JP5750801B2 - Electrode manufacturing method, electrode manufacturing apparatus and electrode - Google Patents
Electrode manufacturing method, electrode manufacturing apparatus and electrode Download PDFInfo
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- JP5750801B2 JP5750801B2 JP2011105396A JP2011105396A JP5750801B2 JP 5750801 B2 JP5750801 B2 JP 5750801B2 JP 2011105396 A JP2011105396 A JP 2011105396A JP 2011105396 A JP2011105396 A JP 2011105396A JP 5750801 B2 JP5750801 B2 JP 5750801B2
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Battery Electrode And Active Subsutance (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electroplating Methods And Accessories (AREA)
- Inert Electrodes (AREA)
Description
本発明は、例えば、バイオセンサー用のセンシング電極、有機合成反応用の触媒電極および固体触媒、燃料電池やリチウム二次電池などの正極および負極などに適用可能な電極製造方法、電極製造装置および電極に関する。 The present invention relates to, for example, a sensing electrode for a biosensor, a catalyst electrode and a solid catalyst for an organic synthesis reaction, an electrode manufacturing method, an electrode manufacturing apparatus, and an electrode applicable to a positive electrode and a negative electrode such as a fuel cell and a lithium secondary battery. About.
キラル分子は、右手と左手の関係にある光学異性体であり、２つの異性体は互いに鏡像異性体と呼ばれる。鏡像異性体のこれらの選択的検出は、医薬分野および工業的に重要な要素である。 A chiral molecule is an optical isomer in a right-handed and left-handed relationship, and the two isomers are called enantiomers of each other. These selective detections of enantiomers are important elements in the pharmaceutical field and in industry.
電極面に対して垂直に磁場を加えて金属、酸化物、有機化合物等を電析（電解析出、めっきなどともいう。）させた場合、キラルならせん転位からなる表面をもつ薄膜を形成することができる。このようにして形成した銅や銀薄膜を電極として使用し、アミノ酸などキラルな構造をもつ試薬に反応（光学異性体反応）を行わせると、電極表面に対応するキラル特性を持つ試薬は、そうでない試薬に比べて高い反応速度をもつ（キラル選択性）。また、磁場と電解電流の向きを同じ方向にした場合と反対の方向にした場合では、キラル選択性が反転する。一方で、磁場の無い場合には、このような選択性は現れない。 When a magnetic field is applied perpendicular to the electrode surface to deposit metal, oxide, organic compound, etc. (also called electrolytic deposition, plating, etc.), a thin film with a surface consisting of chiral screw dislocations is formed. be able to. When the copper or silver thin film thus formed is used as an electrode and a reagent having a chiral structure such as an amino acid is reacted (optical isomer reaction), a reagent having chiral properties corresponding to the electrode surface is High reaction rate compared to non-reagents (chiral selectivity). Moreover, when the direction of the magnetic field and the electrolysis current is set in the opposite direction, the chiral selectivity is reversed. On the other hand, in the absence of a magnetic field, such selectivity does not appear.
非特許文献１、２には、垂直磁場を用いた電析によりキラル選択性を持たせるための表面形状を形成する過程で、電解電流と磁場の相互作用によるローレンツ力が生み出す二つの渦流が重要な役割を果たすと記載されている。図９に示すように、一つは、電極上層部の電流線の広がりが生み出すローレンツ力による竜巻状の回転運動（垂直ＭＨＤ（Magnetohydrodynamic）流れ）であり、もう一つは、図１０に示すように、電極表面近傍における電解電流のゆらぎと磁場Ｂの作用により生じる微小渦流（マイクロＭＨＤ流れ）である。 In Non-Patent Documents 1 and 2, two eddy currents generated by Lorentz force due to the interaction between the electrolysis current and the magnetic field are important in the process of forming the surface shape for imparting chiral selectivity by electrodeposition using a vertical magnetic field It is described that it plays an important role. As shown in FIG. 9, one is a tornado-like rotational motion (vertical MHD (Magnetohydrodynamic) flow) due to the Lorentz force generated by the spreading of current lines in the upper layer of the electrode, and the other is as shown in FIG. Furthermore, a micro eddy current (micro MHD flow) generated by the fluctuation of the electrolysis current in the vicinity of the electrode surface and the action of the magnetic field B.
このうち、マイクロＭＨＤ流れは、電析により、電極の表面にキラルならせん転位を直接生じさせるという重要な役割を担い、垂直ＭＨＤ流れは、マイクロＭＨＤ流れに歳差運動（図１０参照）を起こさせることで電析の際のイオンの流れを渦巻状にし、キラル選択性を持たせるための表面形状、つまり、キラルならせん転位の形成を助長するという重要な役割を担う。 Of these, the micro MHD flow plays an important role of directly generating chiral screw dislocations on the electrode surface by electrodeposition, and the vertical MHD flow precesses the micro MHD flow (see FIG. 10). By doing so, the ion flow during electrodeposition is swirled, and plays an important role in promoting the formation of a surface shape for imparting chiral selectivity, that is, the formation of chiral screw dislocations.
非特許文献３、４には、金といったキラルでは無い無機材料の電極上に被検出対象の有機性のキラル分子と対となるキラル分子をあらかじめ修飾し、そのような電極にキラル選択性をもたせた表面形状を形成することが可能であり、生体分子の認識に適用可能な利点を有する旨が記載されている。 In Non-Patent Documents 3 and 4, a chiral molecule that is paired with an organic chiral molecule to be detected is preliminarily modified on an electrode of a non-chiral inorganic material such as gold, and such an electrode has chiral selectivity. It is described that it has a merit that can be applied to the recognition of biomolecules.
しかしながら、非特許文献１、２では、電極上層部分での電流線の曲がりから発生する垂直ＭＨＤ流れを利用する必要があるため、垂直ＭＨＤ流れの回転速度と方向の制御が困難であった。そのため、例えば、電極にキラル選択性を持たせるのに適した、特定の表面形状を形成するのが困難であった。 However, in Non-Patent Documents 1 and 2, since it is necessary to use the vertical MHD flow generated from the bending of the current line in the electrode upper layer portion, it is difficult to control the rotational speed and direction of the vertical MHD flow. Therefore, for example, it has been difficult to form a specific surface shape suitable for imparting chiral selectivity to the electrode.
また、非特許文献３、４では、例えば、電極にキラル選択性を持たせるのに適した、特定の表面形状を形成するにあたって、被検出対象のキラル分子と対となるキラル分子を、電極上にあらかじめ修飾しておかなければならず、製造工程が複雑であった。 In Non-Patent Documents 3 and 4, for example, when forming a specific surface shape suitable for imparting chiral selectivity to an electrode, a chiral molecule paired with a chiral molecule to be detected is placed on the electrode. The manufacturing process was complicated.
本発明は前記状況に鑑みてなされたものであり、例えば、キラル選択性を持たせるのに適した、特定の表面形状を形成した電極を簡便に製造することのできる電極製造方法、電極製造装置および電極を提供することを課題とする。 The present invention has been made in view of the above circumstances. For example, an electrode manufacturing method and an electrode manufacturing apparatus capable of easily manufacturing an electrode having a specific surface shape suitable for imparting chiral selectivity. Another object is to provide an electrode.
本発明は、表面に特定の表面形状を形成した電極を製造するための電極製造方法であって、磁石で発生させた磁場の向きと平行に設定された自転軸まわりに特定の方向で電解槽を自転させつつ、前記電解槽とともに前記自転軸まわりに自転するように前記電解槽内に設けられた作動極となる陰極および対極となる陽極からなる一対の電極に対して電解質媒体を通じて電圧および電流のうちの少なくとも一方を印加し、前記対極の電解を行うとともに前記作動極の電析を行い、前記作動極の表面に前記特定の表面形状を形成させることで、前記表面に特定の表面形状を形成した電極を製造することを特徴としている。 The present invention relates to an electrode manufacturing method for manufacturing an electrode having a specific surface shape formed on a surface thereof, and an electrolytic cell in a specific direction around a rotation axis set in parallel with the direction of a magnetic field generated by a magnet. The voltage and current through the electrolyte medium with respect to a pair of electrodes comprising a cathode serving as a working electrode and an anode serving as a counter electrode provided in the electrolytic cell so as to rotate about the rotation axis together with the electrolytic cell. at least one of the applying, the electrolytic counter electrode performs electrodeposition line Utotomoni the working electrode, by the fact that to form a particular surface shape on the surface of the working electrode, the specific surface shape on the surface of the It is characterized by manufacturing an electrode in which the electrode is formed .
本発明は、表面に特定の表面形状を形成した電極を製造するための電極製造方法であって、磁石により磁場を発生させる磁場発生ステップと、発生させた前記磁場中において、電解質媒体を収納した電解槽を、前記磁場の向きと平行に設定された自転軸まわりに特定の方向で自転させる電解槽自転ステップと、自転している前記電解槽とともに前記自転軸まわりに自転するように前記電解槽内に設けられた作動極となる陰極および対極となる陽極からなる一対の電極に対して前記電解質媒体を通じて電圧および電流のうちの少なくとも一方を印加し、前記対極の電解を行うとともに前記作動極の電析を行い、前記作動極の表面に前記特定の表面形状を形成させることで、前記表面に特定の表面形状を形成した電極を製造する電解ステップと、を含むことを特徴としている。 The present invention is an electrode manufacturing method for manufacturing an electrode having a specific surface shape formed on a surface thereof, and a magnetic field generation step for generating a magnetic field by a magnet, and an electrolyte medium is accommodated in the generated magnetic field. An electrolytic cell rotation step for rotating the electrolytic cell in a specific direction around a rotation axis set parallel to the direction of the magnetic field, and the electrolytic cell so as to rotate around the rotation axis together with the rotating electrolytic cell. at least one of the applied, the electrolyte of the counter line Utotomoni the working electrode of the voltage through the electrolyte medium and current to the pair of electrodes composed of an anode as a cathode and the counter electrode serving as a working electrode which is provided within perform the electrolytic deposition, by forming the specific surface shape on the surface of the working electrode, and electrolytic step of manufacturing an electrode formed with a specific surface shape to the surface, It is characterized in that it comprises.
