JP2021014629A - Reductive reaction electrode, and reaction device using the same - Google Patents
Reductive reaction electrode, and reaction device using the same Download PDFInfo
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
本発明は、還元反応用電極、およびそれを用いた反応デバイスに関する。 The present invention relates to an electrode for a reduction reaction and a reaction device using the same.
太陽光エネルギーを用いて水（Ｈ２Ｏ）から水素（Ｈ２）、水（Ｈ２Ｏ）と二酸化炭素（ＣＯ２）から一酸化炭素（ＣＯ）、ギ酸（ＨＣＯＯＨ）、メタノール（ＣＨ３ＯＨ）等を合成する人工光合成に用いられる反応デバイスの技術が開示されている。これを実用化するためには、高い効率で反応を生じさせる反応用電極を実現することが望まれる。 Using solar energy, water (H 2 O) to hydrogen (H 2 ), water (H 2 O) and carbon dioxide (CO 2 ) to carbon monoxide (CO), formic acid (HCOOH), methanol (CH 3 OH) ) Etc. are disclosed. The technology of the reaction device used for artificial photosynthesis is disclosed. In order to put this into practical use, it is desired to realize a reaction electrode that causes a reaction with high efficiency.
反応デバイスでは、還元反応用電極と酸化反応用電極とが組み合わせて用いられる。例えば、特許文献１には、金属または半導体を含む基板と、前記基板の表面の少なくとも一部を覆い、構造体単体のサイズが１μｍ以下のカーボン素材からなるカーボン層と、前記カーボン層の表面を覆う錯体触媒層と、を備える還元反応用電極が開示されている。 In the reaction device, a reduction reaction electrode and an oxidation reaction electrode are used in combination. For example, Patent Document 1 describes a substrate containing a metal or a semiconductor, a carbon layer made of a carbon material that covers at least a part of the surface of the substrate and has a structure alone having a size of 1 μm or less, and the surface of the carbon layer. A reduction reaction electrode comprising a complex catalyst layer to cover is disclosed.
特許文献１に記載の技術を始めとして、多くの還元反応用電極の基板としては、金属（Ａｇ、Ａｕ、Ｃｕ、ステンレス等）や半導体（ＴｉＯ２、ＺｎＯ、ＳＴｒＯ３等）や、ガラス等にこれらの金属や半導体が塗布されたものが用いられている。 Including the technique described in Patent Document 1, many substrates for electrodes for reduction reactions include metals (Ag, Au, Cu, stainless steel, etc.), semiconductors (TiO 2 , ZnO, StrO 3, etc.), glass, and the like. Those coated with these metals and semiconductors are used.
特許文献２には、還元反応用電極の基板としてガラス基板やプラスチック等が用いられることが記載され、例えば、フッ素ドープ酸化錫（ＦＴＯ）透明導電膜付きのガラスが用いられている。 Patent Document 2 describes that a glass substrate, plastic, or the like is used as a substrate for a reduction reaction electrode. For example, glass with a fluorine-doped tin oxide (FTO) transparent conductive film is used.
Ａｇ、Ａｕ、Ｃｕ、ステンレスの基板は、何れも水素（Ｈ２）生成電極として機能する。したがって、これらが露出している電極を用いると水素が生成するので、ＣＯ２還元能等の性能が低下する。また、意図しない水素の生成は望ましくない。 The Ag, Au, Cu, and stainless steel substrates all function as hydrogen (H 2 ) generating electrodes. Therefore, if these exposed electrodes are used, hydrogen is generated, and the performance such as CO 2 reducing ability is deteriorated. Also, unintended hydrogen production is not desirable.
ＴｉＯ２等の半導体の基板の場合、例えば数ｃｍ角以上のサイズの電極を作製するためには、ガラス等の別の基材の表面にＴｉＯ２等を形成する加工が必要である。例えば特許文献１にはＩＴＯ上にスパッタリングで形成したＴｉＯ２を基板として用いることが開示されているが、コストの問題に加えて長期的にはＴｉＯ２膜の剥離等の劣化の恐れがある。 In the case of a semiconductor substrate such as TiO 2 , for example, in order to produce an electrode having a size of several cm square or more, it is necessary to process the surface of another substrate such as glass to form TiO 2 or the like. For example, Patent Document 1 discloses that TiO 2 formed on ITO by sputtering is used as a substrate, but in addition to the problem of cost, there is a risk of deterioration such as peeling of the TiO 2 film in the long term.
ＦＴＯ付きガラス基板の場合は、ＦＴＯのシート抵抗が約１０Ω／ｓｑと大きいため、数ｃｍ角以上のサイズの電極を作製するためには、金属製集電電極の形成が必要である。その際、コストの問題に加えて、ガラスによる重量の問題や、長期的には腐食等の劣化の恐れがある。また、基板自体の形状加工は極めて難しい。 In the case of a glass substrate with an FTO, the sheet resistance of the FTO is as large as about 10 Ω / sq, so it is necessary to form a metal current collecting electrode in order to produce an electrode having a size of several cm square or more. At that time, in addition to the problem of cost, there is a risk of weight problem due to glass and deterioration such as corrosion in the long term. Moreover, it is extremely difficult to process the shape of the substrate itself.
本発明の目的は、軽量化、低コスト化が可能であり、高性能、耐腐食性、かつ加工性に優れた還元反応用電極、およびそれを用いた反応デバイスを提供することにある。 An object of the present invention is to provide a reduction reaction electrode which can be reduced in weight and cost and has excellent high performance, corrosion resistance, and workability, and a reaction device using the same.
本発明は、Ｔｉ基板と、カーボン系材料と金属錯体とを含む還元触媒層と、を有する還元反応用電極である。 The present invention is an electrode for a reduction reaction having a Ti substrate and a reduction catalyst layer containing a carbon-based material and a metal complex.
前記還元反応用電極において、前記カーボン系材料は、炭素繊維を含むことが好ましい。 In the reduction reaction electrode, the carbon-based material preferably contains carbon fibers.
前記還元反応用電極において、前記還元触媒層は、さらにカーボンナノチューブを含むことが好ましい。 In the reduction reaction electrode, the reduction catalyst layer preferably further contains carbon nanotubes.
前記還元反応用電極において、前記金属錯体は、ルテニウム錯体であることが好ましい。 In the electrode for reduction reaction, the metal complex is preferably a ruthenium complex.
前記還元反応用電極において、前記還元触媒層は、前記Ｔｉ基板にカーボン系接着剤を含む接着層によって接着されていることが好ましい。 In the reduction reaction electrode, the reduction catalyst layer is preferably adhered to the Ti substrate by an adhesive layer containing a carbon-based adhesive.
前記還元反応用電極において、前記Ｔｉ基板の一部が露出していてもよい。 In the reduction reaction electrode, a part of the Ti substrate may be exposed.
本発明は、前記還元反応用電極と、酸化反応用電極と、を組み合わせて構成される、反応デバイスである。 The present invention is a reaction device configured by combining the reduction reaction electrode and the oxidation reaction electrode.
