JP2015036389A - Production method of graphene quantum dot emitter - Google Patents
Production method of graphene quantum dot emitter Download PDFInfo
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- JP2015036389A JP2015036389A JP2013167351A JP2013167351A JP2015036389A JP 2015036389 A JP2015036389 A JP 2015036389A JP 2013167351 A JP2013167351 A JP 2013167351A JP 2013167351 A JP2013167351 A JP 2013167351A JP 2015036389 A JP2015036389 A JP 2015036389A
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- graphene quantum
- acid catalyst
- quantum dot
- acid
- solution
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Abstract
Description
本発明は、発光特性に優れ、かつ、耐久性の高いグラフェン量子ドット発光体の製造方法に関するものである。 The present invention relates to a method for producing a graphene quantum dot luminescent material having excellent luminescent properties and high durability.
特定の波長を吸収し蛍光や燐光を発する発光体は、下記の3種類に大別される。
先ず、1)イオンがドープされた発光中心を持つ無機化合物で構成される発光体が挙げられる。代表例は半導体量子ドットである。次に、2)有機化合物で構成される発光体が挙げられる。代表例は希土類錯体である。最後に、3)グラフェン等が構成成分とされる炭素系発光体が挙げられる。
The phosphors that absorb a specific wavelength and emit fluorescence or phosphorescence are roughly classified into the following three types.
First, 1) a light emitter composed of an inorganic compound having an emission center doped with ions may be mentioned. A typical example is a semiconductor quantum dot. Next, 2) a light-emitting body composed of an organic compound is exemplified. A typical example is a rare earth complex. Finally, 3) a carbon-based light emitter in which graphene or the like is a constituent component.
中でも炭素系発光体で近年注目を集めているグラフェン量子ドットは、他の発光体に比較して、安全性、価格、さらには、化学的安定性における優位性が期待されている。
しかしながら、優れた発光特性を有するグラフェン量子ドットを、高収率で再現性良く製造できる手法は確立されておらず、優れた発光特性を有するグラフェン量子ドットの高収率で再現性の良い製法が切望されている。
Among these, graphene quantum dots, which have attracted attention in recent years for carbon-based light emitters, are expected to have superiority in safety, price, and chemical stability compared to other light emitters.
However, no method has been established to produce graphene quantum dots with excellent light emission characteristics with high yield and good reproducibility, and there is no method for producing graphene quantum dots with excellent light emission characteristics with high yield and good reproducibility. Longed for.
既存の製法は、トップダウン法とボトムアップ法の2種類に大別される(非特許文献4)。
一方のトップダウン法は、原料の黒鉛や炭素繊維に酸化剤を作用させて、酸化グラフェンまたは積層酸化グラフェンとして微粒子(微ディスク)を切り出した後、切り出した酸化グラフェンまたは積層酸化グラフェンの微粒子(微ディスク)を還元してグラフェン量子ドットに仕上げる手法である(非特許文献1、3、特許文献1〜4)。
トップダウン法は、量産も可能な手法であるが、狭帯発光が難しく、工業的に通用する発光特性を備えたグラフェン量子ドットは本手法では作製されていない。酸化グラフェンまたは積層酸化グラフェンを、均一な粒子径(ディスク径)に切り出せる酸化剤や反応条件を見出すことが困難と考えられる。
Existing manufacturing methods are roughly classified into two types, a top-down method and a bottom-up method (Non-Patent Document 4).
In one top-down method, an oxidizing agent is allowed to act on raw graphite or carbon fiber to cut out fine particles (fine discs) as graphene oxide or laminated graphene oxide, and then cut out graphene oxide or laminated graphene oxide fine particles (fine particles). This is a method of reducing a disk to a graphene quantum dot (Non-patent Documents 1 and 3, Patent Documents 1 to 4).
Although the top-down method is a method that can be mass-produced, a graphene quantum dot having a light emission characteristic that is difficult to produce narrow-band light emission and that can be applied industrially has not been produced by this method. It is considered difficult to find an oxidizing agent and reaction conditions that can cut out graphene oxide or laminated graphene oxide into a uniform particle diameter (disk diameter).
他方のボトムアップ法は、低分子量の糖類やアミノ酸類を原料に縮合を繰り返しながらグラフェン量子ドットを作製する手法である。生成物に適切なドープを施すことで約70%以上の極めて高い量子収率を示すグラフェン量子ドットも、シスチンを原料に焼成する乾式法で作製されているものの残念ながら収率は極めて低い(非特許文献2)。 The other bottom-up method is a method for producing graphene quantum dots while repeating condensation using low molecular weight sugars and amino acids as raw materials. Graphene quantum dots that exhibit an extremely high quantum yield of about 70% or more by appropriately doping the product are also produced by a dry method in which cystine is fired as a raw material, but unfortunately the yield is very low (non- Patent Document 2).