本発明は、表面に特定の表面形状を形成した電極を製造するための電極製造方法であって、電解質媒体を収納した電解槽を、磁石により発生させる磁場の向きと平行に設定された自転軸まわりに特定の方向で自転させる電解槽自転ステップと、自転している前記電解槽に対し、前記磁石により磁場を発生させる磁場発生ステップと、発生させた前記磁場中で自転している前記電解槽内において前記電解槽とともに前記自転軸まわりに自転するように前記電解槽内に設けられた作動極となる陰極および対極となる陽極からなる一対の電極に対して前記電解質媒体を通じて電圧および電流のうちの少なくとも一方を印加し、前記対極の電解を行うとともに前記作動極の電析を行い、前記作動極の表面に前記特定の表面形状を形成させることで、前記表面に特定の表面形状を形成した電極を製造する電解ステップと、を含むことを特徴としている。 The present invention relates to an electrode manufacturing method for manufacturing an electrode having a specific surface shape formed on a surface thereof, wherein an electrolytic cell containing an electrolyte medium is set in parallel with a direction of a magnetic field generated by a magnet. An electrolytic cell rotation step that rotates around in a specific direction, a magnetic field generation step that generates a magnetic field with the magnet for the rotating electrolytic cell, and the electrolytic cell that rotates in the generated magnetic field. Of the voltage and current through the electrolyte medium with respect to a pair of electrodes comprising a cathode as a working electrode and an anode as a counter electrode provided in the electrolytic cell so as to rotate around the rotation axis together with the electrolytic cell. of applying at least one, the electrolysis of the counter perform electrodeposition line Utotomoni the working electrode, by the fact that to form a particular surface shape on the surface of the working electrode, prior to It is characterized in that it comprises an electrolyte steps of manufacturing an electrode formed with a specific surface shape to the surface.
前記したいずれの発明も、磁石により発生させた磁場の向きと平行に設定された自転軸まわりを反時計回りまたは時計回りに電解槽を自転させる。自転する電解槽内には、電解槽とともに自転軸まわりに自転するように一対の電極が設けられており、電解質媒体が収納されているので、電解槽を自転させつつ、電解質媒体を通じて一対の電極に対して外部電源から電圧および電流のうちの少なくとも一方を印加すると電極表面には電解反応による非平衡ゆらぎによって次第に微小な凹凸部が形成される。電解によって形成された凹部と凸部では、凹部の方が、摩擦が少なくすべりが良い。電極面に向けて磁場を垂直に印加する本発明における電解電流の方向は、電極面に対して垂直な成分に加えて平行な水平成分が存在する。そのため、ローレンツ力が働き、凸部では電極の回転方向と同方向のマイクロＭＨＤ流れが発生し、凹部では電極の回転方向と逆方向のマイクロＭＨＤ流れが発生すると考えられる。このとき、すべりの良い凹部で生じる流れが優勢になることから、電極の回転方向と逆方向の回転の析出面が優勢になる。そして、電解槽全体の自転によって、図１（ａ）に示すように、マイクロＭＨＤ流れに歳差運動が生じ、例えば、キラル選択性を持たせるのに適した、特定の表面形状を電極の表面に形成させることが可能になると考えられる（図７（ａ）および（ｂ）参照）。つまり、本発明によれば、図１（ｂ）に示すような、回転速度と方向の制御が困難な垂直ＭＨＤ流れを積極的に発生させなくても、マイクロＭＨＤ流れに歳差運動を起こさせることができ、前記したような特定の表面形状を電極の表面に形成させることが可能となる。 In any of the above-described inventions, the electrolytic cell is rotated counterclockwise or clockwise around the rotation axis set in parallel with the direction of the magnetic field generated by the magnet. In the rotating electrolytic cell, a pair of electrodes are provided so as to rotate around the rotation axis together with the electrolytic cell, and the electrolyte medium is accommodated, so that the pair of electrodes are passed through the electrolytic medium while rotating the electrolytic cell. On the other hand, when at least one of voltage and current is applied from an external power source, minute uneven portions are gradually formed on the electrode surface due to non-equilibrium fluctuation due to electrolytic reaction. Of the recesses and protrusions formed by electrolysis, the recesses have less friction and better slip. The direction of the electrolytic current in the present invention in which a magnetic field is applied perpendicularly to the electrode surface has a parallel horizontal component in addition to a component perpendicular to the electrode surface. Therefore, the Lorentz force acts, and it is considered that a micro MHD flow in the same direction as the rotation direction of the electrode is generated in the convex portion and a micro MHD flow in the direction opposite to the rotation direction of the electrode is generated in the concave portion. At this time, since the flow generated in the slippery recess becomes dominant, the precipitation surface of the rotation in the direction opposite to the rotation direction of the electrode becomes dominant. Then, due to the rotation of the entire electrolytic cell, as shown in FIG. 1A, precession occurs in the micro MHD flow. For example, a specific surface shape suitable for imparting chiral selectivity is formed on the surface of the electrode. (See FIGS. 7A and 7B). That is, according to the present invention, as shown in FIG. 1 (b), it is possible to cause precession in the micro MHD flow without actively generating a vertical MHD flow that is difficult to control the rotation speed and direction. It is possible to form a specific surface shape as described above on the surface of the electrode.
本発明は、表面に特定の表面形状を形成した電極を製造するための電極製造装置であって、磁場を発生させる磁石と、発生させた前記磁場中において、当該磁場の向きと平行に設定された自転軸まわりを特定の方向に自転するように設けられ、電解質媒体を入出自在に収納することのできる電解槽と、前記電解槽内に、当該電解槽とともに前記自転軸まわりに自転するように互いに離間して設けられた作動極となる陰極および対極となる陽極からなる一対の電極と、前記電解槽を前記自転軸まわりに任意の自転速度で自転させるアクチュエータと、を備え、前記電解槽を前記自転軸まわりに特定の方向へ自転させつつ、前記一対の電極に対して前記電解質媒体を通じて電圧および電流のうちの少なくとも一方を印加し、前記対極の電解を行うとともに前記作動極の電析を行い、前記作動極の表面に前記特定の表面形状を形成させることで、前記表面に特定の表面形状を形成した電極を製造することを特徴としている。 The present invention is an electrode manufacturing apparatus for manufacturing an electrode having a specific surface shape formed on a surface thereof, and is set in parallel with the direction of the magnetic field in the generated magnetic field and the magnet. An electrolytic cell provided to rotate around a rotation axis in a specific direction and capable of accommodating an electrolyte medium in a freely enterable and retractable manner, and to rotate around the rotation axis together with the electrolytic cell in the electrolytic cell. comprising a pair of electrodes composed of an anode as a cathode and the counter electrode serving as the working electrode being spaced from each other, an actuator for rotating at an arbitrary rotation speed the electrolyzer around the rotation axis, to said electrolytic cell The electrode is electrolyzed by applying at least one of voltage and current to the pair of electrodes through the electrolyte medium while rotating in a specific direction around the rotation axis. Both perform electrodeposition of the working electrode, by forming the specific surface shape on the surface of the working electrode, is characterized by manufacturing an electrode formed with a specific surface shape to the surface.
本発明は、このような構成としているので、磁石により発生させた磁場中で、当該磁場の向きと平行に設定された自転軸まわりを反時計回りまたは時計回りに電解槽を自転させることができる。従って、当該電解槽内に電解質媒体を収納してこれを自転させ、電解槽とともに自転軸まわりに自転する一対の電極の間で電圧および電流のうちの少なくとも一方を印加すると、作動極として機能する電極の表面にマイクロＭＨＤ流れを生じさせ、さらに、生じたマイクロＭＨＤ流れに歳差運動を起こさせることが可能になる。そのため、例えば、キラル選択性を持たせるのに適した、特定の表面形状を電極の表面に形成させることが可能になると考えられる。つまり、本発明によれば、図１（ｂ）に示すような、回転速度と方向の制御が難しい垂直ＭＨＤ流れを積極的に発生させなくても、マイクロＭＨＤ流れに歳差運動を起こさせることができ、前記したような特定の表面形状を電極の表面に形成させることが可能となる。 Since the present invention has such a configuration, in the magnetic field generated by the magnet, the electrolytic cell can be rotated counterclockwise or clockwise around the rotation axis set in parallel with the direction of the magnetic field. . Therefore, when an electrolytic medium is accommodated in the electrolytic cell and rotated, and when at least one of voltage and current is applied between the pair of electrodes rotating about the rotation axis together with the electrolytic cell, the electrolytic cell functions as an operating electrode. It is possible to generate a micro MHD flow on the surface of the electrode and to cause precession of the generated micro MHD flow. Therefore, for example, it is considered that a specific surface shape suitable for imparting chiral selectivity can be formed on the surface of the electrode. That is, according to the present invention, it is possible to cause precession in the micro MHD flow without actively generating a vertical MHD flow that is difficult to control the rotation speed and direction as shown in FIG. Thus, the specific surface shape as described above can be formed on the surface of the electrode.
