JP2008057023A - Noble metal nanosheet and its production method - Google Patents
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Abstract
Description
本発明は、金に代表される貴金属の二次元ナノ構造体とその製造方法に関する。 The present invention relates to a two-dimensional nanostructure of a noble metal typified by gold and a method for producing the same.
ナノシート、ナノプレート状の二次元金属ナノ構造は、ナノ粒子に比べて薄膜等における電子的特性が勝ることから、近年その合成手法（製造方法）の開発が急速に発展している。金などの金属のナノシート（ナノプレート）をナノテクノロジーへ応用するための重要な課題は、その幾何学形態の制御を行って、新しい物性機能（例えば、光学材料、触媒などとして）を開発することである。 Since nanosheets and nanoplate-like two-dimensional metal nanostructures have better electronic properties in thin films and the like than nanoparticles, in recent years, development of their synthesis methods (manufacturing methods) has been rapidly progressing. An important issue in applying nanosheets (nanoplates) of metals such as gold to nanotechnology is to control their geometrical forms and develop new physical functions (for example, as optical materials and catalysts). It is.
ナノシート（ナノプレート）を合成する従来の手法は、（１）界面活性剤、水溶性高分子、液晶、生体材料を保護剤に用いる化学還元法〔例えば、W.S.Yun他、Chem. Mater., 17, 5558(2005)（非特許文献１）、M.Nakamoto他、Chem. Mater., 17, 5391(2005)（非特許文献２）〕（２）金ナノ結晶を核としてこれをシートへと成長させる核成長法〔例えば、M.Oyama他、Cryst. Growth
Des., 6, 818(2006)（非特許文献３）〕、（３）イオン液体中でのマイクロ波加熱法〔例えば、M.Tsuji他、Chem. Lett., 32, 1114(2003)（非特許文献４）〕、（４）ポリオール合成法〔例えば、W.Cai他、Adv. Func. Mater.,
17, 5391(2005)（非特許文献５）〕など多岐に渡る。しかし、これら既知の手法で得られる構造体は、三角形、あるいは六角形のナノシート（ナノプレート）に限られ、多彩な幾何学形状を有する金属ナノシート（ナノプレート）を合成するための一般的かつ実用的な技術は知られていない。さらに、これらの手法は、複数の工程から成る煩雑な操作を要するものが多い。
Conventional methods for synthesizing nanosheets (nanoplates) include (1) chemical reduction methods using surfactants, water-soluble polymers, liquid crystals, and biomaterials as protective agents [for example, WYun et al., Chem. Mater., 17 , 5558 (2005) (Non-Patent Document 1), M. Nakamoto et al., Chem. Mater., 17 , 5391 (2005) (Non-Patent Document 2)] (2) Growing gold nanocrystals into a sheet Nuclear growth methods (eg M. Oyama et al., Cryst. Growth
Des., 6 , 818 (2006) (Non-Patent Document 3)], (3) Microwave heating methods in ionic liquids [for example, M. Tsuji et al., Chem. Lett., 32 , 1114 (2003) (Non-Patent Document 3) Patent Document 4)], (4) Polyol synthesis method [for example, W. Cai et al., Adv. Func. Mater.,
17 , 5391 (2005) (Non-Patent Document 5)]. However, the structures obtained by these known methods are limited to triangular or hexagonal nanosheets (nanoplates), and are general and practical for synthesizing metal nanosheets (nanoplates) having various geometric shapes. The technology is not known. Furthermore, many of these methods require complicated operations consisting of a plurality of steps.
