WO2021085493A1 - 炭素量子ドット含有組成物、およびその製造方法 - Google Patents
炭素量子ドット含有組成物、およびその製造方法 Download PDFInfo
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Definitions
- the present invention relates to a carbon quantum dot-containing composition and a method for producing the same.
- Carbon quantum dots are stable carbon-based fine particles with a particle size of several nm to several tens of nm. Since carbon quantum dots exhibit good fluorescence characteristics, they are expected to be used as photonics materials for solar cells, displays, security inks, and the like. In addition, since it has low toxicity and high biocompatibility, it is expected to be applied to the medical field such as bioimaging.
- Patent Document 1 describes a method of obtaining carbon quantum dots by heating a solution containing a polyphenol and an amine compound and carbonizing (reacting) them (for example, Patent Document 1).
- Patent Document 2 describes a composition for fingerprint detection, which is a mixture of carbon quantum dots and montmorillonite.
- Patent Document 3 describes a pickering emulsion containing carbon quantum dots and montmorillonite.
- Patent Document 4 describes a water purification material containing carbon quantum dots and clay minerals.
- Patent Document 5 proposes a method for preparing a composition containing carbon quantum dots and clay minerals by mixing minerals such as zeolite and furfuryl alcohol which is liquid at room temperature and heating them. Has been done.
- quantum dots differ in performance, for example, emission wavelength, depending on their particle size.
- carbon quantum dots are prepared by a general method, it is difficult to adjust the particle size to a desired particle size, and it is also difficult to adjust the emission wavelength to a desired range, for example.
- Patent Documents 2 to 4 when carbon quantum dots are prepared and then mixed with clay minerals, it is difficult to mix them uniformly, and the process tends to be complicated.
- Patent Document 5 it is difficult to prepare carbon quantum dots having a maximum fluorescence wavelength in the visible light region and having good fluorescence quantum efficiency.
- the present invention has been made in view of the above problems.
- the present application provides, for example, a composition in which the maximum fluorescence wavelength is in the visible light region and carbon quantum dots and layered clay minerals are uniformly dispersed, and a method for producing the composition for easily obtaining the composition. The purpose.
- the present invention provides the following carbon quantum dot-containing compositions.
- a carbon quantum dot-containing composition containing carbon quantum dots obtained by reacting a solid organic compound having a reactive group in the presence of a layered clay mineral, and the layered clay mineral.
- the present invention also provides the following method for producing a carbon quantum dot-containing composition.
- a method for producing a carbon quantum dot-containing composition containing a layered clay mineral and carbon quantum dots which comprises a step of preparing a mixture of a solid organic compound having a reactive group and a layered clay mineral.
- a method for producing a carbon quantum dot-containing composition which comprises a step of heating the mixture and reacting the organic compound to prepare carbon quantum dots.
- the carbon quantum dots contained in the carbon quantum dot-containing composition of the present invention have a maximum fluorescence wavelength in the visible light region, and their performance is in a desired range. Further, in the carbon quantum dot-containing composition, the carbon quantum dots and the layered clay mineral are uniformly dispersed. Therefore, it can be expected that the desired performance is maintained for a long period of time. Further, according to the production method of the present invention, the carbon quantum dot-containing composition can be prepared by a simple method.
- FIG. 1 is a graph showing the results when powder X-ray diffraction measurement was performed on the compositions of Example 4 and Comparative Example 3.
- FIG. 2 is a graph showing the results of thermogravimetric analysis of the composition of Example 4.
- the carbon quantum dot-containing composition of the present invention contains carbon quantum dots and layered clay minerals.
- the carbon quantum dot refers to a carbon particle having a reactive group and having a particle size of 1 to 100 nm obtained by reacting a solid organic compound.
- reaction means that an organic compound having a functional group forms a fused ring structure (graphite structure) by a reaction such as dehydration, decarboxylation, or dehydrogenation.
- carbon quantum dots were prepared by a conventional general method, it was difficult to control the particle size and the emission wavelength and the like. Further, when preparing a composition containing carbon quantum dots, it was common to prepare such carbon quantum dots and then mix them with a layered clay mineral or the like. However, with this method, it was difficult to uniformly mix carbon quantum dots and layered clay minerals. Furthermore, carbon quantum dots having a maximum fluorescence wavelength in the visible light region could not be obtained only by mixing clay minerals such as zeolite and furfuryl alcohol and heating them.
- a carbon quantum dot-containing composition (hereinafter, also simply referred to as “composition”) is prepared by reacting a solid organic compound having a reactive group in the presence of a layered clay mineral. obtain.
- composition is prepared in this way, it is possible to obtain a composition in which the particle size of the carbon quantum dots is uniform, that is, the performance such as the emission wavelength is controlled.
- the composition can suppress the formation of agglomerates of carbon quantum dots. The reason is not clear, but it is presumed as follows.
- the reaction proceeds three-dimensionally between surrounding molecules, so the particle size of the carbon quantum dots that are produced tends to vary.
- carbon quantum dots have a large intermolecular force, and it is difficult to process the obtained carbon quantum dots into smaller carbon quantum dots, and agglomerates are likely to occur. If the particle size of the carbon quantum dots is relatively large, the carbon quantum dots cannot enter the layers of the layered clay mineral, and it is considered that they are difficult to mix uniformly.
- an organic compound having a reactive group and in a solid state which is a raw material for carbon quantum dots, and a layered clay mineral are mixed, and the organic compound is reacted in this state.
