JPH05311476A - Electrode for electrochemical reduction and device for utilizing the same - Google Patents
Electrode for electrochemical reduction and device for utilizing the sameInfo
- Publication number
- JPH05311476A JPH05311476A JP4120337A JP12033792A JPH05311476A JP H05311476 A JPH05311476 A JP H05311476A JP 4120337 A JP4120337 A JP 4120337A JP 12033792 A JP12033792 A JP 12033792A JP H05311476 A JPH05311476 A JP H05311476A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- carbon dioxide
- ion
- metal
- aldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Landscapes
- Physical Or Chemical Processes And Apparatus (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は溶液中の炭酸ガス，炭
酸，炭酸イオン，重炭酸イオン，カルボン酸，アルデヒ
ドなどを電気化学的または光電気化学的に還元する電極
およびそれを利用した装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode for electrochemically or photoelectrochemically reducing carbon dioxide gas, carbonic acid, carbonate ion, bicarbonate ion, carboxylic acid, aldehyde, etc. in a solution and an apparatus using the same. ..
【０００２】[0002]
【従来の技術】炭酸ガス，炭酸，炭酸イオン，重炭酸イ
オン，カルボン酸，アルデヒドなどを電気化学または光
電気化学的に還元する反応の速度および選択性に大きな
影響を与えるのは電極材料の種類および表面の形状であ
る。これまで、白金，パラジュウム，イリジュウム，ロ
ジュウム，鉄，ニッケル，コバルト，銅，スズ，亜鉛，
金，銀など多くの金属が研究されている。例えば、電気
化学５８巻、Ｎｏ１１、１９９０年の９８４ページから
９８９ページ、および９９６ページから１００２ペー
ジ、さらに、ケミストリーレターズ１９８５年の１６９
５ページによれば、炭酸ガスと重炭酸イオンの還元反応
に対して金属銅が最も高い反応選択性（電流効率）を示
し、メタン，エチレン，エタノールの電流効率を合計す
ると約７０％に達するとされている。また、特開平1−2
8462号では、白金，パラジウム，イリジウム，ロジウ
ム，鉄，ニッケル，コバルトの少なくとも一種を第１金
属とし、鉛，銅，亜鉛，カドミニウムの少なくとも一種
を第２金属として含む電極が炭酸ガスの変換に優れると
している。2. Description of the Related Art The type of electrode material has a great influence on the reaction rate and selectivity for electrochemically or photoelectrochemically reducing carbon dioxide, carbonic acid, carbonate ion, bicarbonate ion, carboxylic acid, aldehyde, etc. And the shape of the surface. So far, platinum, palladium, iridium, rhodium, iron, nickel, cobalt, copper, tin, zinc,
Many metals such as gold and silver have been studied. For example, Electrochemistry 58, No 11, 1990 pages 984-989 and 996 pages-1002, and Chemistry Letters 1985 169.
According to page 5, metallic copper has the highest reaction selectivity (current efficiency) for the reduction reaction of carbon dioxide and bicarbonate ions, and when the current efficiency of methane, ethylene, and ethanol reaches about 70%, Has been done. In addition, JP-A 1-2
In No. 8462, an electrode containing at least one of platinum, palladium, iridium, rhodium, iron, nickel and cobalt as the first metal and at least one of lead, copper, zinc and cadmium as the second metal is excellent in conversion of carbon dioxide gas. I am trying.
【０００３】[0003]
【発明が解決しようとする課題】従来技術は、水素原子
が吸着して活性化される第１金属の原子間を第２金属で
分断することによって、水素原子同志が結合して水素ガ
スが発生するのを抑制し、水素原子を炭酸ガスの還元に
利用するというものである。しかし、これらいずれの公
知技術においても電流密度は５〜１０ｍＡ／cm2 程度で
あり、実用的な反応速度レベルに達していない。In the prior art, the hydrogen atoms are adsorbed and activated, and the atoms of the first metal are separated from each other by the second metal, whereby the hydrogen atoms are bonded to each other to generate hydrogen gas. The use of hydrogen atoms for reducing carbon dioxide gas is suppressed. However, in any of these known techniques, the current density is about 5 to 10 mA / cm 2, which is not a practical reaction rate level.