特開２００６−３７２２１号公報（特許文献１）には、塩化金酸の水溶液から金ナノ構造体（金ナノシート）を製造する方法が提案されている。しかし、この方法も、塩化金酸の水溶液を加熱する工程に後続して、分散安定化剤を添加する工程、還元剤を添加する工程、さらに加熱工程を必要とする煩雑な方法である。得られる金ナノシートは、多角形または円形の板状構造を備えると称しているが、現実に生成されているのは既述の従来技術と同様に三角形または六角形のものと理解される。 Japanese Patent Laying-Open No. 2006-37221 (Patent Document 1) proposes a method for producing a gold nanostructure (gold nanosheet) from an aqueous solution of chloroauric acid. However, this method is also a complicated method requiring a step of adding a dispersion stabilizer, a step of adding a reducing agent, and a heating step following the step of heating the aqueous solution of chloroauric acid. The resulting gold nanosheet is said to have a polygonal or circular plate-like structure, but what is actually generated is understood to be triangular or hexagonal as in the prior art described above.
従来より、ナノ構造体の形状を制御する手法の一つとして、所定の構造体を結晶成長させた後に、電気化学的処理、酸処理または酸化剤を用いる処理などにより、結晶の一部を除去（エッチング）することが行われていた〔例えば、M. Hakamada他、Nano Lett., 6, 882(2006)（非特許文献６）〕。しかし、このような手法も結晶成長とエッチングを別々に行う点で面倒である。
本発明の目的は、金などの貴金属のナノシート（ナノプレート）をその幾何学的形態を制御して、簡便且つ低コストで製造することのできる新しい技術を提供することにある。 An object of the present invention is to provide a new technique capable of producing a nanosheet (nanoplate) of a noble metal such as gold by controlling its geometric form easily and at low cost.
本発明者は、研究を重ねた結果、単一の工程により貴金属のナノシートを形成させることのできる技術を確立し本発明を導き出した。
かくして、本発明は、貴金属の錯体、前記貴金属の可溶化剤、および前記貴金属の保護ポリマーを混合、含有する水溶液に紫外線を照射する工程を含むことを特徴とする貴金属ナノシートの製造方法を提供するものである。
As a result of extensive research, the inventor has established a technique capable of forming a nanosheet of noble metal by a single process and derived the present invention.
Thus, the present invention provides a method for producing a noble metal nanosheet, comprising a step of irradiating an aqueous solution containing a noble metal complex, a solubilizing agent for the noble metal, and a protective polymer for the noble metal with an ultraviolet ray. Is.
本発明の方法は、常温、常圧における単一の反応工程により、金などの貴金属のナノシートの製造を可能にするものであり、きわめて簡便であり低コストである。
本発明の貴金属ナノシートの製造方法に従えば、反応条件を制御することにより、ナノシートの形状や大きさを制御することができ、これまでに知られていない形状、例えば、形状が九角形である金ナノシート、あるいは合弁花状の構造を呈する金ナノシートを得ることもできる。
The method of the present invention enables the production of nanosheets of noble metals such as gold by a single reaction step at normal temperature and normal pressure, and is extremely simple and low cost.
According to the method for producing a noble metal nanosheet of the present invention, the shape and size of the nanosheet can be controlled by controlling the reaction conditions, and the previously unknown shape, for example, the shape is a hexagon. Gold nanosheets or gold nanosheets having a joint flower-like structure can also be obtained.
本発明に従えば、貴金属の錯体、該金属の可溶化剤および該金属の保護ポリマーが混合されて含有されている水溶液に紫外光を照射するという実質的に単一の工程により、従来は知られていなかった特異な形状のものも含む金属ナノシートを調製することができる。これは、上記各原料の存在下に光照射を行うことにより、結晶成長とエッチングが同時に進行するためと考えられる。 According to the present invention, conventionally known is a substantially single step of irradiating an aqueous solution containing a mixture of a noble metal complex, a solubilizer for the metal and a protective polymer for the metal, with ultraviolet light. It is possible to prepare a metal nanosheet including a specific shape that has not been provided. This is presumably because crystal growth and etching proceed simultaneously by irradiating light in the presence of each of the above raw materials.
本発明が対象とするのは、貴金属、すなわち、金、銀、白金、パラジウム、ルテニウム、ロジウム、オスミウム、およびイリジウムであるが、本発明は、特に金に対して好ましく適用される。 The present invention is directed to noble metals, that is, gold, silver, platinum, palladium, ruthenium, rhodium, osmium, and iridium, but the present invention is particularly preferably applied to gold.