- both the organic compound and the layered clay mineral are mixed in a solid state, it is considered that an appropriate amount is subjected to the reaction by allowing a part of the organic compound to enter between the layers of the layered clay mineral. Since the layers of the layered clay mineral are narrow, the aggregates of organic compounds are easily divided, and carbon quantum dots having a uniform particle size are easily prepared.
- the layered clay mineral since the layers are substantially constant, the particle size of the carbon quantum dots tends to be uniform. Furthermore, since the organic compound as a raw material is finely dispersed, it is possible to reduce the particle size of the obtained carbon quantum dots.
- carbon quantum dots are prepared as in the present invention, a part of the carbon quantum dots is in a state (composite) in which a part of the carbon quantum dots is inserted between layers of layered clay minerals. Therefore, not only the dispersed state of the carbon quantum dots and the layered clay mineral becomes uniform, but also the carbon quantum dots are less likely to aggregate over a long period of time, and the desired performance can be stably obtained.
- the carbon quantum dots cover the surface of each layer constituting the layered clay mineral.
- the specific surface area of the composition becomes smaller.
- the surface of each layer constituting the layered clay mineral means not only the outer surface of the layered clay mineral but also the surface of each layer located inside the layered clay mineral. Then, in such a composition, the specific surface area can be used as one of the indexes of the dispersibility of the carbon quantum dots.
- the value of the specific surface area of the clay itself is small, and the difference in the dispersibility of carbon dots may not appear as the difference in the specific surface area.
- the maximum fluorescence wavelength of the composition of the present invention is preferably in the range of 380 to 800 nm, and more preferably in the range of 400 to 750 nm. When the maximum fluorescence wavelength is in this range, the amount of visible light emitted from the composition tends to be sufficient.
- the maximum fluorescence wavelength is a value measured by sandwiching the composition between KBr plates and pressing it to prepare a measurement sample, and irradiating the measurement sample with excitation light using a spectral fluorometer. Of the measured fluorescence, the wavelength at which the fluorescence intensity is maximized when excited at the wavelength that maximizes the internal quantum efficiency is defined as the maximum fluorescence wavelength.
- the internal quantum efficiency of the carbon quantum dot-containing composition of the present invention is preferably 2.0% or more, more preferably 2.3% or more.
- the internal quantum efficiency is defined as "a value obtained by dividing the energy of light emitted from the composition by the energy of excitation light absorbed by the composition" and is a value measured by a spectrofluorometer.
- composition of the present invention may contain carbon quantum dots and layered clay minerals, but other than surfactants and carbon quantum dots that enhance dispersibility within a range that does not impair the purpose and effect of the present invention. It may contain other components such as the illuminant of.
- the carbon quantum dots contained in the composition of the present invention are quantum dots obtained by reacting a solid organic compound having a reactive group in the presence of a layered clay mineral.
- the method for preparing an organic compound having a reactive group and carbon quantum dots will be described in detail in the method for preparing a composition described later.
- the emission wavelength and structure of carbon quantum dots are not particularly limited.
- the emission wavelength and structure of the carbon quantum dots are determined according to the type of organic compound used for preparing the carbon quantum dots, the type of layered clay mineral, the average layer spacing of the layered clay mineral, and the like.
- the height observed in the cross section is preferably 1 to 100 nm, more preferably 1 to 80 nm.
- the size of the carbon quantum dot is within this range, the properties as a quantum dot can be sufficiently obtained.
- the carbon quantum dot preferably emits visible light or near-infrared light when irradiated with light having a wavelength of 250 to 1000 nm, and the emission wavelength at this time is preferably 300 to 2000 nm, more preferably 300 to 1500 nm. It is preferable, but it is more preferable that it can emit visible light, and more specifically, it is more preferable that it emits light having a wavelength of 380 to 800 nm. When the emission wavelength is in this range, the composition of the present invention can be used for various purposes.
- the carbon quantum dot preferably has at least one group selected from the group consisting of a carboxy group, a carbonyl group, a hydroxy group, an amino group, a phosphonic acid group, a phosphoric acid group, a sulfo group, and a boronic acid group.
- the carbon quantum dots may have only one of these groups, or may have two or more groups. When the carbon quantum dots contain these groups, the dispersibility of the carbon quantum dots and the composition with respect to the solvent and the like is improved, and the carbon quantum dots can be easily used for various purposes.
- the type of functional group possessed by the carbon quantum dot can be specified by, for example, an IR spectrum or the like. Further, the functional group of the carbon quantum dot is usually derived from the functional group of the organic compound.
- the amount of carbon quantum dots in the composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30 parts by mass. When the amount of carbon quantum dots in the composition is in the above range, sufficient light emission can be obtained from the composition. Further, when the amount of carbon quantum dots is in the above range, the carbon quantum dots are less likely to aggregate in the composition, and the stability of the composition is enhanced.
- the layered clay mineral has a structure in which layered crystals in which silicon, aluminum, oxygen and the like are arranged in a predetermined structure are laminated, and each layer is formed by an electrostatic interaction or the like. Generally, water, metal ions, potassium, magnesium, water, organic substances, etc. are taken in between the crystal layers.
- the layered clay mineral may be anion-exchangeable or cation-exchangeable.
- layered clay minerals include smectite, layered double hydroxides, kaolinite, mica and the like.