前記反応デバイスにおいて、前記酸化反応用電極は、Ｔｉ基板を有することが好ましい。 In the reaction device, the oxidation reaction electrode preferably has a Ti substrate.
本発明により、軽量化、低コスト化が可能であり、高性能、耐腐食性、かつ加工性に優れた還元反応用電極、およびそれを用いた反応デバイスを提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an electrode for reduction reaction, which can be reduced in weight and cost, and has excellent high performance, corrosion resistance, and workability, and a reaction device using the same.
本発明の実施の形態について以下説明する。本実施形態は本発明を実施する一例であって、本発明は本実施形態に限定されるものではない。 Embodiments of the present invention will be described below. The present embodiment is an example of carrying out the present invention, and the present invention is not limited to the present embodiment.
［還元反応用電極］
図１は、本発明の実施形態に係る還元反応用電極の構成の一例を示す概略構成図である。図１の還元反応用電極１０は、Ｔｉ基板１２と、カーボン系材料と金属錯体とを含む還元触媒層１６と、を有する。還元触媒層１６は、接着層１４によってＴｉ基板１２と接着されていてもよい。還元反応用電極１０に電圧が印加されると、Ｔｉ基板１２に生じた電荷が還元触媒層１６に渡され、還元触媒層１６における還元触媒反応、例えば、二酸化炭素（ＣＯ２）がギ酸（ＨＣＯＯＨ）に還元される反応に利用される。
[Electrodes for reduction reaction]
FIG. 1 is a schematic configuration diagram showing an example of the configuration of a reduction reaction electrode according to an embodiment of the present invention. The reduction reaction electrode 10 of FIG. 1 has a Ti substrate 12 and a reduction catalyst layer 16 containing a carbon-based material and a metal complex. The reduction catalyst layer 16 may be adhered to the Ti substrate 12 by the adhesive layer 14. When a voltage is applied to the reduction reaction electrode 10, the charge generated in the Ti substrate 12 is passed to the reduction catalyst layer 16, and the reduction catalyst reaction in the reduction catalyst layer 16, for example, carbon dioxide (CO 2 ), is converted to formic acid (HCOOH). ) Is used for the reaction.
Ｔｉ基板１２は、実質的にチタン（Ｔｉ）からなる基板である。Ｔｉ基板１２の表面には、不動態層が形成されていてもよい。不動態層の厚みは、１０ｎｍ以下である。 The Ti substrate 12 is a substrate substantially made of titanium (Ti). A passivation layer may be formed on the surface of the Ti substrate 12. The thickness of the passivation layer is 10 nm or less.
Ｔｉ基板は、水素（Ｈ２）生成過電圧が高いので、ＣＯ２還元等の使用条件ではＨ２がほとんど生成されない。Ｔｉ基板は、表面に不動態層が形成されるので耐食性に優れる。かつガラスに比べて軽量、貴金属に比べて低コスト、かつ形状加工が容易であるという特長がある。 Since the Ti substrate has a high hydrogen (H 2 ) generation overvoltage, H 2 is hardly generated under usage conditions such as CO 2 reduction. The Ti substrate is excellent in corrosion resistance because a passivation layer is formed on the surface of the Ti substrate. In addition, it is lighter than glass, lower in cost than precious metals, and easy to shape.
還元触媒層１６は、カーボン系材料を含む。カーボン系材料は、例えば、炭素繊維を含み、例えば、カーボンペーパー、カーボンクロス等が挙げられる。カーボンペーパーは、例えば、ポリアクリロニトリル（ＰＡＮ）繊維等の有機繊維をポリビニルアルコールと水系媒体との分散液に含浸させ、約２０００℃で炭化させて結着させたものをシート状にしたものである。カーボンペーパーには、約２５質量％程度のテフロン（登録商標）系素材が含まれることもある。カーボンクロスは、有機繊維を焼成、炭化することで得られる炭素繊維を紡織したものである。カーボンペーパー、カーボンクロスは、多孔質体であり、無数の数十μｍ（１０μｍ〜１００μｍ程度）の細孔を有する。カーボンペーパー、カーボンクロスの厚さは、例えば、０．１ｍｍ〜０．４ｍｍ／１枚の範囲である。カーボンペーパー、カーボンクロスとしては、多層化（例えば、５〜１０層）されて厚みが約１０倍になった１ｍｍ〜４ｍｍの範囲のものを使用してもよい。 The reduction catalyst layer 16 contains a carbon-based material. The carbon-based material contains, for example, carbon fiber, and examples thereof include carbon paper and carbon cloth. The carbon paper is, for example, impregnated with an organic fiber such as polyacrylonitrile (PAN) fiber in a dispersion liquid of polyvinyl alcohol and an aqueous medium, carbonized at about 2000 ° C., and bound to form a sheet. .. The carbon paper may contain about 25% by mass of a Teflon (registered trademark) -based material. The carbon cloth is made by spinning carbon fibers obtained by firing and carbonizing organic fibers. The carbon paper and carbon cloth are porous bodies and have innumerable pores of several tens of μm (about 10 μm to 100 μm). The thickness of the carbon paper and the carbon cloth is, for example, in the range of 0.1 mm to 0.4 mm / sheet. As the carbon paper and carbon cloth, those in the range of 1 mm to 4 mm, which are multi-layered (for example, 5 to 10 layers) and have a thickness of about 10 times, may be used.
還元反応用電極にカーボン系材料を使用することにより、大面積化、高出力化が可能となる。また、カーボン系材料は高導電性の確保ができ、多孔性であることから気孔率が高いので反応基質および反応生成物の流れが良好となり、水素発生等の副反応の抑制や炭素化合物の還元反応効率向上が達成されると考えられる。また、例えばｐＨ６．５〜７の電解液中でも耐食性に優れる。 By using a carbon-based material for the electrode for the reduction reaction, it is possible to increase the area and output. In addition, carbon-based materials can ensure high conductivity, and since they are porous, they have a high porosity, so that the flow of reaction substrates and reaction products is good, suppressing side reactions such as hydrogen generation, and reducing carbon compounds. It is considered that the reaction efficiency is improved. Further, for example, it has excellent corrosion resistance even in an electrolytic solution having a pH of 6.5 to 7.
還元触媒層１６は、接着層１４を介してＴｉ基板１２上に貼り合わせることができる。このとき、接着剤として、導電性のカーボン素材、例えばグラファイトまたはグラフェンを含むポリマーを含むカーボン系接着剤を用いることが好適である。接着層１４には、例えば、少なくとも直径が１μｍ以上１００μｍ以下のサイズのグラファイトまたはグラフェンを含むことが好適である。 The reduction catalyst layer 16 can be bonded onto the Ti substrate 12 via the adhesive layer 14. At this time, it is preferable to use a conductive carbon material, for example, a carbon-based adhesive containing a polymer containing graphite or graphene as the adhesive. It is preferable that the adhesive layer 14 contains, for example, graphite or graphene having a diameter of at least 1 μm or more and 100 μm or less.