【０００４】本発明の目的は、炭酸ガス，炭酸，炭酸イ
オン，重炭酸イオン，カルボン酸，アルデヒドなどを高
い電流効率で還元できる電極およびその製造法、さらに
その電極を利用した装置を提供することにある。An object of the present invention is to provide an electrode capable of reducing carbon dioxide gas, carbonic acid, carbonate ion, bicarbonate ion, carboxylic acid, aldehyde, etc. with high current efficiency, a method for producing the electrode, and an apparatus using the electrode. It is in.
【０００５】[0005]
【課題を解決するための手段】本発明の電極は、金属銅
の表面とIIａに属する金属（第２成分）の表面とが同時
に存在することを特徴とする電極である。このうち、特
に好ましい第２成分はマグネシウム，カルシウム，スト
ロンチウム，バリウムである。これらの第２成分がアイ
ランド状をなして銅の表面に分散していると効果的であ
る。アイランド状以外にも、リソグラフィーを用いれ
ば、台形，立方形，線形などに分散させることが可能で
あり、銅の表面と第２成分の表面とを同時に電極表面に
存在させればよい。これらの第２成分の電子配列は、電
子がエネルギー準位の順序に従って軌道に充満してい
る。これらの金属の表面が銅の表面と共存すると、炭酸
ガス還元反応の中間体であるアニオンラジカル(ＣＯ2 -)
の吸着状態が変わり、反応が炭化水素、アルコールの生
成に有利な方向へ進行する。The electrode of the present invention is characterized in that the surface of metallic copper and the surface of the metal (second component) belonging to IIa are present at the same time. Among these, particularly preferable second components are magnesium, calcium, strontium, and barium. It is effective that these second components are dispersed in the form of islands on the copper surface. In addition to the island shape, it is possible to disperse trapezoidal, cubic, linear, etc. by using lithography, and it suffices that the surface of copper and the surface of the second component be present on the electrode surface at the same time. In the electron arrangement of these second components, the orbits are filled with electrons according to the order of energy levels. When the surface of these metals coexist with the surface of the copper, the anion radical is an intermediate of the carbon dioxide reduction (CO 2 -)
The adsorbed state of is changed, and the reaction proceeds in a direction advantageous for the production of hydrocarbons and alcohols.
【０００６】第２成分は蒸着，塗着，焼結拡散，リソグ
ラフィー，イオン打ち込みなどで金属銅の表面に分散さ
せることが可能である。母材の形状は板，網，発泡体，
薄膜，微粒子のいずれでもよい。また、金属銅を不活性
または還元雰囲気で加熱しながらその表面に第２金属の
化合物を含む溶液をその化合物の分解温度以下で付け、
さらにその化合物の分解温度以上で加熱処理する、いわ
ゆる塗着拡散処理によって製造してもよい。The second component can be dispersed on the surface of metallic copper by vapor deposition, coating, sintering diffusion, lithography, ion implantation or the like. The shape of the base material is plate, net, foam,
Either thin film or fine particles may be used. Further, while heating the metallic copper in an inert or reducing atmosphere, a solution containing a compound of the second metal is attached to the surface of the metallic copper at a temperature not higher than the decomposition temperature of the compound,
Further, it may be produced by a so-called coating diffusion treatment, which is a heat treatment at a decomposition temperature of the compound or higher.
【０００７】本発明による電極は、他の電極（アノー
ド）と組合わせて炭酸ガス，炭酸，炭酸イオン，重炭酸
イオン，カルボン酸，アルデヒドの還元装置として使用
することができる。アノードとして、通常の白金，金，
銅などの金属はもちろん、ｎ型光半導体を薄膜化した光
電極を使用できる。炭酸ガスは化学的に非常に安定であ
り、その還元には多くのエネルギーを必要とするので、
太陽光エネルギーを吸収してアノードとして働く光電極
に組合わせるのに好ましい電極である。The electrode according to the present invention can be used as a reduction device for carbon dioxide gas, carbonic acid, carbonate ion, bicarbonate ion, carboxylic acid and aldehyde in combination with another electrode (anode). As the anode, ordinary platinum, gold,
Not only metals such as copper but also photoelectrodes formed by thinning an n-type optical semiconductor can be used. Since carbon dioxide is chemically very stable and its reduction requires a lot of energy,
It is a preferred electrode for combination with a photoelectrode that absorbs solar energy and acts as an anode.
