluorescence carbon dots from sweet potato for Fe3+ sensing and cell imaging", 《MATERIALS SCIENCE AND ENGINEERING C》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112794297A (en) * 2021-01-08 2021-05-14 上海理工大学 Synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics

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Application publication date: 20200508