還元触媒層１６は、二酸化炭素還元反応等の還元反応の還元触媒を含む。還元触媒層１６は、例えば、カーボン系材料に還元触媒を担持させたものでもよいし、カーボン系材料の上に還元触媒を含む還元触媒層を形成したものでもよい。 The reduction catalyst layer 16 contains a reduction catalyst for a reduction reaction such as a carbon dioxide reduction reaction. The reduction catalyst layer 16 may be, for example, a carbon-based material on which a reduction catalyst is supported, or a carbon-based material on which a reduction catalyst layer containing a reduction catalyst is formed.
還元触媒は、ルテニウム（Ｒｕ）錯体等の金属錯体を含む。ルテニウム錯体としては、例えば、［Ｒｕ｛４，４’−ｄｉ（１−Ｈ−１−ｐｙｒｒｏｌｙｐｒｏｐｙｌ ｃａｒｂｏｎａｔｅ）−２，２’−ｂｉｐｙｒｉｄｉｎｅ｝（ＣＯ）（ＭｅＣＮ）Ｃｌ２］、［Ｒｕ｛４，４’−ｄｉ（１−Ｈ−１−ｐｙｒｒｏｌｙｐｒｏｐｙｌ ｃａｒｂｏｎａｔｅ）−２，２’−ｂｉｐｙｒｉｄｉｎｅ｝（ＣＯ）２Ｃｌ２］、［Ｒｕ｛４，４’−ｄｉ（１−Ｈ−１−ｐｙｒｒｏｌｙｐｒｏｐｙｌ ｃａｒｂｏｎａｔｅ）−２，２’−ｂｉｐｙｒｉｄｉｎｅ｝（ＣＯ）２］ｎ、［Ｒｕ｛４，４’−ｄｉ（１−Ｈ−１−ｐｙｒｒｏｌｙｐｒｏｐｙｌ ｃａｒｂｏｎａｔｅ）−２，２’−ｂｉｐｙｒｉｄｉｎｅ｝（ＣＯ）（ＣＨ３ＣＮ）Ｃｌ２］等が挙げられる。さらに、ルテニウム錯体は、Ｒｕ錯体モノマーと重合開始剤（例えばピロール）、触媒（例えば塩化鉄）を含むＲｕ錯体が高分子化（ポリマー）された状態のＲｕ錯体ポリマーであってもよい。 The reduction catalyst includes a metal complex such as a ruthenium (Ru) complex. Examples of the ruthenium complex include [Ru {4,4'-di (1-H-1-pyrrolipropyl carbonate) -2,2'-bipyridine} (CO) (MeCN) Cl 2 ], [Ru {4,4 '-Di (1-H-1-pyrrolipyropyl carbonate) -2,2'-bipyridine} (CO) 2 Cl 2 ], [Ru {4,4'-di (1-H-1-pyrrolipyropyl carbonate) -2 , 2'-bipyridine} (CO) 2 ] n , [Ru {4,4'-di (1-H-1-pyrrolipropyl carbonate) -2,2'-bipyridine} (CO) (CH 3 CN) Cl 2 ] Etc. can be mentioned. Further, the ruthenium complex may be a Ru complex polymer in which a Ru complex containing a Ru complex monomer, a polymerization initiator (for example, pyrrole) and a catalyst (for example, iron chloride) is polymerized.
還元触媒の担持は、例えば、金属錯体（触媒）をアセトニトリル（ＭｅＣＮ）溶液に溶解した液（例えば、Ｒｕ錯体ポリマー溶液）をカーボン系材料の上に塗布、乾燥することで作製することができる。また、還元触媒の担持は、電解重合法により行うこともできる。例えば、作用極としてカーボン系材料の電極、対極にフッ素含有酸化スズ（ＦＴＯ）で被覆したガラス基板、参照電極にＡｇ／Ａｇ＋電極を用い、還元触媒を含む電解液中においてＡｇ／Ａｇ＋電極に対して負電圧となるようにカソード電流を流した後、Ａｇ／Ａｇ＋電極に対して正電位となるようにアノード電流を流すことによりカーボン系材料に還元触媒で担持することができる。電解質の溶液には、例えば、アセトニトリル（ＭｅＣＮ）、電解質には、例えば、Ｔｅｔｒａｂｕｔｙｌａｍｍｏｎｉｕｍｐｅｒｃｈｌｏｒａｔｅ（ＴＢＡＰ）を用いることができる。 The support of the reduction catalyst can be produced, for example, by applying a solution (for example, Ru complex polymer solution) in which a metal complex (catalyst) is dissolved in an acetonitrile (MeCN) solution on a carbon-based material and drying it. Further, the reduction catalyst can be supported by an electrolytic polymerization method. For example, the electrodes of the carbon-based material as a working electrode, a glass substrate coated with fluorine-containing tin oxide (FTO) on the counter electrode, using Ag / Ag + electrode as a reference electrode, Ag / Ag + electrode in an electrolytic solution containing a reducing catalyst After a cathode current is passed so as to have a negative voltage with respect to the electrode, an anode current is passed so as to have a positive potential with respect to the Ag / Ag + electrode so that the carbon-based material can be supported by a reduction catalyst. For the solution of the electrolyte, for example, acetonitrile (MeCN) can be used, and for the electrolyte, for example, Tetrabutylammioniumperchlate (TBAP) can be used.
還元触媒層１６は、マルチウォール・カーボンナノチューブ（ＭＷＣＮＴｓ）等のカーボンナノチューブ等のカーボン素材を含んでもよい。マルチウォール・カーボンナノチューブ（ＭＷＣＮＴｓ）等のカーボン素材を含ませることにより、ナノカーボンの３次元ネットワーク構造を形成することができる。マルチウォール・カーボンナノチューブとしては、少なくとも直径が１ｎｍ以上１００ｎｍ以下のものを含むことが好適である。マルチウォール・カーボンナノチューブ（ＭＷＣＮＴｓ）等のカーボン素材は、例えばエタノール等の溶媒にカーボン素材を高分散させたインクを用意して、ディップ塗布や含浸塗布等の方法によって塗布し、乾燥することにより、還元触媒層１６に含ませることができる。 The reduction catalyst layer 16 may contain a carbon material such as carbon nanotubes such as multiwall carbon nanotubes (MWCNTs). By including a carbon material such as multiwall carbon nanotubes (MWCNTs), a three-dimensional network structure of nanocarbon can be formed. The multiwall carbon nanotubes preferably have a diameter of at least 1 nm or more and 100 nm or less. For carbon materials such as multiwall carbon nanotubes (MWCNTs), for example, an ink in which the carbon material is highly dispersed in a solvent such as ethanol is prepared, applied by a method such as dip coating or impregnation coating, and dried. It can be included in the reduction catalyst layer 16.