本発明においては、前記作動極は、これを固定する作動極固定手段によって固定され、当該作動極固定手段は、（垂直ＭＨＤ流れなどの）対流を抑制する対流抑制手段を有していることが好ましい。なお、前記対流は、作動極上層部の電流線の広がりが生み出すローレンツ力による竜巻状の回転運動である垂直ＭＨＤ流れである。 In the present invention, the working electrode is fixed by working electrode fixing means for fixing the working electrode, and the working electrode fixing means has convection suppressing means for suppressing convection (such as a vertical MHD flow). preferable. The convection is a vertical MHD flow that is a tornado-like rotational motion by Lorentz force generated by the spreading of current lines in the upper layer of the working pole.
このようにすれば、作動極と対極の間で電圧および電流のうちの少なくとも一方を印加した際に不可避的に生じる垂直ＭＨＤ流れ（溶液対流）などの磁気対流といった、マイクロＭＨＤ流れを乱す対流を抑制することができる。そのため、例えば、キラル選択性を持たせるのに適した、特定の表面形状を電極の表面に、より好適に形成することができるようになる。 In this way, convection that disturbs the micro MHD flow, such as magnetic convection such as vertical MHD flow (solution convection) inevitably generated when at least one of a voltage and a current is applied between the working electrode and the counter electrode. Can be suppressed. Therefore, for example, a specific surface shape suitable for imparting chiral selectivity can be more suitably formed on the surface of the electrode.
本発明は、前記したいずれかの電極製造方法によって製造された電極であって、表面に特定の表面形状が形成されていることを特徴としている。 The present invention is an electrode manufactured by any one of the electrode manufacturing methods described above, and is characterized in that a specific surface shape is formed on the surface.
本発明はこのような構成としているので、電極として用いると、表面に形成された特定の表面形状に対応したキラルな構造をもつ分子に対する反応電流（反応速度）が選択的に高くなる。つまり、本発明によれば、電極にキラル選択性を持たせることができる。また、光学異性体反応に対する固体触媒としてキラル選択性を持たせることができる。 Since the present invention has such a configuration, when it is used as an electrode, a reaction current (reaction rate) for a molecule having a chiral structure corresponding to a specific surface shape formed on the surface is selectively increased. That is, according to the present invention, the electrode can have chiral selectivity. Moreover, chiral selectivity can be given as a solid catalyst with respect to optical isomer reaction.
本発明によれば、例えば、キラル選択性を持たせるのに適した、特定の表面形状を形成した電極を簡便に製造することのできる電極製造方法および電極製造装置を提供することができる。
また、本発明によれば、例えば、キラル選択性を持たせるのに適した、特定の表面形状を形成した電極を提供することができる。
ADVANTAGE OF THE INVENTION According to this invention, the electrode manufacturing method and electrode manufacturing apparatus which can manufacture simply the electrode which formed the specific surface shape suitable for giving chiral selectivity, for example can be provided.
Moreover, according to the present invention, for example, an electrode having a specific surface shape suitable for imparting chiral selectivity can be provided.
以下、適宜図面を参照して本発明に係る電極製造方法、電極製造装置および電極を実施するための形態について説明する。 DESCRIPTION OF EMBODIMENTS Hereinafter, an electrode manufacturing method, an electrode manufacturing apparatus, and an embodiment for carrying out an electrode according to the present invention will be described with reference to the drawings as appropriate.
まず、本発明に係る電極製造方法について説明する。
本発明に係る電極製造方法は、表面に特定の表面形状を形成した電極を製造するための電極製造方法であって、磁石で発生させた磁場の向きと平行に設定された自転軸まわりを特定の方向（反時計回りまたは時計回り（なお、電解槽の上方から見たときの反時計回りは、対極から作動極の表面を見たときに時計回りとなる。））に電解槽を自転させつつ（つまり、自転軸を中心とした反時計回りまたは時計回りに電解槽を自転させつつ）、電解槽とともに自転軸まわりに自転するように電解槽内に設けられた作動極となる陰極および対極となる陽極からなる一対の電極（以下、単に「一対の電極」と呼称することもある。）に対して電解質媒体を通じて電圧および電流のうちの少なくとも一方を印加し、対極の電解を行うとともに作動極の電析を行い、作動極の表面に前記特定の表面形状を形成させることで、前記表面に特定の表面形状を形成した電極を製造するというものである。なお、電極表面に形成される特定の表面形状としては、マイクロメートルオーダーの直径と深さを有する微小な凹部が電極表面に無数に形成されている状態をいう。
First, the electrode manufacturing method according to the present invention will be described.
Electrode manufacturing method according to the present invention is an electrode production method for producing an electrode formed with a specific surface shape to the surface, identified around rotation shaft which is set parallel to the direction of the magnetic field generated by the magnet Rotate the electrolytic cell in the direction of ( counterclockwise or clockwise ( note that counterclockwise when viewed from above the electrolytic cell is clockwise when the surface of the working electrode is viewed from the counter electrode)). (That is, while rotating the electrolytic cell counterclockwise or clockwise around the rotation axis) and the cathode and counter electrode serving as working electrodes provided in the electrolytic cell so as to rotate around the rotation axis together with the electrolytic cell a pair of electrodes composed of an anode comprising (hereinafter, sometimes simply referred to as "a pair of electrodes.") at least one of the voltage and current through the electrolyte medium is applied against the row of electrolysis counter Utotomoni Working electrode power Was carried out, by the fact that to form a particular surface shape on the surface of the working electrode, is that the production of electrodes forming a specific surface shape to the surface. Note that the specific surface shape formed on the electrode surface refers to a state in which an infinite number of minute concave portions having a diameter and depth on the order of micrometers are formed on the electrode surface.
より具体的に説明すると、図２に示す一態様のように、磁場発生ステップＳ１１と、電解槽自転ステップＳ１２と、電解ステップＳ１３と、を含み、これらのステップをこの手順で行うことが挙げられる。
また、図３に示す他の態様のように、電解槽自転ステップＳ２１と、磁場発生ステップＳ２２と、電解ステップＳ２３と、を含み、これらのステップをこの手順で行ってもよい。
More specifically, as shown in FIG. 2, the magnetic field generation step S <b> 11, the electrolytic cell rotation step S <b> 12, and the electrolysis step S <b> 13 are included, and these steps are performed in this procedure. .
Moreover, like the other aspect shown in FIG. 3, electrolysis tank autorotation step S21, magnetic field generation | occurrence | production step S22, and electrolysis step S23 may be included, and these steps may be performed in this procedure.
ここで、図２および図３を参照して電極製造方法の態様について説明する前に、図４を参照して電極製造方法の実施に直接使用できる装置の一例を説明する。 Here, before describing the aspect of the electrode manufacturing method with reference to FIG. 2 and FIG. 3, an example of an apparatus that can be directly used for carrying out the electrode manufacturing method will be described with reference to FIG.
図４に示すように、かかる電極製造装置１は、表面に特定の表面形状を形成した電極を製造するための装置であり、磁場Ｂを発生させる磁石２と、発生させた磁場Ｂ中において、当該磁場Ｂの向きと平行に設定された自転軸ＡＲまわりを反時計回りまたは時計回りに自転するように設けられ、電解質媒体５（図５参照）を入出自在に収納することのできる電解槽６と、この電解槽６内に、電解槽６とともに自転軸ＡＲまわりに自転するように互いに離間して設けられた一対の電極７、７（図５参照）と、電解槽６を自転軸ＡＲまわりに任意の自転速度で自転させるアクチュエータ８と、を備えている。
なお、この電極製造装置１は、電解槽６の自転を行わせるために、電解槽６とアクチュエータ８とを軸部材９で接続している。また、軸部材９の一部には、図示しない配線により作動極７１、対極７２、照合極７３のそれぞれと接続された接続部７１ａ、７２ａ、７３ａが設けられており、これらはブラシ電極７１ｂ、７２ｂ、７３ｂによって図示しない外部電源と接続されている。これにより、電解槽６への通電を可能にしている。また、電解槽６の自転をスムーズに行わせるためのベアリング１０も備えている。
As shown in FIG. 4, the electrode manufacturing apparatus 1 is an apparatus for manufacturing an electrode having a specific surface shape formed on the surface thereof. In the magnet 2 that generates the magnetic field B and the generated magnetic field B, An electrolytic cell that is provided so as to rotate counterclockwise or clockwise around a rotation axis AR set in parallel to the direction of the magnetic field B, and that can accommodate the electrolyte medium 5 (see FIG. 5) in a freely detachable manner. 6, a pair of electrodes 7 and 7 (see FIG. 5) which are provided in the electrolytic cell 6 so as to rotate around the rotation axis AR together with the electrolytic cell 6, and the electrolytic cell 6 is connected to the rotation axis AR. And an actuator 8 that rotates around at an arbitrary rotation speed.