また、ボトムアップ法において、湿式法でグラフェン量子ドットを製造する方法が非特許文献3に開示されているが、同様の反応条件を繰り返して実施してもグラフェン量子ドットを得られず、再現性に問題を有していた。 Further, in the bottom-up method, a method for producing graphene quantum dots by a wet method is disclosed in Non-Patent Document 3, but even if the same reaction conditions are repeated, graphene quantum dots cannot be obtained, and reproducibility Had a problem.
本発明が解決しようとする課題は、高い量子収率を示し、発光スペクトルの半値幅の狭い狭帯発光し、優れたグラフェン量子ドットを高収率で再現性良く簡便に合成できる新規な手法を提供することである。 The problem to be solved by the present invention is to develop a novel technique that can easily synthesize excellent graphene quantum dots with high yield and high reproducibility, exhibiting high quantum yield, narrow band emission with a narrow half-value width of emission spectrum. Is to provide.
湿式のボトムアップ法において、溶液中に適切な酸触媒を添加して、加温することで上記課題を解決した。すなわち、本発明は、以下の技術的手段から構成される。 In the wet bottom-up method, an appropriate acid catalyst was added to the solution and heated to solve the above problem. That is, the present invention comprises the following technical means.
〔1〕 ヘテロ原子含有化合物を溶解又は分散させた溶液中に、酸触媒を添加して加熱することを特徴とするグラフェン量子ドット発光体の製造方法。
〔2〕
前記ヘテロ原子含有化合物として、糖類、アミノ酸類及び核酸類から選ばれる1種類以上の化合物を用いることを特徴とする前記〔1〕に記載のグラフェン量子ドット発光体の製造方法。
〔3〕 前記酸触媒として、細孔を有する多孔質体不均一酸触媒を用いることを特徴とする前記〔1〕又は前記〔2〕に記載のグラフェン量子ドット発光体の製造方法。
〔4〕 前記酸触媒として、均一酸触媒を用いることを特徴とする前記〔1〕又は前記〔2〕に記載のグラフェン量子ドット発光体の製造方法。
〔5〕 前記均一酸触媒ともに界面活性剤を添加することを特徴とする前記〔4〕に記載のグラフェン量子ドット発光体の製造方法。
[1] A method for producing a graphene quantum dot phosphor, comprising adding an acid catalyst to a solution in which a heteroatom-containing compound is dissolved or dispersed and heating the solution.
[2]
One or more types of compounds chosen from saccharides, amino acids, and nucleic acids are used as said hetero atom containing compound, The manufacturing method of the graphene quantum dot light-emitting body of said [1] characterized by the above-mentioned.
[3] The method for producing a graphene quantum dot luminescent material according to [1] or [2], wherein a porous material heterogeneous acid catalyst having pores is used as the acid catalyst.
[4] The method for producing a graphene quantum dot luminescent material according to [1] or [2], wherein a homogeneous acid catalyst is used as the acid catalyst.
[5] The method for producing a graphene quantum dot luminescent material according to [4], wherein a surfactant is added together with the homogeneous acid catalyst.
本発明の製造法により、高い量子収率を示し、発光スペクトルの半値幅の狭い狭帯発光し、優れたグラフェン量子ドットを高収率で再現性良く簡便に製造することが可能になった。 According to the production method of the present invention, it is possible to easily produce excellent graphene quantum dots with high yield and high reproducibility by exhibiting high quantum yield, narrow band emission with a narrow half-value width of the emission spectrum.
以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明は、ヘテロ原子含有化合物を溶解又は分散させた溶液中に、酸触媒を添加して加熱することを特徴とするグラフェン量子ドット発光体の製造方法である。 The present invention is a method for producing a graphene quantum dot luminescent material, wherein an acid catalyst is added and heated in a solution in which a heteroatom-containing compound is dissolved or dispersed.
本発明は、湿式法であり、原料を溶媒に溶解または分散し、触媒添加後、適切な反応温度でもって適切な時間でもって反応を行う。反応は、還流及び/又は撹拌しながら行うのが好まし。通常、撹拌は、撹拌子又は撹拌機によって撹拌される。 The present invention is a wet method, in which a raw material is dissolved or dispersed in a solvent, and after the addition of a catalyst, the reaction is performed at an appropriate reaction temperature and at an appropriate time. The reaction is preferably carried out under reflux and / or stirring. Usually, stirring is stirred by a stirrer or a stirrer.
原料を溶媒に溶解または分散させて反応させる本発明においては、界面活性剤を添加することも有効である。特に、界面活性剤の添加は、原料を溶媒に分散させて反応する場合及び後述する均一酸触媒を用いて反応する場合に有効である。 In the present invention in which raw materials are dissolved or dispersed in a solvent and reacted, it is also effective to add a surfactant. In particular, the addition of a surfactant is effective when the raw material is dispersed in a solvent for reaction and when the reaction is performed using a homogeneous acid catalyst described later.
上記のような反応により、粒子状あるいはディスク状のグラフェン量子ドット発光体を得ることができる。粒子状のものは球状又は楕円球状である。 By the reaction as described above, a particle-shaped or disk-shaped graphene quantum dot light emitter can be obtained. The particles are spherical or elliptical.