本実施形態に係る還元反応用電極１０において、Ｔｉ基板１２の一部が露出していてもよい。すなわち、Ｔｉ基板１２は全て還元触媒層１６や接着層１４等により覆われていなくてもよい。Ｔｉ基板１２を全て還元触媒層１６や接着層１４等により覆わなくてもよいため、これを用いた反応デバイスの構造設計の自由度が拡がる上に、作製工程を簡略化することができる。 In the reduction reaction electrode 10 according to the present embodiment, a part of the Ti substrate 12 may be exposed. That is, the Ti substrate 12 does not have to be completely covered with the reduction catalyst layer 16, the adhesive layer 14, or the like. Since it is not necessary to cover the entire Ti substrate 12 with the reduction catalyst layer 16, the adhesive layer 14, or the like, the degree of freedom in structural design of the reaction device using the reduction catalyst layer 16 and the adhesive layer 14 can be expanded, and the manufacturing process can be simplified.
［反応デバイス］
本発明の実施形態に係る反応デバイスは、上記還元反応用電極と、酸化反応用電極と、を組み合わせて構成される反応デバイスである。反応デバイスは、例えば、二酸化炭素還元装置とすることができ、その二酸化炭素還元装置と、太陽電池セルと、を組み合わせた人工光合成装置とすることもできる。
[Reaction device]
The reaction device according to the embodiment of the present invention is a reaction device configured by combining the above-mentioned electrode for reduction reaction and the electrode for oxidation reaction. The reaction device can be, for example, a carbon dioxide reduction device, or an artificial photosynthesis device in which the carbon dioxide reduction device and a solar cell are combined.
二酸化炭素還元装置は、例えば、二酸化炭素の還元反応を進行させる上記還元反応用電極と、還元反応用電極と電気的に接続され、酸化反応を生起する酸化反応用電極と、が離間されて対向する位置に配置され、還元反応用電極と酸化反応用電極との間を、反応基質（二酸化炭素）を含む電解液が流れる流路を有する電気化学反応装置である。二酸化炭素還元装置は、例えば、二酸化炭素の還元反応を進行させる上記還元反応用電極と、還元反応用電極と電気的に接続され、酸化反応を生起する酸化反応用電極と、を有し、還元反応用電極および酸化反応用電極が反応基質（二酸化炭素）を含む電解液に浸漬されている装置であってもよい。 In the carbon dioxide reduction device, for example, the reduction reaction electrode for advancing the carbon dioxide reduction reaction and the oxidation reaction electrode electrically connected to the reduction reaction electrode to cause an oxidation reaction are separated from each other and face each other. It is an electrochemical reaction apparatus that is arranged at a position where the reaction substrate (carbon dioxide) is contained and has a flow path through which an electrolytic solution containing a reaction substrate (carbon dioxide) flows between the electrode for reduction reaction and the electrode for oxidation reaction. The carbon dioxide reduction apparatus has, for example, the above-mentioned electrode for reduction reaction for advancing the reduction reaction of carbon dioxide, and an electrode for oxidation reaction which is electrically connected to the electrode for reduction reaction and causes an oxidation reaction. The device may be a device in which the reaction electrode and the oxidation reaction electrode are immersed in an electrolytic solution containing a reaction substrate (carbon dioxide).
人工光合成装置は、上記二酸化炭素還元装置と、二酸化炭素還元装置の還元反応用電極および酸化反応用電極に供給される電力を生成する太陽電池セルと、を備える装置である。 The artificial photosynthesis device is a device including the carbon dioxide reduction device, a reduction reaction electrode of the carbon dioxide reduction device, and a solar cell that generates electric power supplied to the oxidation reaction electrode.
図２は、上記還元反応用電極を用いた反応デバイスの一例として人工光合成装置の構成の一例を示す概略構成図である。人工光合成装置１は、二酸化炭素の還元反応を進行させる上記還元反応用電極１０と、酸化反応を生起する酸化反応用電極１８と、が離間されて対向する位置に配置され、還元反応用電極１０と酸化反応用電極１８との間を、反応基質を含む電解液が流れる流路２０を有する二酸化炭素還元装置３と、二酸化炭素還元装置３の還元反応用電極１０および酸化反応用電極１８に供給される電力を生成する太陽電池セル２２と、を備える装置である。 FIG. 2 is a schematic configuration diagram showing an example of the configuration of an artificial photosynthesis apparatus as an example of a reaction device using the reduction reaction electrode. The artificial photosynthesis apparatus 1 is arranged at a position where the reduction reaction electrode 10 for advancing the carbon dioxide reduction reaction and the oxidation reaction electrode 18 for causing the oxidation reaction are separated from each other and face each other, and the reduction reaction electrode 10 A carbon dioxide reducing device 3 having a flow path 20 through which an electrolytic solution containing a reaction substrate flows, and a reduction reaction electrode 10 and an oxidation reaction electrode 18 of the carbon dioxide reducing device 3 are supplied between the redox and the redox electrode 18. It is a device including a solar cell 22 for generating the generated electric power.
人工光合成装置１は、流路入口から還元反応用電極１０と酸化反応用電極１８との間の流路２０に二酸化炭素等の反応基質を含む電解液が導入されることによって機能する。電解液は流路出口から排出される。酸化反応用電極１８においては、水（Ｈ２Ｏ）が酸化されて酸素（１／２Ｏ２）が得られるとともに、電位が得られる。還元反応用電極１０においては、酸化反応を生起する電極から電位を得ることによって、例えば二酸化炭素が還元されてギ酸（ＨＣＯＯＨ）等が生成される。 The artificial photosynthesis apparatus 1 functions by introducing an electrolytic solution containing a reaction substrate such as carbon dioxide into the flow path 20 between the reduction reaction electrode 10 and the oxidation reaction electrode 18 from the flow path inlet. The electrolytic solution is discharged from the flow path outlet. In the oxidation reaction electrode 18, water (H 2 O) is oxidized to obtain oxygen (1 / 2 O 2 ) and an electric potential is obtained. In the reduction reaction electrode 10, formic acid (HCOOH) or the like is produced, for example, by reducing carbon dioxide by obtaining an electric potential from the electrode that causes an oxidation reaction.
（酸化反応用電極）
酸化反応用電極１８は、酸化反応によって物質を酸化するために利用される電極である。酸化反応用電極１８は、例えば、基板上に導電層が形成された基板とその上に形成された酸化触媒層とを含んで構成される。
(Electrode for oxidation reaction)
The oxidation reaction electrode 18 is an electrode used for oxidizing a substance by an oxidation reaction. The oxidation reaction electrode 18 is composed of, for example, a substrate having a conductive layer formed on the substrate and an oxidation catalyst layer formed on the substrate.
基板は、酸化反応用電極１８を構造的に支持する部材である。基板は、特に材料が限定されるものではないが、例えば、ガラス基板やプラスチック等としてもよい。 The substrate is a member that structurally supports the oxidation reaction electrode 18. The material of the substrate is not particularly limited, but may be, for example, a glass substrate, plastic, or the like.
