TWI767345B - Composition of carbon quantum dots and method for producing the same - Google Patents
Composition of carbon quantum dots and method for producing the same Download PDFInfo
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Abstract
本發明之課題在於提供一種組成物及用於簡便獲得該組成物之組成物之製造方法，該組成物之碳量子點之發光波長等性能為所需範圍，且碳量子點及層狀黏土礦物均勻分散。 解決上述課題之含碳量子點之組成物含有：碳量子點，其係於層狀黏土礦物之存在下使具有反應性基之有機化合物碳化而獲得；及前述層狀黏土礦物。An object of the present invention is to provide a composition and a method for easily obtaining the composition, the composition having properties such as emission wavelength of carbon quantum dots in a desired range, and carbon quantum dots and layered clay minerals Evenly dispersed. The composition containing carbon quantum dots for solving the above-mentioned problems comprises: carbon quantum dots obtained by carbonizing an organic compound having a reactive group in the presence of a layered clay mineral; and the aforementioned layered clay mineral.
Description
本發明係關於一種含碳量子點之組成物及其製造方法。The present invention relates to a composition of carbon quantum dots and a manufacturing method thereof.
碳量子點係粒徑為數nm至數10 nm左右之穩定的碳系微粒子。碳量子點由於顯示良好之螢光特性，因此期待其作為太陽電池、顯示器、防偽油墨等光子材料的用途。另外，由於其低毒性且活體親和性亦高，因此亦期待向生物影像等醫療領域之應用。Carbon quantum dots are stable carbon-based fine particles with a particle size ranging from several nm to several 10 nm. Carbon quantum dots are expected to be used as photonic materials such as solar cells, displays, and anti-counterfeiting inks because of their excellent fluorescent properties. In addition, due to its low toxicity and high bio-affinity, its application to medical fields such as bioimaging is also expected.
先前，作為碳量子點之製造方法，提出有各種方法。例如，專利文獻1中記載有如下方法：藉由將含有多酚與胺化合物之溶液加熱，使該等碳化而獲得碳量子點（例如專利文獻1）。Various methods have been proposed as methods for producing carbon quantum dots. For example,
另一方面，亦提出有根據碳量子點之用途而將利用如上述之方法所得之碳量子點與各種黏土礦物混合。例如，專利文獻2中記載有將碳量子點與蒙脫石混合而成之指紋檢測用組成物。另外，專利文獻3中記載有含有碳量子點與蒙脫石之皮克林乳液(Pickering emulsion)。此外，專利文獻4中記載有含有碳量子點與黏土礦物之淨水材料。On the other hand, it is also proposed to mix the carbon quantum dots obtained by the above method with various clay minerals according to the use of the carbon quantum dots. For example, Patent Document 2 describes a composition for fingerprint detection in which carbon quantum dots and montmorillonite are mixed. In addition, Patent Document 3 describes a Pickering emulsion containing carbon quantum dots and montmorillonite. In addition, Patent Document 4 describes a water purification material containing carbon quantum dots and clay minerals.
先行技術文獻 專利文獻 專利文獻1：日本專利特開2018-35035號公報 專利文獻2：中國專利申請公開第108951280號說明書 專利文獻3：中國專利申請公開第107129804號說明書 專利文獻4：美國專利申請公開第2018/0291266號說明書prior art literature Patent Literature Patent Document 1: Japanese Patent Laid-Open No. 2018-35035 Patent Document 2: Chinese Patent Application Publication No. 108951280 Specification Patent Document 3: Chinese Patent Application Publication No. 107129804 Specification Patent Document 4: Specification of US Patent Application Publication No. 2018/0291266
發明欲解決之課題 通常，量子點之性能，例如發光波長會根據其粒徑而有所不同。但，若利用通常之方法製備碳量子點，則難以調整成所需粒徑，亦難以將例如發光波長調整成所需範圍。另外，如專利文獻2至4般於碳量子點之製備後與黏土礦物進行混合時難以均勻混合，此外其步驟易變得繁雜。The problem to be solved by the invention Generally, the properties of quantum dots, such as emission wavelength, vary according to their particle size. However, when carbon quantum dots are prepared by a common method, it is difficult to adjust the particle size to a desired particle size, and it is also difficult to adjust, for example, the emission wavelength to a desired range. In addition, as in Patent Documents 2 to 4, it is difficult to mix uniformly with clay minerals after the carbon quantum dots are prepared, and the steps are easily complicated.
本發明係鑒於上述課題而完成。本案之目的在於提供一種組成物及用於簡便獲得該組成物之組成物之製造方法，該組成物之例如發光波長等性能為所需範圍，且碳量子點及層狀黏土礦物均勻分散。The present invention has been accomplished in view of the above-mentioned problems. The purpose of this application is to provide a composition and a method for easily obtaining the composition, the composition having properties such as emission wavelengths in a desired range, and uniform dispersion of carbon quantum dots and layered clay minerals.
解決問題之技術手段 本發明提供以下之含碳量子點之組成物。technical means to solve problems The present invention provides the following composition of carbon quantum dots.
一種含碳量子點之組成物，其含有：碳量子點，其係於層狀黏土礦物之存在下使具有反應性基之有機化合物碳化而獲得；及前述層狀黏土礦物。A composition containing carbon quantum dots, comprising: carbon quantum dots obtained by carbonizing an organic compound having a reactive group in the presence of a layered clay mineral; and the aforementioned layered clay mineral.
本發明亦提供以下之含碳量子點之組成物之製造方法。The present invention also provides the following manufacturing method of the carbon quantum dot composition.
一種含碳量子點之組成物之製造方法，該含碳量子點之組成物含有層狀黏土礦物與碳量子點，該製造方法包括以下步驟：製備具有反應性基之有機化合物與層狀黏土礦物之混合物之步驟；及將前述混合物加熱，使前述有機化合物碳化而製備碳量子點之步驟。A manufacturing method of a composition containing carbon quantum dots, the composition containing carbon quantum dots contains layered clay minerals and carbon quantum dots, the manufacturing method comprises the following steps: preparing organic compounds with reactive groups and layered clay minerals and the step of heating the aforementioned mixture to carbonize the aforementioned organic compound to prepare carbon quantum dots.
發明效果 本發明之含碳量子點之組成物所含有之碳量子點的性能，例如發光波長等為所需範圍。此外，該含碳量子點之組成物內，碳量子點與層狀黏土礦物均勻分散。因此，可期待跨及長時間維持所需性能。另外，根據本案發明之製造方法，可利用簡便之方法製備上述含碳量子點之組成物。Invention effect The properties of the carbon quantum dots contained in the carbon quantum dot-containing composition of the present invention, such as the emission wavelength, are within a desired range. In addition, in the composition containing carbon quantum dots, the carbon quantum dots and the layered clay minerals are uniformly dispersed. Therefore, the desired performance can be expected to be maintained over and over a long period of time. In addition, according to the production method of the present invention, the above-mentioned carbon-containing quantum dot composition can be produced by a simple method.
本發明之含碳量子點之組成物含有碳量子點與層狀黏土礦物。本說明書中，所謂碳量子點係指使具有反應性基之有機化合物碳化而獲得之粒徑為1至100 nm之碳粒子。另外，所謂本說明書中之碳化係指具有官能基之有機化合物藉由脫水、脫碳酸、脫氫等反應而形成稠環結構（石墨結構）。The composition containing carbon quantum dots of the present invention contains carbon quantum dots and layered clay minerals. In this specification, the so-called carbon quantum dots refer to carbon particles with a particle size of 1 to 100 nm obtained by carbonizing an organic compound having a reactive group. In addition, carbonization in this specification means that the organic compound which has a functional group forms a condensed-ring structure (graphite structure) by reaction, such as dehydration, decarbonation, and dehydrogenation.