本発明の原料は、酸素、窒素、硫黄、および、リンと言ったヘテロ原子を含有している化合物であればよいが、その中でも糖類、アミノ酸類、核酸類といった安全かつ安価な原料を、低分子量からオリゴマー領域分子量さらに高分子量まで幅広く選択できる。 The raw material of the present invention may be any compound containing heteroatoms such as oxygen, nitrogen, sulfur, and phosphorus. Among them, safe and inexpensive raw materials such as saccharides, amino acids, and nucleic acids are used. A wide range of molecular weight, oligomer region molecular weight and high molecular weight can be selected.
上記の原料は、半導体量子ドットの原料の様に、カドミウムやセレンといった安全性が懸念されたり、イリジウムやガリウムといった高価であったり供給安定性が懸念される原料を用いることもない。 The above raw materials do not use materials such as cadmium and selenium that are concerned about safety, expensive materials such as iridium and gallium, and concerns about supply stability like the materials of semiconductor quantum dots.
本発明に用いることができる代表的な糖類としては、次に示す化合物が挙げられる。単糖類や二糖類としては、ブドウ糖、マルトース、ガラクトース、麦芽糖、乳糖、セロビオース、ショ糖、トレハロース、キシロース、アラビノース、グルクロン酸、および、グルコサミンの他、ソルビトールやキシリトール等も選択できる。多糖類としては、デンプン、セルロース、β-グルカン、キチン、キトサン、ヘパリン、および、コンドロイチン硫酸等が挙げられる。 Typical saccharides that can be used in the present invention include the following compounds. As monosaccharides and disaccharides, sorbitol, xylitol, and the like can be selected in addition to glucose, maltose, galactose, maltose, lactose, cellobiose, sucrose, trehalose, xylose, arabinose, glucuronic acid, and glucosamine. Examples of the polysaccharide include starch, cellulose, β-glucan, chitin, chitosan, heparin, and chondroitin sulfate.
また、本発明に用いることができる代表的なアミノ酸類としては、次に示す化合物が挙げられる。アミノ酸としては、シスチン、オルニチン、スレオニン、リジン、アスパラギン、トルプトファン、セリン、チロキシン、グルタミン酸、アスパラギン酸、グリシン、アラニン、バリン、および、フェニルアラニンが、一方、蛋白質類としては、BSA、γ-グロブリン、リゾチーム、リパーゼ、トリプシン、および、カゼインの他、様々な酵素類や、ホエー等の産業余剰物も挙げられる。 In addition, typical amino acids that can be used in the present invention include the following compounds. Amino acids include cystine, ornithine, threonine, lysine, asparagine, torptophan, serine, thyroxine, glutamic acid, aspartic acid, glycine, alanine, valine, and phenylalanine, while proteins include BSA, γ-globulin, lysozyme. In addition to lipase, trypsin, and casein, various enzymes and industrial surplus such as whey are also included.
本発明に用いることができる代表的な核酸類としては、次に示す化合物が挙げられる。デオキシリボ核酸(DNA)やリボ核酸(RNA)の他、ヌクレオチド類やヌクレオシド類も挙げることができる。 Representative nucleic acids that can be used in the present invention include the following compounds. In addition to deoxyribonucleic acid (DNA) and ribonucleic acid (RNA), nucleotides and nucleosides can also be mentioned.
原料の濃度は、溶液または分散液が調製できればこだわらない。しかしながら、得量をできるだけ多くしたい場合には、原料の仕込量はできるだけ多く、反応液の粘度をできるだけ抑制したい場合は、原料の仕込量はできるだけ少なくすることになる。原料の仕込量は、1重量%〜90重量%、好ましくは、5重量%〜60重量%、さらに好ましくは、10重量%から30重量%である。 The concentration of the raw material is not particularly limited as long as a solution or dispersion can be prepared. However, when it is desired to increase the yield as much as possible, the raw material charge is as large as possible, and when the viscosity of the reaction solution is to be suppressed as much as possible, the raw material charge is as small as possible. The amount of raw materials charged is 1% to 90% by weight, preferably 5% to 60% by weight, and more preferably 10% to 30% by weight.
原料を溶解又は分散させる溶媒には、親水性の溶媒又は疎水性の溶媒の溶媒を用いることができる。
親水性の溶媒としては、水をはじめとしてDMSO、DMF、DMA、NMP、HMPA、アセトニトリル、および、アセトン等の他、メタノール、エタノール、n−プロピルアルコール、i−プロピルアルコール等のアルコール類や、エチレングリコールおよびトリエチレングリコール等のグリコール類、エチルセロソルブおよびメチルセロソロロソルブ等のセロソルブ類、グリセリン、ペンタエリスリトール等も挙げられる。
疎水性の溶媒としては、THF、酢酸エチル、酢酸ブチル、ベンゼン、トルエン、キシレン、ペンタン、ヘキサン、へプタン、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン等が挙げられる。
As a solvent for dissolving or dispersing the raw material, a hydrophilic solvent or a hydrophobic solvent can be used.