In this electrode manufacturing apparatus 1, the electrolytic cell 6 and the actuator 8 are connected by a shaft member 9 in order to cause the electrolytic cell 6 to rotate. Further, a part of the shaft member 9 is provided with connection portions 71a, 72a, 73a connected to the working electrode 71, the counter electrode 72, and the verification electrode 73 by wiring (not shown), and these include brush electrodes 71b, 72b and 73b are connected to an external power source (not shown). Thereby, electricity supply to the electrolytic cell 6 is enabled. Moreover, the bearing 10 for performing the autorotation of the electrolytic cell 6 smoothly is also provided.
前記した電極製造方法や電極製造装置１で用いられる磁石２としては、永久磁石、超電導磁石、常電導磁石などを挙げることができる。磁石２で発生させる磁場Ｂは、回転させない静磁場であるのが好ましいが、回転磁場や時間変動磁場であってもよい。 Examples of the magnet 2 used in the electrode manufacturing method and the electrode manufacturing apparatus 1 include a permanent magnet, a superconducting magnet, and a normal conducting magnet. The magnetic field B generated by the magnet 2 is preferably a static magnetic field that is not rotated, but may be a rotating magnetic field or a time-varying magnetic field.
電解槽６は、絶縁性を有し、かつ耐酸性および耐アルカリ性を有する材料、例えば、ガラス、フッ素系樹脂などで構成することができる。なお、電解槽６は、電解質媒体５を入出自在に収納するため、図５に示すように、容器本体６１と蓋体６２でこれを収納できるように構成するのが好ましい。この際、容器本体６１と蓋体６２をＯリング６３等のシール部材でシールすると液密性が向上するので好適である。 The electrolytic cell 6 can be made of a material having insulation properties and acid resistance and alkali resistance, such as glass and fluorine resin. In addition, since the electrolytic cell 6 accommodates the electrolyte medium 5 so that it can enter and exit, it is preferable that the electrolytic cell 6 be configured so as to be accommodated by a container body 61 and a lid 62 as shown in FIG. At this time, it is preferable that the container main body 61 and the lid 62 are sealed with a sealing member such as an O-ring 63 because liquid tightness is improved.
電解質媒体５に含まれる電解質は、媒体中で電解を行おうとする金属イオンを生成できるものであれば好適に用いることができ、例えば、銅、ニッケル、コバルト、クロム、亜鉛、カドミウム、スズ、鉛、鉄、金、銀、ロジウム、白金、パラジウム、シリコンの電析、これらの合金電析およびこれらの酸化物や硫化物といった化合物電析さらには微粒子物質との複合電析の中から選択できる。また、電気化学的に使用可能であり、電析可能である導電性ポリマーや、前記金属群からなる電極の溶解、気相成長法などの乾式薄膜製造法で使用される窒化物や酸化物、半導体、磁性体などの様々な材料も用いることができる。 The electrolyte contained in the electrolyte medium 5 can be suitably used as long as it can generate metal ions to be electrolyzed in the medium. For example, copper, nickel, cobalt, chromium, zinc, cadmium, tin, lead , Iron, gold, silver, rhodium, platinum, palladium, silicon electrodeposition, alloy electrodeposition thereof, compound electrodeposition of these oxides and sulfides, and composite electrodeposition with fine particles. In addition, a conductive polymer that can be used electrochemically, and can be electrodeposited, a nitride or an oxide used in a dry thin film manufacturing method such as dissolution of an electrode made of the metal group, vapor phase growth method, semiconductor can Ru also used a variety of materials such as magnetic material.
電解質媒体５に用いられる媒体は、例えば、水溶液、有機溶媒、溶融塩、イオン性液体などの溶媒を好適に用いることができるが、導電性を有し、前記した電解質を含ませることができるものであればよいため、プラズマなどの気体を用いることも可能である。 As the medium used for the electrolyte medium 5, for example, a solvent such as an aqueous solution, an organic solvent, a molten salt, or an ionic liquid can be suitably used. However, the medium has conductivity and can contain the above-described electrolyte. Therefore, a gas such as plasma can be used.
溶媒を用いた電解質媒体５であれば、電気化学的に使用することのできる公知の液体組成物（めっき液）を用いることができる。かかるめっき液としては、例えば、市販の酸性硫酸銅溶液などを好適に用いることができる。 If it is the electrolyte medium 5 using a solvent, the well-known liquid composition (plating liquid) which can be used electrochemically can be used. As such a plating solution, for example, a commercially available acidic copper sulfate solution can be suitably used.
一対の電極７、７は、図示しない外部電源と接続され、電解質媒体５を通じて電圧および電流のうちの少なくとも一方が印加される。従って、一対の電極７、７のうち一方は作動極７１（図５参照）として機能し、他方は対極７２（図５参照）として機能する。電圧および電流のうちの少なくとも一方が印加されると、電解質が電解してＣｕ2+などの金属イオンｊが生じ、作動極７１の表面に析出する。 The pair of electrodes 7 and 7 are connected to an external power source (not shown), and at least one of voltage and current is applied through the electrolyte medium 5. Accordingly, one of the pair of electrodes 7 and 7 functions as the working electrode 71 (see FIG. 5), and the other functions as the counter electrode 72 (see FIG. 5). When at least one of voltage and current is applied, the electrolyte is electrolyzed and metal ions j such as Cu 2+ are generated and deposited on the surface of the working electrode 71.
一対の電極７、７はともに、導電性を有する金属で形成することができ、例えば、銅、ニッケル、コバルト、クロム、亜鉛、カドミウム、スズ、鉛、鉄、金、銀、ロジウム、白金、パラジウム、シリコンおよびこれらの合金の中から適宜選択して形成することができる。なお、電解により特定の表面形状が形成される電極７（作動極７１）は、板状、薄膜状だけでなく、粉体、針状や樹枝状などさまざまな形態とすることができる。従って、製造された電極７（作動極７１）は単に電気化学反応用だけでなく、種々の化学反応用の固体触媒などとしても利用することができる。 The pair of electrodes 7 and 7 can both be formed of a conductive metal, for example, copper, nickel, cobalt, chromium, zinc, cadmium, tin, lead, iron, gold, silver, rhodium, platinum, palladium It can be formed by appropriately selecting from silicon and alloys thereof. In addition, the electrode 7 (working electrode 71) on which a specific surface shape is formed by electrolysis can have various forms such as a powder, a needle shape, a dendritic shape as well as a plate shape and a thin film shape. Therefore, the manufactured electrode 7 (working electrode 71) can be used not only for an electrochemical reaction but also as a solid catalyst for various chemical reactions.
自転軸ＡＲは、磁石２で発生させた磁場Ｂの向きと平行に設定されていればよい。従って、図示しない床面に対して直角となるように設けると確実に特定の表面形状を電極７（作動極７１）表面に形成することができるので好ましいが、床面と平行となるように設けることも可能である。 The rotation axis AR only needs to be set parallel to the direction of the magnetic field B generated by the magnet 2. Therefore, it is preferable to provide the surface so as to be perpendicular to a floor surface (not shown) because a specific surface shape can be surely formed on the surface of the electrode 7 (working electrode 71), but it is provided so as to be parallel to the floor surface. It is also possible.
なお、図５に示すように、一対の電極７、７のうちの一方が作動極７１として機能し、他方が対極７２として機能する場合において、その一態様として、作動極７１を電解槽６内の上部に下向きに配置し、対極７２を電解槽６内の下部に上向きで配置することができる。 As shown in FIG. 5, when one of the pair of electrodes 7 and 7 functions as the working electrode 71 and the other functions as the counter electrode 72, the working electrode 71 is placed in the electrolytic cell 6 as one mode. The counter electrode 72 can be disposed upward at the bottom of the electrolytic cell 6.
この配置状態で磁場Ｂを作動極７１に向かうように発生させた場合において、電解槽６の上方から見たときに、電解槽６を自転軸ＡＲまわりに反時計回りＲ１に回転させると、非平衡ゆらぎによって形成された微小な凸部に生じる作動極７１の回転方向と同じ回転方向のマイクロＭＨＤ流れ、および微小な凹部に生じる作動極７１の回転方向と反対の回転方向のマイクロＭＨＤ流れのうち、後者のマイクロＭＨＤ流れが優勢になり、作動極７１の表面にキラル選択性を持たせるのに適した、特定の表面形状を好適に形成することができる（図７（ａ）および（ｂ）参照）。その結果、例えば、サイクリックボルタンメトリーでＤ−ＡｌａｎｉｎｅよりもＬ−Ａｌａｎｉｎｅの電流値を高くすることができるといった、キラル選択性を得ることができるようになる。これは、前記した配置状態で磁場Ｂを対極７２に向かうように発生させた場合において、電解槽６の上方から見たときに、電解槽６を自転軸ＡＲまわりに時計回りＲ２に回転させたときも全く同様の結果が得られると考えられる。 In the case where the magnetic field B is generated toward the working electrode 71 in this arrangement state, when the electrolytic cell 6 is rotated counterclockwise R1 around the rotation axis AR when viewed from above the electrolytic cell 6, non-rotation occurs. Among the micro MHD flow in the same rotation direction as the rotation direction of the working pole 71 generated in the minute convex portion formed by the equilibrium fluctuation, and the micro MHD flow in the rotation direction opposite to the rotation direction of the working pole 71 generated in the minute concave portion The latter micro MHD flow becomes dominant, and a specific surface shape suitable for imparting chiral selectivity to the surface of the working electrode 71 can be suitably formed (FIGS. 7A and 7B). reference). As a result, for example, it is possible to obtain chiral selectivity such that the current value of L-Alane can be made higher than that of D-Alane by cyclic voltammetry. This is because when the magnetic field B is generated toward the counter electrode 72 in the arrangement state described above, the electrolytic cell 6 is rotated clockwise around the rotation axis AR clockwise R2 when viewed from above the electrolytic cell 6. Sometimes the same result is expected.
