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WO2022025517A1 - Points quantiques de carbone spécifiques de forme susceptibles de présenter une émission de fluorescence multicouleur et leur procédé de fabrication - Google Patents

Points quantiques de carbone spécifiques de forme susceptibles de présenter une émission de fluorescence multicouleur et leur procédé de fabrication Download PDF

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Publication number
WO2022025517A1
WO2022025517A1 PCT/KR2021/009413 KR2021009413W WO2022025517A1 WO 2022025517 A1 WO2022025517 A1 WO 2022025517A1 KR 2021009413 W KR2021009413 W KR 2021009413W WO 2022025517 A1 WO2022025517 A1 WO 2022025517A1
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Prior art keywords
carbon quantum
quantum dots
quantum dot
shape
phloroglucinol
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English (en)
Korean (ko)
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김종성
무하마드모니루자만
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Industry Academic Cooperation Foundation of Gachon University
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Industry Academic Cooperation Foundation of Gachon University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/001—Controlling catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
    • B82B3/0038—Manufacturing processes for forming specific nanostructures not provided for in groups B82B3/0014 - B82B3/0033
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to a shape-specific carbon quantum dot capable of emitting multicolor fluorescence and a method for manufacturing the same, and more particularly, to a multicolor fluorescence emission capable of controlling the shape, size, and fluorescence color of the carbon quantum dot through a reaction time and a solvent. It relates to a shape-specific carbon quantum dot and a method for manufacturing the same.
  • Carbon quantum dots are carbon particles with a size of several nm.
  • Carbon quantum dots are an amorphous carbon-type nanostructure, and are a completely new type of material that is distinguished from nanodiamonds, which are diamond-shaped nanostructures, and graphene, nanotubes, and fullerenes, which are graphite-type nanostructures.
  • nanodiamonds which are diamond-shaped nanostructures
  • graphene, nanotubes, and fullerenes which are graphite-type nanostructures.
  • carbon quantum dots are attracting attention as candidates to complement the shortcomings of existing quantum dots because they not only use cheap and safe materials, but also have biocompatibility and stability.
  • Carbon quantum dots have been manufactured for the purpose of bio-imaging, photocatalysts, and detection of biomaterials or specific compounds. Carbon quantum dots have low toxicity and biocompatibility.
  • Korean Registration No. 10-1403534 discloses a method for preparing carbon quantum dots by heating an organic compound, an organic solvent, and an accelerator in a high-pressure reactor at a high temperature of 220° C.
  • the registered patent prepares carbon quantum dots in an organic solvent or high-temperature and high-pressure conditions, and controls the size of carbon quantum dots as a concentration of organic matter.
  • the organic solvent or high pressure method makes the process complicated and it is difficult to efficiently control the size of the carbon quantum dots by using the concentration of the organic material.
  • the present invention is to provide a method for producing carbon quantum dots in a simple and environmentally friendly method.
  • An object of the present invention is to provide a method capable of controlling the shape and fluorescence color as well as the size of carbon quantum dots.
  • One aspect of the present invention is
  • a method for producing multicolor carbon quantum dots comprising heating a mixed solution to 150 to 250° C., wherein the method controls the size and fluorescence color of carbon quantum dots generated by controlling the time of the heating step. It relates to the manufacturing method.
  • the present invention relates to carbon quantum dots prepared by mixing phloroglucinol, water and a catalyst, wherein the carbon quantum dots are shape-specific carbon quantum dots that are triangular and quadrangular crystals.