Examples of hydrophilic solvents include water, DMSO, DMF, DMA, NMP, HMPA, acetonitrile, and acetone, as well as alcohols such as methanol, ethanol, n-propyl alcohol, and i-propyl alcohol, and ethylene. Also included are glycols such as glycol and triethylene glycol, cellosolves such as ethyl cellosolve and methyl cellosololosolv, glycerin, pentaerythritol and the like.
Examples of the hydrophobic solvent include THF, ethyl acetate, butyl acetate, benzene, toluene, xylene, pentane, hexane, heptane, chlorobenzene, dichlorobenzene, and trichlorobenzene.
原料を溶解又は分散させた溶媒に加える界面活性剤としては、イオン性界面活性剤(カチオン性若しくはアニオン性)又は中性界面活性剤がある。 Examples of the surfactant added to the solvent in which the raw material is dissolved or dispersed include an ionic surfactant (cationic or anionic) or a neutral surfactant.
カチオン性の界面活性剤としては、セチルトリメチルアンモニウムブロマイド(CTABr)、セチルトリメチルアンモニウムクロライド(CTACl)、アニオン性の界面活性剤としては、中性の界面活性剤としては、ポリエチレングリコール(PEG)やポリプロピレングリコール(PPG)を挙げることができる。 Examples of cationic surfactants include cetyltrimethylammonium bromide (CTABr) and cetyltrimethylammonium chloride (CTACl). Examples of anionic surfactants include polyethylene glycol (PEG) and polypropylene. A glycol (PPG) can be mentioned.
エチルセルロースやヒドロキシプロピルセルロースといったセルロース誘導体も界面活性剤として有効である。その場合、セルロース誘導体は、酸触媒下、原料としても消費されることがあり、これらを原料として界面活性剤を兼ねて用いることができる。また、オリゴマー領域分子量から高分子量の原料を用いる場合は、それらが適切なミセルを形成する界面活性剤としても機能することも有る。 Cellulose derivatives such as ethyl cellulose and hydroxypropyl cellulose are also effective as surfactants. In that case, the cellulose derivative may be consumed as a raw material in the presence of an acid catalyst, and these can be used as a raw material also as a surfactant. Moreover, when using a high molecular weight raw material from an oligomer area | region molecular weight, they may function also as surfactant which forms a suitable micelle.
10nm程度より小さい粒径又はディスク径のグラフェン量子ドットを作製する場合には、イオン性の界面活性剤が、一方、10nm以上の粒径又はディスク径のグラフェン量子ドットを作製する場合には、中性の界面活性剤を使用するのが良い。 When producing graphene quantum dots having a particle size or disk diameter smaller than about 10 nm, an ionic surfactant is used. On the other hand, when producing graphene quantum dots having a particle diameter or disk diameter of 10 nm or more, It is preferable to use a surfactant.
界面活性剤の添加量は、原料、溶媒の種類及び添加する界面活性剤の種類によって適正な添加量がきまるが、カチオン性やアニオン性のイオン性界面活性剤の添加量は、中性の界面活性剤に比較してごく少量で効果を発揮する。
カチオン性やアニオン性のイオン性界面活性剤の添加量は、通常、原料に対して0.1重量%から100重量%の範囲にあり、好ましくは、0.5重量%から50重量%の範囲で、さらに好ましくは、1.0重量%から10重量%の範囲で添加する。
中性の界面活性剤は、原料に対して5.0重量%から5000重量%の範囲にあり、好ましくは、25重量%から1000重量%の範囲で、さらに好ましくは、50重量%から200重量%の範囲で添加する。
The amount of surfactant to be added depends on the raw material, the type of solvent, and the type of surfactant to be added, but the amount of cationic or anionic ionic surfactant added is neutral. It is effective in a very small amount compared to the active agent.
The addition amount of the cationic or anionic ionic surfactant is usually in the range of 0.1 to 100% by weight, preferably in the range of 0.5 to 50% by weight, based on the raw material. More preferably, it is added in the range of 1.0 wt% to 10 wt%.
The neutral surfactant is in the range of 5.0 wt% to 5000 wt%, preferably in the range of 25 wt% to 1000 wt%, and more preferably in the range of 50 wt% to 200 wt% with respect to the raw material. Add in the range of%.
本発明に用いる酸触媒としては、酸触媒であれば良く、均一酸触媒でも不均一酸触媒でも良い。 The acid catalyst used in the present invention may be an acid catalyst, and may be a homogeneous acid catalyst or a heterogeneous acid catalyst.
不均一酸触媒としては、次の様な固体酸触媒が挙げられる。ポリスチレンスルホン酸とその共重合体を主成分とするカチオン性のイオン交換樹脂(市販品では、アンバーライトやアンバーリスト等が良く知られている)や、原らの作製したショ糖の焼成品をスルホン化して得られる固体酸触媒等も使用することができる(Hara,M.,et al.,Nature,438,178(2005))。 Examples of the heterogeneous acid catalyst include the following solid acid catalysts. Cationic ion-exchange resins based on polystyrenesulfonic acid and its copolymers (commercially known products such as Amberlite and Amberlist are well known) and sucrose baked products made by Hara A solid acid catalyst obtained by sulfonation can also be used (Hara, M., et al., Nature, 438, 178 (2005)).