基板は、耐食性を有する金属を表面とする導電性基板であってもよく、例えば、耐食性を有する金属からなる基板、または下地基板の表面に耐食性を有する金属層を形成してなる基板等が挙げられる。ここで、「耐食性を有する金属」とは、ｐＨ４以上の電解液中で、かつ水の酸化還元電位以上の電位で腐食しない金属を指す。 The substrate may be a conductive substrate having a metal having corrosion resistance as a surface, and examples thereof include a substrate made of a metal having corrosion resistance, a substrate having a metal layer having corrosion resistance formed on the surface of a base substrate, and the like. Be done. Here, the “metal having corrosion resistance” refers to a metal that does not corrode in an electrolytic solution having a pH of 4 or higher and at a potential equal to or higher than the redox potential of water.
耐食性を有する金属としては、高い導電性、高い耐食性等の点で、Ｔｉ、Ａｕ、Ｐｔ、Ｒｕ、Ｉｒ、Ｓｎ、Ｒｈからなる群から選択される少なくとも１種を含むことが好ましく、特に、Ｔｉを含むことが好ましい。基板としては、上記還元反応用電極１０と同様の実質的にチタン（Ｔｉ）からなるＴｉ基板であることが特に好ましい。これによって、軽量化、低コスト化が可能であり、高性能、耐腐食性、かつ加工性に優れるという利点がある。 The metal having corrosion resistance preferably contains at least one selected from the group consisting of Ti, Au, Pt, Ru, Ir, Sn, and Rh in terms of high conductivity, high corrosion resistance, and the like, and in particular, Ti. Is preferably included. As the substrate, it is particularly preferable that the substrate is a Ti substrate substantially made of titanium (Ti) similar to the reduction reaction electrode 10. This makes it possible to reduce the weight and cost, and has the advantages of high performance, corrosion resistance, and excellent workability.
下地基板の表面に耐食性を有する金属層を形成する方法としては、特に限定されないが、電気めっき、溶融めっき、真空蒸着、スパッタリング等が挙げられる。これらの中では、金属層の薄膜化が容易である等の点で、スパッタリングが好ましい。下地基板としては、特に限定されるものではなく、ガラス基板、プラスチック基板、酸化インジウム錫（ＩＴＯ）、フッ素ドープ酸化錫（ＦＴＯ）、酸化亜鉛（ＺｎＯ）等を被覆したガラス基板やプラスチック基板等が挙げられる。また、下地基板は、ｐＨ４以上の電解液中で、かつ水の酸化還元電位以上の電位で腐食しないまたは腐食する金属基板でもよく、例えば、Ｔｉ、Ａｕ、Ｐｔ、Ｒｕ、Ｉｒ、Ｓｎ、Ｒｈ、Ｃｕ、Ａｇ等の基板等でもよい。 The method for forming a metal layer having corrosion resistance on the surface of the base substrate is not particularly limited, and examples thereof include electroplating, hot dip galvanizing, vacuum deposition, and sputtering. Among these, sputtering is preferable because it is easy to thin the metal layer. The base substrate is not particularly limited, and a glass substrate, a plastic substrate, a glass substrate coated with indium tin oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide (ZnO), etc., a plastic substrate, or the like can be used. Can be mentioned. Further, the base substrate may be a metal substrate that does not corrode or corrodes in an electrolytic solution having a pH of 4 or higher and at a potential equal to or higher than the redox potential of water. For example, Ti, Au, Pt, Ru, Ir, Sn, Rh, etc. A substrate such as Cu or Ag may be used.
導電層は、酸化反応用電極１８における集電を効果的にするために設けられる。導電層は、特に限定されるものではないが、例えば、酸化インジウム錫（ＩＴＯ）、フッ素ドープ酸化錫（ＦＴＯ）、酸化亜鉛（ＺｎＯ）等の透明導電層等が挙げられる。特に、熱的および化学的な安定性を考慮すると、フッ素ドープ酸化錫（ＦＴＯ）を用いることが好適である。 The conductive layer is provided in order to effectively collect current in the oxidation reaction electrode 18. The conductive layer is not particularly limited, and examples thereof include transparent conductive layers such as indium tin oxide (ITO), fluorine-doped tin oxide (FTO), and zinc oxide (ZnO). In particular, considering thermal and chemical stability, it is preferable to use fluorine-doped tin oxide (FTO).
酸化触媒層は、酸化触媒機能を有する材料を含んで構成される。酸化触媒機能を有する材料としては、例えば、酸化イリジウム（ＩｒＯｘ）、酸化ルテニウムを含む材料等が挙げられる。これらは１種単独でも２種以上を混合してもよい。酸化イリジウムや酸化ルテニウムは、ナノコロイド溶液として導電層または基板の表面上に担持することができる（T.Arai et.al, Energy Environ. Sci 8, 1998 (2015)参照）。 The oxidation catalyst layer is composed of a material having an oxidation catalyst function. Examples of the material having an oxidation catalyst function include a material containing iridium oxide (IrOx) and ruthenium oxide. These may be used alone or in admixture of two or more. Iridium oxide and ruthenium oxide can be supported on the surface of the conductive layer or substrate as a nanocolloidal solution (see T. Arai et.al, Energy Environ. Sci 8, 1998 (2015)).
例えば、酸化イリジウム（ＩｒＯｘ）のナノコロイドを合成する。２ｍＭの塩化イリジウム酸（ＩＶ）カリウム（Ｋ２ＩｒＣｌ６）水溶液５０ｍＬに１０ｗｔ％の水酸化ナトリウム（ＮａＯＨ）水溶液を加えてｐＨ１３に調整した黄色溶液を、ホットスターラを用いて９０℃で２０分加熱する。これによって得られた青色溶液を氷水で１時間冷却する。そして、冷やした溶液（２０ｍＬ）に３Ｍ硝酸（ＨＮＯ３）を滴下してｐＨ１に調整し、８０分撹拌し、酸化イリジウム（ＩｒＯｘ）のナノコロイド水溶液を得る。さらに、この溶液に１．５ｗｔ％ＮａＯＨ水溶液（１−２ｍＬ）を滴下してｐＨ１２に調整する。このようにして得られた酸化イリジウム（ＩｒＯｘ）のナノコロイド水溶液を、導電層上にｐＨ１２で塗布し、乾燥炉内において６０℃で４０分間保持して乾燥させる。乾燥後、析出した塩を超純水で洗浄し、酸化反応用電極１８を形成することができる。なお、酸化イリジウム（ＩｒＯｘ）のナノコロイド水溶液の塗布および乾燥を複数回繰り返してもよい。 For example, iridium oxide (IrOx) nanocolloids are synthesized. A yellow solution adjusted to pH 13 by adding a 10 wt% sodium hydroxide (NaOH) aqueous solution to 50 mL of a 2 mM potassium (IV) chloride (K 2 IrCl 6 ) aqueous solution is heated at 90 ° C. for 20 minutes using a hot stirrer. To do. The blue solution thus obtained is cooled with ice water for 1 hour. Then, 3M nitric acid (HNO 3 ) is added dropwise to the cooled solution (20 mL) to adjust the pH to 1, and the mixture is stirred for 80 minutes to obtain a nanocolloidal aqueous solution of iridium oxide (IrOx). Further, a 1.5 wt% NaOH aqueous solution (1-2 mL) is added dropwise to this solution to adjust the pH to 12. The nanocolloidal aqueous solution of iridium oxide (IrOx) thus obtained is applied onto the conductive layer at pH 12, and held in a drying oven at 60 ° C. for 40 minutes for drying. After drying, the precipitated salt can be washed with ultrapure water to form the oxidation reaction electrode 18. The application and drying of the nanocolloidal aqueous solution of iridium oxide (IrOx) may be repeated a plurality of times.
