WO2012011209A1 - Method for reducing carbon dioxide - Google Patents
Method for reducing carbon dioxide Download PDFInfo
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- WO2012011209A1 WO2012011209A1 PCT/JP2011/001521 JP2011001521W WO2012011209A1 WO 2012011209 A1 WO2012011209 A1 WO 2012011209A1 JP 2011001521 W JP2011001521 W JP 2011001521W WO 2012011209 A1 WO2012011209 A1 WO 2012011209A1
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- carbon dioxide
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- electrolytic solution
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
Definitions
- the present invention relates to a method for reducing carbon dioxide.
- Patent Document 1 Patent Document 2, Non-Patent Document 1, Non-Patent Document 2, and Non-Patent Document 3 disclose methods for reducing carbon dioxide.
- An object of the present invention is to provide a novel method for reducing carbon dioxide.
- the present invention is a method for reducing carbon dioxide using an apparatus for reducing carbon dioxide, comprising the following steps: A step (a) of preparing the device comprising: Tank, Working electrode and counter electrode, where An electrolyte is held inside the tank, The working electrode contains boron; The counter electrode contains a metal; The boron is in contact with the electrolyte; The metal is in contact with the electrolyte; The electrolytic solution contains the carbon dioxide, and a negative voltage and a positive voltage are applied to the working electrode and the counter electrode, respectively, to reduce carbon dioxide contained in the electrolytic solution (b).
- the present invention provides a novel method for reducing carbon dioxide.
- the apparatus which reduces a carbon dioxide by Embodiment 1 is shown.
- the graph of the result of the measurement of the reaction current-electric field potential (CV measurement) in Example 1 is shown.
- the graph of the result of gas chromatography in Example 1 is shown.
- the graph of the result of the liquid chromatography in Example 1 is shown.
- step (a) an apparatus for reducing carbon dioxide is prepared.
- the apparatus includes a tank 21, a working electrode 11, and a counter electrode 13.
- the electrolytic solution 15 is held inside the tank 21.
- An example of the electrolytic solution 15 is an aqueous potassium hydrogen carbonate solution.
- the electrolytic solution 15 contains carbon dioxide. In a state where carbon dioxide is dissolved in the electrolytic solution 15, the electrolytic solution 15 is preferably weakly acidic.
- the working electrode 11 contains boron.
- the working electrode 11 can be manufactured as follows. First, boron particles are dispersed in an organic solvent to form a slurry. Next, this slurry is applied to a porous conductive substrate to obtain the working electrode 11.
- the substrate preferably has a film shape. Examples of the substrate are carbon paper, an inert metal substrate, a glassy carbon substrate, or a conductive silicon substrate.
- the working electrode 11 can also be formed by a sputtering method.
- the working electrode 11 is in contact with the electrolytic solution 15. More precisely, boron included in the working electrode 11 contacts the electrolytic solution 15. In FIG. 1, the working electrode 11 is immersed in the electrolytic solution 15. As long as boron contacts the electrolytic solution 15, only a part of the working electrode 11 may be immersed in the electrolytic solution 15.
- the counter electrode 13 contains a metal.
- suitable metals are platinum, gold, silver, copper, nickel, and titanium.
- the material of the metal is not particularly limited.
- the counter electrode 13 is in contact with the electrolytic solution 15. More precisely, the metal included in the counter electrode 13 is in contact with the electrolytic solution 15. In FIG. 1, the counter electrode 13 is immersed in the electrolytic solution 15. As long as the metal contacts the electrolytic solution 15, only a part of the counter electrode 13 may be immersed in the electrolytic solution 15.
- the tank 21 preferably includes a tube 17. Carbon dioxide is supplied to the electrolyte solution 15 through the pipe 17. One end of the tube 17 is immersed in the electrolytic solution 15.
- the solid electrolyte membrane 16 is provided inside the tank 21. The reason for this will be described later in step (b).
- the solid electrolyte membrane 16 is sandwiched between the working electrode 11 and the counter electrode 13, and divides the electrolytic solution 15 into a first liquid 15L and a second liquid 15R.
- the counter electrode 13 is in contact with the first liquid 15L.
- the working electrode 11 is in contact with the second liquid 15R.
- step (b) a negative voltage and a positive voltage are applied to the working electrode 11 and the counter electrode 13, respectively.
- This causes the carbon dioxide contained in the electrolytic solution 15 (more precisely, the second liquid 15R) to be reduced on the working electrode 11.
- the carbon dioxide contained in the electrolytic solution 15 more precisely, the second liquid 15R
- at least one selected from carbon monoxide, formic acid, and methane is generated on the working electrode 11.