不均一酸触媒の場合、生成したグラフェン量子ドットを内包できる容積を有する細孔を持つ多孔質体でありことが好ましい。
この細孔の大きさにより生成するグラフェン量子ドットの粒子径又はディスク径を制御することができる。一般的には、20nm程度までの細孔径を有する多孔質体の固体酸触媒により、20nmまでの粒子径(ディスク径)のグラフェン量子ドットを製造するのが好ましい。
In the case of a heterogeneous acid catalyst, a porous body having pores having a volume capable of enclosing the generated graphene quantum dots is preferable.
The particle diameter or disk diameter of the graphene quantum dots generated can be controlled by the size of the pores. In general, it is preferable to produce graphene quantum dots having a particle size (disk diameter) of up to 20 nm using a porous solid acid catalyst having a pore size of up to about 20 nm.
そして、不均一酸触媒の場合、均一酸触媒に比較して数倍のプロトン濃度に調製すると良い結果が得られる。例えば、イオン交換容量が1meq/gのポリスチレンスルホン酸型のカチオン性のイオン交換樹脂の場合、原料の重量に対して凡そ0.1〜100重量%の添加が好ましい。原料の重量に対して1.0〜50重量%の添加がより好ましく、原料の重量に対して5.0〜10重量%の添加がさらに好ましい。 In the case of a heterogeneous acid catalyst, good results can be obtained by adjusting the proton concentration to several times that of a homogeneous acid catalyst. For example, in the case of a polystyrenesulfonic acid type cationic ion exchange resin having an ion exchange capacity of 1 meq / g, addition of about 0.1 to 100% by weight with respect to the weight of the raw material is preferable. Addition of 1.0 to 50% by weight with respect to the weight of the raw material is more preferable, and addition of 5.0 to 10% by weight with respect to the weight of the raw material is more preferable.
均一酸触媒としては次の様な化合物が挙がられる。無機酸としては、塩酸、硫酸、硝酸、リン酸等、有機酸としては、スルホン酸、P−トルエンスルホン酸、カルボン酸、蟻酸、酢酸、プロピオン酸、酪酸、蓚酸、コハク酸、トリフルオロ酢酸等、超強酸としては、副反応が抑制できるようであればカルボラン酸等が使用できる。 Examples of the homogeneous acid catalyst include the following compounds. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of organic acids include sulfonic acid, P-toluenesulfonic acid, carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, succinic acid, succinic acid, and trifluoroacetic acid. As the super strong acid, carborane acid or the like can be used as long as side reactions can be suppressed.
均一酸触媒の場合、通常、均一酸触媒を原料の重量に対して0.01〜10重量%を添加するが、原料の重量に対して0.1〜5重量%の添加がより好ましく、原料の重量に対して0.5〜1重量%の添加がさらに好ましい。 In the case of a homogeneous acid catalyst, 0.01 to 10% by weight of the homogeneous acid catalyst is usually added to the weight of the raw material, but 0.1 to 5% by weight of the raw material is more preferably added. The addition of 0.5 to 1% by weight based on the weight of is more preferable.
酸触媒として均一酸触媒を添加する場合には、溶液中で適切なミセルを形成する界面活性剤を共存させる手法が有効であり、均一酸触媒とともに、界面活性剤を適量溶存させることでグラフェン量子ドットの製造は顕著な改善を示す。 When adding a homogeneous acid catalyst as an acid catalyst, it is effective to coexist with a surfactant that forms appropriate micelles in the solution, and graphene quantum can be obtained by dissolving an appropriate amount of the surfactant together with the homogeneous acid catalyst. Dot manufacture shows a marked improvement.
本発明の反応は、以下のような条件で行われる。
反応温度は使用する溶媒の沸点によるが、室温〜250℃程度、好ましくは、60〜200℃程度、さらに好ましくは、100〜150℃程度である。オートクレーブを使用することで、常圧での沸点以上に反応温度を上げることもできる。例えば、水を溶媒に選択する場合も、オートクレーブで反応させることで200℃程度の反応温度は容易に達成される。
通常水浴やオイルバスで加熱するが、マイクロウェーブで加熱することもできる。例えば水を溶媒にして反応を行う場合、水浴やオイルバスで加熱した場合に比較して短時間で生成物を得ることができる。水浴やオイルバスで1日加熱して生成物を得る反応も、マイクロウェーブで加熱することで1時間以内に反応を終了することができることがある。
The reaction of the present invention is carried out under the following conditions.
Although the reaction temperature depends on the boiling point of the solvent used, it is about room temperature to 250 ° C, preferably about 60 to 200 ° C, and more preferably about 100 to 150 ° C. By using an autoclave, the reaction temperature can be raised above the boiling point at normal pressure. For example, when water is selected as a solvent, a reaction temperature of about 200 ° C. can be easily achieved by reacting in an autoclave.