如前述，利用先前通常之方法製備碳量子點時，難以控制其粒徑，而難以控制發光波長等。另外，於製備含有碳量子點之組成物時，通常在製備此種碳量子點後與層狀黏土礦物等進行混合。然而，利用該方法難以將碳量子點與層狀黏土礦物等均勻混合。As mentioned above, when carbon quantum dots are prepared by conventional methods, it is difficult to control the particle size, and it is difficult to control the emission wavelength and the like. In addition, when preparing a composition containing carbon quantum dots, it is usually mixed with a layered clay mineral or the like after preparing such carbon quantum dots. However, it is difficult to uniformly mix carbon quantum dots with layered clay minerals and the like using this method.
相對於此，本案發明中，於層狀黏土礦物之存在下使具有反應性基之有機化合物碳化而獲得含碳量子點之組成物（以下亦簡稱為「組成物」）。若如此製備組成物，則獲得碳量子點之粒徑一致，即發光波長等性能得到控制之組成物。另外，於該組成物中，亦可抑制碳量子點之凝聚體之生成。其原因雖不確定，但推測為如下。On the other hand, in the present invention, an organic compound having a reactive group is carbonized in the presence of a layered clay mineral to obtain a composition of carbon-containing quantum dots (hereinafter also simply referred to as a "composition"). If the composition is prepared in this way, the particle size of the carbon quantum dots is uniform, that is, the composition whose properties such as emission wavelength are controlled can be obtained. In addition, in this composition, the formation of aggregates of carbon quantum dots can also be suppressed. The reason for this is not certain, but is presumed as follows.
於使作為碳量子點之原料之有機化合物碳化時，在周邊之分子間會三維地進行反應，因此生成之碳量子點之粒徑易不均。另外，碳量子點之分子間力大，難以將所得之碳量子點加工成更微小之碳量子點，且易產生凝聚體。認為若碳量子點之粒徑相對較大，則碳量子點不會進入至層狀黏土礦物之層間，而難以均勻混合。When the organic compound used as the raw material of the carbon quantum dots is carbonized, three-dimensional reaction occurs between the molecules in the periphery, so that the particle size of the produced carbon quantum dots tends to be uneven. In addition, the intermolecular force of the carbon quantum dots is large, so it is difficult to process the obtained carbon quantum dots into smaller carbon quantum dots, and agglomerates are easily generated. It is considered that if the particle size of the carbon quantum dots is relatively large, the carbon quantum dots will not enter between the layers of the layered clay minerals, and it is difficult to mix uniformly.
相對於此，本發明中，將成為碳量子點之原料之具有反應性基之有機化合物與層狀黏土礦物混合，於該狀態下使有機化合物碳化。若將有機化合物與層狀黏土礦物混合，則有機化合物之一部分會進入至層狀黏土礦物之層間。而且，由於層狀黏土礦物之層間狹窄，因此有機化合物之集合體易被分斷。因此，若於層狀黏土礦物之存在下使有機化合物碳化，則層狀黏土礦物之層間會成為模板(template)，因此易製備粒徑一致之碳量子點。此外，由於成為原料之有機化合物被微細地分散，因此亦可減小所得之碳量子點之粒徑。On the other hand, in the present invention, an organic compound having a reactive group, which is a raw material of carbon quantum dots, is mixed with a layered clay mineral, and the organic compound is carbonized in this state. If the organic compound is mixed with the layered clay minerals, a part of the organic compound will enter between the layers of the layered clay minerals. Moreover, since the layers of the layered clay minerals are narrow, the aggregates of organic compounds are easily broken up. Therefore, if the organic compound is carbonized in the presence of the layered clay minerals, the layers of the layered clay minerals will become templates, so carbon quantum dots with uniform particle size can be easily prepared. In addition, since the organic compound used as the raw material is finely dispersed, the particle size of the obtained carbon quantum dots can also be reduced.
另外，若如本發明般製備碳量子點，則成為碳量子點之一部分進入至層狀黏土礦物之層間的狀態（複合體）。因此，不僅碳量子點及層狀黏土礦物之分散狀態變得均勻，而且碳量子點跨及長時間不易凝聚，從而易穩定獲得所需性能。In addition, when carbon quantum dots are prepared as in the present invention, a part of the carbon quantum dots is in a state (complex) in which a part of the carbon quantum dots enter between layers of layered clay minerals. Therefore, not only the dispersion state of the carbon quantum dots and the layered clay minerals becomes uniform, but also the carbon quantum dots are not easy to agglomerate over a long period of time, so that the desired properties can be stably obtained.
此處，於如本發明之組成物般碳量子點之凝聚少，碳量子點分散存在之比率多時，碳量子點會覆蓋構成層狀黏土礦物之各層之表面，因此組成物之比表面積變小。另外，所謂構成層狀黏土礦物之各層之表面，不僅指層狀黏土礦物之外表面，亦指位於層狀黏土礦物之內部之各層之表面。而且，於此種組成物中，將該比表面積作為碳量子點之分散性之指標之一。但，根據層狀黏土礦物之種類之不同，亦有黏土本身之比表面積之值小，碳點之分散性之差異不會作為比表面積之差而表現出的情況。Here, as in the composition of the present invention, the agglomeration of the carbon quantum dots is small and the carbon quantum dots are dispersed in a high ratio, the carbon quantum dots cover the surfaces of the layers constituting the layered clay mineral, so that the specific surface area of the composition changes. Small. In addition, the surface of each layer constituting the layered clay mineral refers not only to the outer surface of the layered clay mineral, but also to the surface of each layer located inside the layered clay mineral. Furthermore, in such a composition, the specific surface area is used as one of the indexes of the dispersibility of carbon quantum dots. However, depending on the type of layered clay minerals, the value of the specific surface area of the clay itself may be small, and the difference in the dispersibility of carbon dots may not appear as the difference in the specific surface area.
此處，本發明之組成物只要含有碳量子點與層狀黏土礦物即可，亦可於無損本發明之目的及效果之範圍內含有提高分散性之界面活性劑、碳量子點以外之發光體等其他成分。另外，以下將碳量子點進行發光之情況作為示例進行說明，但碳量子點也可不一定要發光。 （碳量子點）Here, the composition of the present invention only needs to contain carbon quantum dots and layered clay minerals, and may also contain surfactants for improving dispersibility and light-emitting bodies other than carbon quantum dots within the range that does not impair the object and effect of the present invention and other ingredients. In addition, the case where the carbon quantum dots emit light will be described below as an example, but the carbon quantum dots do not necessarily have to emit light. (carbon quantum dots)
本發明之組成物所含有之碳量子點係於層狀黏土礦物之存在下使具有反應性基之有機化合物碳化而獲得之量子點。另外，關於具有反應性基之有機化合物、碳量子點之製備方法，於後述之組成物之製備方法中詳細說明。The carbon quantum dots contained in the composition of the present invention are quantum dots obtained by carbonizing an organic compound having a reactive group in the presence of a layered clay mineral. In addition, the preparation method of the organic compound having a reactive group and the carbon quantum dot will be described in detail in the preparation method of the composition described later.
碳量子點之發光波長、結構並無特別限制。碳量子點之發光波長、結構根據碳量子點之製備所使用之有機化合物之種類、層狀黏土礦物之種類、層狀黏土礦物之平均層間隔等而定。The emission wavelength and structure of the carbon quantum dots are not particularly limited. The emission wavelength and structure of carbon quantum dots depend on the type of organic compounds used in the preparation of carbon quantum dots, the type of layered clay minerals, and the average interlayer spacing of layered clay minerals.