- water is oxidized to generate oxygen.
- a potentiostat 14 is used and a potential difference is applied between the working electrode 11 and the counter electrode 13.
- the potential difference applied between the working electrode 11 and the counter electrode 13 is preferably 2 V or more. In Example 1 described later, this corresponds to the fact that a CO 2 reduction current was observed at ⁇ 0.7 V or less (and ⁇ 1.5 V or more).
- a solid electrolyte membrane 16 is provided. Only protons permeate the solid electrolyte membrane 16.
- An example of the solid electrolyte membrane 16 is a Nafion (registered trademark) membrane available from DuPont.
- the solid electrolyte membrane 16 suppresses the reverse reaction on the counter electrode 13. That is, if carbon monoxide, formic acid, or methane generated on the working electrode 11 reaches the counter electrode 13, it is oxidized on the counter electrode 13 and returns to oxygen dioxide. The solid electrolyte membrane 16 prevents this reverse reaction.
- a reference electrode 12 is preferably provided.
- the reference electrode 12 is in contact with the electrolytic solution 15.
- the reference electrode 12 is in contact with the second liquid 15R.
- the reference electrode 12 is electrically connected to the working electrode 11.
- An example of the reference electrode 12 is a silver / silver oxide electrode.
- Example 1 About 1 ⁇ 10 7 pieces / cm 2 of boron (B particles, Mitsuwa Chemical Co., Ltd., purity 96%) having an average particle diameter of 0.8 ⁇ m on conductive carbon paper (CP) having a thickness of 0.5 mm
- the electrode catalyst (working electrode) according to the present invention was prepared by carrying it at a distribution density. Using this electrode catalyst, an electrochemical reduction reaction of CO 2 was performed.
- a schematic diagram of the structure of the electrochemical cell used for this measurement is shown in FIG. This cell uses a produced B particle-supporting electrode as a working electrode 11, and uses a silver / silver chloride electrode (Ag / AgCl electrode) as a reference electrode 12 and a platinum electrode (Pt electrode) as a counter electrode 13. It was.
- the CO 2 reduction reaction was evaluated by sweeping the potential of the triode cell with a potentiostat 14.
- a 0.1 M potassium hydrogen carbonate aqueous solution KHCO 3 aqueous solution
- the working electrode 11 and the counter electrode 13 are partitioned by a solid electrolyte membrane 16 in order to prevent mixing of gas components generated by catalytic action.
- CO 2 gas was introduced by placing the gas introduction pipe 17 in the cell and bubbling it into the KHCO 3 electrolyte.
- the product obtained by the CO 2 reduction reaction using the electrode carrying the B particles was analyzed.
- the gas component analysis was performed using a flame ion detector (FID) type gas chromatograph, and the liquid component was analyzed using a UV detection type liquid chromatograph.
- FID flame ion detector
- FIG. 3 shows the measurement results of methane (CH 4 ), ethylene (C 2 H 4 ), and ethane (C 2 H 6 ) by FID gas chromatography.
- a PorapakQ separation column is used, and the valve is controlled in a preset time sequence, so that CH 4 is about 1.5 minutes after the start of measurement, and C 2 H is about 4.5 minutes. 4 is programmed so that C 2 H 6 is detected around 6.5 minutes, respectively.
- voltage peak values were observed in the time domain corresponding to them, and it was confirmed that CH 4 , C 2 H 4 , and C 2 H 6 were generated.
- the present invention provides a novel method for reducing carbon dioxide.
Abstract
Description
以下を具備する前記装置を用意する工程(a)、
槽、
作用極、および
対極、ここで、
前記槽の内部には電解液が保持され、
前記作用極は硼素を含有し、
前記対極は金属を含有し、
前記硼素は前記電解液に接し、
前記金属は前記電解液に接し、
前記電解液は前記二酸化炭素を含有し、および
前記作用極および前記対極にそれぞれ負の電圧および正の電圧を印加し、前記電解液に含有される二酸化炭素を還元する工程(b)。 The present invention is a method for reducing carbon dioxide using an apparatus for reducing carbon dioxide, comprising the following steps:
A step (a) of preparing the device comprising:
Tank,
Working electrode and counter electrode, where
An electrolyte is held inside the tank,
The working electrode contains boron;
The counter electrode contains a metal;
The boron is in contact with the electrolyte;
The metal is in contact with the electrolyte;
The electrolytic solution contains the carbon dioxide, and a negative voltage and a positive voltage are applied to the working electrode and the counter electrode, respectively, to reduce carbon dioxide contained in the electrolytic solution (b).