電解液に含まれる反応基質は、例えば、炭素化合物が挙げられ、例えば、二酸化炭素（ＣＯ２）とすることができる。また、電解液は、リン酸緩衝水溶液やホウ酸緩衝水溶液とすることが好適である。具体的な構成例では、例えば、二酸化炭素（ＣＯ２）飽和リン酸緩衝液のタンクを設け、ポンプによってこの溶液を還元反応用電極１０と酸化反応用電極１８との間に設けられた流路２０に供給し、還元反応によって生じたギ酸（ＨＣＯＯＨ）や酸素（Ｏ２）等を外部の燃料タンクに回収すればよい。 Examples of the reaction substrate contained in the electrolytic solution include carbon compounds, and for example, carbon dioxide (CO 2 ). Further, the electrolytic solution is preferably a phosphate buffered aqueous solution or a boric acid buffered aqueous solution. In a specific configuration example, for example, a tank of a carbon dioxide (CO 2 ) saturated phosphate buffer solution is provided, and this solution is supplied by a pump between the reduction reaction electrode 10 and the oxidation reaction electrode 18. Formic acid (HCOOH), oxygen (O 2 ), etc. generated by the reduction reaction may be recovered in an external fuel tank by supplying to 20.
窓材２４は、太陽電池セル２２を保護する部材である。太陽電池セル２２に対しては、受光面側に窓材２４を設けることが好適である。窓材２４は、太陽電池セル２２において発電に寄与する波長の光を透過する部材とし、例えば、ガラス、プラスチック等とすることができる。 The window material 24 is a member that protects the solar cell 22. For the solar cell 22, it is preferable to provide the window material 24 on the light receiving surface side. The window material 24 is a member that transmits light having a wavelength that contributes to power generation in the solar cell 22, and may be, for example, glass, plastic, or the like.
還元反応用電極１０、酸化反応用電極１８、太陽電池セル２２および窓材２４は、枠材２６によって構造的に支持されている。枠材２６は、還元反応用電極１０および酸化反応用電極１８を支持するとともに、電解液が流れる流路２０を構成する部材である。枠材２６は、電気化学反応装置をセルとして構成するために必要な機械的な強度を備える材料で構成される。例えば、枠材２６は、金属、プラスチック等によって構成することができる。 The reduction reaction electrode 10, the oxidation reaction electrode 18, the solar cell 22, and the window material 24 are structurally supported by the frame material 26. The frame material 26 is a member that supports the reduction reaction electrode 10 and the oxidation reaction electrode 18 and constitutes a flow path 20 through which the electrolytic solution flows. The frame material 26 is made of a material having the mechanical strength required to form the electrochemical reactor as a cell. For example, the frame material 26 can be made of metal, plastic, or the like.
還元反応用電極１０と酸化反応用電極１８との間を電気的に接続し、適切なバイアス電圧を印加した状態とする。バイアス電圧を印加する手段は、特に限定されるものではなく、化学的電池（一次電池、二次電池等を含む）、定電圧源、太陽電池セル等が挙げられる。このとき、酸化反応用電極１８に正極が接続され、還元反応用電極１０に負極が接続される。 The reduction reaction electrode 10 and the oxidation reaction electrode 18 are electrically connected to each other, and an appropriate bias voltage is applied. The means for applying the bias voltage is not particularly limited, and examples thereof include a chemical battery (including a primary battery, a secondary battery, etc.), a constant voltage source, a solar cell, and the like. At this time, the positive electrode is connected to the oxidation reaction electrode 18, and the negative electrode is connected to the reduction reaction electrode 10.
図２のように、バイアス電圧を印加する手段として太陽電池セル２２を用いることにより、二酸化炭素還元装置等の電気化学反応装置と、還元反応用電極および酸化反応用電極に供給される電力を生成する太陽電池セルと、を備える人工光合成装置とすることができる。バイアス電圧を印加する手段として太陽電池セルを用いる場合、太陽電池セルは、例えば、酸化反応用電極および還元反応用電極に隣接して配置することができる。例えば、還元反応用電極の背面に太陽電池セルを配置し、太陽電池セルの正極を酸化反応用電極に接続し、負極を還元反応用電極に接続すればよい。 As shown in FIG. 2, by using the solar cell 22 as a means for applying a bias voltage, electric power supplied to an electrochemical reaction device such as a carbon dioxide reduction device, a reduction reaction electrode, and an oxidation reaction electrode is generated. It can be an artificial photosynthesis device including a solar cell. When a solar cell is used as a means for applying a bias voltage, the solar cell can be arranged adjacent to, for example, an electrode for an oxidation reaction and an electrode for a reduction reaction. For example, the solar cell may be arranged on the back surface of the reduction reaction electrode, the positive electrode of the solar cell may be connected to the oxidation reaction electrode, and the negative electrode may be connected to the reduction reaction electrode.
二酸化炭素（ＣＯ２）からギ酸（ＨＣＯＯＨ）等を合成する場合、水（Ｈ２Ｏ）は酸化されて二酸化炭素（ＣＯ２）に電子とプロトンを供給する。ｐＨ７付近では水（Ｈ２Ｏ）の酸化電位は０．８２Ｖ、還元電位は−０．４１Ｖ（いずれも標準水素電極（ＮＨＥ））である。また、二酸化炭素（ＣＯ２）から一酸化炭素（ＣＯ）、ギ酸（ＨＣＯＯＨ）、メチルアルコール（ＣＨ３ＯＨ）への還元電位はそれぞれ−０．５３Ｖ，−０．６１Ｖ，−０．３８Ｖである。したがって、酸化電位と還元電位の電位差は１．２０〜１．４３Ｖである。炭素化合物である二酸化炭素（ＣＯ２）を還元する場合、太陽電池セルは、例えば４〜６枚の結晶系シリコン太陽電池を直接に接続した構成やアモルファスシリコン系３接合太陽電池とすることが好適である。 When synthesizing formic acid (HCOOH) or the like from carbon dioxide (CO 2 ), water (H 2 O) is oxidized to supply electrons and protons to carbon dioxide (CO 2 ). At around pH 7, the oxidation potential of water (H 2 O) is 0.82 V, and the reduction potential is −0.41 V (both are standard hydrogen electrodes (NHE)). The reduction potentials of carbon dioxide (CO 2 ) to carbon monoxide (CO), formic acid (HCOOH), and methyl alcohol (CH 3 OH) are -0.53V, -0.61V, and -0.38V, respectively. .. Therefore, the potential difference between the oxidation potential and the reduction potential is 1.20 to 1.43 V. When reducing carbon dioxide (CO 2 ), which is a carbon compound, it is preferable that the solar cell has, for example, a configuration in which 4 to 6 crystalline silicon solar cells are directly connected or an amorphous silicon 3-junction solar cell. Is.