原料となる貴金属の錯体は、水溶性であり、光（紫外光）照射により分解・還元されて対応する金属を生成し得る（例えば、金の場合、Ａｕ3+→Ａｕ）ものであれば、いずれも適用可能である。好ましい錯体として、金および白金族金属にみられる下記の式（Ａ）で表されるようなハロゲノ錯体が挙げられるが、これに限られるものではない。
かくして、金の場合、好ましい金錯体として、次の一般式（Ａ）で表されるものが挙げられる。
The noble metal complex as a raw material is water-soluble and can be decomposed and reduced by irradiation with light (ultraviolet light) to produce a corresponding metal (for example, Au 3+ → Au in the case of gold). Either is applicable. Preferred complexes include, but are not limited to, halogeno complexes represented by the following formula (A) found in gold and platinum group metals.
Thus, in the case of gold, preferred gold complexes include those represented by the following general formula (A).
本発明に従い貴金属のナノ構造体を製造するには、上記のごとき貴金属錯体に加えて、該貴金属の可溶化剤を存在させておくことが必要である。この可溶化剤は生成した金属を溶解（エッチング）する作用を有するものである。本発明において使用されるのに特に好ましい可溶化剤の例は、Ｃｌ−、Ｂｒ−やＩ−のようなハロゲンアニオンであり、実際の操作に当たっては、例えば、ＮａＢｒ、ＫＢｒ、ＨＢｒなどとして添加、使用される。かくして、ハロゲンアニオンは、光還元により生成した金属に配位して錯体として該金属をゆるやかに溶解する（例えば、金の場合、Ａｕ＋４Ｂｒ−→ＡｕＢｒ4 −）ものと考えられる。 In order to produce a noble metal nanostructure according to the present invention, it is necessary that a solubilizer of the noble metal is present in addition to the noble metal complex as described above. This solubilizer has an action of dissolving (etching) the produced metal. Examples of particularly preferred solubilizers to be used in the present invention are halogen anions such as Cl − , Br − and I − , which are added as, for example, NaBr, KBr, HBr, etc. in actual operation. used. Thus, it is considered that the halogen anion coordinates with the metal generated by photoreduction and dissolves the metal gently as a complex (for example, Au + 4Br − → AuBr 4 − in the case of gold).
本発明の貴金属ナノシートの製造方法においては、貴金属の錯体および該貴金属の可溶化剤を含有する水溶液に保護ポリマーが混合されている。この保護ポリマーは、高分子電解質であり、光還元で生じた金の表面を弱く保護して、水溶液中におけるその分散を促進する作用を有するものである。本発明において使用される保護ポリマーとして特に好適なものは、ポリビニルピロリドン（以下、ＰＶＰと称することがある）であるが、これに限られるものではなく、例えば、ポリエチレングリコールなども使用できる。 In the method for producing a noble metal nanosheet of the present invention, a protective polymer is mixed in an aqueous solution containing a noble metal complex and a solubilizing agent for the noble metal. This protective polymer is a polymer electrolyte, and has a function of weakly protecting the gold surface generated by photoreduction and promoting its dispersion in an aqueous solution. A particularly suitable protective polymer for use in the present invention is polyvinylpyrrolidone (hereinafter sometimes referred to as PVP), but is not limited thereto, and for example, polyethylene glycol can also be used.