工程(a)では、二酸化炭素を還元する装置を用意する。
図1に示されるように、装置は、槽21、作用極11、および対極13を具備する。
電解液15が槽21の内部に保持されている。電解液15の例は、炭酸水素カリウム水溶液である。電解液15は、二酸化炭素を含有する。二酸化炭素が電解液15に溶解した状態において、電解液15は弱酸性であることが好ましい。 (Process (a))
In step (a), an apparatus for reducing carbon dioxide is prepared.
As shown in FIG. 1, the apparatus includes a
The
まず、硼素粒子を有機溶媒に分散させ、スラリーを形成する。次に、このスラリーを多孔性の導電性基材に塗布し、作用極11を得る。この基材は、フィルムの形状を有することが好ましい。基材の例は、カーボンペーパー、不活性金属基板、グラッシーカーボン基板、または導電性シリコン基板である。 The working
First, boron particles are dispersed in an organic solvent to form a slurry. Next, this slurry is applied to a porous conductive substrate to obtain the working
工程(b)では、作用極11および対極13にそれぞれ負の電圧および正の電圧を印加する。このことが、電解液15(より正確には、第2液15R)に含有される二酸化炭素が作用極11上にて還元されることを引き起こす。その結果、作用極11上では、一酸化炭素、蟻酸、およびメタンから選択される少なくとも1種が発生する。対極13上では、水が酸化されて酸素が発生する。 (Process (b))
In the step (b), a negative voltage and a positive voltage are applied to the working
以下の実施例により、本発明をさらに詳細に説明する。 (Example)
The following examples illustrate the invention in more detail.
厚さが0.5mmの導電性カーボンペーパー(CP)に平均粒径が0.8μmの硼素(B粒子、三津和化学薬品株式会社、純度96%)を約1×107個/cm2の分布密度で担持させて、本発明に係る電極触媒(作用極)を作製した。この電極触媒を用いて、CO2の電気化学的な還元反応を行った。今回の測定に用いた電気化学セルの構造模式図を図1に示す。このセルは、作製したB粒子担持電極を作用極11に用い、そして参照極12として銀/塩化銀電極(Ag/AgCl電極)、対極13に白金電極(Pt電極)を用いた三極セル構成とした。この三極セルに対して、ポテンシオスタット14で電位を掃引することにより、CO2還元反応の評価を行った。電解液15には、0.1Mの炭酸水素カリウム水溶液(KHCO3水溶液)を用いた。また、作用極11と対極13の間は、触媒作用により生成するガス成分の混合を防ぐために、固体電解質膜16で仕切ってある。CO2ガスは、ガス導入管17をセル内に配置し、KHCO3電解液中へバブリングさせることで導入した。 Example 1
About 1 × 10 7 pieces / cm 2 of boron (B particles, Mitsuwa Chemical Co., Ltd., purity 96%) having an average particle diameter of 0.8 μm on conductive carbon paper (CP) having a thickness of 0.5 mm The electrode catalyst (working electrode) according to the present invention was prepared by carrying it at a distribution density. Using this electrode catalyst, an electrochemical reduction reaction of CO 2 was performed. A schematic diagram of the structure of the electrochemical cell used for this measurement is shown in FIG. This cell uses a produced B particle-supporting electrode as a working
比較のため、硼素粒子担持に用いたカーボンぺーバー(CP)のみでの電解反応を測定した。その結果、CO2還元による還元電流は観測されず、CO2還元に対して不活性であり、電解反応による生成物は水素(H2)のみであった。 (Comparative Example 1)
For comparison, the electrolytic reaction with only the carbon paper (CP) used for supporting boron particles was measured. As a result, a reduction current due to CO 2 reduction was not observed, it was inactive to CO 2 reduction, and the product of the electrolytic reaction was only hydrogen (H 2 ).
比較のため、シリコン(Si)基板のみでの電解反応を測定した。その結果、CO2還元に対して、電解反応による生成物は水素が(H2)主成分であり、炭化水素や蟻酸(HCOOH)の生成は得られなかった。 (Comparative Example 2)
For comparison, the electrolytic reaction with only a silicon (Si) substrate was measured. As a result, with respect to CO 2 reduction, the product of the electrolytic reaction is mainly composed of hydrogen (H 2 ), and no hydrocarbon or formic acid (HCOOH) was produced.