以下、実施例および比較例を挙げ、本発明をより具体的に詳細に説明するが、本発明は、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
以下の４種類の基板を用意し、下記実験１〜３を行った。
（１）実施例１：Ｔｉ板（ＪＩＳ Ｈ４６００：２０１２ 純チタン１種 ＴＲ２７０Ｃ）
（２）比較例１：Ｔｉ板／ＴｉＯ２
実施例１のＴｉ板を大気中４３０℃で３０分間、熱処理して、表面にＴｉＯ２被膜（厚さ推定５０ｎｍ）を形成したもの
（３）比較例２：ステンレス板（ＳＵＳ３０４）
（４）比較例３：ＦＴＯガラス
The following four types of substrates were prepared, and the following experiments 1 to 3 were performed.
(1) Example 1: Ti plate (JIS H4600: 2012 pure titanium type 1 TR270C)
(2) Comparative Example 1: Ti plate / TiO 2
The Ti plate of Example 1 was heat-treated in the air at 430 ° C. for 30 minutes to form a TiO 2 coating (thickness estimated 50 nm) on the surface (3) Comparative Example 2: Stainless steel plate (SUS304).
(4) Comparative Example 3: FTO glass
［実験１］
各基板の表面１０ｍｍ角範囲以外をシリコーンゴムで被覆した。これを作用極に用い、Ｐｔ対極、参照電極Ｈｇ／Ｈｇ２ＳＯ４を用いて電気化学反応特性を評価した。電解液には、０．４Ｍのリン酸バッファ水溶液（Ｋ２ＨＰＯ４＋ＫＨ２ＰＯ４）を用い、ＣＯ２ガスをバブリングにより供給した。
[Experiment 1]
The surface of each substrate other than the 10 mm square area was covered with silicone rubber. This was used as the working electrode, and the electrochemical reaction characteristics were evaluated using the Pt counter electrode and the reference electrode Hg / Hg 2 SO 4 . A 0.4 M phosphate buffer aqueous solution (K 2 HPO 4 + KH 2 PO 4 ) was used as the electrolytic solution, and CO 2 gas was supplied by bubbling.
図３は、電流ｖｓ電位の測定結果である。ＣＯ２還元に用いられる電位−１．２〜−１．５Ｖの範囲（図４参照）では、Ｔｉ板、Ｔｉ板／ＴｉＯ２、ＦＴＯガラスの場合は電流値がほぼゼロであった。その中でも、Ｔｉ板は、電位−２Ｖでの電流が最も小さいため、Ｔｉ板／ＴｉＯ２およびＦＴＯガラスよりも優れた材料であるといえる。一方、ステンレス板の場合は電流が流れ、表面から気泡が発生したので、ＣＯ２還元反応用電極として用いるためには、ステンレス板を被覆することが必須であることがわかった。 FIG. 3 shows the measurement result of the current vs. the potential. In the potential range of −1.2 to −1.5 V (see FIG. 4) used for CO 2 reduction, the current value was almost zero in the case of Ti plate, Ti plate / TiO 2 , and FTO glass. Among them, the Ti plate has the smallest current at a potential of -2V, so it can be said that the Ti plate is a superior material to the Ti plate / TiO 2 and FTO glass. On the other hand, in the case of a stainless steel plate, an electric current flows and bubbles are generated from the surface, so it was found that it is essential to cover the stainless steel plate in order to use it as an electrode for a CO 2 reduction reaction.
［実験２］
溶媒にマルチウォールカーボンナノチューブ（ＭＷＣＮＴｓ）を分散させたインクを用い、カーボンペーパー（ＣＰ）にディップ塗布、乾燥することによって、ＣＰ／ＭＷＣＮＴｓシートを作製した。その後、カーボンペーパー（ＣＰ）にＲｕ錯体ポリマー溶液を用いてＲｕ錯体を担持させ、マルチウォールカーボンナノチューブ（ＭＷＣＮＴｓ）を含有させたＣＰ／ＭＷＣＮＴｓ／ＲｕＣＰシート（触媒を担持した導電性ポリマーを含んだシート）を作製した。このＣＰ／ＭＷＣＮＴｓ／ＲｕＣＰシートを、各基板上にカーボン系接着剤（導電性のグラファイトとポリマーを含む）を用いて接着し、還元反応用電極を作製した。基板の露出部分がないように、１０ｍｍ角範囲以外をシリコーンゴムで被覆した。
[Experiment 2]
A CP / MWCNTs sheet was prepared by dipping and drying carbon paper (CP) using an ink in which multiwall carbon nanotubes (MWCNTs) were dispersed in a solvent. After that, a Ru complex was supported on carbon paper (CP) using a Ru complex polymer solution, and a CP / MWCNTs / RuCP sheet containing multiwall carbon nanotubes (MWCNTs) (a sheet containing a conductive polymer supporting a catalyst). ) Was prepared. The CP / MWCNTs / RuCP sheets were adhered onto each substrate using a carbon-based adhesive (including conductive graphite and polymer) to prepare electrodes for reduction reaction. The area other than the 10 mm square area was covered with silicone rubber so that there was no exposed portion of the substrate.
図４は、電流ｖｓ電位の測定結果である。Ｔｉ板、Ｔｉ板／ＴｉＯ２、ＦＴＯガラスの特性はほぼ同じであった。 FIG. 4 is a measurement result of current vs. potential. The characteristics of the Ti plate, Ti plate / TiO 2 , and FTO glass were almost the same.
図５は、電位−１．３Ｖを保持したときの電流値の変化の測定結果である。経過時間２時間ごとに電圧印加を停止し、電解液を採取してギ酸濃度をイオンクロマトグラフィにより測定した後、電解液を新しいものに入れ替えた。Ｔｉ板の場合には、Ｔｉ板／ＴｉＯ２、ＦＴＯガラスの場合よりも電流値の絶対値が大きかったので、活性がより高いと結論した。なお、Ｔｉ板とＴｉ板／ＴｉＯ２とは特性が異なることから、Ｔｉ板の表面に形成される不動態層は、熱酸化により形成された厚さ数１０ｎｍのＴｉＯ２膜とは異なる状態であることがわかった。 FIG. 5 shows the measurement result of the change in the current value when the potential −1.3 V is maintained. The voltage application was stopped every 2 hours of elapsed time, the electrolytic solution was collected, the formic acid concentration was measured by ion chromatography, and then the electrolytic solution was replaced with a new one. In the case of the Ti plate, the absolute value of the current value was larger than in the case of the Ti plate / TiO 2 and FTO glass, so it was concluded that the activity was higher. Since the characteristics of the Ti plate and the Ti plate / TiO 2 are different, the passivation layer formed on the surface of the Ti plate is in a state different from that of the TiO 2 film having a thickness of several tens of nm formed by thermal oxidation. It turned out that there was.