但，於利用原子力顯微鏡(Atomic Force Microscope，AFM)觀察碳量子點時，以剖面觀察到之高度較佳為1至100 nm，更較佳為1至80 nm。若碳量子點之大小為該範圍，則易充分獲得作為量子點之性質。However, when the carbon quantum dots are observed with an atomic force microscope (AFM), the height observed in the cross section is preferably 1 to 100 nm, more preferably 1 to 80 nm. When the size of the carbon quantum dot is within this range, it is easy to obtain sufficient properties as a quantum dot.
另外，該碳量子點較佳於照射波長為250至1000 nm之光時發出可見光或近紅外光，此時之發光波長較佳為300至2000 nm，更較佳為300至1500 nm。若發光波長為該範圍，則可將本發明之組成物用於各種用途。In addition, the carbon quantum dots preferably emit visible light or near-infrared light when irradiated with light with 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. If the emission wavelength is within this range, the composition of the present invention can be used in various applications.
碳量子點較佳具有選自羧基、羰基、羥基、胺基、膦酸基、磷酸基、磺基及硼酸基所組成之群中之至少一種基。碳量子點可僅具有該等中之一種基，亦可具有兩種以上之基。若碳量子點含有該等基，則碳量子點、進而組成物對於溶劑等之分散性變得良好，易用於各種用途。碳量子點所具有之官能基之種類可藉由例如紅外光譜(IR spectrum)等特定出。另外，碳量子點所具有之官能基通常源自有機化合物所具有之官能基。The carbon quantum dot preferably has at least one group selected from the group consisting of a carboxyl group, a carbonyl group, a hydroxyl group, an amine group, a phosphonic acid group, a phosphoric acid group, a sulfonic acid 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 carbon quantum dots and the composition have good dispersibility with respect to solvents and the like, and can be easily used in various applications. The types of functional groups possessed by the carbon quantum dots can be identified by, for example, infrared spectroscopy (IR spectrum). In addition, the functional groups possessed by carbon quantum dots are usually derived from functional groups possessed by organic compounds.
組成物中之碳量子點之量較佳為0.1至50質量百分比，更較佳為0.5至30質量份。若組成物中之碳量子點之量為上述範圍，則自組成物獲得充分之發光。另外，若碳量子點之量為上述範圍，則組成物內碳量子點不易凝聚，組成物之穩定性提高。 （層狀黏土礦物）The amount of carbon quantum dots in the composition is preferably 0.1 to 50 mass percent, more preferably 0.5 to 30 mass parts. When the amount of carbon quantum dots in the composition is within the above range, sufficient light emission can be obtained from the composition. In addition, when the amount of carbon quantum dots is within the above range, the carbon quantum dots in the composition are less likely to aggregate, and the stability of the composition is improved. (layered clay minerals)
層狀黏土礦物係矽、鋁、氧等以特定結構排列而成之結晶層之層疊體，且通常於結晶層彼此之間混入有水、金屬離子、鉀、鎂、水、有機物等。層狀黏土礦物可為陰離子交換性，亦可為陽離子交換性。Layered clay minerals are a stack of crystalline layers of silicon, aluminum, oxygen, etc. arranged in a specific structure, and usually water, metal ions, potassium, magnesium, water, organic matter, etc. are mixed between the crystalline layers. Layered clay minerals can be either anion-exchangeable or cation-exchangeable.
層狀黏土礦物之示例中，包含膨潤石、層狀雙氫氧化物、高嶺石及雲母等。該等中，就具有適於擔載碳量子點（或後述之有機化合物）之平均層間隔，且易製備所需粒徑之碳量子點的方面而言，較佳為膨潤石或層狀雙氫氧化物。Examples of layered clay minerals include bentonite, layered double hydroxide, kaolinite, and mica. Among them, bentonite or layered bilayer is preferred in terms of having an average interlayer spacing suitable for supporting carbon quantum dots (or organic compounds described later) and easy preparation of carbon quantum dots with a desired particle size. hydroxide.
膨潤石係藉由水等會膨潤之黏土礦物，其示例中，包含皂石、蒙脫石、鋰膨潤石、鋁膨潤石、鐵膨潤石、鋅膨潤石、矽鎂石等。Bentonite is a clay mineral that swells by water or the like, and examples thereof include saponite, montmorillonite, lithium bentonite, aluminum bentonite, iron bentonite, zinc bentonite, and stevensite.
另一方面，層狀雙氫氧化物係三價金屬離子固溶於二價金屬氧化物而成之雙氫氧化物，其示例中，包含菱水鎂鋁石、水鋁鈣石、水菱鎂礦、菱水鐵鎂石等。On the other hand, the layered double hydroxide is a double hydroxide in which trivalent metal ions are dissolved in a divalent metal oxide, and examples thereof include magnesite, hydromagnesite, and hydromagnesite. Mine, bromite, etc.
層狀黏土礦物可為天然物，亦可為人工物。另外，亦可為結晶層中所含之羥基被氟取代而成者。此外，亦可為層間離子被鹼金屬離子、鹼土金屬離子、鋁離子、鐵離子、銨離子等取代而成者。另外，層狀黏土礦物可藉由各種有機物改質，例如可為經過四級銨鹽化合物、四級吡啶鎓鹽化合物化學改質而成之膨潤石。Layered clay minerals can be natural or artificial. In addition, the hydroxyl group contained in the crystal layer may be substituted with fluorine. In addition, interlayer ions may be substituted by alkali metal ions, alkaline earth metal ions, aluminum ions, iron ions, ammonium ions, or the like. In addition, the layered clay minerals can be modified by various organic substances, such as bentonite which is chemically modified by a quaternary ammonium salt compound and a quaternary pyridinium salt compound.
組成物中之層狀黏土礦物之量較佳為50至99.9質量百分比，更較佳為70至99.5質量百分比。若層狀黏土礦物之量為上述範圍，則相對地碳量子點之量充分變多，獲得充分之發光量。另外，若層狀黏土礦物之量為上述範圍，則可利用層狀黏土礦物充分擔載碳量子點，碳量子點之分散性易變得良好。 （組成物之製備方法）The amount of the layered clay minerals in the composition is preferably 50 to 99.9 mass percent, more preferably 70 to 99.5 mass percent. When the amount of the layered clay mineral is within the above range, the amount of carbon quantum dots is relatively large enough to obtain a sufficient amount of light emission. In addition, when the amount of the layered clay mineral is in the above range, the carbon quantum dots can be sufficiently supported by the layered clay mineral, and the dispersibility of the carbon quantum dots is likely to be good. (the preparation method of the composition)
含有上述碳量子點及層狀黏土礦物之組成物可藉由進行以下步驟而製備：製備具有反應性基之有機化合物與層狀黏土礦物之混合物之步驟（混合物製備步驟）；及將前述混合物加熱，使前述有機化合物碳化而製備碳量子點之步驟（碳量子點製備步驟）。 混合物製備步驟The composition containing the above-mentioned carbon quantum dots and layered clay mineral can be prepared by performing the following steps: a step of preparing a mixture of an organic compound having a reactive group and a layered clay mineral (mixture preparation step); and heating the aforementioned mixture , the step of carbonizing the aforementioned organic compound to prepare carbon quantum dots (carbon quantum dot preparation step). Mixture preparation steps
混合物製備步驟中，製備將具有反應性基之有機化合物與層狀黏土礦物大致均勻混合而成之混合物。有機化合物只要為具有反應性基且可藉由碳化而生成碳量子點之化合物，則並無特別限制。本說明書中，所謂「反應性基」係於後述之碳量子點製備步驟中用於使有機化合物彼此之縮聚反應等發生之基，且為有助於形成碳量子點之主骨架之基。另外，於製備（碳化）成碳量子點後，亦可殘存有該等反應性基之一部分。反應性基之示例中，包含羧基、羥基、胺基及硼酸基等。另外，混合物製備步驟中，亦可將兩種以上之有機化合物與層狀黏土礦物混合。此時，複數種有機化合物較佳具有易於相互反應之基。In the mixture preparation step, a mixture obtained by substantially uniformly mixing the organic compound having a reactive group and the layered clay mineral is prepared. The organic compound is not particularly limited as long as it has a reactive group and can generate carbon quantum dots by carbonization. In this specification, the so-called "reactive group" refers to a group for causing a polycondensation reaction between organic compounds in the carbon quantum dot preparation step described later, and is a group that contributes to the formation of the main skeleton of the carbon quantum dot. In addition, after the carbon quantum dots are prepared (carbonized), a part of these reactive groups may remain. Examples of reactive groups include carboxyl groups, hydroxyl groups, amine groups, boronic acid groups, and the like. In addition, in the mixture preparation step, two or more organic compounds may also be mixed with the layered clay mineral. In this case, it is preferable that a plurality of organic compounds have groups which are easily reacted with each other.
