WO2011135783A1 - 二酸化炭素を還元する方法 - Google Patents
二酸化炭素を還元する方法 Download PDFInfo
- Publication number
- WO2011135783A1 WO2011135783A1 PCT/JP2011/002071 JP2011002071W WO2011135783A1 WO 2011135783 A1 WO2011135783 A1 WO 2011135783A1 JP 2011002071 W JP2011002071 W JP 2011002071W WO 2011135783 A1 WO2011135783 A1 WO 2011135783A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrode
- carbon dioxide
- working electrode
- reduction
- counter electrode
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- 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
Definitions
- the present invention relates to a method for reducing carbon dioxide.
- a carbon dioxide (CO 2 ) reduction technique using a catalyst is expected as a technique for fixing CO 2 and producing useful substances.
- This reduction technology is one of the important means for solving the global warming problem caused by greenhouse gases that are expected to become apparent in the future.
- catalytic hydrogenation methods and electrochemical methods have been studied as CO 2 reduction techniques using catalysts.
- CO 2 is catalytically reacted with hydrogen (H 2 ) and reduced under high temperature and high pressure gas phase conditions.
- H 2 hydrogen
- Patent Document 1 and Patent Document 2 By catalytic hydrogenation, CO 2 can be converted into a highly useful substance such as methanol
- the reduction reaction proceeds even at room temperature and normal pressure.
- the electrolytic reduction method does not require large-scale equipment.
- the electrolytic reduction method is simpler than the catalytic hydrogenation method. From this, the electrolytic reduction method is considered as one of the effective CO 2 reduction methods.
- catalysts capable of reducing CO 2 using an electrolytic reduction method so far solid solid metals such as copper (Cu) and silver (Ag) and their alloy materials, and cobalt (Co), nickel ( Complex materials (molecular catalysts) such as Ni) and iron (Fe) have been developed (Non-Patent Document 1, Non-Patent Document 2, and Non-Patent Document 3).
- CO 2 is a very stable molecule. Therefore, the reduction treatment of CO 2 by the catalytic hydrogenation method requires a high temperature (heating temperature: 300 ° C.) and a high pressure (reaction pressure: 50 atm) to advance the reaction. Further, in the catalytic hydrogenation method, a combustible gas such as H 2 is used. For these reasons, the catalytic hydrogenation method requires large-scale equipment introduction. The catalytic hydrogenation method has a problem that a large amount of input energy is required for the reduction treatment and energy use efficiency is very low.
- the solid simple metal and alloy materials and the molecular materials used as catalysts in the electrolytic reduction method have a durability problem such that the deterioration due to a long-term catalytic reaction is severe.
- a catalyst material that can reduce CO 2 by the electrolytic reduction method and has high practicality has not yet been found.
- an object of the present invention is to reduce CO 2 under an overvoltage condition equivalent to or smaller than that of a conventional catalyst, and to obtain highly useful substances (formic acid (HCOOH), methane (CH 4 ), ethylene (C 2 H 4). ) And ethane (C 2 H 6 ), etc.), and a method for reducing carbon dioxide using a highly durable catalyst.
- the present invention is a method for reducing carbon dioxide, comprising the following steps: Preparing an electrochemical cell (a), wherein: The electrochemical cell includes a working electrode, a counter electrode, and a tank, The tank stores electrolyte, The working electrode contains boron carbide; The electrolyte contains carbon dioxide; The working electrode is in contact with the electrolytic solution, The counter electrode is in contact with the electrolyte solution, and a negative voltage and a positive voltage are respectively applied to the working electrode and the counter electrode to reduce the carbon dioxide (b).
- a Preparing an electrochemical cell (a), wherein: The electrochemical cell includes a working electrode, a counter electrode, and a tank, The tank stores electrolyte, The working electrode contains boron carbide; The electrolyte contains carbon dioxide; The working electrode is in contact with the electrolytic solution, The counter electrode is in contact with the electrolyte solution, and a negative voltage and a positive voltage are respectively applied to the working electrode and the counter electrode to reduce the carbon dioxide (b).
- an electrochemical cell In the method for reducing carbon dioxide of the present invention, an electrochemical cell is used.
- the electrochemical cell has a working electrode that reduces carbon dioxide, which contains boron carbide.