本発明に従う貴金属ナノシートの製造方法は、如上の貴金属錯体、貴金属の可溶化剤および貴金属の保護ポリマーを混合、含有する水溶液に、常温・常圧下において紫外光を照射するというきわめて簡便な方法により実施される。かくして、本発明に従えば、金錯体の光還元による結晶成長（金の生成）と可溶化剤（好ましくはハロゲン化アニオン）による金の溶解（エッチング）とを同じ反応系で同時に進行させることになる。ここで、本発明に従う光還元の利点は、結晶成長のスピードを光量により連続的に調節できることにあり、このようなことは化学還元法では困難である。紫外光の照射は、一般に、水銀灯（特に超高圧水銀灯）を用いて行われるが、その他の光源、例えば、キセノンランプを用いることも可能である。
図１には、本発明に従う金ナノシートの製造における反応スキームが模式的に示されている。
The method for producing a noble metal nanosheet according to the present invention is carried out by an extremely simple method of irradiating an aqueous solution containing the above noble metal complex, a noble metal solubilizer and a noble metal protective polymer with ultraviolet light at room temperature and normal pressure. Is done. Thus, according to the present invention, crystal growth (gold generation) by photoreduction of a gold complex and gold dissolution (etching) by a solubilizing agent (preferably a halogenated anion) are allowed to proceed simultaneously in the same reaction system. Become. Here, the advantage of the photoreduction according to the present invention is that the speed of crystal growth can be continuously adjusted by the amount of light, which is difficult in the chemical reduction method. Irradiation with ultraviolet light is generally performed using a mercury lamp (particularly an ultra-high pressure mercury lamp), but other light sources such as a xenon lamp can also be used.
FIG. 1 schematically shows a reaction scheme in the production of a gold nanosheet according to the present invention.
本発明に従えば、如上の製造に際して反応条件、すなわち、貴金属錯体水溶液のｐＨ、ハロゲンアニオン（例えばＮａＢｒとして使用）に代表される可溶化剤の濃度、または光照射時間を制御することにより、得られる貴金属ナノシートの形状や大きさ（結晶サイズ）を制御できる。 According to the present invention, the production conditions can be obtained by controlling the reaction conditions, that is, the pH of the aqueous solution of the noble metal complex, the concentration of the solubilizer represented by the halogen anion (for example, used as NaBr), or the light irradiation time. It is possible to control the shape and size (crystal size) of the precious metal nanosheet.
例えば、金の場合、ｐＨが低いとき（例えば、ｐＨ2.2）、金錯体はＡｕＣｌ4 −の構造を呈するが、これから得られる金ナノシートは九角形（nonagonal）の形状を有する。従来の方法においては、金結晶が最安定状態となる三角形か六角形のナノシートしか得られていないことを考慮すると、九角形のナノシートは、初めて得られた新規な形状である。さらにｐＨが高いとき（例えば、ｐＨ10）、金錯体はＡｕ(ＯＨ)4 −の構造を呈するが、これからは、合弁花状とでも称すべき構造の金ナノシート、すなわち、一枚一枚の花弁（はなびら）に相当する薄片状の金結晶が根元で融合しているような構造の金ナノシートが得られ、これもこれまでに知られていない形状のナノシートである。 For example, in the case of gold, when the pH is low (for example, pH 2.2), the gold complex has a structure of AuCl 4 − , but the gold nanosheet obtained therefrom has a nonagonal shape. In the conventional method, considering that only the triangular or hexagonal nanosheet in which the gold crystal is in the most stable state is obtained, the nine-sided nanosheet is a novel shape obtained for the first time. Further, when the pH is high (for example, pH 10), the gold complex exhibits a structure of Au (OH) 4 − , but from now on, gold nanosheets having a structure that should be called a joint flower shape, that is, petals ( A gold nanosheet having a structure in which flaky gold crystals corresponding to Hanabira are fused at the root is obtained, and this is also a nanosheet having a shape that has not been known so far.
また、可溶化剤（例えばＮａＢｒとして使用）の濃度増加に伴い、上記のような合弁花状構造（あるいは樹枝状構造）における薄片の分岐（枝分かれ）の程度が進行した形状の金ナノシートが得られる。これは可溶化剤のエッチング（結晶の溶解）効果に因るものと考えられる。 In addition, as the concentration of the solubilizer (for example, used as NaBr) increases, a gold nanosheet having a shape in which the degree of branching (branching) of the flakes in the joint flower-like structure (or dendritic structure) as described above proceeds is obtained. . This is considered to be due to the effect of the solubilizer etching (dissolution of crystals).