上述具有反應性基之有機化合物之示例中，包含羧酸、醇、多酚、胺化合物、硼化合物及糖。有機化合物於常溫下可為固體狀，亦可為液體狀。Examples of the above-mentioned organic compound having a reactive group include carboxylic acid, alcohol, polyphenol, amine compound, boron compound, and sugar. The organic compound may be solid or liquid at room temperature.
羧酸只要為分子中具有一個以上之羧基之化合物（其中，相當於多酚、胺化合物或糖者除外）即可。羧酸之示例中，包含：甲酸、乙酸等一元羧酸；乙二酸、丙二酸、丁二酸、順丁烯二酸、反丁烯二酸、伊康酸、聚丙烯酸等二元以上之多元羧酸；檸檬酸、乙醇酸、乳酸、酒石酸、蘋果酸等羥基酸。The carboxylic acid may be a compound having one or more carboxyl groups in the molecule (except for those corresponding to polyphenols, amine compounds or sugars). Examples of carboxylic acids include monobasic carboxylic acids such as formic acid and acetic acid; dibasic or higher carboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, itaconic acid, and polyacrylic acid polycarboxylic acids; hydroxy acids such as citric acid, glycolic acid, lactic acid, tartaric acid, and malic acid.
醇只要為具有一個以上之羥基之化合物（其中，相當於羧酸、多酚、胺化合物或糖者除外）即可。醇之示例中，包含乙二醇、甘油、赤藻糖醇、新戊四醇、抗壞血酸、聚乙二醇等多元醇。The alcohol may be a compound having one or more hydroxyl groups (except for those corresponding to a carboxylic acid, a polyphenol, an amine compound, or a sugar). Examples of alcohols include polyhydric alcohols such as ethylene glycol, glycerol, erythritol, neotaerythritol, ascorbic acid, and polyethylene glycol.
多酚只要為具有苯環上鍵結有羥基之結構之化合物即可。多酚之示例中，包含鄰苯二酚、間苯二酚、對苯二酚、間苯三酚、鄰苯三酚、1,2,4-三羥基苯、沒食子酸、單寧、木質素、兒茶素、花青素、芸香苷、漂木酸、樹脂腦、薑黃素等。The polyphenol may be a compound having a structure in which a hydroxyl group is bonded to a benzene ring. Examples of polyphenols include catechol, resorcinol, hydroquinone, phloroglucinol, pyrogallol, 1,2,4-trihydroxybenzene, gallic acid, tannin, Lignin, catechin, anthocyanin, rutin, balsic acid, resin brain, curcumin, etc.
胺化合物之示例中，包含1,2-苯二胺、1,3-苯二胺、1,4-苯二胺、脲、硫脲、硫氰酸銨、乙醇胺、1-胺基-2-丙醇、三聚氰胺、三聚氰酸、巴比妥酸、葉酸、乙二胺、聚乙烯亞胺、雙氰胺、胍、胺基胍、甲醯胺、麩氨酸、天冬醯胺酸、半胱胺酸、精胺酸、組胺酸、離胺酸、麩胱甘肽、核糖核酸(Ribonucleic acid，RNA)、脫氧核糖核酸(Deoxyribonucleic acid，DNA)等。Examples of amine compounds include 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, urea, thiourea, ammonium thiocyanate, ethanolamine, 1-amino-2- Propanol, melamine, cyanuric acid, barbituric acid, folic acid, ethylenediamine, polyethyleneimine, dicyandiamide, guanidine, aminoguanidine, formamide, glutamic acid, aspartic acid, Cysteine, arginine, histidine, lysine, glutathione, ribonucleic acid (RNA), deoxyribonucleic acid (DNA), etc.
硼化合物之示例中，包含具有硼酸基之化合物，具體而言包含苯基硼酸、吡啶硼酸等。Examples of the boron compound include compounds having a boronic acid group, specifically phenylboronic acid, pyridineboronic acid, and the like.
糖之示例中，包含葡萄糖、蔗糖、葡糖胺、纖維素、甲殼素、聚葡萄胺糖等。Examples of sugars include glucose, sucrose, glucosamine, cellulose, chitin, polyglucosamine, and the like.
上述中，較佳為縮合反應會有效率地進行之有機化合物，作為較佳者之一例，可列舉羧酸、多酚、胺化合物、或羧酸與胺化合物之組合。另外，若有機化合物含有胺化合物，則藉由摻雜氮(N)原子，發光特性會提高，因此較佳。另外，於有機化合物具有N原子以外之雜原子時亦期待同樣之效果。Among the above, organic compounds in which the condensation reaction proceeds efficiently are preferable, and examples of preferable ones include carboxylic acid, polyphenol, amine compound, or a combination of carboxylic acid and amine compound. In addition, when the organic compound contains an amine compound, since the light emission characteristics are improved by doping with nitrogen (N) atoms, it is preferable. In addition, the same effect is expected when the organic compound has a hetero atom other than the N atom.
另一方面，與有機化合物組合之層狀黏土礦物與上述層狀黏土礦物（組成物所含有之層狀黏土礦物）相同。層狀黏土礦物較佳根據有機化合物所具有之反應性基之種類、所需之碳量子點之發光波長即所需之碳量子點之粒徑而選擇。例如，於有機化合物所具有之反應性基成為陰離子時，可選擇陰離子交換性之層狀黏土礦物。同樣地，於有機化合物所具有之反應性基成為陽離子時，可選擇陽離子交換性之層狀黏土礦物。On the other hand, the layered clay mineral 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 minerals are preferably selected according to the type of reactive groups possessed by the organic compound, the desired emission wavelength of the carbon quantum dots, that is, the desired particle size of the carbon quantum dots. For example, when the reactive group possessed by the organic compound becomes an anion, an anion-exchangeable layered clay mineral can be selected. Similarly, when the reactive group possessed by the organic compound becomes a cation, a cation-exchangeable layered clay mineral can be selected.