- This boron carbide can reduce carbon dioxide under overvoltage conditions comparable or less than conventional catalysts that reduce carbon dioxide. Therefore, according to the method of the present invention, highly useful substances such as HCOOH, CH 4 , C 2 H 4 and C 2 H 6 can be produced under an overvoltage condition equivalent to or smaller than that of the conventional method. Furthermore, since boron carbide has high durability, the working electrode can achieve high durability.
- FIG. 1 Graph comparing adsorption energy value of carbon (C) surface and boron carbide in (B 4 C) surface, carbon monoxide (CO).
- the structure schematic diagram of the electrochemical cell used for the measurement in this invention The figure which shows the result of reaction current-electrolytic potential measurement (CV measurement) when boron carbide (B 4 C) is used. Shows when the boron carbide (B 4 C) is used, the methane by gas chromatography (CH 4), the component analysis results of the ethylene (C 2 H 4) and ethane (C 2 H 6). Shows when the boron carbide (B 4 C) is used, the component analysis results of the carbon monoxide by gas chromatography (CO) and methane (CH 4).
- the method for reducing carbon dioxide (CO 2 ) of the present invention is a method for electrochemically reducing CO 2 .
- an electrochemical cell is first prepared.
- the electrochemical cell includes an electrode (working electrode) used to reduce CO 2 .
- the working electrode contains boron carbide (B 4 C).
- a slurry solution in which boron carbide particles (B 4 C particles) having an average particle diameter of about several ⁇ m obtained by carbonization is dispersed in an organic solvent is prepared. Then, an appropriate amount of the slurry solution is applied to conductive carbon paper (CP) woven with carbon fibers used as an electrode substrate. As a result, a working electrode (catalyst) in which B 4 C particles are supported on CP is produced. CP is porous. Therefore, it is difficult to clearly define the loading amount of B 4 C particles. However, the supported amount of B 4 C particles is approximately several tens of ⁇ g / cm 2 to 1 mg / cm 2 .
- the electrode substrate is not limited to CP as long as it has conductivity.
- an inert metal substrate such as gold (Au), a glassy carbon substrate, and a conductive silicon substrate are generally used.
- the production method and shape of the B 4 C particles are not limited.
- B 4 C in the form of a thin film may be used.
- impurities may be mixed in during the manufacturing process.
- catalytic activity appears depending on the type of compound used as the catalyst. Therefore, impurities mixed in during the preparation process do not affect the result of the catalytic activity of the compound.
- the electrode substrate and the shape of boron carbide supported on the substrate are various.
- an electrolytic reaction in an electrolytic solution or an electrolytic reaction using a gas diffusion electrode is performed. Therefore, in order for boron carbide to be stably supported or deposited on the substrate, it is necessary to adjust the loading method and deposition method suitable for boron carbide.
- a product obtained by CO 2 reduction using this working electrode includes a gas component (gas component) and a liquid component.
- a gas chromatograph is used for gas component analysis
- a liquid chromatograph is used for liquid component analysis.
- FIG. 1 shows the adsorption energy value (E a ) of CO on a graphite (C) surface and boron carbide (B 4 C) surface estimated from a simulation based on density functional theory (electronic state calculation).
- E a adsorption energy value
- C graphite
- B 4 C boron carbide
- B 4 C used in the method for reducing CO 2 of the present invention as described above, CO 2 can be adsorbed on the solid surface with a small adsorption energy. This suggests that B 4 C can reduce the CO 2 reduction overvoltage.
- the method for reducing CO 2 of the present invention can be applied to a method using a solar cell as an external power source.
- This catalyst for reducing CO 2 can be combined with a photocatalyst and developed into a catalyst capable of using solar energy.
- the method of reducing CO 2 using B 4 C can be carried out by a method of blowing CO 2 gas into the electrolytic solution or a method of forming a three-phase interface using a gas diffusion electrode, and is extremely simple. . Therefore, it can be said that the method of reducing CO 2 using B 4 C is a very promising technique as an energy-saving CO 2 countermeasure in homes and areas where so-called large-scale facilities cannot be introduced.
- the electrochemical cell of the present embodiment includes a working electrode 21, a counter electrode 23, and a tank 28, as shown in FIG.
- the tank 28 stores an electrolytic solution 27.
- the working electrode 21 and the counter electrode 23 are electrically connected to each other and are in contact with the electrolytic solution 27.
- the electrolytic solution 27 contains CO 2 .
- the tank 28 includes a solid electrolyte membrane (for example, a cation exchange membrane) 25.