さらに、光照射時間の増大に伴い、平面方向に金ナノシートが結晶成長し、さらに、光照射時間を増加すると、それぞれの薄片状シートの重なり合いが進むことが観察されている。
貴金属錯体、貴金属の可溶化剤および貴金属の保護ポリマーを混合、含有する水溶液に紫外光を照射した後の溶液には、一般に、超純水を加えた後、遠心分離に供することにより、所望の貴金属ナノシートが得られる。
Furthermore, it has been observed that as the light irradiation time increases, the gold nanosheets grow in the plane direction, and when the light irradiation time is further increased, the overlapping of the flaky sheets progresses.
In general, ultrapure water is added to an aqueous solution containing a precious metal complex, a precious metal solubilizer, and a precious metal protective polymer, and then irradiated with ultraviolet light. A noble metal nanosheet is obtained.
以上のようにして得られる本発明の金ナノシート、特に合弁花状の構造を呈する金ナノシートは、生体の光の窓と呼ばれ生体が光を透過しやすい近赤外域（波長700〜1200nm）の光を充分に吸収するという特性を有する。 The gold nanosheet of the present invention obtained as described above, particularly a gold nanosheet exhibiting a joint flower-like structure, is called a biological light window and has a near-infrared region (wavelength 700 to 1200 nm) in which the living body easily transmits light. It has the property of absorbing light sufficiently.
以下に、本発明の特徴を更に具体的に示すために実施例を記すが、本発明はこの実施例によって制限されるものではない。なお、それらの実施例からも理解されるように、本発明の貴金属ナノシートは、一般に、断面形状の差渡し長さが1nm乃至500nｍ程度、好ましくは1nm乃至200nm程度、厚さが1nm乃至10nm程度である。本発明の説明においては、ナノシートとナノプレートを同義で使用している。 In the following, examples will be described in order to more specifically show the features of the present invention, but the present invention is not limited to these examples. As can be understood from those examples, the noble metal nanosheet of the present invention generally has a cross-sectional shape difference length of about 1 nm to 500 nm, preferably about 1 nm to 200 nm, and a thickness of about 1 nm to 10 nm. It is. In the description of the present invention, nanosheet and nanoplate are used synonymously.
標準的な反応条件として、24mMのＡｕＣｌ４水溶液1mL、ＰＶＰ（分子量40,000g/mol）0.3g、およびＮａＢｒ水溶液0.2mLをサンプル管に入れ、50rpmで回転子を回しながら超高圧水銀灯の光（λ＞300nm、16mW/cm2）を所定時間照射した。ＡｕＣｌ4水溶液は、ＨＡｕＣｌ4・４Ｈ2Ｏ（塩化金酸・４水和物）の結晶1gをMilliQ水100mLに溶解させて調製した。その初期のｐＨは約2.2である。 As standard reaction conditions, 1 mL of 24 mM AuCl 4 aqueous solution, 0.3 g of PVP (molecular weight 40,000 g / mol), and 0.2 mL of NaBr aqueous solution were put in a sample tube, and light of an ultrahigh pressure mercury lamp (λ > 300 nm, 16 mW / cm 2 ) for a predetermined time. The AuCl 4 aqueous solution was prepared by dissolving 1 g of HAuCl 4 .4H 2 O (chloroauric acid tetrahydrate) crystals in 100 mL of MilliQ water. Its initial pH is about 2.2.
1MのＮａＯＨを添加することによりＡｕＣｌ4水溶液のｐＨを変化させた。また、ＮａＢｒの濃度を変化させた。さらに、光照射時間を変化させた反応も行った。
それぞれの条件の反応について、光照射後のサンプル水溶液にMilliQ水1mLを加えた後、遠心分離（15,000rpm、7分程度）によりナノシートを回収した。これにさらにMilliQ水1mlを加え、超音波照射により金ナノシートを再分散させ、これをさらに遠心分離した。上記の洗浄操作を6回繰り返した。
The pH of the aqueous AuCl 4 solution was changed by adding 1M NaOH. Further, the concentration of NaBr was changed. Furthermore, the reaction which changed light irradiation time was also performed.