- smectite or layered double hydroxide has an average layer spacing suitable for supporting carbon quantum dots (or organic compounds described later), and it is easy to prepare carbon quantum dots having a desired particle size. Is preferable.
- Smectite is a clay mineral that swells with water, etc., and examples include saponite, montmorillonite, hectorite, biderite, nontronite, saponite, and stephensite.
- the layered double hydroxide is a double hydroxide in which a trivalent metal ion is dissolved in a divalent metal oxide, and examples thereof include hydrotalcite, hydrocarmite, hydromagnesite, and pyro. Includes aurite and the like.
- the layered clay mineral may be a natural product or an artificial product. Further, the hydroxy group contained in the crystal layer may be substituted with fluorine. Further, the metalloid ion may be substituted with an alkali metal ion, an alkaline earth metal ion, an aluminum ion, an iron ion, an ammonium ion or the like. Further, the layered clay mineral may be modified with various organic substances, and may be, for example, smectite chemically modified with a quaternary ammonium salt compound or a quaternary pyridinium salt compound.
- the amount of the layered clay mineral in the composition is preferably 50 to 99.9% by mass, more preferably 70 to 99.5% by mass.
- the amount of carbon quantum dots is relatively large enough, and a sufficient amount of light emission can be obtained.
- the layered clay mineral can sufficiently support the carbon quantum dots, and the dispersibility of the carbon quantum dots tends to be good.
- composition containing the carbon quantum dots and the layered clay mineral has a reactive group and has a step of preparing a mixture of the solid organic compound and the layered clay mineral (mixture preparation step) and heating the mixture. Then, it can be prepared by carrying out a step of reacting the organic compound to prepare carbon quantum dots (carbon quantum dot preparation step).
- a mixture having a reactive group and in which a solid organic compound and a layered clay mineral are mixed substantially uniformly is prepared.
- the organic compound is not particularly limited as long as it has a reactive group, is in a solid state, and can generate carbon quantum dots by the reaction.
- the "reactive group” is a group for causing a polycondensation reaction between organic compounds in the carbon quantum dot preparation step described later, and contributes to the formation of the main skeleton of the carbon quantum dots. Is the basis. After preparing (reacting) the carbon quantum dots, some of these reactive groups may remain. Examples of reactive groups include carboxy groups, hydroxy groups, amino groups, boronic acid groups and the like.
- two or more kinds of organic compounds may be mixed with the layered clay mineral.
- the plurality of organic compounds have groups that easily react with each other.
- solid state means that it is in a solid state when mixed with a layered clay mineral.
- the layered clay mineral and the organic compound are mixed at room temperature, so a compound that is solid at room temperature is preferable.
- organic compounds having a reactive group examples include carboxylic acids, alcohols, phenols, amine compounds, boron compounds, and sugars.
- the organic compound may be in a solid state at a temperature of mixing with the layered clay mineral, or may be in a liquid state at room temperature.
- the carboxylic acid may be a compound having one or more carboxy groups in the molecule (excluding those corresponding to phenols, amine compounds, or sugars).
- carboxylic acids include monocarboxylic acids such as formic acid and acetic acid; divalent or higher polyvalent carboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, itaconic acid and polyacrylic acid; citric acid. , Glycoic acid, lactic acid, tartrate acid, hydroxy acid such as malic acid;
- the alcohol may be a compound having one or more hydroxy groups (excluding those corresponding to carboxylic acids, phenols, amine compounds, or sugars).
- examples of alcohols include polyhydric alcohols such as ethylene glycol, glycerol, erythritol, pentaerythritol, ascorbic acid and polyethylene glycol.
- Phenols may be compounds having a structure in which a hydroxy group is bonded to a benzene ring.
- examples of phenols include phenol, catechol, resorcinol, hydroquinone, phloroglucinol, pyrogallol, 1,2,4-trihydroxybenzene, gallic acid, tannin, lignin, catechin, anthocyanin, rutin, chlorogenic acid, lignan, curcumin. Etc. are included.
- amine compounds include 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, urea, thiourea, ammonium thiocyanate, ethanolamine, 1-amino-2-propanol, melamine, Includes cyanulic acid, barbituric acid, folic acid, ethylenediamine, polyethyleneimine, dicyandiamide, guanidine, aminoguanidine, formamide, glutamate, aspartic acid, cysteine, arginine, histidine, lysine, glutathione, RNA, DNA and the like.
- boron compounds include compounds having a boronic acid group, and specifically, phenylboronic acid, pyridineboronic acid and the like.
- sugar examples include glucose, sucrose, glucosamine, cellulose, chitin, chitosan and the like.
- an organic compound in which the condensation reaction proceeds efficiently is preferable, and examples of the preferable one include a carboxylic acid, a phenol, an amine compound, or a combination of a carboxylic acid and an amine compound.
- the organic compound contains an amine compound, it is preferable because the N atom is doped and the light emission characteristics are improved. The same effect can be expected when the organic compound has a hetero atom other than the N atom.
- those that are solid at room temperature are preferable in that they can be mixed with layered clay minerals at room temperature.
- a compound having a melting point of 30 ° C. or higher is more preferable, and a compound having a melting point of 45 ° C. or higher is even more preferable.
- the layered clay mineral to be combined with the organic compound is the same as the above-mentioned layered clay mineral (layered clay mineral contained in the composition).