これとは反対に、前記した配置状態で磁場Ｂを作動極７１に向かうように発生させた場合において、電解槽６の上方から見たときに、電解槽６を自転軸ＡＲまわりに時計回りＲ２に回転させると、優勢なマイクロＭＨＤ流れが逆転するので、反時計回りＲ１とは異なる表面形状を作動極７１の表面に形成することができると考えられる。その結果、例えば、サイクリックボルタンメトリーでＬ−ＡｌａｎｉｎｅよりもＤ−Ａｌａｎｉｎｅの電流値を高くすることができるといった、キラル選択性を得ることができるようになる。これは、前記した配置状態で磁場Ｂを対極７２に向かうように発生させた場合において、電解槽６の上方から見たときに、電解槽６を自転軸ＡＲまわりに反時計回りＲ１に回転させたときも全く同様の結果が得られると考えられる。 On the contrary, when the magnetic field B is generated toward the working electrode 71 in the arrangement state described above, when viewed from above the electrolytic cell 6, the electrolytic cell 6 is rotated clockwise around the rotation axis AR R2. Since the dominant micro-MHD flow is reversed when rotated to, it is considered that a surface shape different from the counterclockwise direction R1 can be formed on the surface of the working electrode 71. As a result, for example, it is possible to obtain chiral selectivity such that the current value of D-Aline can be made higher than that of L-Aline by cyclic voltammetry. This is because when the magnetic field B is generated so as to go to the counter electrode 72 in the arrangement state described above, the electrolytic cell 6 is rotated counterclockwise R1 around the rotation axis AR when viewed from above the electrolytic cell 6. It is considered that exactly the same result can be obtained.
作動極７１は、図５に示すように、これを固定する任意の手段（作動極固定手段７４）によって固定されている。作動極固定手段７４としては、図５に示すように、Ｏリング６３を介して蓋体６２と電極押込部材６４とで作動極７１を挟んで固定することが例示される。 As shown in FIG. 5, the working electrode 71 is fixed by an arbitrary means (working electrode fixing means 74) for fixing the working electrode 71. As the working electrode fixing means 74, as shown in FIG. 5, the working electrode 71 is fixed with the lid 62 and the electrode pushing member 64 sandwiched via an O-ring 63.
なお、図５では、蓋体６２の作動極７１に通じる筒状の内壁部６２ａが、作動極７１と対極７２の間に電圧および電流のうちの少なくとも一方を印加した際に不可避的に生じる垂直ＭＨＤ流れ（溶液対流）などの磁気対流といった、マイクロＭＨＤ流れに歳差運動を生じさせる対流を抑制する対流抑制手段７５として機能している。なお、図６（ａ）に示すように、作動極７１の表面と蓋体６２の内面部６２ｂとがほぼ同じ高さの場合は対流を抑制する効果が得られない。このような場合、図６（ｂ）に示すように、作動極７１から図６（ｂ）において図示しない対極７２（図５参照）に向けて筒状体を設けたり、図示しないハニカム構造体を設けたりすることによって、対流を抑制する効果を得ることができる。このとき、電解させるにあたって電位パルス法および電流パルス法を併用するとより好ましい。電位および電流をパルスで印加するので垂直ＭＨＤ流れが形成され難く、対流抑制手段７５の効果と相まってさらにキラル選択性の制御性向上を図ることが可能となる。 In FIG. 5, the cylindrical inner wall portion 62 a that communicates with the working electrode 71 of the lid 62 inevitably occurs when at least one of voltage and current is applied between the working electrode 71 and the counter electrode 72. It functions as convection suppression means 75 that suppresses convection that causes precession in the micro MHD flow, such as magnetic convection such as MHD flow (solution convection). As shown in FIG. 6A, when the surface of the working electrode 71 and the inner surface 62b of the lid 62 are substantially the same height, the effect of suppressing convection cannot be obtained. In such a case, as shown in FIG. 6B, a cylindrical body is provided from the working electrode 71 toward the counter electrode 72 (see FIG. 5) not shown in FIG. By providing, the effect which suppresses a convection can be acquired. At this time, it is more preferable to use both the potential pulse method and the current pulse method for electrolysis. Since the potential and current are applied in pulses, it is difficult to form a vertical MHD flow, and in combination with the effect of the convection suppression means 75, it is possible to further improve the controllability of chiral selectivity.
また、電解槽６が照合極７３を設けていると、電位制御の場合は正確な制御のために使用でき、電流制御のときは電極表面状態のモニタリングのために使用することができるので、これを設けておくのが好ましい。
図４では、３電極方式の電解槽６を例示しているが、２電極方式や４電極方式の電解槽６によっても好適に特定の表面形状を形成した電極７（作動極７１）を製造することが可能である。
Further, when the electrolytic cell 6 is provided with the reference electrode 73, it can be used for accurate control in the case of potential control, and can be used for monitoring of the electrode surface state in the case of current control. Is preferably provided.
In FIG. 4, a three-electrode type electrolytic cell 6 is illustrated, but the electrode 7 (working electrode 71) having a specific surface shape is preferably manufactured also by the two-electrode type or four-electrode type electrolytic cell 6. It is possible.
電解槽６の自転軸ＡＲまわりの任意の自転速度での自転は、例えば、任意のアクチュエータによって行わせることができるが、非磁性のアクチュエータを用いるのが好ましい。例えば、超音波モーターや油圧モーター、空気圧モーター、容積式モーターなどを用いることができる。
なお、一対の電極７、７およびこれらと接するように収納された電解質媒体５を含む電解槽６は、電気化学セルとも呼ばれている。従って、電気化学セル全体を、磁石２で発生させた磁場Ｂの向きと平行に設定された自転軸ＡＲまわりに自転させるという言い方もできる。
The rotation at an arbitrary rotation speed around the rotation axis AR of the electrolytic cell 6 can be performed by, for example, an arbitrary actuator, but it is preferable to use a nonmagnetic actuator. For example, an ultrasonic motor, a hydraulic motor, a pneumatic motor, a positive displacement motor, or the like can be used.
The electrolytic cell 6 including the pair of electrodes 7 and 7 and the electrolyte medium 5 accommodated so as to be in contact therewith is also called an electrochemical cell. Therefore, it can be said that the entire electrochemical cell rotates about the rotation axis AR set in parallel with the direction of the magnetic field B generated by the magnet 2.
電解槽６（電気化学セル）の自転速度は、電解槽６を上方から見たときに、反時計回りＲ１または時計回りＲ２に０ヘルツ（Ｈｚ）を超え１００Ｈｚ以下とすればよく、例えば、２Ｈｚ（１２０ｒｐｍ）とすればよい。しかしながら、後述するように、自転速度は磁束密度との関係で適宜に設定するのがよいから、前記した自転速度を超えて設定することもできる。 The rotation speed of the electrolytic cell 6 (electrochemical cell) may be set to 0 Hz (Hz) exceeding 100 Hz or less in the counterclockwise direction R1 or clockwise direction R2 when the electrolytic cell 6 is viewed from above, for example, 2 Hz. (120 rpm) may be used. However, as will be described later, since the rotation speed is preferably set appropriately in relation to the magnetic flux density, it can be set beyond the above-described rotation speed.
電解は、定電流法、電流パルス法などの電流規制法や、定電位電解法、定電位パルス法など公知の手法を用いることができる。
なお、電圧および電流については、使用する電極７、７の種類、電解質媒体５の種類および電解質の種類に応じて、公知の適切な値を取ることができる。また、電圧および電流は、直流、交流またはパルス状に印加することができる。
電析の際の磁束密度は、例えば、０．００１テスラ（Ｔ）以上４０Ｔ以下とするのが好ましい。
For electrolysis, a known method such as a current regulation method such as a constant current method or a current pulse method, a constant potential electrolysis method, or a constant potential pulse method can be used.
In addition, about a voltage and an electric current, well-known appropriate value can be taken according to the kind of electrodes 7 and 7 to be used, the kind of electrolyte medium 5, and the kind of electrolyte. Moreover, a voltage and an electric current can be applied in direct current, alternating current, or a pulse form.
The magnetic flux density at the time of electrodeposition is preferably 0.001 Tesla (T) or more and 40 T or less, for example.
電気化学セル全体を磁石２により発生させる磁場Ｂの向きと平行に設定された自転軸ＡＲまわりに自転させる本発明においては、電極７（作動極７１）表面に特定の表面形状を形成する能力を自転周波数ｆと磁束密度Ｂとの積ｆＢによって算定することができる。 In the present invention in which the entire electrochemical cell is rotated about the rotation axis AR set in parallel with the direction of the magnetic field B generated by the magnet 2, the ability to form a specific surface shape on the surface of the electrode 7 (working electrode 71) is provided. It can be calculated by the product fB of the rotation frequency f and the magnetic flux density B.