【０００８】[0008]
【作用】本発明による電極（カソード）では還元反応、
他の電極（アノード）では、水の酸化反応が起こる。例
えば、重炭酸イオンからメタンが生成する反応で示すと
次の２式で表すことができる。Function: Reduction reaction at the electrode (cathode) according to the present invention,
At the other electrode (anode), an oxidation reaction of water occurs. For example, the reaction of producing methane from bicarbonate ion can be represented by the following two equations.
【０００９】[0009]
【数１】 [Equation 1]
【００１０】[0010]
【数２】 [Equation 2]
【００１１】これら２つの反応式を総括すると下記の式
となる。These two reaction equations are summarized as follows.
【００１２】[0012]
【数３】 [Equation 3]
【００１３】この反応式の標準自由エネルギー変化は＋
８１８ｋＪ／mol であり、外部から何らかのエネルギー
を加えないと反応は進行しない。これに対する最も理想
的なエネルギー源は太陽光である。太陽光を利用するに
は、光を吸収して第２の式の反応を促進するＴｉＯ2 の
ようなｎ型光半導体をアノードとし、本発明による電極
をカソードとして組合わせればよい。このとき、下記の
式に示す反応が進行しＴｉＯ2 は光を吸収して表面に酸
化力のあるホール（ｈ）が生成し、内部に電子が生成す
る。この（ｈ）でＨ2Ｏが酸化され、プロトンが生成す
る。プロントおよび電子は数１の反応に利用される。The standard free energy change of this reaction formula is +
It is 818 kJ / mol, and the reaction does not proceed unless some energy is externally applied. The most ideal energy source for this is sunlight. To utilize sunlight, an n-type photo-semiconductor such as TiO 2 that absorbs light and promotes the reaction of the second equation may be used as an anode and the electrode according to the present invention may be used as a cathode. At this time, the reaction represented by the following formula proceeds, and TiO 2 absorbs light to generate a hole (h) having an oxidizing power on the surface and an electron inside. In this (h), H 2 O is oxidized and protons are generated. The proton and the electron are used in the reaction of the number 1.
【００１４】[0014]
【数４】 [Equation 4]
【００１５】[0015]
【数５】 [Equation 5]
【００１６】太陽光を利用する他の方法としては、たと
えば太陽光を太陽電池で一旦電気に変換し、その電気を
上記還元装置に供給して炭酸ガスの還元反応を促進する
ことが可能である。As another method of utilizing sunlight, for example, sunlight can be once converted into electricity by a solar cell, and the electricity can be supplied to the reducing device to accelerate the reduction reaction of carbon dioxide gas. ..
【００１７】[0017]
【実施例】以下実施例により本発明をさらに詳細に説明
する。The present invention will be described in more detail with reference to the following examples.
【００１８】実施例１〜４：純度９９.９９％ の金属銅
板の表面に、平均膜厚み１０Åとなるようにマグネシウ
ム，カルシウム，ストロンチウム，バリウムのイオンク
ラスタビームを蒸着して実施例１〜４の電極を作製し
た。Ｈ型セル内に電解液として０.１mol／ｌの重炭酸カ
リウムを入れ、上記電極をカソード，白金板をアノー
ド，Ａｇ／ＡｇＣｌを参照極とし、両極間を陽イオン交
換膜で仕切り、室温、−１.７Ｖ ｖｓ.Ａｇ／ＡｇＣｌ
で炭酸ガスを吹き込みながら還元実験を行ったところ、
比較例１（金属銅板をカソードとした以外は実施例１〜
４に同じ）と比較してメタン，アルコール，ギ酸，一酸
化炭素の電流効率が増大し、水素のそれは減少した。表
１に結果を示す。Examples 1 to 4: Ion cluster beams of magnesium, calcium, strontium and barium were vapor-deposited on the surface of a metal copper plate having a purity of 99.99% so as to have an average film thickness of 10 Å. An electrode was prepared. 0.1 mol / l potassium bicarbonate was placed as an electrolytic solution in an H-shaped cell, the above electrode was used as a cathode, the platinum plate was used as an anode, and Ag / AgCl was used as a reference electrode. -1.7V vs. Ag / AgCl
When I conducted a reduction experiment while blowing carbon dioxide,
Comparative Example 1 (Examples 1 to 1 except that the metal copper plate was used as the cathode)
(Same as 4), the current efficiency of methane, alcohol, formic acid and carbon monoxide was increased, and that of hydrogen was decreased. The results are shown in Table 1.