- the layered clay mineral is preferably selected according to the type of reactive group contained in the organic compound, the emission wavelength of the desired carbon quantum dots, that is, the particle size of the desired carbon quantum dots.
- the reactive group of the organic compound is an anion
- an anion-exchangeable layered clay mineral may be selected.
- a cation-exchangeable layered clay mineral may be selected.
- the average layer spacing of the layered clay mineral to be combined with the organic compound is appropriately selected according to the molecular structure of the organic compound and the particle size of the desired carbon quantum dots, but is preferably 0.1 to 10 nm, preferably 0.1. ⁇ 8 nm is more preferable.
- the average layer spacing of layered clay minerals can be analyzed by an X-ray diffractometer or the like.
- the average layer spacing of the layered clay mineral refers to the spacing between one bottom surface and the other top surface of adjacent crystal layers of the layered clay mineral.
- carbon quantum dots are synthesized using layers of layered clay minerals as a template.
- the average layer spacing of the layered clay mineral is 10 nm or less, carbon quantum dots having a short emission wavelength can be easily obtained.
- the average layer spacing is 0.1 nm or more, a part of the organic compound easily enters between them, and carbon quantum dots are easily formed using the layers of the layered clay mineral as a template.
- the layered clay mineral may be swollen with water or various solvents in order to adjust the average layer spacing of the layered clay mineral.
- the organic solvent include methanol, ethanol, hexane, toluene, chloroform, dimethylformamide, dimethyl sulfoxide and the like.
- the amount of the solvent in the mixture (organic compound, layered clay mineral and solvent) is preferably 10 to 80% by mass, more preferably 10 to 70% by weight.
- the method of mixing the organic compound and the layered clay mineral is not particularly limited as long as they can be mixed uniformly.
- it may be mixed while being crushed in a mortar, or may be mixed while being crushed by a ball mill or the like.
- the mixing ratio of the organic compound and the layered clay mineral is appropriately selected according to the desired content ratio of the carbon dot quantum and the layered clay mineral.
- the carbon quantum dot preparation step is a step of heating the above-mentioned mixture and reacting an organic compound to form carbon quantum dots.
- the method for heating the mixture is not particularly limited as long as the organic compound can react, and includes, for example, a method for heating, a method for irradiating an electromagnetic wave (for example, microwave), and the like.
- the heating temperature is preferably 70 to 700 ° C, more preferably 100 to 500 ° C, and even more preferably 100 to 300 ° C.
- the heating time is preferably 0.01 to 45 hours, more preferably 0.1 to 30 hours, and even more preferably 0.5 to 10 hours.
- the particle size of the obtained carbon quantum dots, and thus the emission wavelength can be adjusted by the heating time. At this time, heating may be performed in a non-oxidizing atmosphere while an inert gas such as nitrogen is circulated.
- the wattage is preferably 1 to 1500 W, more preferably 1 to 1000 W.
- the heating time by electromagnetic waves is preferably 0.01 to 10 hours, more preferably 0.01 to 5 hours, and even more preferably 0.01 to 1 hour.
- the particle size of the obtained carbon quantum dots, and thus the emission wavelength, can be adjusted by the irradiation time of electromagnetic waves (microwaves).
- the electromagnetic wave irradiation can be performed by, for example, a semiconductor type electromagnetic wave irradiation device or the like. It is preferable to irradiate the electromagnetic wave while checking the temperature of the mixture. For example, it is preferable to irradiate the electromagnetic wave while adjusting the temperature to 70 to 700 ° C., more preferably 100 to 500 ° C.
- a carbon quantum dot-containing composition in which carbon quantum dots and layered clay minerals are uniformly dispersed can be obtained.
- the composition may be washed with an organic solvent to remove unreacted substances and by-products and purified.
- the dispersibility of the carbon quantum dots is higher than that in the case where the carbon quantum dots are prepared and then mixed with the layered clay mineral. Will increase.
- the carbon quantum dot-containing composition having high dispersibility of carbon quantum dots is useful as a separating agent having good luminescence in the visible light region and separating a specific substance by utilizing the functional group of the carbon quantum dots. Or something like that. Therefore, the composition can be used for various purposes.
- carbon quantum dot-containing composition is not particularly limited, and according to the performance of the carbon quantum dots, for example, solar cells, displays, security inks, quantum dot lasers, biomarkers, lighting materials, thermoelectric materials, photocatalysts, etc. It can be used as a separating agent for specific substances.
- Example 1 1.0 g of saponite (Smecton SA, manufactured by Kunimine Kogyo Co., Ltd., the same applies hereinafter) and 0.15 g of phloroglucinol dihydrate were ground in a mortar. The mixture was placed in a screw cap test tube having an internal volume of 15 ml and sealed with a screw cap with rubber packing. Then, while nitrogen was circulated in the screw cap test tube, it was heated at 200 ° C. for 3 hours to prepare a carbon quantum dot-containing composition (composite) containing carbon quantum dots and layered clay minerals.
- Example 2 0.5 g of hydrotalcite (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.15 g of citric acid, and 0.1 g of dicyandiamide were ground in a mortar. The mixture was placed in a screw cap test tube having an internal volume of 15 ml and sealed with a screw cap with rubber packing. Then, while nitrogen was circulated in the screw cap test tube, it was heated at 170 ° C. for 90 minutes to prepare a carbon quantum dot-containing composition (composite) containing carbon quantum dots and layered clay minerals.