  • the shape-specific carbon quantum dot manufacturing method of the present invention uses phloroglucinol, water and a catalyst, and can control the size and fluorescence color of the carbon quantum dots through time control at a temperature of 150 to 250 ° C.
  • triangular and rectangular compounds are formed by dehydrating phloroglucin, and blue, green, and yellow carbon quantum dots can be prepared respectively by controlling the time of the dehydration polymerization reaction.
  • the shape-specific carbon quantum dot manufacturing method of the present invention can control the triangular and square shape, size, and fluorescence color of carbon quantum dots through reaction time and solvent.
  • FIG 1 shows the manufacturing process of the carbon quantum dots of the present invention in which the size and fluorescence are controlled with time.
  • 2 is a TEM image, XRD pattern, Raman spectrum and current measurement curve of the carbon quantum dots prepared in the present invention.
  • the shape-specific carbon quantum dot manufacturing method of the present invention includes a mixing step and a heating step.
  • the mixing step is a step of mixing phloroglucinol and a catalyst in water.
  • the phloroglucinol is an organic compound having a structure of the following formula (1).
  • Phloroglucinol has symmetrical active protons and active hydroxyl groups. That is, phloroglucinol has a triple symmetric structure and there are three OH groups and three H groups. The OH group of one molecule reacts with the H group of the other molecule, and the H 2 O falls through the dehydration condensation reaction and bonds. Due to this triple symmetric structure, one molecule is bound to three other molecules in three meta-positions, and as the reaction time is increased, more molecules are combined to form carbon quantum dots that emit different colors.
  • Phloroglucinol removes adjacent -OH and -H groups by dehydration condensation reaction at high temperature by heat and catalyst, so that the ring of phloroglucinol is made up of three molecules of carbon quantum dots (CQD). due to the reaction pathway.
  • CQD carbon quantum dots
  • hydroxyquinol and pyrrogallol which are isomers of phloroglucinol, cannot form shape-specific carbon quantum dots as in the present invention.
  • the phloroglucinol may be added in an amount of 90 to 110 mg compared to 1 ml of water.
  • the catalyst may be sulfuric acid or the like capable of accelerating the dehydration condensation reaction of phloroglucinol.
  • the heating step is a step of heating the mixed solution to 150 ⁇ 250 °C.
  • the heating step is a step in which the dehydration condensation reaction of phloroglucinol is continuously performed to generate nanoparticle crystals.
  • the heating step may be 150 ⁇ 250 °C, preferably 180 ⁇ 220 °C.
  • the heating step may be performed without a separate pressurization.
  • the pressure may be atmospheric pressure.
  • the phloroglucinol molecules are dehydrated and polymerized to form a cyclic compound, and the phloroglucinol molecules are additionally dehydrated and condensed to the cyclic compound to form triangular and quadrangular crystalline carbons. It may include a crystallization step of growing into quantum dots.
  • the heating step occurs at a high temperature of 150 to 250 ° C, solvents such as nitric acid, hydrogen peroxide, and potassium permanganate evaporate directly at high temperature to obtain a carbonized mass as a final product, but since the boiling point of sulfuric acid is very high ( ⁇ 340 °C) can act as a catalyst in a high-temperature reaction. Therefore, sulfuric acid is preferable as the catalyst.
  • the step of forming the compound in the ring form is a step in which a six-membered ring cyclization ( ⁇ ) is made by the dehydration reaction of the phloroglucinol molecules and the compound is formed.
  • the crystallization step is a step in which the phloroglucinol atoms are additionally grown into crystals by a dehydration reaction in the cyclic compound.
  • -OH in phloroglucinol is disposed at 1, 3, and 5 carbons, so that it can be uniformly grown into triangular and rectangular crystals.
  • the size and fluorescence color of the generated carbon quantum dots can be controlled by adjusting the time of the heating step.