Usually heated in a water bath or oil bath, but can also be heated in a microwave. For example, when the reaction is carried out using water as a solvent, the product can be obtained in a shorter time than when heated in a water bath or oil bath. The reaction to obtain a product by heating in a water bath or an oil bath for 1 day may be completed within 1 hour by heating in a microwave.
反応時間は、1分〜10日程度、好ましくは、10分〜2日程度で、さらに好ましくは、30時間〜半日程度である。 The reaction time is about 1 minute to 10 days, preferably about 10 minutes to 2 days, and more preferably about 30 hours to half a day.
また、アンバーリスト等の固体触媒を用いる場合は、撹拌して反応させることが好ましく、固体触媒が砕けない範囲で、撹拌速度を上げると良い結果が得られる。10〜500rpm程度、好ましくは、50−300rpm程度、さらに好ましくは。50−300rpm程度である。 When a solid catalyst such as amberlist is used, the reaction is preferably carried out with stirring, and good results can be obtained by increasing the stirring speed within a range where the solid catalyst does not break. About 10 to 500 rpm, preferably about 50 to 300 rpm, more preferably. It is about 50-300 rpm.
反応が終了した生成物は、以下のような操作によって精製される。まず、透析や限外濾過で低分子量の不純物を除去し、その後、遠心分離等で高分子量の不純物を分級して行う。さらに高純度に生成する場合は、カラム精製を実施する。充填剤としては、順相逆相いずれも使用可能である。 The finished product is purified by the following procedure. First, low molecular weight impurities are removed by dialysis or ultrafiltration, and then high molecular weight impurities are classified by centrifugation or the like. If it is produced with higher purity, column purification is performed. As the filler, any of normal phase and reverse phase can be used.
透析は、精製したい反応終了後の反応液を透析膜に封入し、一般的には純水中に浸漬する。使用する透析膜の細孔径に応じた精製が可能となる。細孔径の小さい透析膜の場合、グラフェン量子ドットが透析膜の外に漏れる恐れが低くなる一方、不純物の除去に長時間要する。細孔径の大きな透析膜の場合、グラフェン量子ドットが透析膜の外に漏れる恐れがあるものの、不純物の除去は短時間に達成できる。
一方、限外濾過の場合、細孔の小さな限外濾過膜を用いた場合も、加圧すること所要時間を短くすることができる点で都合良い。
In dialysis, the reaction solution after completion of the reaction to be purified is sealed in a dialysis membrane and generally immersed in pure water. Purification according to the pore diameter of the dialysis membrane to be used becomes possible. In the case of a dialysis membrane having a small pore diameter, the risk of graphene quantum dots leaking out of the dialysis membrane is reduced, but it takes a long time to remove impurities. In the case of a dialysis membrane having a large pore size, the removal of impurities can be achieved in a short time, although the graphene quantum dots may leak out of the dialysis membrane.
On the other hand, in the case of ultrafiltration, even when an ultrafiltration membrane having small pores is used, pressurization is advantageous in that the required time can be shortened.
その後の遠心分離等で高分子量の不純物の除去は、遠心分離器の回転数を制御することによって行うことができる。 The removal of high molecular weight impurities by subsequent centrifugation or the like can be performed by controlling the rotation speed of the centrifuge.
さらに高純度に生成する場合は、カラム精製を実施する。充填剤としては、順相逆相いずれも使用可能である。順相充填材としては、各種粒径のシリカ粒子やアルミナ粒子が選択できる。一方、逆相充填剤の場合は、長鎖アルキル基で表面修飾したシリカ粒子が使用できる。また、カラム精製中に加圧するフラッシュカラム精製も時間短縮の点で都合良い。 If it is produced with higher purity, column purification is performed. As the filler, any of normal phase and reverse phase can be used. As the normal phase filler, silica particles and alumina particles having various particle sizes can be selected. On the other hand, in the case of a reverse phase filler, silica particles whose surface is modified with a long-chain alkyl group can be used. Further, flash column purification in which pressure is applied during column purification is also convenient in terms of shortening the time.
以下、実施例を示すが、本発明の効果は、これらに限られるものではない。
〔実施例1〕
ショ糖10gをイオン交換水100gに溶解した後、0.1gの濃硫酸をさらに添加し良く撹拌した。冷却器を備えた丸底フラスコに、準備した溶液を注ぎ入れ、続いてオイルバスで加熱した。還流開始後、反応液を間欠的にサンプリングしながらグラフェン量子ドットの生成を反応液の蛍光をモニターしながら追跡し、蛍光強度が一定になったところを反応の終点とした。還流開始を確認後、約2時間加熱を継続した。反応液の蛍光が最大になった時点における発光スペクトルのピーク波長と半値幅を表1に記載した。反応終了後の反応液を透析膜に注ぎ入れ、十分量のイオン交換水に浸漬した。イオン交換水は半日ごとに交換し3日間透析を続けた。透析終了後の反応液を遠心分離(12000rpmx30分)処理し、上澄み液を取り出しロータリーエバポレーターで濃縮乾燥後得られた固形分を、真空乾燥機(5Torrx50℃x1日)でさらに乾燥し高純度グラフェン量子ドットを得た。得られたグラフェン量子ドットの収率(重量%)を表1に記載した。
Hereinafter, although an Example is shown, the effect of this invention is not restricted to these.