- Example 3 1.0 g of saponite and 0.15 g of phloroglucinol dihydrate were ground in a mortar. The mixture was placed in a screw cap test tube having an internal volume of 15 ml and sealed with a screw cap with rubber packing. Then, while nitrogen was circulated in the screw cap test tube, it was heated at 155 ° C. for 3 hours to prepare a carbon quantum dot-containing composition (composite) containing carbon quantum dots and layered clay minerals.
- Example 4 1.0 g of saponite and 0.4 g of phloroglucinol dihydrate were ground in a mortar. The mixture was placed in a screw cap test tube having an internal volume of 15 ml and sealed with a screw cap with rubber packing. Then, while nitrogen was circulated in the screw cap test tube, it was heated at 200 ° C. for 3 hours to prepare a carbon quantum dot-containing composition (composite) containing carbon quantum dots and layered clay minerals.
- Example 5 0.5 g of saponite, 0.15 g of citric acid, and 0.1 g of dicyandiamide were ground in a mortar. The mixture was placed in a screw cap test tube having an internal volume of 15 ml and sealed with a screw cap with rubber packing. Then, while nitrogen was circulated in the screw cap test tube, it was heated at 170 ° C. for 90 minutes to prepare a carbon quantum dot-containing composition (composite) containing carbon quantum dots and layered clay minerals.
- a carbon quantum dot-containing composition composite
- Example 6 1.0 g of saponite, 0.02 g of phloroglucinol dihydrate, and 0.1 g of resorcinol were ground in a mortar. The mixture was placed in a screw cap test tube having an internal volume of 15 ml and sealed with a screw cap with rubber packing. Then, while nitrogen was circulated in the screw cap test tube, it was heated at 200 ° C. for 3 hours to prepare a carbon quantum dot-containing composition (composite) containing carbon quantum dots and layered clay minerals.
- a carbon quantum dot-containing composition composite
- Example 7 0.56 g of saponite and 0.084 g of phloroglucinol dihydrate were ground in a mortar. The mixture was placed in a screw cap test tube having an internal volume of 15 ml and sealed with a screw cap with rubber packing. Then, while circulating nitrogen in the screw cap test tube, the screw cap test tube is installed at the maximum electric field point of the semiconductor electromagnetic wave irradiation device (rectangular waveguide type resonator) manufactured by Fuji Denpa Koki Co., Ltd. under stirring. A carbon quantum dot-containing composition (complex) containing carbon quantum dots and layered clay minerals was prepared by irradiating an electromagnetic wave of 2.45 GHz.
- the semiconductor electromagnetic wave irradiation device rectangular waveguide type resonator
- the TE103 single mode was adopted for electromagnetic wave irradiation by the semiconductor type electromagnetic wave irradiation device.
- the semiconductor electromagnetic wave irradiator comprises a three-stub tuner, an iris, and a resonator equipped with a plunger, a semiconductor electromagnetic wave oscillator, and a monitor for monitoring input power and reflected power.
- the temperature at the time of electromagnetic wave irradiation was measured using an infrared radiation thermometer.
- the reflected power was suppressed to less than 0.1 W by adjusting the three-stub tuner and the plunger while oscillating an electromagnetic wave of 2 W and 2.45 GHz from the semiconductor electromagnetic wave oscillator.
- the temperature indicated by the infrared radiation thermometer reached 200 ° C., and the reaction was carried out for 4 minutes after the thermometer showed 200 ° C.
- Example 8 1.0 g of saponite and 0.15 g of phloroglucinol dihydrate were ground in a mortar. The mixture was placed in a screw cap test tube having an internal volume of 15 ml and sealed with a screw cap with rubber packing. Then, while nitrogen was circulated in the screw cap test tube, it was heated at 120 ° C. for 3 hours to prepare a carbon quantum dot-containing composition (composite) containing carbon quantum dots and layered clay minerals.
- the average layer spacing of the layered clay mineral was evaluated by powder X-ray diffraction measurement at a characteristic X-ray wavelength of 1.54 ⁇ using X'Pert-PRO MPD (manufactured by PANalytical).
- the average layer spacing of the layered clay mineral means the spacing between the crystal layers constituting the layered clay mineral (the spacing between one bottom surface and the other top surface).
- the composition was sandwiched between KBr plates and pressed to prepare a sample for measurement.
- the maximum fluorescence wavelength when the measurement sample was irradiated with excitation light having a wavelength that maximizes the internal quantum efficiency was evaluated using a spectrofluorescence fluorometer FP-8500 (manufactured by Nippon Kogaku Co., Ltd.).
- thermogravimetric analyzer TGA2 manufactured by Mettler
- the composition was sandwiched between KBr plates and pressed to prepare a sample for measurement.
- a spectral fluorometer FP-8500 manufactured by JASCO Corporation
- the measurement sample was sequentially irradiated with excitation light having a maximum in the range of 300 to 700 nm, and the internal quantum efficiency was evaluated.
- layered clay minerals and solid organic compounds are mixed to prepare carbon quantum dots in the presence of layered clay minerals, and carbon quantum dots containing carbon quantum dots and layered clay minerals.
- the contained composition had a maximum fluorescence wavelength in the range of 380 nm to 800 nm (Examples 1 to 8)).
- the internal quantum efficiency of each of these exceeded 2.0%.