另一方面，與有機化合物組合之層狀黏土礦物之平均層間隔根據有機化合物之分子結構、所需之碳量子點之粒徑而適當選擇，較佳為0.1至10 nm，更較佳為0.1至8 nm。層狀黏土礦物之平均層間隔可藉由X射線繞射裝置等進行分析。另外，所謂層狀黏土礦物之平均層間隔係指層狀黏土礦物之相鄰結晶層之其中一者之底面與另一者之頂面的間隔。如前述，碳量子點係以層狀黏土礦物之層間為模板而合成。因此，若層狀黏土礦物之平均層間隔為10 nm以下，則易於獲得發光波長短之碳量子點。另一方面，若平均層間隔為0.1 nm以上，則有機化合物之一部分容易進入至該等之間，易於以層狀黏土礦物之層間為模板而形成碳量子點。On the other hand, the average interlayer spacing of the layered clay minerals combined with the organic compound is appropriately selected according to the molecular structure of the organic compound and the desired particle size of the carbon quantum dots, preferably 0.1 to 10 nm, more preferably 0.1 to 8 nm. The average interlayer interval of the layered clay minerals can be analyzed by an X-ray diffraction apparatus or the like. In addition, the so-called average interlayer interval of the layered clay mineral refers to the interval between the bottom surface of one of the adjacent crystalline layers of the layered clay mineral and the top surface of the other. As mentioned above, carbon quantum dots are synthesized using the interlayers of layered clay minerals as templates. Therefore, if the average interlayer spacing of the layered clay minerals is 10 nm or less, it is easy to obtain carbon quantum dots with short emission wavelengths. On the other hand, if the average interlayer spacing is 0.1 nm or more, a part of the organic compound is likely to enter between them, and carbon quantum dots are likely to be formed using the interlayers of the layered clay minerals as a template.
另外，為了調整層狀黏土礦物之平均層間隔，亦可利用水、各種溶劑使層狀黏土礦物膨潤。作為有機溶劑，例如可列舉：甲醇、乙醇、己烷、甲苯、氯仿、二甲基甲醯胺、二甲基亞碸等。混合物（有機化合物、層狀黏土礦物及溶劑）中之溶劑之量較佳為10至80質量百分比，更較佳為10至70重量百分比。In addition, in order to adjust the average interval of the layered clay minerals, the layered clay minerals can also be swelled with water or various solvents. As an organic solvent, methanol, ethanol, hexane, toluene, chloroform, dimethylformamide, dimethylsulfoxide, etc. are mentioned, for example. 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.
此處，將有機化合物與層狀黏土礦物混合之方法只要可將該等均勻混合，則並無特別限制。例如，可一面利用研缽磨碎一面混合，或一面利用球磨機等粉碎一面混合。Here, the method of mixing the organic compound and the layered clay mineral is not particularly limited as long as these can be uniformly mixed. For example, the mixture may be mixed while being ground with a mortar, or may be mixed while being ground with a ball mill or the like.
另外，有機化合物與層狀黏土礦物之混合比根據所需之碳點量子與層狀黏土礦物之含有比而適當選擇。 碳量子點製備步驟In addition, the mixing ratio of the organic compound and the layered clay mineral is appropriately selected according to the desired content ratio of the carbon dots and the layered clay mineral. Preparation steps of carbon quantum dots
碳量子點製備步驟係將上述混合物加熱，使有機化合物碳化而製成碳量子點之步驟。混合物之加熱方法只要可使有機化合物反應而碳化，則並無特別限制，例如包含進行加熱之方法、照射電磁波（例如微波）之方法等。The carbon quantum dot preparation step is a step of heating the above mixture to carbonize the organic compound to form carbon quantum dots. The heating method of the mixture is not particularly limited as long as the organic compound can be reacted and carbonized, and includes, for example, a method of heating, a method of irradiating electromagnetic waves (such as microwaves), and the like.
於將混合物加熱時，加熱溫度較佳為70至700℃，更較佳為100至500℃，進而較佳為100至300℃。另外，加熱時間較佳為0.01至45小時，更較佳為0.1至30小時，進而較佳為0.5至10小時。可利用加熱時間調整所得之碳量子點之粒徑、進而調整發光波長。另外，此時亦可一面流通氮氣等惰性氣體一面於非氧化性氣體氛圍下進行加熱。When heating the mixture, the heating temperature is preferably 70 to 700°C, more preferably 100 to 500°C, and further preferably 100 to 300°C. In addition, the heating time is preferably 0.01 to 45 hours, more preferably 0.1 to 30 hours, and still more preferably 0.5 to 10 hours. The particle size of the obtained carbon quantum dots can be adjusted by heating time, and then the emission wavelength can be adjusted. In addition, in this case, heating may be performed in a non-oxidizing gas atmosphere while flowing an inert gas such as nitrogen gas.
於照射電磁波（例如微波）時，瓦數較佳為1至1500 W，更較佳為1至1000 W。另外，利用電磁波（例如微波）之加熱時間較佳為0.01至10小時，更較佳為0.01至5小時，進而較佳為0.01至1小時。可利用電磁波（微波）之照射時間調整所得之碳量子點之粒徑、進而調整發光波長。When irradiating electromagnetic waves (such as microwaves), the wattage is preferably 1 to 1500 W, more preferably 1 to 1000 W. In addition, the heating time using electromagnetic waves (eg microwaves) is preferably 0.01 to 10 hours, more preferably 0.01 to 5 hours, and still more preferably 0.01 to 1 hour. The particle size of the carbon quantum dots obtained can be adjusted by the irradiation time of electromagnetic waves (microwaves), and then the emission wavelength can be adjusted.
上述電磁波照射可藉由例如半導體式電磁波照射裝置等進行。電磁波之照射較佳一面確認上述混合物之溫度一面進行。較佳一面以例如溫度成為70至700℃之方式進行調整，一面照射電磁波。The above-mentioned electromagnetic wave irradiation can be performed by, for example, a semiconductor-type electromagnetic wave irradiation device or the like. The irradiation of electromagnetic waves is preferably performed while confirming the temperature of the above-mentioned mixture. It is preferable to irradiate an electromagnetic wave, for example, so that a temperature may be adjusted so that it may become 70-700 degreeC.
藉由該碳量子點製備步驟，而獲得碳量子點與層狀黏土礦物均勻分散之含碳量子點之組成物。另外，此時亦可利用有機溶劑將該組成物洗淨，且去除未反應物、副產物而進行精製。 （用途）Through the preparation step of carbon quantum dots, a composition of carbon quantum dots in which carbon quantum dots and layered clay minerals are uniformly dispersed is obtained. In addition, in this case, the composition may be washed with an organic solvent, and unreacted substances and by-products may be removed and purified. (use)
如上所述，若經過混合物製備步驟及上述碳量子點製備步驟而製備含碳量子點之組成物，則與在製備碳量子點後與層狀黏土礦物進行混合時相比，碳量子點之分散性提高。另外，碳量子點之分散性高之含碳量子點之組成物的發光性良好，或作為利用碳量子點所具有之官能基使特定物質分離之分離劑而有用。因此，可將組成物用於各種用途。As described above, if the composition containing carbon quantum dots is prepared through the mixture preparation step and the above carbon quantum dot preparation step, the dispersion of carbon quantum dots is compared with when the carbon quantum dots are mixed with the layered clay minerals after the preparation of the carbon quantum dots. Sexual improvement. In addition, a composition containing carbon quantum dots having high dispersibility of carbon quantum dots has good luminescence properties, or is useful as a separating agent for separating specific substances using functional groups possessed by carbon quantum dots. Therefore, the composition can be used for various purposes.