For the reaction under each condition, 1 mL of MilliQ water was added to the sample aqueous solution after light irradiation, and then the nanosheet was collected by centrifugation (15,000 rpm, about 7 minutes). To this was further added 1 ml of MilliQ water, the gold nanosheet was redispersed by ultrasonic irradiation, and this was further centrifuged. The above washing operation was repeated 6 times.
ＡｕＣｌ4水溶液のｐＨ、ＮａＢｒの濃度、および光照射時間を変化させて得られた金ナノシートの一部について透過電子顕微鏡写真を図２に示す。
図２に示すように、ｐＨが低いとき（ｐＨ2.2）に、形状が九角形のナノシートが得られ、一方、ｐＨが高いとき（ｐＨ10）には合弁花状の構造の金ナノシートが得られ、これらは、いずれもこれまで知られていなかった形状の金ナノシートである。図３には、金ナノシートの吸収スペクトルを示すが、ｐＨ10で得られる合弁花状構造の金ナノシートは近赤外域に十分な吸収を有することが認められる。
図２から、ＮａＢｒの濃度が増加すると合弁花状構造の金ナノシートにおける各薄片の分岐の程度が進行することも認められる。さらに、光照射時間の増大に伴い平面方向に金ナノシートが結晶成長し薄片状シートの重なり合いが進む傾向があることも観察される。
FIG. 2 shows a transmission electron micrograph of a part of the gold nanosheet obtained by changing the pH of the AuCl 4 aqueous solution, the concentration of NaBr, and the light irradiation time.
As shown in FIG. 2, when the pH is low (pH 2.2), a nine-sided nanosheet is obtained, while when the pH is high (pH 10), a gold nanosheet with a joint flower-like structure is obtained. These are gold nanosheets having a shape that has not been known so far. FIG. 3 shows an absorption spectrum of the gold nanosheet. It is recognized that the gold nanosheet having a joint flower-like structure obtained at pH 10 has sufficient absorption in the near infrared region.
From FIG. 2, it is also recognized that the degree of branching of each flake proceeds in the gold nanosheet with a joint flower-like structure as the concentration of NaBr increases. Furthermore, it is observed that the gold nanosheets grow in the plane direction as the light irradiation time increases and the overlapping of the flaky sheets tends to progress.
本発明は、簡便に低コストで金ナノシートをはじめとする貴金属ナノシートを製造する技術として有用である。
得られる貴金属ナノシートは、導電性接着剤や導電性薄膜、ガスセンサーやラマン散乱の基体としての応用が期待される。また、金ンシートは近赤外域に十分な吸収を持ち、生体を比較的良く透過する近赤外光を利用した悪性腫瘍の温熱療法などへの応用が期待される。近接場２光子誘起蛍光を利用したバイオイメージングのツールとしての応用も見込まれる。
The present invention is useful as a technique for producing noble metal nanosheets including gold nanosheets easily and at low cost.
The obtained noble metal nanosheet is expected to be applied as a conductive adhesive, a conductive thin film, a gas sensor, or a Raman scattering substrate. In addition, the gold sheet is expected to be applied to hyperthermia for malignant tumors using near-infrared light that has sufficient absorption in the near-infrared region and transmits the living body relatively well. Application as a bioimaging tool using near-field two-photon induced fluorescence is also expected.
Claims (6)
A gold nanosheet manufactured by the method according to claim 4 and exhibiting a joint flower-like structure.
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| JP2006037221A (en) * | 2004-07-26 | 2006-02-09 | Korea Research Inst Of Standards & Science | Gold nanostructure and method for producing the same |
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