- Comparative Example 1 and Comparative Example 3 in which the carbon quantum dots were synthesized and then the carbon quantum dots and the layered clay mineral were mixed, light emission was confirmed, but the internal quantum efficiency was low. Further, it is considered that the specific surface area was large in each case, the dispersion was not performed well, and the carbon quantum dots were aggregated. Further, in Comparative Example 2, although the carbon quantum dots were prepared at the same reaction temperature and the same reaction time as in Example 2, the maximum fluorescence wavelength of the carbon quantum dots was long and the internal quantum efficiency was low. In Example 2, it is considered that the fluorescence wavelength was shorter than that in Comparative Example 2 because the particle size of the carbon quantum dots was reduced by preparing the carbon quantum dots in the presence of the layered clay mineral.
- Comparative Example 4 had a large specific surface area even though the ratio of the organic compound and the layered clay mineral was the same as that of Example 5.
- Example 5 since the carbon quantum dots were prepared in the presence of the layered clay mineral, the carbon quantum dots were effectively encapsulated in the pores of the layered compound, and the dispersibility of the carbon quantum dots became better than that of Comparative Example 4. It is thought that it was.
- the dispersibility between the carbon quantum dots and the layered clay mineral is good, and further, the performance of the carbon quantum dots (for example, the maximum fluorescence wavelength is in the visible light region) can be improved. It can be adjusted to a desired range. Therefore, a carbon quantum dot-containing composition that can be used for various purposes can be obtained.
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Abstract
Description
層状粘土鉱物の存在下、反応性基を有し、かつ固体状の有機化合物を反応させて得られる炭素量子ドットと、前記層状粘土鉱物と、を含む、炭素量子ドット含有組成物。
層状粘土鉱物と、炭素量子ドットとを含む炭素量子ドット含有組成物の製造方法であって、反応性基を有し、かつ固体状の有機化合物と、層状粘土鉱物との混合物を調製する工程と、前記混合物を加熱し、前記有機化合物を反応させて炭素量子ドットを調製する工程と、を含む、炭素量子ドット含有組成物の製造方法。
本発明の組成物が含む炭素量子ドットは、層状粘土鉱物の存在下、反応性基を有し、かつ固体状の有機化合物を反応させて得られる量子ドットである。なお、反応性基を有する有機化合物や、炭素量子ドットの調製方法については、後述の組成物の調製方法で詳しく説明する。
層状粘土鉱物は、ケイ素、アルミニウム、酸素等が所定の構造で配列した層状の結晶が積層された構造を有し、各層どうしの間は、静電相互作用等によって構成されている。一般的に、結晶層どうしの間には、水や金属イオン、カリウムやマグネシウム、水、有機物等が取り込まれている。層状粘土鉱物は、アニオン交換性であってもよく、カチオン交換性であってもよい。
上記炭素量子ドットおよび層状粘土鉱物を含む組成物は、反応性基を有し、かつ固体状の有機化合物と、層状粘土鉱物との混合物を調製する工程(混合物調製工程)と、前記混合物を加熱し、前記有機化合物を反応させて炭素量子ドットを調製する工程(炭素量子ドット調製工程)と、を行うことで調製できる。
混合物調製工程では、反応性基を有し、かつ固体状の有機化合物と、層状粘土鉱物とを略均一に混合した混合物を調製する。有機化合物は、反応性基を有し、固体状であり、かつ反応によって炭素量子ドットを生成可能な化合物であれば特に制限されない。本明細書では、「反応性基」とは、後述の炭素量子ドット調製工程において、有機化合物どうしの重縮合反応等を生じさせるための基であり、炭素量子ドットの主骨格の形成に寄与する基である。なお、炭素量子ドットを調製(反応)後、これらの反応性基の一部が残存していてもよい。反応性基の例には、カルボキシ基、ヒドロキシ基、アミノ基、およびボロン酸基等が含まれる。なお、混合物調製工程では、二種以上の有機化合物を層状粘土鉱物と混合してもよい。この場合、複数の有機化合物は、互いに反応しやすい基を有することが好ましい。また、本明細書では「固体状」とは、層状粘土鉱物と混合する際に固体状であることをいう。通常、層状粘土鉱物と有機化合物との混合は、常温で行うため、常温で固体の化合物が好ましい。