【００１９】[0019]
【表１】 [Table 1]
【００２０】実施例５：バリウムと同時に亜鉛を同じ量
蒸着した以外は実施例１と同じ方法および条件で炭酸ガ
スの還元を行ったところ、比較例１と比較してメタン，
アルコール，ギ酸，一酸化炭素の電流効率が増大し、水
素のそれは減少した。表２に結果を示す。Example 5 Carbon dioxide gas was reduced by the same method and conditions as in Example 1 except that the same amount of zinc was vapor-deposited at the same time as barium.
The current efficiency of alcohol, formic acid and carbon monoxide increased, and that of hydrogen decreased. The results are shown in Table 2.
【００２１】[0021]
【表２】 [Table 2]
【００２２】実施例６：実施例１で使用した金属銅板を
不活性雰囲気中で１００℃に加熱しながら、その表面に
１ｍmol／ｌ の硝酸マグネシウム溶液をスプレーした
後、５００℃で１時間加熱して電極を作製した。その電
極を用いて実施例１〜４と同じ方法および条件で炭酸ガ
スの還元を行ったところ、比較例１と比較してメタン，
アルコール，ギ酸，一酸化炭素の電流効率が顕著に増大
し、水素のそれは減少した。表３に結果を示す。Example 6 While heating the metallic copper plate used in Example 1 at 100 ° C. in an inert atmosphere, the surface was sprayed with a 1 mMol / l magnesium nitrate solution and then heated at 500 ° C. for 1 hour. To produce an electrode. When carbon dioxide was reduced using the electrode under the same method and conditions as in Examples 1 to 4, methane,
The current efficiency of alcohol, formic acid and carbon monoxide increased remarkably, and that of hydrogen decreased. The results are shown in Table 3.
【００２３】[0023]
【表３】 [Table 3]
【００２４】実施例７：電解液として０.１mol／ｌのギ
酸ナトリウムを入れた以外は実施例４と同じ条件で還元
実験を行ったところ、比較例２（金属銅板をカソードと
した以外は実施例７に同じ）と比較して炭化水素および
アルコールのエネルギー変換効率が増大した。表４に結
果を示す。Example 7: A reduction experiment was conducted under the same conditions as in Example 4 except that 0.1 mol / l sodium formate was added as an electrolyte, and Comparative Example 2 (Except that a metal copper plate was used as the cathode) The energy conversion efficiencies of hydrocarbons and alcohols were increased compared to (same as Example 7). The results are shown in Table 4.
【００２５】[0025]
【表４】 [Table 4]
【００２６】実施例８：厚さ１μｍの酸化チタン薄膜を
アノードに用いた以外は実施例３と同じ方法および条件
で炭酸ガスの還元実験を行ったところ、比較例３（金属
銅電極をカソードとして使用した以外は実施例８と同
じ）と比較して炭化水素，アルコール、およびギ酸の電
流効率が増大した。表５に結果を示す。Example 8: A carbon dioxide reduction experiment was conducted under the same method and conditions as in Example 3 except that a titanium oxide thin film having a thickness of 1 μm was used for the anode, and Comparative Example 3 (using a metal copper electrode as a cathode) The current efficiency of hydrocarbons, alcohols, and formic acid was increased compared to Example 8 except that it was used). The results are shown in Table 5.