  • the present invention prepares blue carbon quantum dots by maintaining the time of the heating step for 20 to 35 minutes, maintaining the time of the heating step for 45 to 60 minutes to produce green carbon quantum dots, and the heating By maintaining the time of the step for 80 to 100 minutes, it is possible to prepare yellow carbon quantum dots.
  • a blue carbon quantum dot having a size of 3 to 5 nm, a green carbon quantum dot having a size of 4 to 6 nm, and a yellow carbon quantum dot having a size of 5 to 8 nm can be prepared.
  • the present invention can produce carbon quantum dots by dehydration condensation reaction at high temperature.
  • carbon quantum dots can be obtained by centrifuging the mixed solution after the heating reaction step.
  • centrifugation may be performed at 5,000 to 20,000 rpm.
  • the shape-specific carbon quantum dots prepared by the above method may be triangular and quadrangular crystals.
  • the blue carbon quantum dots may have a size of 3 to 5 nm
  • the green carbon quantum dots may have a size of 4 to 6 nm
  • the yellow carbon quantum dots may have a size of 5 to 8 nm.
  • the fluorescence color of the green carbon quantum dots and the yellow carbon quantum dots may be redshifted as the polarity of the dispersed solvent increases.
  • phloroglucinol 200 mg was added to a 100-mL glass beaker, and then 2 mL of water and concentrated H2SO4 were added respectively.
  • the pale yellowish solution was stored in a hot-air oven preheated to a constant temperature of 190 °C and the reaction time was maintained for 25, 50 and 90 min, respectively, for blue, green and yellow carbon quantum dots (B-CQDs, G-CQDs and Y- CQDs) were obtained. After each period of thermal reaction, the beaker was immediately removed and cooled to room temperature.
  • Figures 2a-c are HR-TEM of B-CQDs, G-CQDs and Y-CQDs
  • Figure 2d is an XRD pattern
  • 2e is a Raman spectrum
  • 4f is an I-t curve.
  • the obtained carbon quantum dots have a size of 3 to 5 nm (B-CQDs), 4 to 6 nm (G-CQDs), and 5 to 8 nm (Y-CQDs), and the shapes are triangular and square. decision can be confirmed.
  • Figure 3a is a UV-vis absorption spectrum of phloroglucinol and the prepared carbon quantum dots. Although phloroglucinol shows a peak at 266 nm, it can be seen that the peaks of B-CQDs, G-CQDs and Y-CQDs are redshifted to 280 nm, 289 nm, and 305 nm, respectively. Figure 3a shows that as the reaction time is longer, larger quantum dots are generated, and the redshift phenomenon is also larger.
  • Figure 3b shows the excitation and emission spectra of B-CQDs, G-CQDs and Y-CQDs dispersed in ethanol.
  • all three carbon quantum dots have excitation wavelengths of 345 to 350 nm, but the maximum emission wavelengths are located at 438 nm, 512 nm, and 550 nm.
  • Figure 3c shows the PL emission wavelength according to various excitation wavelengths. This shows that the carbon quantum dots dispersed in ethanol are excitation wavelength dependent.
  • Figure 3d is a graph showing the quantum yield measured using quinine sulfate (quinine sulfate). The quantum yields of B-, G-, and Y-CQDs are 1.03, 23, and 6,95%, respectively.
  • FIGS. 4a and 4b are PL emission distribution curves of G-CQDs and Y-CQDs dispersed in various solvents, respectively.
  • G-CQDs were redshifted from 435 (blue, ethyl acetate) to 512 nm (green, ethanol), and for Y-CQDs from 446 nm (blue, ethyl acetate) to 566 nm (yellow orange, DMSO).
  • the PL maximum emission wavelengths of G-CQDs are 435 nm (ethyl acetate), 436 nm (THF), 435 nm (acetonenitrile), 470 nm (water), 500 nm (DMF), 501 nm (DMSO), and 512 nm (ethanol) )to be.
  • the PL maximum emission wavelength of Y-CQDs is 446nm (ethyl acetate), 449nm (THF), 459nm (acetonenitrile), 520nm (DMF) 535nm (water), 550nm (ethanol), 566nm (DMSO) to be.
  • Y-CQDs and G-CQDs show solvent-dependent color development at a wavelength of 350 nm.
  • the maximum emission wavelengths of Y-CQDs and G-CQDs were 77-120 nm, respectively, and were redshifted.
  • 4c and 4d are UV-visible absorption spectra of Y-CQDs and G-CQDs in different polar solvents. Referring to FIGS. 4c and 4d , it can be seen that the absorption spectra of Y-CQDs and G-CQDs are located near 305 nm, and the absorption spectra are almost similar regardless of the characteristics of the solvent.
  • the carbon quantum dots of the present invention can be used for bio-imaging, photocatalyst, and detection of biomaterials or specific compounds.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Luminescent Compositions (AREA)