つまり、ｆＢが等しい場合、電極７（作動極７１）表面に特定の表面形状を形成する能力は同じとなる。例えば、ｆ＝１Ｈｚ、Ｂ＝５Ｔという条件で得られる能力は、ｆ＝１０Ｈｚ、Ｂ＝０．５Ｔという条件で得られる能力と同じとなる。従って、５Ｔというような超電導磁石や消費電力が大きな常電導磁石で達成されるような高磁場を用いなくても、０．５Ｔというような永久磁石で達成し得る磁場中で自転周波数ｆを速くすることにより高磁場の場合と同等の能力が得られる。また、これによれば、Ｂ＝５Ｔ、ｆ＝１０Ｈｚという条件であれば、ｆ＝１Ｈｚのときと比べて１０倍のキラル選択性能力を有する特定の表面形状を形成することも期待できる。さらに、自転方向を反転させるだけで簡単にキラル選択性を逆転させた表面形状を形成することも可能である。 That is, when fB is equal, the ability to form a specific surface shape on the surface of the electrode 7 (working electrode 71) is the same. For example, the ability obtained under the conditions of f = 1 Hz and B = 5T is the same as the ability obtained under the conditions of f = 10 Hz and B = 0.5T. Accordingly, the rotation frequency f can be increased quickly in a magnetic field that can be achieved with a permanent magnet such as 0.5T without using a high magnetic field that can be achieved with a superconducting magnet such as 5T or a normal conducting magnet with high power consumption. By doing so, the same ability as in the case of a high magnetic field can be obtained. Moreover, according to this, if the conditions of B = 5T and f = 10 Hz, it can be expected to form a specific surface shape having a chiral selectivity ability 10 times that in the case of f = 1 Hz. Furthermore, it is possible to easily form a surface shape with the chiral selectivity reversed simply by reversing the rotation direction.
図２および図３に戻って電極製造方法の態様の説明を続ける。
なお、図２で示した磁場発生ステップＳ１１と図３で示した磁場発生ステップＳ２２は実質的に同じ内容を実施するものであり、図２で示した電解槽自転ステップＳ１２と図３で示した電解槽自転ステップＳ２１は実質的に同じ内容を実施するものであり、図２で示した電解ステップＳ１３と図３で示した電解ステップＳ２３は実質的に同じ内容を実施するものであるが、それぞれのステップの詳細を説明すると次のようになる。なお、電極製造装置１の説明にて既に説明した構成要素と同一の構成要素についてはその説明を省略する。
Returning to FIG. 2 and FIG. 3, the description of the embodiment of the electrode manufacturing method will be continued.
The magnetic field generation step S11 shown in FIG. 2 and the magnetic field generation step S22 shown in FIG. 3 perform substantially the same contents, and are shown in the electrolytic cell rotation step S12 shown in FIG. 2 and FIG. The electrolytic cell rotation step S21 carries out substantially the same contents, and the electrolysis step S13 shown in FIG. 2 and the electrolysis step S23 shown in FIG. 3 carry out substantially the same contents. The details of the steps are as follows. In addition, the description is abbreviate | omitted about the component same as the component already demonstrated by description of the electrode manufacturing apparatus 1. FIG.
図２に示す磁場発生ステップＳ１１では、磁石２により磁場Ｂを発生させる。
次いで行う電解槽自転ステップＳ１２では、磁場発生ステップＳ１１で発生させた磁場Ｂ中において、電解質媒体５を収納した電解槽６を、磁場Ｂの向きと平行に設定された自転軸ＡＲまわりに自転させる。
続く電解ステップＳ１３では、電解槽自転ステップＳ１２で自転させた電解槽６内において当該電解槽６とともに自転軸ＡＲまわりを反時計回りまたは時計回りに自転するように電解槽６内に設けられた一対の電極７、７に対して電解質媒体５を通じて電圧および電流のうちの少なくとも一方を印加し、電解を行う。
In the magnetic field generation step S <b> 11 shown in FIG. 2, the magnetic field B is generated by the magnet 2.
In the subsequent electrolytic cell rotation step S12, the electrolytic cell 6 containing the electrolyte medium 5 is rotated around the rotation axis AR set parallel to the direction of the magnetic field B in the magnetic field B generated in the magnetic field generation step S11. .
In the subsequent electrolysis step S13, a pair provided in the electrolysis cell 6 so as to rotate around the rotation axis AR together with the electrolysis cell 6 in the electrolysis cell 6 rotated in the electrolysis cell rotation step S12 counterclockwise or clockwise. Electrolysis is performed by applying at least one of voltage and current to the electrodes 7 and 7 through the electrolyte medium 5.
また、図３に示す電解槽自転ステップＳ２１では、電解質媒体５を収納した電解槽６を、磁石２により発生させる磁場Ｂの向きと平行に設定された自転軸ＡＲまわりを反時計回りまたは時計回りに自転させる。
次いで行う磁場発生ステップＳ２２では、電解槽自転ステップＳ２１で自転させた電解槽６に対し、磁石２により磁場Ｂを発生させる。
続く電解ステップＳ２３は、磁場発生ステップＳ２２で発生させた磁場Ｂ中で自転している電解槽６内において当該電解槽６とともに自転軸ＡＲまわりに自転するように電解槽６内に設けられた一対の電極７、７に対して電解質媒体５を通じて電圧および電流のうちの少なくとも一方を印加し、電解を行う。
Further, in the electrolytic cell rotation step S21 shown in FIG. 3, the electrolytic cell 6 containing the electrolyte medium 5 is rotated counterclockwise or clockwise around the rotation axis AR set in parallel with the direction of the magnetic field B generated by the magnet 2. Rotate to
Next, in the magnetic field generation step S22 to be performed, the magnetic field B is generated by the magnet 2 with respect to the electrolytic cell 6 rotated in the electrolytic cell rotation step S21.
The subsequent electrolysis step S23 is a pair provided in the electrolytic cell 6 so as to rotate about the rotation axis AR together with the electrolytic cell 6 in the electrolytic cell 6 rotating in the magnetic field B generated in the magnetic field generation step S22. Electrolysis is performed by applying at least one of voltage and current to the electrodes 7 and 7 through the electrolyte medium 5.
図２および図３に示したいずれの態様の電極製造方法によっても、磁石２で発生させた磁場Ｂの向きと平行に設定された自転軸ＡＲまわりを反時計回りまたは時計回りに電解槽６を自転させつつ、電解質媒体５を通じて一対の電極７、７に対して電圧および電流のうちの少なくとも一方を印加して電解を行うため、電極７（作動極７１）表面に特定の表面形状を形成することができる。 2 and 3, the electrolytic cell 6 is moved counterclockwise or clockwise around the rotation axis AR set in parallel with the direction of the magnetic field B generated by the magnet 2. In order to perform electrolysis by applying at least one of voltage and current to the pair of electrodes 7 and 7 through the electrolyte medium 5 while rotating, a specific surface shape is formed on the surface of the electrode 7 (working electrode 71). be able to.
本発明の一実施形態に係る電極製造方法や電極製造装置１で製造された電極７（作動極７１）は、特定の表面形状（キラルな結晶表面）が形成されている（図７（ａ）および（ｂ）参照）ので、キラル選択性を有する。そのため、例えば、バイオセンサー用途のセンシング電極や有機合成反応用の触媒電極および個体触媒、さらには燃料電池やリチウム２次電池の正極や負極など、光学異性体の関与する反応において好ましい電極となり得る。
また、かかる電極７（作動極７１）は、光学異性体反応のキラル選択性向上に利用することができる。加えて、当該電極７（作動極７１）を用いて光学異性体反応を行わせることで、溶液中に発生するキラルなマイクロＭＨＤ渦流を反応の選択性向上に利用することができる。さらに、かかる電極７を光学異性体反応装置の触媒として用いると、当該触媒を常にキラルな環境で使用することになるため、触媒活性の低下を防ぎ、触媒の寿命を長くする上で有効である。
The electrode 7 (working electrode 71) manufactured by the electrode manufacturing method and the electrode manufacturing apparatus 1 according to one embodiment of the present invention has a specific surface shape (chiral crystal surface) (FIG. 7A). And (b)) so that it has chiral selectivity. Therefore, it can be a preferable electrode in reactions involving optical isomers such as sensing electrodes for biosensors, catalyst electrodes and solid catalysts for organic synthesis reactions, and positive and negative electrodes of fuel cells and lithium secondary batteries.
Moreover, this electrode 7 (working electrode 71) can be utilized for the chiral selectivity improvement of an optical isomer reaction. In addition, by performing the optical isomer reaction using the electrode 7 (working electrode 71), the chiral micro MHD vortex generated in the solution can be used for improving the selectivity of the reaction. Furthermore, when such an electrode 7 is used as a catalyst for an optical isomer reaction apparatus, the catalyst is always used in a chiral environment, which is effective in preventing a decrease in catalyst activity and extending the life of the catalyst. .