【００２７】[0027]
【表５】 [Table 5]
【００２８】実施例９：本実施例を図１を用いて説明す
る。Ｈ型セル１内に電解液２として０.１mol／ｌの重炭
酸カリウム水溶液を入れ、実施例４の電極をカソード
３，白金板をアノード４とし、両極間を陽イオン交換膜
５で仕切り、両極間に２Ｗの太陽電池７を接続し、室温
で炭酸ガス６の還元実験を行ったところ、比較例４（金
属銅電極をカソードとして使用した以外は実施例９と同
じ）と比較して炭化水素，アルコールおよびギ酸の電流
効率が増大した。表６に結果を示す。Embodiment 9: This embodiment will be described with reference to FIG. A 0.1 mol / l potassium bicarbonate aqueous solution was put into the H-shaped cell 1 as the electrolytic solution 2, the electrode of Example 4 was used as the cathode 3, the platinum plate was used as the anode 4, and both electrodes were partitioned by the cation exchange membrane 5. When a 2 W solar cell 7 was connected between both electrodes and a carbon dioxide 6 reduction experiment was performed at room temperature, carbonization was performed in comparison with Comparative Example 4 (same as Example 9 except that a metal copper electrode was used as the cathode). The current efficiency of hydrogen, alcohol and formic acid was increased. The results are shown in Table 6.
【００２９】[0029]
【表６】 [Table 6]
【００３０】実施例１０：本実施例を図２により説明す
る。カソード３に実施例５の電極を用い、アノード４に
厚さ０.５μｍ の酸化チタン薄膜を用い、それに５００
Ｗのキセノンランプ８から光を照射した以外は実施例９
と同じ方法および条件で炭酸ガスの還元実験を行ったと
ころ、比較例５（金属銅電極をカソードとして使用した
以外は実施例１０と同じ）と比較して炭化水素，ギ酸お
よびアルコールを増大した。表７に結果を示す。Embodiment 10: This embodiment will be described with reference to FIG. The cathode of Example 5 was used as the cathode 3, and the anode 4 was made of a titanium oxide thin film having a thickness of 0.5 μm.
Example 9 except that light was emitted from the W xenon lamp 8.
When a carbon dioxide gas reduction experiment was conducted under the same method and conditions as in Example 1, the amount of hydrocarbons, formic acid and alcohol was increased as compared with Comparative Example 5 (same as Example 10 except that a metal copper electrode was used as the cathode). The results are shown in Table 7.
【００３１】[0031]
【表７】 [Table 7]
【００３２】[0032]
【発明の効果】本発明では、クリーンで無尽蔵のエネル
ギー源である太陽光を利用して溶液中の炭酸イオン，重
炭酸イオン，カルボン酸，アルデヒド、および一酸化炭
素，炭酸ガスを還元できる。化石燃料を用いる火力発電
所および化学工場のボイラ，セメント工場のキルン、製
鉄所の高炉等の固定燃焼装置から排出される燃焼排ガス
から炭酸ガスを回収し、それを本発明により再資源化し
て燃焼装置ヘリサイクルすると、化石燃料の消費量が削
減され、炭酸ガスの排出量も削減されるので、地球温暖
化問題の解決に寄与する。INDUSTRIAL APPLICABILITY According to the present invention, sunlight, which is a clean and inexhaustible energy source, can be used to reduce carbonate ions, bicarbonate ions, carboxylic acids, aldehydes, and carbon monoxide and carbon dioxide in a solution. Carbon dioxide is recovered from combustion exhaust gas discharged from fixed combustion devices such as boilers of thermal power plants and chemical plants that use fossil fuels, kilns of cement plants, and blast furnaces of steel plants, and the carbon dioxide gas is recycled by the present invention and burned. Recycling to equipment reduces fossil fuel consumption and carbon dioxide emissions, contributing to the solution of global warming.
【図１】本発明の一実施例による電気化学的還元装置の
概略図。FIG. 1 is a schematic view of an electrochemical reduction device according to an embodiment of the present invention.
【図２】本発明の一実施例による電気化学的還元装置の
概略図。FIG. 2 is a schematic view of an electrochemical reduction device according to an embodiment of the present invention.
１…Ｈ型セル、２…電解液、３…カソード、４…アノー
ド、５…陽イオン交換膜、６…炭酸ガス、７…キセノン
ランプ。1 ... H type cell, 2 ... electrolyte, 3 ... cathode, 4 ... anode, 5 ... cation exchange membrane, 6 ... carbon dioxide gas, 7 ... xenon lamp.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 土井 良太 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内 (72)発明者 飛田 紘 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内 (72)発明者 宮寺 博 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryota Doi 4026 Kujimachi, Hitachi City, Ibaraki Prefecture, Hitachi Research Institute Ltd. Hitachi Research Laboratory (72) Inventor Hiroshi Miyadera 4026 Kuji Town, Hitachi City, Ibaraki Prefecture Hitachi Research Laboratory, Hitachi, Ltd.