炭素量子ドット調製工程は、上述の混合物を加熱し、有機化合物を反応させて炭素量子ドットとする工程である。混合物の加熱方法は、有機化合物が反応可能であれば特に制限されず、例えば加熱する方法や、電磁波(例えばマイクロ波)を照射する方法等が含まれる。
上述のように、混合物調製工程および上記炭素量子ドット調製工程を経て炭素量子ドット含有組成物を調製すると、炭素量子ドットを調製してから層状粘土鉱物と混合した場合より、炭素量子ドットの分散性が高まる。なお、炭素量子ドットの分散性が高い炭素量子ドット含有組成物は、可視光域における発光性が良好であったり、炭素量子ドットが有する官能基を利用して特定物質を分離させる分離剤として有用であったりする。したがって、組成物を各種用途に利用可能である。
サポナイト(スメクトンSA、クニミネ工業社製、以下、同じ)1.0gと、フロログルシノール二水和物0.15gと、を乳鉢ですりつぶした。当該混合物を内容積15mlのねじ口試験管に入れ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、200℃で3時間加熱し、炭素量子ドットと、層状粘土鉱物と、を含む炭素量子ドット含有組成物(複合体)を調製した。
ハイドロタルサイト(富士フイルム和光純薬社製)0.5gと、クエン酸0.15gと、ジシアンジアミド0.1gとを乳鉢ですりつぶした。当該混合物を内容積15mlのねじ口試験管に入れ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、170℃で90分加熱し、炭素量子ドットと、層状粘土鉱物と、を含む炭素量子ドット含有組成物(複合体)を調製した。
サポナイト1.0gと、フロログルシノール二水和物0.15gと、を乳鉢ですりつぶした。当該混合物を内容積15mlのねじ口試験管に入れ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、155℃で3時間加熱し、炭素量子ドットと、層状粘土鉱物と、を含む炭素量子ドット含有組成物(複合体)を調製した。
サポナイト1.0gと、フロログルシノール二水和物0.4gと、を乳鉢ですりつぶした。当該混合物を内容積15mlのねじ口試験管に入れ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、200℃で3時間加熱し、炭素量子ドットと、層状粘土鉱物と、を含む炭素量子ドット含有組成物(複合体)を調製した。
サポナイト0.5gと、クエン酸0.15gと、ジシアンジアミド0.1gとを乳鉢ですりつぶした。当該混合物を内容積15mlのねじ口試験管に入れ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、170℃で90分加熱し、炭素量子ドットと、層状粘土鉱物と、を含む炭素量子ドット含有組成物(複合体)を調製した。
サポナイト1.0gと、フロログルシノール二水和物0.02gと、レゾルシノール0.1gとを乳鉢ですりつぶした。当該混合物を内容積15mlのねじ口試験管に入れ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、200℃で3時間加熱し、炭素量子ドットと、層状粘土鉱物と、を含む炭素量子ドット含有組成物(複合体)を調製した。
サポナイト0.56gと、フロログルシノール二水和物0.084gと、を乳鉢ですりつぶした。当該混合物を内容積15mlのねじ口試験管に入れ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、撹拌下、富士電波工機社製の半導体式電磁波照射装置(矩形導波管型共振器)の電場最大点に上記ねじ口試験管を設置して、2.45GHzの電磁波を照射し、炭素量子ドットと、層状粘土鉱物と、を含む炭素量子ドット含有組成物(複合体)を調製した。
サポナイト1.0gと、フロログルシノール二水和物0.15gとを乳鉢ですりつぶした。当該混合物を内容積15mlのねじ口試験管に入れ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、120℃で3時間加熱し、炭素量子ドットと、層状粘土鉱物と、を含む炭素量子ドット含有組成物(複合体)を調製した。
フロログルシノール二水和物1.2gを内容積15mlのねじ口試験管に入れ、窒素気流下、200℃で3時間加熱して炭素量子ドットを合成した。合成した炭素量子ドットを0.12g測り取り、サポナイト1.0gとともに乳鉢ですりつぶすことで両者を混合し、炭素量子ドット含有組成物を得た。
クエン酸0.15gと、ジシアンジアミド0.1gとを乳鉢ですりつぶした。当該混合物を内容積15mlのねじ口試験管に入れ、窒素気流下、170℃で90分加熱して炭素量子ドットを合成した。合成した炭素量子ドットを35.0mg測り取り、ハイドロタルサイト70.0mgとともに乳鉢ですりつぶすことで両者を混合し、炭素量子ドット含有組成物を得た。
フロログルシノール二水和物1.2gを内容積15mlのねじ口試験管に入れ、窒素気流下、200℃で3時間加熱して炭素量子ドットを合成した。合成した炭素量子ドットを0.31g測り取り、サポナイト1.0gとともに乳鉢ですりつぶすことで両者を混合し、炭素量子ドット含有組成物を得た。
クエン酸0.15gと、ジシアンジアミド0.1gとを乳鉢ですりつぶした。当該混合物を内容積15mlのねじ口試験管に入れ、窒素気流下、170℃で90分加熱して炭素量子ドットを合成した。合成した炭素量子ドットを50.0mg測り取り、サポナイト100.0mgとともに乳鉢ですりつぶすことで両者を混合し、炭素量子ドット含有組成物を得た。
内容積15mlのねじ口試験管内で、サポナイト1.0gに対して、フルフリルアルコール(液体)0.15gを含侵させ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、200℃で3時間加熱し、炭素量子ドットと、層状粘土鉱物と、を含む炭素量子ドット含有組成物(複合体)を調製した。
内容積15mlのねじ口試験管内で、活性白土(富士フィルム和光純薬社製)1.0gに対して、フルフリルアルコール(液体)0.15gを含侵させ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、155℃で3時間加熱し、炭素量子ドットと、層状粘土鉱物と、を含む炭素量子ドット含有組成物(複合体)を調製した。