上述含碳量子點之組成物之用途並無特別限制，可根據碳量子點之性能，用於例如太陽電池、顯示器、防偽油墨、量子點雷射、生物標記、照明材料、熱電材料、光觸媒、特定物質之分離劑等。 [實施例]The use of the composition containing carbon quantum dots is not particularly limited, and can be used in, for example, solar cells, displays, anti-counterfeiting inks, quantum dot lasers, biological markers, lighting materials, thermoelectric materials, photocatalysts, Separating agent for specific substances, etc. [Example]
以下，將本發明之具體實施例與比較例一併進行說明，但本發明並不限定於該等。 [實施例1]Hereinafter, although the specific Example of this invention is demonstrated together with a comparative example, this invention is not limited to these. [Example 1]
利用研缽將皂石（Sumecton SA，Kunimine Industries公司製造）1.0 g與間苯三酚二水合物0.15 g磨碎。將該混合物放入至內容積為15 ml之螺口試驗管，並利用帶有橡膠墊圈之螺口蓋封上。然後，一面於螺口試驗管內流通氮氣，一面以200℃加熱3小時，而製備含有碳量子點與層狀黏土礦物之含碳量子點之組成物（複合體）。 [實施例2]1.0 g of saponite (Sumecton SA, manufactured by Kunimine Industries) and 0.15 g of phloroglucinol dihydrate were ground in a mortar. The mixture was put into a screw test tube with an inner volume of 15 ml and closed with a screw cap with a rubber gasket. Then, nitrogen gas was circulated in the screw test tube and heated at 200° C. for 3 hours to prepare a composition (composite) of carbon quantum dots containing carbon quantum dots and layered clay minerals. [Example 2]
利用研缽將菱水鎂鋁石（富士膠片和光純藥公司製造）0.5 g、檸檬酸0.15 g及雙氰胺0.1 g磨碎。將該混合物放入至內容積為15 ml之螺口試驗管，並利用帶有橡膠墊圈之螺口蓋封上。然後，一面於螺口試驗管內流通氮氣，一面以170℃加熱90分鐘，而製備含有碳量子點與層狀黏土礦物之含碳量子點之組成物（複合體）。 [實施例3]0.5 g of magnesite (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 put into a screw test tube with an inner volume of 15 ml and closed with a screw cap with a rubber gasket. Then, nitrogen gas was circulated in the screw test tube, while heating at 170° C. for 90 minutes to prepare a composition (composite) of carbon quantum dots containing carbon quantum dots and layered clay minerals. [Example 3]
利用研缽將皂石（Sumecton SA，Kunimine Industries公司製造）1.0 g、間苯三酚二水合物0.15 g及二甲基亞碸0.5 ml磨碎。將該混合物放入至內容積為15 ml之螺口試驗管，並利用帶有橡膠墊圈之螺口蓋封上。然後，一面於螺口試驗管內流通氮氣，一面以155℃加熱3小時之後，於40℃真空乾燥8小時，而製備含有碳量子點與層狀黏土礦物之含碳量子點之組成物（複合體）。 [實施例4]1.0 g of saponite (Sumecton SA, manufactured by Kunimine Industries), 0.15 g of phloroglucinol dihydrate, and 0.5 ml of dimethylsulfite were ground in a mortar. The mixture was put into a screw test tube with an inner volume of 15 ml and closed with a screw cap with a rubber gasket. Then, nitrogen gas was circulated in the screw test tube, heated at 155°C for 3 hours, and then vacuum-dried at 40°C for 8 hours to prepare a carbon quantum dot composition (composite) containing carbon quantum dots and layered clay minerals. body). [Example 4]
利用研缽將皂石（Sumecton SA，Kunimine Industries公司製造）1.0 g與間苯三酚二水合物0.15 g磨碎。將該混合物放入至內容積為15 ml之螺口試驗管，並利用帶有橡膠墊圈之螺口蓋封上。然後，一面於螺口試驗管內流通氮氣，一面以155℃加熱3小時，而製備含有碳量子點與層狀黏土礦物之含碳量子點之組成物（複合體）。 [實施例5]1.0 g of saponite (Sumecton SA, manufactured by Kunimine Industries) and 0.15 g of phloroglucinol dihydrate were ground in a mortar. The mixture was put into a screw test tube with an inner volume of 15 ml and closed with a screw cap with a rubber gasket. Then, while nitrogen gas was circulated in the screw test tube, it was heated at 155° C. for 3 hours to prepare a composition (composite) of carbon quantum dots containing carbon quantum dots and layered clay minerals. [Example 5]
利用研缽將皂石（Sumecton SA，Kunimine Industries公司製造）1.0 g與間苯三酚二水合物0.4 g磨碎。將該混合物放入至內容積為15 ml之螺口試驗管，並利用帶有橡膠墊圈之螺口蓋封上。然後，一面於螺口試驗管內流通氮氣，一面以200℃加熱3小時，而製備含有碳量子點與層狀黏土礦物之含碳量子點之組成物（複合體）。 [實施例6]1.0 g of saponite (Sumecton SA, manufactured by Kunimine Industries) and 0.4 g of phloroglucinol dihydrate were ground in a mortar. The mixture was put into a screw test tube with an inner volume of 15 ml and closed with a screw cap with a rubber gasket. Then, nitrogen gas was circulated in the screw test tube and heated at 200° C. for 3 hours to prepare a composition (composite) of carbon quantum dots containing carbon quantum dots and layered clay minerals. [Example 6]
利用研缽將皂石（Sumecton SA，Kunimine Industries公司製造）0.5 g、檸檬酸0.15 g及雙氰胺0.1 g磨碎。將該混合物放入至內容積為15 ml之螺口試驗管，並利用帶有橡膠墊圈之螺口蓋封上。然後，一面於螺口試驗管內流通氮氣，一面以170℃加熱90分鐘，而製備含有碳量子點與層狀黏土礦物之含碳量子點之組成物（複合體）。 [實施例7]0.5 g of soapstone (Sumecton SA, manufactured by Kunimine Industries), 0.15 g of citric acid, and 0.1 g of dicyandiamide were ground in a mortar. The mixture was put into a screw test tube with an inner volume of 15 ml and closed with a screw cap with a rubber gasket. Then, nitrogen gas was circulated in the screw test tube, while heating at 170° C. for 90 minutes to prepare a composition (composite) of carbon quantum dots containing carbon quantum dots and layered clay minerals. [Example 7]
利用研缽將皂石（Sumecton SA，Kunimine Industries公司製造）1.0 g、間苯三酚二水合物0.02 g及間苯二酚0.1 g磨碎。將該混合物放入至內容積為15 ml之螺口試驗管，並利用帶有橡膠墊圈之螺口蓋封上。然後，一面於螺口試驗管內流通氮氣，一面以200℃加熱3小時，而製備含有碳量子點與層狀黏土礦物之含碳量子點之組成物（複合體）。 [實施例8]1.0 g of saponite (Sumecton SA, manufactured by Kunimine Industries), 0.02 g of phloroglucinol dihydrate, and 0.1 g of resorcinol were ground in a mortar. The mixture was put into a screw test tube with an inner volume of 15 ml and closed with a screw cap with a rubber gasket. Then, nitrogen gas was circulated in the screw test tube and heated at 200° C. for 3 hours to prepare a composition (composite) of carbon quantum dots containing carbon quantum dots and layered clay minerals. [Example 8]
利用研缽將皂石（Sumecton SA，Kunimine Industries公司製造）0.56 g與間苯三酚二水合物0.084 g磨碎。將該混合物放入至內容積為15 ml之螺口試驗管，並利用帶有橡膠墊圈之螺口蓋封上。然後，一面於螺口試驗管內流通氮氣，一面於攪拌下將上述螺口試驗管設置於富士電波工機公司製造之半導體式電磁波照射裝置（矩形波導管型共振器）之電場最大點，並照射2.45 GHz之電磁波，而製備含有碳量子點與層狀黏土礦物之含碳量子點之組成物（複合體）。Saponite (Sumecton SA, manufactured by Kunimine Industries) 0.56 g and phloroglucinol dihydrate 0.084 g were ground in a mortar. The mixture was put into a screw test tube with an inner volume of 15 ml and closed with a screw cap with a rubber gasket. Then, while flowing nitrogen gas in the screw test tube, the screw test tube was set at the maximum point of the electric field of the semiconductor type electromagnetic wave irradiation device (rectangular waveguide type resonator) manufactured by Fuji Electric Machinery Co., Ltd. under stirring, and The composition (composite) of carbon quantum dots containing carbon quantum dots and layered clay minerals is prepared by irradiating electromagnetic waves of 2.45 GHz.