Claims (11)
とが同時に存在することを特徴とする電気化学的還元用
電極。1. An electrode for electrochemical reduction, wherein the surface of metallic copper and the surface of a metal belonging to Group IIa are present at the same time.
ム，ストロンチウム，バリウムの少なくとも一つ以上の
金属の表面とが同時に存在することを特徴とする電気化
学的還元用電極。2. An electrode for electrochemical reduction, wherein the surface of metallic copper and the surface of at least one metal of magnesium, calcium, strontium and barium are present at the same time.
のいずれかであることを特徴とする請求項１記載の電気
化学的還元用電極。3. The electrode for electrochemical reduction according to claim 1, wherein the metallic copper is any one of a plate, a net, a foam, a thin film and fine particles.
結，リソグラフィー或いはイオン打ち込みで作製するこ
とを特徴とする電気化学的還元用電極の製造方法。4. A method for producing an electrode for electrochemical reduction, which comprises producing the electrode according to claim 1 by vapor deposition, coating, sintering, lithography or ion implantation.
酸イオン，重炭酸イオン，アルデヒド，カルボン酸のい
ずれかを電気化学的に還元する装置に備えたことを特徴
とする電気化学的還元装置。5. An electrochemical device comprising the electrode according to claim 1 in an apparatus for electrochemically reducing any one of carbon dioxide gas, carbonic acid, carbonate ion, bicarbonate ion, aldehyde, and carboxylic acid. Reduction device.
アノードとすることを特徴とする炭酸ガス，炭酸，炭酸
イオン，重炭酸イオン，アルデヒド，カルボン酸のいず
れかを光電気化学的に還元する装置。6. The electrode according to claim 1 is used as a cathode, and the photoelectrode is used as an anode. Any one of carbon dioxide gas, carbonic acid, carbonate ion, bicarbonate ion, aldehyde, and carboxylic acid is photoelectrochemically A device to give back.
成されることを特徴とする炭酸ガス，炭酸，炭酸イオ
ン，重炭酸イオン，アルデヒド，カルボン酸のいずれか
を光電気化学的に還元する装置。7. The photoelectrode according to claim 6, wherein the photoelectrode is composed of an n-type photo-semiconductor, and photochemically reacts with any one of carbon dioxide gas, carbonic acid, carbonate ion, bicarbonate ion, aldehyde and carboxylic acid. Device that returns to.
であることを特徴とする炭酸ガス，炭酸，炭酸イオン，
重炭酸イオン，アルデヒド，カルボン酸のいずれかを光
電気化学的に還元する装置。8. The carbon dioxide gas, carbonic acid, carbonate ion, wherein the n-type optical semiconductor according to claim 7 is titanium oxide,
A device that photoelectrochemically reduces any of bicarbonate ion, aldehyde, and carboxylic acid.
ン，アルデヒド，カルボン酸のいずれかを還元するのに
要するエネルギーを、太陽光または太陽電池から供給す
ることを特徴とする請求項５ないし８記載の電気化学的
または光電気化学的還元装置。9. The energy required to reduce any one of carbon dioxide, carbonic acid, carbonate ion, bicarbonate ion, aldehyde and carboxylic acid is supplied from sunlight or a solar cell. 8. The electrochemical or photoelectrochemical reduction device according to 8.