（特定の表面形状の形成）
はじめに、電極に特定の表面形状を形成したので、これについて説明する。
作動極７１と対極７２からなる一対の銅製水平平板電極のうち作動極７１を、自然対流を防止するため、図５に示す電解槽６の上部に、下向きとなるように固定し、対極を当該電解槽６の下部に、上向きとなるように固定した。そして、電解槽６全体を超電導磁石の常温ボア空間内に吊り下げた。電解槽６の自転軸まわりの回転には、非磁性超音波モーターを使用した。電解槽６内を満たす電解質媒体として、硫酸銅０．２５ｍｏｌ／Ｌと硫酸０．５ｍｏｌ／Ｌとからなる硫酸銅溶液を用いた。照合極には銅線を用いた。電析は、過電圧−０．４Ｖ（ｖｓ Ｃｕ）一定で１０分間行った。なお、磁束密度は１Ｔで図５に示す電解槽６に対して下向きとなるように設定し、電解槽６全体を回転速度１Ｈｚで電解槽６の上方から見て反時計回り（電極表面で見ると時計回り）に回転させた。かかる条件で電析を行った後、走査型電子顕微鏡（三次元ＳＥＭ）で電極の析出表面を観察した。電子顕微鏡写真を図７（ａ）に示す。なお、図７（ａ）中のスケールバーは２０μｍを示す。
(Specific surface shape formation)
First, a specific surface shape is formed on the electrode, which will be described.
In order to prevent natural convection, the working electrode 71 of the pair of copper horizontal plate electrodes composed of the working electrode 71 and the counter electrode 72 is fixed to the upper part of the electrolytic cell 6 shown in FIG. It fixed to the lower part of the electrolytic cell 6 so that it might face upward. Then, the entire electrolytic cell 6 was suspended in the room temperature bore space of the superconducting magnet. A nonmagnetic ultrasonic motor was used for rotation around the rotation axis of the electrolytic cell 6. A copper sulfate solution composed of 0.25 mol / L of copper sulfate and 0.5 mol / L of sulfuric acid was used as the electrolyte medium filling the electrolytic cell 6. A copper wire was used as a reference electrode. Electrodeposition was performed for 10 minutes at a constant overvoltage of −0.4 V (vs Cu). The magnetic flux density is set to 1 T so as to face downward with respect to the electrolytic cell 6 shown in FIG. 5, and the entire electrolytic cell 6 is rotated counterclockwise when viewed from above the electrolytic cell 6 at a rotational speed of 1 Hz (viewed on the electrode surface). And clockwise). After performing electrodeposition under such conditions, the deposition surface of the electrode was observed with a scanning electron microscope (three-dimensional SEM). An electron micrograph is shown in FIG. In addition, the scale bar in Fig.7 (a) shows 20 micrometers.
図７（ａ）に示すように、電極の表面に、同心円状の平坦な底部を持つ、特徴的な形状が形成されていた。図７（ｂ）は、三次元ＳＥＭによって当該特徴的な形状の直径（ｘ）および深さ（ｚ）を測定した結果を示すグラフである。ここで、図７（ｂ）中の横軸は当該特徴的な形状の直径を示し、縦軸は当該特徴的な形状の深さを示す。単位はいずれもマイクロメートル［μｍ］である。
なお、図には示していないが、回転速度を２Ｈｚに上げると同様の形状が単位面積あたり５倍程度多く形成されていた。
As shown in FIG. 7 (a), a characteristic shape having a concentric flat bottom was formed on the surface of the electrode. FIG. 7B is a graph showing the results of measuring the diameter (x) and depth (z) of the characteristic shape by a three-dimensional SEM. Here, the horizontal axis in FIG. 7B indicates the diameter of the characteristic shape, and the vertical axis indicates the depth of the characteristic shape. All units are micrometers [μm].
Although not shown in the figure, when the rotational speed is increased to 2 Hz, the same shape is formed about five times as much per unit area.
（キラル選択性）
次に、キラル選択性について検討したので、これについて説明する。
まず、銅板を用意し、図５に示すように、電極表面となる面（作動極７１の表面）に対して磁場を垂直に、そして向かう方向となるように印加した。電極はφ３．２ｍｍの円板状である。対極に銅板、照合極には銅線を使用した。溶液は、硫酸銅０．０５ｍｏｌ／Ｌおよび硫酸０．５ｍｏｌ／Ｌからなる硫酸酸性の硫酸銅溶液を使用し、共通の実験条件として、過電圧を−０．４５３Ｖ（ｖｓ Ｃｕ）、磁場を超電導磁石により磁束密度３Ｔ上向き（図５参照）で、電解時間１０ｓ×４回のパルス状の電析を行った。電解槽６の自転速度は、電解槽の上方から見て時計回りで約２Ｈｚ（１２０ｒｐｍ）、反時計回りで約２Ｈｚ、および自転のない場合である０Ｈｚで行い、３つの電極を製造した。なお、電極系および溶液を含めた電解槽全体（すなわち電気化学セル全体）を自転させた。
(Chiral selectivity)
Next, since chiral selectivity was examined, this is demonstrated.
First, a copper plate was prepared, and as shown in FIG. 5, a magnetic field was applied so as to be perpendicular to and in the direction toward the surface to be the electrode surface (the surface of the working electrode 71). The electrode has a disk shape of φ3.2 mm. A copper plate was used for the counter electrode and a copper wire for the reference electrode. As the solution, an acidic copper sulfate solution composed of 0.05 mol / L of copper sulfate and 0.5 mol / L of sulfuric acid was used. As common experimental conditions, an overvoltage was -0.453 V (vs Cu) and a magnetic field was a superconducting magnet. Thus, pulsed electrodeposition with an electrolysis time of 10 s × 4 times was performed with a magnetic flux density of 3T upward (see FIG. 5). The rotation speed of the electrolytic cell 6 was about 2 Hz (120 rpm) clockwise as viewed from above the electrolytic cell, about 2 Hz counterclockwise, and 0 Hz when there was no rotation, and three electrodes were manufactured. In addition, the whole electrolytic cell (namely, the whole electrochemical cell) including an electrode system and a solution was rotated.
次に、それぞれの条件で製造した電極について、前処理として水酸化ナトリウム０．１ｍｏｌ／Ｌ中で−０．３〜０．４Ｖ（ｖｓ Ａｇ／ＡｇＣｌ）、１０ｍＶ／ｓの条件でサイクリックボルタンメトリー（ＣＶ）を行い、安定な酸化膜ＣｕＯを形成した後、０．０２ｍｏｌ／ＬのＬ−Ａｌａｎｉｎｅを含む水酸化ナトリウム０．１ｍｏｌ／Ｌの溶液中、または０．０２ｍｏｌ／ＬのＤ−Ａｌａｎｉｎｅを含む水酸化ナトリウム０．１ｍｏｌ／Ｌの溶液中で、−０．３〜０．８Ｖ（ｖｓ Ａｇ／ＡｇＣｌ）、１０ｍＶ／ｓの条件でＣＶを行い、Ｌ−ＡｌａｎｉｎｅとＤ−Ａｌａｎｉｎｅに対するキラル選択性を確認した。なお、対極に白金板、照合極には銀塩化銀電極を使用し、磁場なしおよび自転なしの条件で実施した。ここで、Ｌ−ＡｌａｎｉｎｅとＤ−Ａｌａｎｉｎｅのキラル選択性を確認するための電極は、それぞれ同一の実験条件で作製した別個の電極を用いた。その結果を図８（ａ）〜（ｃ）に示す。 Next, for the electrodes manufactured under each condition, cyclic voltammetry (as a pretreatment under conditions of -0.3 to 0.4 V (vs Ag / AgCl) and 10 mV / s in 0.1 mol / L sodium hydroxide) CV) to form a stable oxide film CuO, and then in a solution of sodium hydroxide 0.1 mol / L containing 0.02 mol / L L-Aline, or containing 0.02 mol / L D-Aline. CV is performed in a solution of 0.1 mol / L sodium hydroxide under the conditions of -0.3 to 0.8 V (vs Ag / AgCl) and 10 mV / s, and the chiral selectivity to L-Aline and D-Alane is obtained. confirmed. A platinum plate was used as the counter electrode, and a silver / silver chloride electrode was used as the reference electrode, and the test was performed without magnetic field and without rotation. Here, as the electrodes for confirming the chiral selectivity of L-Aline and D-Aline, separate electrodes prepared under the same experimental conditions were used. The results are shown in FIGS.
図８（ａ）に示すとおり、自転なし（０Ｈｚ）で製造した電極では、本来の垂直ＭＨＤ流れによる対流効果でＬ−Ａｌａｎｉｎｅの電流値がやや高くなることから、Ｌ−Ａｌａｎｉｎｅを選択したといえる。
そして、図８（ｂ）に示すとおり、電気化学セルの上方（図５参照）から見て反時計回りに２Ｈｚの条件で自転させて製造した電極では、Ｌ−Ａｌａｎｉｎｅの電流値が大幅に増幅されていることから、Ｌ体のキラル選択性が増幅したといえる。
一方、図８（ｃ）に示すとおり、電気化学セルの上方（図５参照）から見て時計回りに２Ｈｚの条件で自転させて製造した電極では、Ｄ−Ａｌａｎｉｎｅの電流値が高くなったので、Ｄ体のキラル選択性が増幅されたといえる。また、図８（ｃ）に示す測定結果は、磁場中で電気化学セル全体を自転させて製造した電極は、回転方向の変化のみで簡単にキラル選択性を逆転できることを明らかにしている。
As shown in FIG. 8A, in the electrode manufactured without rotation (0 Hz), the current value of L-Aline is slightly higher due to the convection effect due to the original vertical MHD flow, so it can be said that L-Aline is selected. .