図６は、ギ酸濃度と電流の積算値から求めたギ酸生成のファラデー効率である。実験誤差の範囲で、３種類の基板のファラデー効率は同等であり、測定時間の範囲内では著しい劣化は認められなかった。 FIG. 6 shows the Faraday efficiency of formic acid production obtained from the integrated values of formic acid concentration and current. Within the range of experimental error, the Faraday efficiencies of the three types of substrates were the same, and no significant deterioration was observed within the measurement time range.
［実験３］
１５ｍｍ×２０ｍｍのＴｉ板およびＦＴＯガラスの長手方向の一端にそれぞれ導線をはんだ付けした。基板の中央１０ｍｍ角部分に、実験２と同様のＣＰ／ＭＷＣＮＴｓ／ＲｕＣＰシートを、カーボン系接着剤（導電性のグラファイトとポリマーを含む）を用いて接着して、還元反応用電極を作製した。その他の部分は、基板が露出している。同じ形状の酸化反応用電極を、Ｔｉ板およびＦＴＯガラスの１０ｍｍ角部分にそれぞれＩｒＯｘコロイドを担持することにより作製した。両者を組み合わせて特性を評価した。比較のために、Ｔｉ板を用い、裏面、側面、および表面のＴｉが露出している部分をシリコーンゴムで被覆した電極も作製した。
[Experiment 3]
A lead wire was soldered to one end of a 15 mm × 20 mm Ti plate and FTO glass in the longitudinal direction. A CP / MWCNTs / RuCP sheet similar to that in Experiment 2 was adhered to a central 10 mm square portion of the substrate using a carbon-based adhesive (including conductive graphite and a polymer) to prepare an electrode for a reduction reaction. The substrate is exposed in other parts. An electrode for oxidation reaction having the same shape was produced by supporting IrOx colloid on a 10 mm square portion of a Ti plate and FTO glass, respectively. The characteristics were evaluated by combining both. For comparison, an electrode was also produced using a Ti plate and having the back surface, side surface, and front surface where Ti was exposed covered with silicone rubber.
図７は、電流ｖｓ電位差の測定結果である。実験誤差の範囲で、３種類の基板の値は同等であった。 FIG. 7 is a measurement result of current vs. potential difference. Within the range of experimental error, the values of the three types of substrates were equivalent.
図８は、電位差１．７Ｖを印加したときの電流値の変化の測定結果である。実験誤差の範囲で、３種類の基板の値は同等であり、測定時間の範囲内では著しい劣化は認められなかった。 FIG. 8 is a measurement result of a change in the current value when a potential difference of 1.7 V is applied. Within the range of experimental error, the values of the three types of substrates were equivalent, and no significant deterioration was observed within the range of measurement time.
表１は、ギ酸濃度と電流の積算値から求めたギ酸生成のファラデー効率である。こちらも、実験誤差の範囲で、３種類の基板の値は同等であった。 Table 1 shows the Faraday efficiency of formic acid production obtained from the integrated values of formic acid concentration and current. Again, within the range of experimental error, the values of the three types of substrates were the same.
これらの実験結果より、以下のことがわかった。
・Ｔｉ基板は、Ｈ２生成過電圧が高いので、ＣＯ２還元反応のカソード基板に用いることができる。
・従来のＦＴＯ基板、Ｔｉ板／ＴｉＯ２基板と同等以上の活性と耐久性が得られる。
・Ｔｉ基板が露出していても悪影響はほとんどない。
From the results of these experiments, the following was found.
-Since the Ti substrate has a high H 2 generation overvoltage, it can be used as a cathode substrate for a CO 2 reduction reaction.
-Activity and durability equal to or higher than those of the conventional FTO substrate and Ti plate / TiO 2 substrate can be obtained.
-There is almost no adverse effect even if the Ti substrate is exposed.
このように、実施例のＴｉ基板を用いることによって、軽量化、低コスト化が可能であり、高性能、耐腐食性、かつ加工性に優れた還元反応用電極が得られた。 As described above, by using the Ti substrate of the example, weight reduction and cost reduction are possible, and an electrode for reduction reaction having excellent high performance, corrosion resistance and workability was obtained.
１ 人工光合成装置、３ 二酸化炭素還元装置、１０ 還元反応用電極、１２ Ｔｉ基板、１４ 接着層、１６ 還元触媒層、１８ 酸化反応用電極、２０ 流路、２２ 太陽電池セル、２４ 窓材、２６ 枠材。 1 Artificial photosynthesis device, 3 Carbon dioxide reduction device, 10 Reduction reaction electrode, 12 Ti substrate, 14 Adhesive layer, 16 Reduction catalyst layer, 18 Oxidation reaction electrode, 20 flow path, 22 Solar cell, 24 Window material, 26 Frame material.
Claims (8)
カーボン系材料と金属錯体とを含む還元触媒層と、
を有することを特徴とする還元反応用電極。 Ti board and
A reduction catalyst layer containing a carbon-based material and a metal complex,
An electrode for a reduction reaction, which comprises.
前記カーボン系材料は、炭素繊維を含むことを特徴とする還元反応用電極。 The reduction reaction electrode according to claim 1.
The carbon-based material is an electrode for a reduction reaction, which comprises carbon fibers.
前記還元触媒層は、さらにカーボンナノチューブを含むことを特徴とする還元反応用電極。 The electrode for reduction reaction according to claim 1 or 2.
The reduction catalyst layer is an electrode for a reduction reaction, which further contains carbon nanotubes.
前記金属錯体は、ルテニウム錯体であることを特徴とする還元反応用電極。 The electrode for reduction reaction according to any one of claims 1 to 3.
The metal complex is an electrode for a reduction reaction, which is a ruthenium complex.
前記還元触媒層は、前記Ｔｉ基板にカーボン系接着剤を含む接着層によって接着されていることを特徴とする還元反応用電極。 The electrode for reduction reaction according to any one of claims 1 to 4.
The reduction reaction electrode is characterized in that the reduction catalyst layer is adhered to the Ti substrate by an adhesive layer containing a carbon-based adhesive.
前記Ｔｉ基板の一部が露出していることを特徴とする還元反応用電極。 The electrode for reduction reaction according to any one of claims 1 to 5.
An electrode for a reduction reaction, characterized in that a part of the Ti substrate is exposed.
酸化反応用電極と、
を組み合わせて構成されることを特徴とする反応デバイス。 The electrode for reduction reaction according to any one of claims 1 to 6,
Electrodes for oxidation reaction and
A reaction device characterized by being composed of a combination of.
前記酸化反応用電極は、Ｔｉ基板を有することを特徴とする反応デバイス。 The reaction device according to claim 7.
The oxidation reaction electrode is a reaction device having a Ti substrate.
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