ながらその表面に他の金属化合物を含む溶液をその金属
化合物の分解温度以下で付け、さらにその金属化合物の
分解温度以上で加熱処理することを特徴とする電気化学
的還元用電極の製造方法。10. A method of applying a solution containing another metal compound to the surface of the metal while heating the metal in an inert or reducing atmosphere at a temperature not higher than the decomposition temperature of the metal compound, and further heat-treating at a temperature not lower than the decomposition temperature of the metal compound. A method for producing an electrode for electrochemical reduction, comprising:
あることを特徴とする請求項１０記載の電気化学的還元
用電極の製造方法。11. The method for producing an electrode for electrochemical reduction according to claim 10, wherein the metal is copper and the metal compound is Group IIa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4120337A JPH05311476A (en) | 1992-05-13 | 1992-05-13 | Electrode for electrochemical reduction and device for utilizing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4120337A JPH05311476A (en) | 1992-05-13 | 1992-05-13 | Electrode for electrochemical reduction and device for utilizing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05311476A true JPH05311476A (en) | 1993-11-22 |
Family
ID=14783763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4120337A Pending JPH05311476A (en) | 1992-05-13 | 1992-05-13 | Electrode for electrochemical reduction and device for utilizing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05311476A (en) |
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| WO2012046362A1 (en) * | 2010-10-06 | 2012-04-12 | パナソニック株式会社 | Method for reducing carbon dioxide |
| CN103119203A (en) * | 2010-05-17 | 2013-05-22 | 本田技研工业株式会社 | Solar fuel cell |
| WO2015133127A1 (en) * | 2014-03-04 | 2015-09-11 | 株式会社デンソー | Carbon dioxide reduction electrode and carbon dioxide reduction device in which same is used |
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| US9598779B2 (en) | 2013-07-05 | 2017-03-21 | Panasonic Intellectual Property Management Co., Ltd. | Method for reducing carbon dioxide |
| US9598781B2 (en) | 2013-05-21 | 2017-03-21 | Panasonic Intellectual Property Management Co., Ltd. | Carbon dioxide reducing method, carbon dioxide reducing cell, and carbon dioxide reducing apparatus |
| AT523650A4 (en) * | 2020-09-10 | 2021-10-15 | Univ Linz | Working electrode for the direct reduction of carbonates to hydrocarbons in an aqueous carbonate electrolyte |
| CN114405438A (en) * | 2022-03-01 | 2022-04-29 | 中山大学 | Photoelectrocatalysis reaction system |
-
1992
- 1992-05-13 JP JP4120337A patent/JPH05311476A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103119203B (en) * | 2010-05-17 | 2016-06-08 | 本田技研工业株式会社 | Solar fuel cell |
| CN103119203A (en) * | 2010-05-17 | 2013-05-22 | 本田技研工业株式会社 | Solar fuel cell |
| US8696883B2 (en) | 2010-10-06 | 2014-04-15 | Panasonic Corporation | Method for reducing carbon dioxide |
| WO2012046362A1 (en) * | 2010-10-06 | 2012-04-12 | パナソニック株式会社 | Method for reducing carbon dioxide |
| US9157158B2 (en) | 2012-07-05 | 2015-10-13 | Panasonic Intellectual Property Management Co., Ltd. | Method for producing alcohol |
| US9551077B2 (en) | 2012-08-27 | 2017-01-24 | Panasonic Intellectual Property Management Co., Ltd. | Photoelectrode used for carbon dioxide reduction and method for reducing carbon dioxide using the photoelectrode |
| US9598781B2 (en) | 2013-05-21 | 2017-03-21 | Panasonic Intellectual Property Management Co., Ltd. | Carbon dioxide reducing method, carbon dioxide reducing cell, and carbon dioxide reducing apparatus |
| US9598779B2 (en) | 2013-07-05 | 2017-03-21 | Panasonic Intellectual Property Management Co., Ltd. | Method for reducing carbon dioxide |
| JP2015180765A (en) * | 2014-03-04 | 2015-10-15 | 株式会社デンソー | Carbon dioxide reduction electrode and carbon dioxide reduction device in which the same is used |
| WO2015133127A1 (en) * | 2014-03-04 | 2015-09-11 | 株式会社デンソー | Carbon dioxide reduction electrode and carbon dioxide reduction device in which same is used |
| AT523650A4 (en) * | 2020-09-10 | 2021-10-15 | Univ Linz | Working electrode for the direct reduction of carbonates to hydrocarbons in an aqueous carbonate electrolyte |
| AT523650B1 (en) * | 2020-09-10 | 2021-10-15 | Univ Linz | Working electrode for the direct reduction of carbonates to hydrocarbons in an aqueous carbonate electrolyte |
| CN114405438A (en) * | 2022-03-01 | 2022-04-29 | 中山大学 | Photoelectrocatalysis reaction system |
| CN114405438B (en) * | 2022-03-01 | 2022-11-11 | 中山大学 | Photoelectrocatalysis reaction system |
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