另外，利用該半導體式電磁波照射裝置之電磁波照射係採用TE103單模。該半導體式電磁波照射裝置包含具備三短截線調諧器(Three-stub tuner)、光圈及柱塞之共振器、半導體式電磁波振動器、以及監視輸入功率及反射功率之監視器。電磁波照射時之溫度係使用紅外放射溫度計進行測定。而且，藉由一面自該半導體式電磁波振動器進行2 W、2.45 GHz之電磁波之振動，一面調節三短截線調諧器及柱塞，而將反射功率抑制為小於0.1 W。於電磁波照射1分鐘後，紅外放射溫度計所顯示之溫度成為200℃，於溫度計顯示200℃之後進行4分鐘反應。 [比較例1]In addition, the electromagnetic wave irradiation system using the semiconductor electromagnetic wave irradiation device adopts TE103 single mode. The semiconductor-type electromagnetic wave irradiation device includes a three-stub tuner, a resonator with an aperture and a plunger, a semiconductor-type electromagnetic wave vibrator, 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. Furthermore, the reflected power was suppressed to less than 0.1 W by adjusting the three-stub tuner and the plunger while oscillating the electromagnetic wave at 2 W and 2.45 GHz from the semiconductor type electromagnetic wave vibrator. After 1 minute of electromagnetic wave irradiation, the temperature indicated by the infrared radiation thermometer became 200°C, and the reaction was performed for 4 minutes after the thermometer indicated 200°C. [Comparative Example 1]
將間苯三酚二水合物1.2 g放入至內容積為15 ml之螺口試驗管，於氮氣氣流下，以200℃加熱3小時而合成碳量子點。量取合成之碳量子點0.12 g，與皂石1.0 g一起利用研缽磨碎，藉此將兩者混合，而獲得含碳量子點之組成物。 [比較例2]1.2 g of phloroglucinol dihydrate was put into a screw test tube with an inner volume of 15 ml, and heated at 200° C. for 3 hours under nitrogen flow to synthesize carbon quantum dots. 0.12 g of the synthesized carbon quantum dots were weighed and ground together with 1.0 g of soapstone using a mortar, thereby mixing the two to obtain a composition containing carbon quantum dots. [Comparative Example 2]
利用研缽將檸檬酸0.15 g與雙氰胺0.1 g磨碎。將該混合物放入至內容積為15 ml之螺口試驗管，於氮氣氣流下以170℃加熱90分鐘，而合成碳量子點。量取合成之碳量子點35.0 mg，與菱水鎂鋁石70.0 mg一起利用研缽磨碎，藉此將兩者混合，而獲得含碳量子點之組成物。 [比較例3]Using a mortar, 0.15 g of citric acid and 0.1 g of dicyandiamide were ground. The mixture was put into a screw test tube with an inner volume of 15 ml, and heated at 170° C. for 90 minutes under nitrogen flow to synthesize carbon quantum dots. 35.0 mg of the synthesized carbon quantum dots were weighed and ground together with 70.0 mg of magnesite in a mortar to mix the two to obtain a composition containing carbon quantum dots. [Comparative Example 3]
將間苯三酚二水合物1.2 g放入至內容積為15 ml之螺口試驗管，於氮氣氣流下，以200℃加熱3小時而合成碳量子點。量取合成之碳量子點0.31 g，與皂石1.0 g一起利用研缽磨碎，藉此將兩者混合，而獲得含碳量子點之組成物。 [比較例4]1.2 g of phloroglucinol dihydrate was put into a screw test tube with an inner volume of 15 ml, and heated at 200° C. for 3 hours under nitrogen flow to synthesize carbon quantum dots. 0.31 g of the synthesized carbon quantum dots were weighed and ground together with 1.0 g of soapstone using a mortar, thereby mixing the two to obtain a composition containing carbon quantum dots. [Comparative Example 4]
利用研缽將檸檬酸0.15 g與雙氰胺0.1 g磨碎。將該混合物放入至內容積為15 ml之螺口試驗管，於氮氣氣流下以170℃加熱90分鐘，而合成碳量子點。量取合成之碳量子點50.0 mg，與皂石100.0 mg一起利用研缽磨碎，藉此將兩者混合，而獲得含碳量子點之組成物。 ［評估］Using a mortar, 0.15 g of citric acid and 0.1 g of dicyandiamide were ground. The mixture was put into a screw test tube with an inner volume of 15 ml, and heated at 170° C. for 90 minutes under nitrogen flow to synthesize carbon quantum dots. 50.0 mg of the synthesized carbon quantum dots were weighed and ground together with 100.0 mg of soapstone using a mortar, thereby mixing the two to obtain a composition containing carbon quantum dots. [Evaluate]
針對實施例及比較例中使用之層狀黏土礦物之平均層間隔、所得之組成物之比表面積、及組成物之發光波長，以如下方式進行評估。其結果示於表1。另外，以如下方式測定實施例5及比較例3之組成物中之碳量子點之凝聚狀態、及實施例5之組成物之碳量子點之含量。將結果分別示於圖1及圖2。 （層狀黏土礦物之平均層間隔之測定）The average interlayer interval of the layered clay minerals used in the Examples and Comparative Examples, the specific surface area of the obtained composition, and the emission wavelength of the composition were evaluated in the following manner. The results are shown in Table 1. In addition, the aggregation state of carbon quantum dots in the compositions of Example 5 and Comparative Example 3, and the content of carbon quantum dots in the composition of Example 5 were measured as follows. The results are shown in Figs. 1 and 2, respectively. (Determination of Average Interlayer Interval of Layered Clay Minerals)
關於層狀黏土礦物之平均層間隔，使用X'Pert-PRO MPD（PANalytical製造），於特性X射線波長1.54Å下進行粉末X射線繞射測定而評估。所謂層狀黏土礦物之平均層間隔係指構成層狀黏土礦物之結晶層之間隔（其中一者之底面與另一者之頂面的間隔）。 （比表面積之評估）The average interlayer spacing of the layered clay minerals was evaluated by powder X-ray diffraction measurement at a characteristic X-ray wavelength of 1.54 Å using X'Pert-PRO MPD (manufactured by PANalytical). The so-called average interlayer interval of layered clay minerals refers to the interval between the crystalline layers constituting the layered clay minerals (the interval between the bottom surface of one and the top surface of the other). (Assessment of specific surface area)
關於組成物之比表面積，使用Monosorb（Quantachrome Instruments製造）進行評估。使用N2 ：He＝20 vol%：80 vol%之混合氣體並利用布厄特（Brunauer-Emmett-Teller，BET）一點法求出比表面積之值。樣品使用於150℃乾燥10分鐘後者。 （發光波長之評估）The specific surface area of the composition was evaluated using Monosorb (manufactured by Quantachrome Instruments). The value of the specific surface area was obtained by the one-point method of Brunauer-Emmett-Teller (BET) using a mixed gas of N 2 : He=20 vol%: 80 vol%. The samples were dried using the latter at 150°C for 10 minutes. (Evaluation of emission wavelength)
將組成物夾於KBr平板間進行壓製，而製作測定用樣品。使用螢光分光光度計FP-8500（日本分光公司製造）對該測定用樣品照射波長為400 nm之激發光，對發光波長（螢光波長）進行評估。 （碳量子點之凝聚狀態之評估）The composition was sandwiched between KBr plates and pressed to prepare a sample for measurement. The sample for measurement was irradiated with excitation light having a wavelength of 400 nm using a spectrofluorophotometer FP-8500 (manufactured by JASCO Corporation), and the emission wavelength (fluorescence wavelength) was evaluated. (Assessment of Condensed State of Carbon Quantum Dots)
關於實施例5及比較例3之組成物中之碳量子點之凝聚狀態，使用X'Pert-PRO MPD（PANalytical製造）於特性X射線波長1.54Å下進行粉末X射線繞射測定而評估。 （碳量子點含量之評估）The aggregation state of the carbon quantum dots in the compositions of Example 5 and Comparative Example 3 was evaluated by powder X-ray diffraction measurement using X'Pert-PRO MPD (manufactured by PANalytical) at a characteristic X-ray wavelength of 1.54 Å. (Assessment of Carbon Quantum Dot Content)
使用熱重分析裝置TGA2（Mettler公司製造），於40 ml/min之空氣氣流下以10℃/min之升溫速度進行測定，根據重量減少量評估實施例5之組成物中之碳量子點含量。Using a thermogravimetric analyzer TGA2 (manufactured by Mettler), the measurement was performed at a heating rate of 10°C/min under an air flow of 40 ml/min, and the content of carbon quantum dots in the composition of Example 5 was evaluated according to the weight loss.