[Example 1]
After 10 g of sucrose was dissolved in 100 g of ion-exchanged water, 0.1 g of concentrated sulfuric acid was further added and stirred well. The prepared solution was poured into a round bottom flask equipped with a condenser and subsequently heated in an oil bath. After the start of reflux, the generation of graphene quantum dots was followed while sampling the reaction solution while monitoring the fluorescence of the reaction solution, and the point where the fluorescence intensity became constant was defined as the end point of the reaction. After confirming the start of reflux, heating was continued for about 2 hours. Table 1 shows the peak wavelength and full width at half maximum of the emission spectrum when the fluorescence of the reaction solution reached the maximum. The reaction solution after completion of the reaction was poured into a dialysis membrane and immersed in a sufficient amount of ion-exchanged water. Ion exchange water was changed every half day and dialysis was continued for 3 days. The reaction solution after completion of dialysis is centrifuged (12000 rpm x 30 minutes), and the supernatant is taken out and concentrated and dried by a rotary evaporator. Got a dot. The yield (% by weight) of the obtained graphene quantum dots is shown in Table 1.
〔実施例2〕
界面活性剤PEGを1g添加した以外は実施例1と同様にして行った。
[Example 2]
The same procedure as in Example 1 was performed except that 1 g of the surfactant PEG was added.
〔実施例3〕
ショ糖10gをイオン交換水100gに溶解した後、0.1gのアンバーリスト1.0gをさらに添加し良く撹拌した。冷却器を備えた丸底フラスコに、準備した分散液を注ぎ入れ、続いてオイルバスで加熱した。還流開始後、反応液を間欠的にサンプリングしながらグラフェン量子ドットの生成を反応液の蛍光をモニターしながら追跡し、蛍光強度が一定になったところを反応の終点とした。
還流開始を確認後、約2時間加熱を継続した。反応液の蛍光が最大になった時点における発光スペクトルのピーク波長と半値幅を表1に記載した。
反応終了後、アンバーリストが反応容器に沈殿した状態で、反応液だけをデカンテーションで注意深く透析膜に注ぎ入れた。イオン交換水100gをさらに反応容器に注ぎ入れ十分洗浄した後、アンバーリストが反応容器に沈殿した状態で、洗浄液だけをデカンテーションで注意深く透析膜に注ぎ入れた。約200gの反応液と洗浄液を封入したイオン交換膜を3Lのイオン交換水に浸漬した。イオン交換水は半日ごとに交換し3日間透析を続けた。透析終了後の反応液を遠心分離(12000rpmx30分)処理し、上澄み液を取り出しロータリーエバポレーターで濃縮乾燥後得られた固形分を、真空乾燥機(5Torrx50℃x1日)でさらに乾燥し高純度グラフェン量子ドットを得た。得られたグラフェン量子ドットの収率(重量%)を表1に記載した。
Example 3
After dissolving 10 g of sucrose in 100 g of ion-exchanged water, 1.0 g of 0.1 g of Amberlyst was further added and stirred well. The prepared dispersion was poured into a round bottom flask equipped with a condenser and subsequently heated in an oil bath. After the start of reflux, the generation of graphene quantum dots was followed while sampling the reaction solution while monitoring the fluorescence of the reaction solution, and the point where the fluorescence intensity became constant was defined as the end point of the reaction.
After confirming the start of reflux, heating was continued for about 2 hours. Table 1 shows the peak wavelength and full width at half maximum of the emission spectrum when the fluorescence of the reaction solution reached the maximum.
After completion of the reaction, the reaction solution alone was carefully poured into the dialysis membrane by decantation with the amberlist precipitated in the reaction vessel. After 100 g of ion-exchanged water was further poured into the reaction vessel and thoroughly washed, only the washing solution was carefully poured into the dialysis membrane by decantation while the amberlist was precipitated in the reaction vessel. An ion exchange membrane in which about 200 g of the reaction solution and the cleaning solution were sealed was immersed in 3 L of ion exchange water. Ion exchange water was changed every half day and dialysis was continued for 3 days. The reaction solution after completion of dialysis is centrifuged (12000 rpm x 30 minutes), and the supernatant is taken out and concentrated and dried by a rotary evaporator. Got a dot. The yield (% by weight) of the obtained graphene quantum dots is shown in Table 1.
図1に、実施例3で合成されたグラフェン量子ドットのTEM写真を示す。生成したグラフェン量子ドットは、平均粒子径約4nmで、約2nmから約6nmの粒子径分布を持っている。
図2に、実施例3で合成されたグラフェン量子ドットの蛍光スペクトルを示す。(1)は吸収スペクトルを表し左側のY軸でプロットされている。(2)および(3)各々励起スペクトルおよび発光スペクトルを示し、共に右側のY軸でプロットされている。発光スペクトルは490nmにピークを持つ緑色の光であることを示すと共に、半値幅約70nmの狭帯発光していることが見て取れる。
FIG. 1 shows a TEM photograph of the graphene quantum dots synthesized in Example 3. The generated graphene quantum dots have an average particle size of about 4 nm and a particle size distribution of about 2 nm to about 6 nm.