Claims (4)
- 二酸化炭素を還元する装置を用いて二酸化炭素を還元する方法であって、以下の工程を具備する:
以下を具備する前記装置を用意する工程(a)、
槽、
作用極、および
対極、ここで、
前記槽の内部には電解液が保持され、
前記作用極は硼素を含有し、
前記対極は金属を含有し、
前記硼素は前記電解液に接し、
前記金属は前記電解液に接し、
前記電解液は前記二酸化炭素を含有し、および
前記作用極および前記対極にそれぞれ負の電圧および正の電圧を印加し、前記電解液に含有される二酸化炭素を還元する工程(b)。 A method for reducing carbon dioxide using an apparatus for reducing carbon dioxide, comprising the following steps:
A step (a) of preparing the device comprising:
Tank,
Working electrode and counter electrode, where
An electrolyte is held inside the tank,
The working electrode contains boron;
The counter electrode contains a metal;
The boron is in contact with the electrolyte;
The metal is in contact with the electrolyte;
The electrolytic solution contains the carbon dioxide, and a negative voltage and a positive voltage are applied to the working electrode and the counter electrode, respectively, to reduce carbon dioxide contained in the electrolytic solution (b). - 請求項1に記載の方法であって、
前記槽は固体電解質膜を具備し、
前記固体電解質膜は、前記作用極および前記対極の間に挟まれている。 The method of claim 1, comprising:
The tank comprises a solid electrolyte membrane,
The solid electrolyte membrane is sandwiched between the working electrode and the counter electrode. - 請求項1に記載の方法であって、
前記工程(b)において前記作用極および前記対極との間に印加される電位差は2.0V以上である。 The method of claim 1, comprising:
The potential difference applied between the working electrode and the counter electrode in the step (b) is 2.0 V or more. - 請求項1に記載の方法であって、
前記工程(b)において、メタン、エチレン、エタン、および蟻酸の少なくとも1種が発生する。 The method of claim 1, comprising:
In the step (b), at least one of methane, ethylene, ethane, and formic acid is generated.
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JP2011544540A JP4907748B2 (en) | 2010-07-23 | 2011-03-15 | How to reduce carbon dioxide |
CN2011800052000A CN102686781A (en) | 2010-07-23 | 2011-03-15 | Method for reducing carbon dioxide |
US13/329,953 US20120318680A1 (en) | 2010-07-23 | 2011-12-19 | Device and method for reducing carbon dioxide |
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JP2018519418A (en) * | 2015-05-22 | 2018-07-19 | シーメンス アクチエンゲゼルシヤフトSiemens Aktiengesellschaft | Electrolytic system with proton donor unit for electrochemical effective utilization of carbon dioxide and reduction method |
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US20140151240A1 (en) * | 2012-11-30 | 2014-06-05 | Alstom Technology Ltd | Electroylytic reduction of carbon capture solutions |
RU2771380C1 (en) * | 2021-09-05 | 2022-05-04 | Сергей Станиславович Беднаржевский | Carbon dioxide utilization device |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH04290526A (en) * | 1991-03-20 | 1992-10-15 | Hitachi Ltd | Method for separating and reutilizing carbon dioxide |
JPH04329888A (en) * | 1991-05-01 | 1992-11-18 | Rikagaku Kenkyusho | Electrode consisting of titanium boride and high-potential electrolysis utilizing this electrode |
JP2001089887A (en) * | 1999-09-22 | 2001-04-03 | Iwasaki Electric Co Ltd | Electrode for electrolytic reaction using diamond thin film and method of reducing carbon dioxide using the same |
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GB0513631D0 (en) * | 2005-07-01 | 2005-08-10 | Alphasense Ltd | Electrode and method for making electrode |
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- 2011-03-15 CN CN2011800052000A patent/CN102686781A/en active Pending
- 2011-03-15 JP JP2011544540A patent/JP4907748B2/en not_active Expired - Fee Related
- 2011-12-19 US US13/329,953 patent/US20120318680A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH04290526A (en) * | 1991-03-20 | 1992-10-15 | Hitachi Ltd | Method for separating and reutilizing carbon dioxide |
JPH04329888A (en) * | 1991-05-01 | 1992-11-18 | Rikagaku Kenkyusho | Electrode consisting of titanium boride and high-potential electrolysis utilizing this electrode |
JP2001089887A (en) * | 1999-09-22 | 2001-04-03 | Iwasaki Electric Co Ltd | Electrode for electrolytic reaction using diamond thin film and method of reducing carbon dioxide using the same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2018519418A (en) * | 2015-05-22 | 2018-07-19 | シーメンス アクチエンゲゼルシヤフトSiemens Aktiengesellschaft | Electrolytic system with proton donor unit for electrochemical effective utilization of carbon dioxide and reduction method |
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JP4907748B2 (en) | 2012-04-04 |
JPWO2012011209A1 (en) | 2013-09-09 |
US20120318680A1 (en) | 2012-12-20 |
CN102686781A (en) | 2012-09-19 |
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