[表1]
如上述表所示，於層狀黏土礦物之存在下製備碳量子點而獲得含有碳量子點及層狀黏土礦物之含碳量子點之組成物時，可獲得所需波長之發光（實施例1至8）。另外，實施例3及實施例4中雖以同一反應溫度及同一反應時間製備碳量子點，但使用藉由添加溶劑而使層間隔擴大之層狀黏土礦物之實施例3中，碳量子點顯示波長更長之發光。因此，認為實施例3中獲得粒徑較實施例4大之碳量子點。As shown in the above table, when carbon quantum dots are prepared in the presence of layered clay minerals to obtain the composition of carbon quantum dots containing carbon quantum dots and layered clay minerals, luminescence of the desired wavelength can be obtained (Example 1 to 8). In addition, although carbon quantum dots were prepared at the same reaction temperature and the same reaction time in Examples 3 and 4, in Example 3 using a layered clay mineral whose interlayer interval was expanded by adding a solvent, the carbon quantum dots showed Longer wavelength light. Therefore, it is considered that carbon quantum dots with larger particle diameters were obtained in Example 3 than in Example 4.
另一方面，於合成碳量子點後將碳量子點與層狀黏土礦物混合之比較例1及比較例3中，無法確認到發光。認為未良好地分散，導致碳量子點凝聚。另外，比較例2中，雖以與實施例2相同之反應溫度及相同之反應時間製備碳量子點，但碳量子點之螢光波長為長。認為實施例2中，藉由在層狀黏土礦物之存在下製備碳量子點，碳量子點之粒徑變小，因此螢光波長較比較例2短。另外，比較例4之組成物雖有機化合物與層狀黏土礦物之比率和實施例6相同，但比表面積大。認為實施例6中，於層狀黏土礦物之存在下製備碳量子點，因此於層狀化合物之空孔中有效地包藏碳量子點，從而碳量子點之分散性較比較例4變得良好。On the other hand, in Comparative Example 1 and Comparative Example 3 in which the carbon quantum dots were mixed with the layered clay mineral after synthesizing the carbon quantum dots, light emission could not be confirmed. It is considered that the carbon quantum dots were not well dispersed, resulting in aggregation of the carbon quantum dots. In addition, 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 fluorescence wavelength of the carbon quantum dots was long. It is considered that in Example 2, by preparing carbon quantum dots in the presence of layered clay minerals, the particle size of the carbon quantum dots becomes smaller, and thus the fluorescence wavelength is shorter than that in Comparative Example 2. In addition, the composition of Comparative Example 4 has a larger specific surface area although the ratio of the organic compound to the layered clay mineral is the same as that of Example 6. It is considered that in Example 6, carbon quantum dots were prepared in the presence of layered clay minerals, so carbon quantum dots were effectively occluded in the pores of the layered compound, so that the dispersibility of carbon quantum dots became better than that of Comparative Example 4.
此外，如圖1所示，實施例5及比較例3之任一組成物均觀察到源自層狀黏土礦物之繞射峰（2θ＝19°附近之峰）。另外，實施例5之組成物中，未觀察到源自碳量子點之凝聚之繞射峰，相對於此，比較例3之組成物中，於繞射角度2θ＝17°、20°、26°、29°附近觀察到源自碳量子點之凝聚之尖銳的峰。此外，實施例5之組成物中，觀察到源自層狀黏土礦物之層秩序之峰（2θ＝8°）向小角度側的移位（2θ＝6°）以及寬化。因此，實施例5之製備方法中，可以說碳量子點於層狀黏土礦物之層間生成。另外，認為所得之組成物中，碳量子點良好地分散於層狀黏土礦物中。In addition, as shown in FIG. 1 , in any of the compositions of Example 5 and Comparative Example 3, diffraction peaks (peaks in the vicinity of 2θ=19°) derived from layered clay minerals were observed. In addition, in the composition of Example 5, the diffraction peak derived from the aggregation of carbon quantum dots was not observed, whereas in the composition of Comparative Example 3, the diffraction angles 2θ=17°, 20°, 26° Sharp peaks originating from the aggregation of carbon quantum dots were observed in the vicinity of ° and 29°. In addition, in the composition of Example 5, the shift (2θ=6°) and broadening of the layer order peak (2θ=8°) derived from the layered clay mineral to the small-angle side were observed. Therefore, in the preparation method of Example 5, it can be said that the carbon quantum dots are formed between the layers of the layered clay minerals. In addition, it is considered that in the obtained composition, the carbon quantum dots are well dispersed in the layered clay mineral.
此外，如圖2所示，於測定實施例5之組成物之重量減少量時，在約300℃至550℃之間可見21質量百分比之重量減少。根據該結果算出實施例5之組成物含有21質量百分比之碳量子點。In addition, as shown in FIG. 2, when the weight loss of the composition of Example 5 was measured, a weight loss of 21 mass percent was observed between about 300°C and 550°C. According to the results, it was calculated that the composition of Example 5 contained 21 mass percent of carbon quantum dots.
本申請主張基於2019年10月29日申請之日本專利特願2019-196094號之優先權。將該申請說明書中記載之內容全部引用於本案說明書中。 產業上之可利用性This application claims priority based on Japanese Patent Application No. 2019-196094 filed on October 29, 2019. All the contents described in the specification of this application are cited in the specification of the present application. industrial availability
根據本發明之含碳量子點之組成物，碳量子點與層狀黏土礦物之分散性良好，此外，可將碳量子點之性能（例如發光波長）調整成所需範圍。因此，獲得可用於各種用途之含碳量子點之組成物。According to the composition containing carbon quantum dots of the present invention, the dispersibility of carbon quantum dots and layered clay minerals is good, and in addition, the properties of carbon quantum dots (eg, emission wavelength) can be adjusted to a desired range. Thus, a composition of carbon quantum dots that can be used for various purposes is obtained.
無none
［圖1］係表示對實施例5及比較例3之組成物進行粉末X射線繞射測定時之結果的曲線圖。 ［圖2］係表示對實施例5之組成物進行熱重分析時之結果之曲線圖。1 is a graph showing the results of powder X-ray diffraction measurement of the compositions of Example 5 and Comparative Example 3. FIG. FIG. 2 is a graph showing the results of thermogravimetric analysis of the composition of Example 5. FIG.
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