ジシアンジアミドを内容積15mlのねじ口試験管に入れ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、200℃で3時間加熱し、炭素量子ドットを調製した。
ゼオライト(HSZ-320NAA、東ソー社製、以下、同じ)1.0gと、フロログルシノール二水和物0.15gと、を乳鉢ですりつぶした。当該混合物を内容積15mlのねじ口試験管に入れ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、200℃で3時間加熱し、炭素量子ドットと、粘土鉱物と、を含む炭素量子ドット含有組成物(複合体)を調製した。
内容積15mlのねじ口試験管内で、ゼオライト1.0gに対して、フルフリルアルコール(常温で液体)0.15gを含侵させ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、80℃で12時間加熱し、炭素量子ドットと、粘土鉱物と、を含む炭素量子ドット含有組成物(複合体)を調製した。
内容積15mlのねじ口試験管内で、ゼオライト1.0gに対して、フルフリルアルコール(常温で液体)0.15gを含侵させ、ゴムパッキン付きねじ口キャップで封をした。そして、ねじ口試験管内に窒素を流通させながら、155℃で3時間加熱し、炭素量子ドットと、粘土鉱物と、を含む炭素量子ドット含有組成物(複合体)を調製した。
実施例および比較例で使用した層状粘土鉱物の平均層間隔、得られた組成物の比表面積、および組成物の発光波長について、以下のように評価した。結果を表1に示す。また、実施例4および比較例3の組成物中での炭素量子ドットの凝集状態、および実施例4の組成物の炭素量子ドットの含有量を以下のように測定した。結果をそれぞれ、図1および図2に示す。
層状粘土鉱物の平均層間隔は、X’Pert-PRO MPD(PANalytical製)を用い、特性X線波長1.54Åにて粉末X線回折測定を行い評価した。層状粘土鉱物の平均層間隔とは、層状粘土鉱物を構成する結晶層の間隔(一方の底面と他方の天面との間隔)を意味する。
組成物の比表面積は、Monosorb(Quantachrome Instruments製)を用いて評価した。N2:He=20vol%:80vol%の混合ガスを用いてBET一点法により比表面積の値を求めた。サンプルは150℃で10分間乾燥したものを用いた。
組成物をKBrプレートに挟み、プレスして測定用サンプルを作製した。当該測定用サンプルに分光蛍光光度計FP-8500(日本分光社製)を用いて、内部量子効率が最大となる波長の励起光を照射したときの、極大蛍光波長を評価した。
実施例5よび比較例3の組成物における炭素量子ドットの凝集状態は、X’Pert-PRO MPD(PANalytical製)を用い、特性X線波長1.54Åにて粉末X線回折測定を行い評価した。
熱重量分析装置TGA2(Mettler社製)を用いて、40ml/分の空気気流下、昇温速度10℃/分で測定を行い、重量減少量から実施例5の組成物中の炭素量子ドット含有量を評価した。
組成物をKBrプレートに挟み、プレスして測定用サンプルを作製した。当該測定用サンプルに分光蛍光光度計FP-8500(日本分光社製)を用いて、300~700nmの範囲に極大をもつ励起光を順次照射し、内部量子効率を評価した。
Claims (10)
- 層状粘土鉱物の存在下、反応性基を有し、かつ固体状の有機化合物を反応させて得られる炭素量子ドットと、
前記層状粘土鉱物と、
を含む、炭素量子ドット含有組成物。 - 極大蛍光波長が、380~800nmの範囲にある、
請求項1に記載の炭素量子ドット含有組成物。 - 内部量子効率が2.0%以上である、
請求項1または2に記載の炭素量子ドット含有組成物。 - 前記層状粘土鉱物が、スメクタイトおよび層状複水酸化物から選ばれる、少なくとも一種を含む、
請求項1~3のいずれか一項に記載の炭素量子ドット含有組成物。 - 前記反応性基を有する有機化合物が、カルボン酸、アルコール、フェノール類、アミン化合物、ホウ素化合物、および糖からなる群から選ばれる、少なくとも一種の化合物である、
請求項1~4のいずれか一項に記載の炭素量子ドット含有組成物。 - 前記炭素量子ドットが、カルボキシ基、カルボニル基、ヒドロキシ基、アミノ基、ホスホン酸基、リン酸基、スルホ基、およびボロン酸基からなる群から選ばれる少なくとも一種の基を有する、
請求項1~5のいずれか一項に記載の炭素量子ドット含有組成物。 - 層状粘土鉱物と、炭素量子ドットとを含む炭素量子ドット含有組成物の製造方法であって、
反応性基を有し、かつ固体状の有機化合物と、層状粘土鉱物との混合物を調製する工程と、
前記混合物を加熱し、前記有機化合物を反応させて炭素量子ドットを調製する工程と、
を含む、
炭素量子ドット含有組成物の製造方法。 - 前記混合物を100℃~500℃に加熱し、前記炭素量子ドットを調製する、
請求項7に記載の炭素量子ドット含有組成物の製造方法。 - 前記混合物に、電磁波を照射して前記混合物を加熱し、前記炭素量子ドットを調製する、
請求項7または8に記載の炭素量子ドット含有組成物の製造方法。 - 前記混合物を調製する工程に使用する、前記層状粘土鉱物の平均層間隔が、0.1nm~10nmである、
請求項7~9のいずれか一項に記載の炭素量子ドット含有組成物の製造方法。
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CN113429964A (zh) * | 2021-06-25 | 2021-09-24 | 南京信息工程大学 | 一种荧光氨基黏土的制备方法 |
CN113683079A (zh) * | 2021-09-14 | 2021-11-23 | 安徽大学 | 一种深紫外b波段荧光碳点、制备方法和应用 |
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US20220380217A1 (en) | 2022-12-01 |
JPWO2021085493A1 (ja) | 2021-05-06 |
CN114502690A (zh) | 2022-05-13 |
EP4053075A1 (en) | 2022-09-07 |
EP4053075A4 (en) | 2023-03-29 |
JP7410165B2 (ja) | 2024-01-09 |
KR20220066967A (ko) | 2022-05-24 |
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