As shown in FIG. 8 (b), the current value of L-Aline is greatly amplified in the electrode manufactured by rotating counterclockwise under the condition of 2 Hz when viewed from above the electrochemical cell (see FIG. 5). Therefore, it can be said that the chiral selectivity of the L form was amplified.
On the other hand, as shown in FIG. 8 (c), in the electrode manufactured by rotating on the condition of 2Hz clockwise as viewed from above the electrochemical cell (see FIG. 5), the current value of D-Aline increased. It can be said that the chiral selectivity of D-form was amplified. Further, the measurement result shown in FIG. 8 (c) reveals that an electrode produced by rotating the entire electrochemical cell in a magnetic field can easily reverse the chiral selectivity only by changing the rotation direction.
Ｓ１１ 磁場発生ステップ
Ｓ１２ 電解槽自転ステップ
Ｓ１３ 電解ステップ
Ｓ２１ 電解槽自転ステップ
Ｓ２２ 磁場発生ステップ
Ｓ２３ 電解ステップ
１ 電極製造装置
２ 磁石
５ 電解質媒体
６ 電解槽
７ 電極
８ アクチュエータ
９ 軸部材
１０ ベアリング
６１ 容器本体
６２ 蓋体
６３ Ｏリング
７１ 作動極
７１ａ、７２ａ、７３ａ 接続部
７１ｂ、７２ｂ、７３ｂ ブラシ電極
７２ 対極
７３ 照合極
７４ 作動極固定手段
７５ 対流抑制手段
ＡＲ 自転軸
Ｂ 磁場
S11 Magnetic field generation step S12 Electrolysis tank rotation step S13 Electrolysis step S21 Electrolysis tank rotation step S22 Magnetic field generation step S23 Electrolysis step 1 Electrode manufacturing apparatus 2 Magnet 5 Electrolyte medium 6 Electrolysis tank 7 Electrode 8 Actuator 9 Shaft member 10 Bearing 61 Container body 62 Lid Body 63 O-ring 71 Working electrode 71a, 72a, 73a Connection part 71b, 72b, 73b Brush electrode 72 Counter electrode 73 Reference electrode 74 Working electrode fixing means 75 Convection suppression means AR Rotating shaft B Magnetic field
Claims (6)
磁石で発生させた磁場の向きと平行に設定された自転軸まわりに特定の方向で電解槽を自転させつつ、前記電解槽とともに前記自転軸まわりに自転するように前記電解槽内に設けられた作動極となる陰極および対極となる陽極からなる一対の電極に対して電解質媒体を通じて電圧および電流のうちの少なくとも一方を印加し、前記対極の電解を行うとともに前記作動極の電析を行い、前記作動極の表面に前記特定の表面形状を形成させることで、前記表面に特定の表面形状を形成した電極を製造する
ことを特徴とする電極製造方法。 An electrode manufacturing method for manufacturing an electrode having a specific surface shape formed on a surface,
Provided in the electrolytic cell to rotate around the rotation axis together with the electrolytic cell while rotating the electrolytic cell in a specific direction around the rotation axis set parallel to the direction of the magnetic field generated by the magnet. at least one of the voltage and current through the electrolyte medium is applied to a pair of electrodes composed of an anode as a cathode and the counter electrode serving as a working electrode, the electrolyte of the counter perform electrodeposition line Utotomoni the working electrode, An electrode manufacturing method , wherein an electrode having a specific surface shape formed on the surface is manufactured by forming the specific surface shape on the surface of the working electrode.
磁石により磁場を発生させる磁場発生ステップと、
発生させた前記磁場中において、電解質媒体を収納した電解槽を、前記磁場の向きと平行に設定された自転軸まわりに特定の方向で自転させる電解槽自転ステップと、
自転している前記電解槽とともに前記自転軸まわりに自転するように前記電解槽内に設けられた作動極となる陰極および対極となる陽極からなる一対の電極に対して前記電解質媒体を通じて電圧および電流のうちの少なくとも一方を印加し、前記対極の電解を行うとともに前記作動極の電析を行い、前記作動極の表面に前記特定の表面形状を形成させることで、前記表面に特定の表面形状を形成した電極を製造する電解ステップと、を含む
ことを特徴とする電極製造方法。 An electrode manufacturing method for manufacturing an electrode having a specific surface shape formed on a surface,
A magnetic field generating step for generating a magnetic field by a magnet;
In the generated magnetic field, an electrolytic cell rotation step for rotating an electrolytic cell containing an electrolyte medium in a specific direction around a rotation axis set parallel to the direction of the magnetic field;
Voltage and current through the electrolyte medium with respect to a pair of electrodes consisting of a cathode serving as a working electrode and an anode serving as a counter electrode provided in the electrolytic cell so as to rotate around the rotation axis together with the rotating electrolytic cell. at least one of the applying, the electrolytic counter electrode performs electrodeposition line Utotomoni the working electrode, by the fact that to form a particular surface shape on the surface of the working electrode, the specific surface shape on the surface of the And an electrolysis step for producing an electrode formed with an electrode .
電解質媒体を収納した電解槽を、磁石により発生させる磁場の向きと平行に設定された自転軸まわりに特定の方向で自転させる電解槽自転ステップと、
自転している前記電解槽に対し、前記磁石により磁場を発生させる磁場発生ステップと、
発生させた前記磁場中で自転している前記電解槽内において前記電解槽とともに前記自転軸まわりに自転するように前記電解槽内に設けられた作動極となる陰極および対極となる陽極からなる一対の電極に対して前記電解質媒体を通じて電圧および電流のうちの少なくとも一方を印加し、前記対極の電解を行うとともに前記作動極の電析を行い、前記作動極の表面に前記特定の表面形状を形成させることで、前記表面に特定の表面形状を形成した電極を製造する電解ステップと、を含む
ことを特徴とする電極製造方法。 An electrode manufacturing method for manufacturing an electrode having a specific surface shape formed on a surface,
An electrolytic cell rotation step for rotating the electrolytic cell containing the electrolyte medium in a specific direction around a rotation axis set parallel to the direction of the magnetic field generated by the magnet;
A magnetic field generation step for generating a magnetic field by the magnet with respect to the electrolytic cell rotating,
A pair of cathodes serving as working electrodes and anodes serving as counter electrodes provided in the electrolytic cell so as to rotate around the rotation axis together with the electrolytic cell in the electrolytic cell rotating in the generated magnetic field. of at least one of the voltage and current through the electrolyte medium is applied to the electrodes, the electrolyte of the counter perform electrodeposition line Utotomoni the working electrode, the specific surface shape on the surface of the working electrode And an electrolysis step of manufacturing an electrode having a specific surface shape formed on the surface by forming the electrode .
磁場を発生させる磁石と、
発生させた前記磁場中において、当該磁場の向きと平行に設定された自転軸まわりを特定の方向に自転するように設けられ、電解質媒体を入出自在に収納することのできる電解槽と、
前記電解槽内に、当該電解槽とともに前記自転軸まわりに自転するように互いに離間して設けられた作動極となる陰極および対極となる陽極からなる一対の電極と、
前記電解槽を前記自転軸まわりに任意の自転速度で自転させるアクチュエータと、
を備え、
前記電解槽を前記自転軸まわりに特定の方向で自転させつつ、前記一対の電極に対して前記電解質媒体を通じて電圧および電流のうちの少なくとも一方を印加し、前記対極の電解を行うとともに前記作動極の電析を行い、前記作動極の表面に前記特定の表面形状を形成させることで、前記表面に特定の表面形状を形成した電極を製造する
ことを特徴とする電極製造装置。 An electrode manufacturing apparatus for manufacturing an electrode having a specific surface shape formed on a surface,
A magnet for generating a magnetic field;
In the generated magnetic field, an electrolytic cell provided so as to rotate in a specific direction around a rotation axis set in parallel with the direction of the magnetic field, and capable of accommodating an electrolyte medium in an freely accessible manner,
In the electrolytic cell, a pair of electrodes composed of a cathode serving as a working electrode and an anode serving as a counter electrode, which are provided apart from each other so as to rotate about the rotation axis together with the electrolytic cell;
An actuator that rotates the electrolytic cell around the rotation axis at an arbitrary rotation speed;
Equipped with a,
While rotating the electrolytic cell around the rotation axis in a specific direction, at least one of voltage and current is applied to the pair of electrodes through the electrolyte medium to perform electrolysis of the counter electrode and the working electrode. The electrode manufacturing apparatus is characterized in that an electrode having a specific surface shape formed on the surface is manufactured by forming the specific surface shape on the surface of the working electrode.
前記作動極は、これを固定する作動極固定手段によって固定され、
当該作動極固定手段は、対流を抑制する対流抑制手段を有しており、
前記対流が、前記作動極上層部の電流線の広がりが生み出すローレンツ力による竜巻状の回転運動である垂直ＭＨＤ流れである
ことを特徴とする電極製造装置。 The electrode manufacturing apparatus according to claim 4,
The working electrode is fixed by a working electrode fixing means for fixing the working electrode,
The working electrode fixing means has convection suppressing means for suppressing convection ,
It said convection, electrode manufacturing apparatus characterized by Ru vertical MHD flow der a tornado-like rotational movement by the Lorentz force spread produces a current line of the actuating finest layer portion.
表面に特定の表面形状が形成されている
ことを特徴とする電極。 An electrode manufactured by the electrode manufacturing method according to any one of claims 1 to 3,
An electrode characterized in that a specific surface shape is formed on the surface.
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