FIG. 2 shows the fluorescence spectrum of the graphene quantum dots synthesized in Example 3. (1) represents an absorption spectrum and is plotted on the left Y-axis. (2) and (3) show the excitation spectrum and emission spectrum, respectively, both plotted on the right Y-axis. The emission spectrum shows that it is green light having a peak at 490 nm, and it can be seen that narrow band light emission with a half width of about 70 nm is emitted.
〔実施例4〕
ショ糖に代えてデンプン添加した以外は実施例3と同様にして行った。
Example 4
The same procedure as in Example 3 was performed except that starch was added instead of sucrose.
〔実施例5〕
ショ糖に代えてグルコサミン添加した以外は実施例3と同様にして行った。
Example 5
The same procedure as in Example 3 was performed except that glucosamine was added instead of sucrose.
〔実施例6〕
ショ糖に代えてキトサン添加した以外は実施例3と同様にして行った。なお、キトサンは、水溶性の酢酸塩を使用した。
Example 6
The same procedure as in Example 3 was performed except that chitosan was added instead of sucrose. In addition, water-soluble acetate was used for chitosan.
〔実施例7〕
ショ糖に代えてシスチンを添加した以外は実施例3と同様にして行った。
Example 7
The same procedure as in Example 3 was performed except that cystine was added instead of sucrose.
〔実施例8〕
ショ糖に代えてDNA添加した以外は実施例1と同様にして行った。なお、DNAは、白子を原料に精製された試供品を使用した。
Example 8
The same procedure as in Example 1 was performed except that DNA was added instead of sucrose. In addition, the sample used for the DNA refined using a white child as a raw material.
〔比較例1〕
ショ糖10gをイオン交換水100gに溶解した。冷却器を備えた丸底フラスコに、準備した溶液を注ぎ入れ、続いてオイルバスで加熱した。還流開始を確認後、約2時間、間欠的にサンプリングし観察したが蛍光の活性を確認することはできなかった。
[Comparative Example 1]
10 g of sucrose was dissolved in 100 g of ion exchange water. The prepared solution was poured into a round bottom flask equipped with a condenser and subsequently heated in an oil bath. After confirming the start of reflux, sampling was observed intermittently for about 2 hours, but the fluorescence activity could not be confirmed.
〔比較例2〕
PEG1.0gを追加添加した以外は、比較例1と同様にして行った。
[Comparative Example 2]
The same operation as in Comparative Example 1 was conducted except that 1.0 g of PEG was additionally added.
表1に、実施例1から8ならびに比較例1および2で得られたグラフェン量子ドットの発光特性と収率の一覧を示す。 Table 1 shows a list of emission characteristics and yields of the graphene quantum dots obtained in Examples 1 to 8 and Comparative Examples 1 and 2.
実施例1から8ならびに比較例1および2で得られたグラフェン量子ドットの発光特性と収率を示す。比較例では目的の生成物は得られず収率0%であるが、実施例は全て良好な収率を示す。均一触媒系では、界面活性剤を添加することで収率が向上することがわかる。不均一触媒系では、均一触媒系に比較して収率は高く、さらに、低分子量体を原料にした方が、高分子量体を原料にするより収率が高い。また、不均一触媒系では、均一触媒系に比較して狭帯発光していることが見て取れる。中でもシスチンを原料に用いた場合、発光スペクトルの半値幅は65nmと優れた狭帯発光している。また、DNAの様な分子量の極めて大きな原料も発光している。 The light emission characteristics and yield of the graphene quantum dots obtained in Examples 1 to 8 and Comparative Examples 1 and 2 are shown. In the comparative example, the desired product is not obtained and the yield is 0%, but all the examples show good yields. In a homogeneous catalyst system, it can be seen that the yield is improved by adding a surfactant. In a heterogeneous catalyst system, the yield is higher than in a homogeneous catalyst system, and the yield is higher when a low molecular weight material is used as a raw material than when a high molecular weight material is used as a raw material. Further, it can be seen that the heterogeneous catalyst system emits narrow band light compared to the homogeneous catalyst system. In particular, when cystine is used as a raw material, the emission spectrum has a half-band width of 65 nm and excellent narrow band emission. In addition, a material having an extremely large molecular weight such as DNA also emits light.
本発明の製造方法で製造されるグラフェン量子ドット発光体は、ディスプレーや照明の光源として使用される。また、LEDの発光スペクトル調整のための材料、耐久性に優れるバイオ・プローブ等にも使用される。
The graphene quantum dot light emitter produced by the production method of the present invention is used as a light source for display or illumination. It is also used for materials for adjusting the emission spectrum of LEDs, bioprobes with excellent durability, and the like.
Claims (5)
The method for producing a graphene quantum dot luminescent material according to claim 4, wherein a surfactant is added together with the homogeneous acid catalyst.
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