Abstract

La présente invention concerne des points quantiques de carbone spécifiques de forme dont la forme, la taille et la couleur de fluorescence peuvent être commandées par le temps de réaction et un solvant et qui sont susceptibles de présenter une émission de fluorescence multicouleur ; et un procédé permettant leur fabrication. Le procédé de fabrication de points quantiques de carbone spécifiques de forme selon la présente invention utilise du phloroglucinol, de l'eau et un catalyseur et peut commander la taille et la couleur de fluorescence des points quantiques de carbone par ajustement de la durée à une température de 150 à 250 °C. Dans le procédé de fabrication de points quantiques de carbone spécifiques de forme selon la présente invention, il y a formation de composés cycliques (comportant un cycle) quadrangulaires par une réaction de déshydratation du phloroglucinol, et des points quantiques de carbone bleus, verts et jaunes peuvent être fabriqués respectivement par ajustement de la durée de la réaction de déshydratation.
PCT/KR2021/009413 2020-07-31 2021-07-21 Points quantiques de carbone spécifiques de forme susceptibles de présenter une émission de fluorescence multicouleur et leur procédé de fabrication Ceased WO2022025517A1 (fr)

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KR1020200095631A KR20220015528A (ko) 2020-07-31 2020-07-31 다색 형광 방출이 가능한 형상 특이적 탄소 양자점 및 이의 제조방법
KR10-2020-0095631 2020-07-31

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KR102882731B1 (ko) * 2023-03-31 2025-11-05 가천대학교 산학협력단 노화 방지 및 상처 드레싱 기능을 가진 탄소 양자점이 로딩된 드레싱 소재 및 이의 제조방법

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019134068A1 (fr) * 2018-01-02 2019-07-11 Beijing Normal University Points quantiques de carbone triangulaires et compositions et utilisations associées
CN111072013A (zh) * 2019-12-24 2020-04-28 三峡大学 利用间苯三酚制备石墨烯量子点的绿色方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019134068A1 (fr) * 2018-01-02 2019-07-11 Beijing Normal University Points quantiques de carbone triangulaires et compositions et utilisations associées
CN111072013A (zh) * 2019-12-24 2020-04-28 三峡大学 利用间苯三酚制备石墨烯量子点的绿色方法

Non-Patent Citations (3)

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Title
MONIRUZZAMAN MD, ANANTHA LAKSHMI BUDDOLLA, KIM SANGHYO, KIM JONGSUNG: "Preparation of shape-specific (trilateral and quadrilateral) carbon quantum dots towards multiple color emission", NANOSCALE, ROYAL SOCIETY OF CHEMISTRY, UNITED KINGDOM, vol. 12, no. 22, 11 June 2020 (2020-06-11), United Kingdom , pages 11947 - 11959, XP055893395, ISSN: 2040-3364, DOI: 10.1039/D0NR02225J *
YUAN FANGLONG, YUAN TING, SUI LAIZHI, WANG ZHIBIN, XI ZIFAN, LI YUNCHAO, LI XIAOHONG, FAN LOUZHEN, TAN ZHAN’AO, CHEN ANMIN, JIN MI: "Engineering triangular carbon quantum dots with unprecedented narrow bandwidth emission for multicolored LEDs", NATURE COMMUNICATIONS, vol. 9, no. 1, 1 December 2018 (2018-12-01), pages 1 - 12, XP055893391, ISSN: 2041-1723, DOI: 10.1038/s41467-018-04635-5 *
ZHAO HAIGUANG, LIU GUIJU, HAN GUANGTING: "High-performance laminated luminescent solar concentrators based on colloidal carbon quantum dots", NANOSCALE ADVANCES, vol. 1, no. 12, 3 December 2019 (2019-12-03), pages 4888 - 4894, XP055893398, ISBN: 2516-0230, DOI: 10.1039/C9NA00527G *

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