- the solid electrolyte membrane 25 is disposed between the working electrode 21 and the counter electrode 23.
- the solid electrolyte membrane 25 separates the inside of the tank 28 into a region on the working electrode 21 side and a region on the counter electrode 23 side.
- the electrolytic chemical cell further includes a gas introduction pipe 26 that functions as a gas introduction port. One end of the gas introduction pipe 26 is disposed inside the electrolytic solution 27.
- a step of applying a negative voltage and a positive voltage to the working electrode 21 and the counter electrode 23 is performed. In this step, for example, CO 2 is supplied from the gas introduction pipe 26 to the electrolyte solution 27.
- the working electrode 21 contains boron carbide (B 4 C). In FIG. 2, the working electrode 21 and the counter electrode 23 are completely immersed in the electrolytic solution 27.
- the working electrode 21 and the counter electrode 23 are not limited to such an arrangement.
- the working electrode 21 and the counter electrode 23 may be disposed in contact with the electrolytic solution 27.
- the electrochemical cell shown in FIG. 2 is a three-electrode cell provided with a reference electrode 22 because it is used for measurement in the examples.
- the reference electrode 22 since the measurement of the potential is not essential, the reference electrode 22 may not be provided.
- the material of the counter electrode 23 are metals such as platinum and nickel or metal oxides such as Cr 2 O 3 . When a material having a small overvoltage of the oxygen generation reaction generated at the counter electrode 23 is selected, carbon dioxide can be reduced with a lower applied voltage.
- the method for reducing CO 2 of the present invention can be carried out using the cell shown in FIG.
- this method first, an electrochemical cell as shown in FIG. 2 is prepared. Next, a negative voltage and a positive voltage are applied to the working electrode 21 and the counter electrode 23, respectively.
- the absolute value of the potential difference is preferably 2.0 V or more.
- An electrode used for reducing carbon dioxide which contains boron carbide.
- a catalyst for reducing carbon dioxide which contains boron carbide.
- Example 1 Conductive carbon paper (CP) having a thickness of 0.3 mm was prepared as an electrode substrate. Boron carbide particles (B 4 C particles, purity: 99.9%) having an average particle diameter of 1 ⁇ m were supported on the CP with a distribution density of about 1 ⁇ 10 7 particles / cm 2 . In this way, the catalyst according to this example was produced. Using this catalyst, an electrochemical reduction reaction of CO 2 was performed.
- FIG. 2 shows a structural schematic diagram of the electrochemical cell used in this measurement. This electrochemical cell was a triode cell having a working electrode 21, a reference electrode 22 and a counter electrode 23. In this cell, the produced catalyst according to this example was used for the working electrode 21.
- a silver / silver chloride electrode As the reference electrode 22, a silver / silver chloride electrode (Ag / AgCl electrode) was used. A platinum electrode (Pt electrode) was used for the counter electrode 23.
- the triode cell was evaluated for CO 2 reduction by sweeping the potential with a potentiostat 24.
- a 0.1 M (0.1 mol / L) potassium hydrogen carbonate aqueous solution KHCO 3 aqueous solution
- the working electrode 21 and the counter electrode 23 are partitioned by a solid electrolyte membrane 25 in order to prevent mixing of gas components generated by catalytic action.
- the CO 2 gas was introduced into the electrolyte solution 27 by bubbling into the electrolyte solution 27 using a gas introduction pipe 26 disposed in the cell.
- the measurement was performed as follows. (1) First, nitrogen (N 2 ) gas was flowed into the electrolytic solution 27 at a flow rate of 200 ml / min for 30 minutes, and the bubbling state of N 2 gas was maintained. The potential was swept with CO 2 in the solution excluded, and a reaction current-electrolysis voltage curve (CV curve) was drawn. (2) Next, the piping was switched to CO 2 gas. CO 2 gas was also allowed to flow through the electrolyte solution 27 at a flow rate of 200 ml / min for 30 minutes, and the bubbling state of the CO 2 gas was maintained. The potential was swept while the electrolyte solution 27 was saturated with CO 2 , and a CV curve in the presence of CO 2 was drawn.
- N 2 nitrogen
- CV curve reaction current-electrolysis voltage curve
- FIG. 3 shows the result.
- a state in which the current value (vertical axis) is negative indicates that a CO 2 reduction reaction occurs.
- the reaction current changed from zero to minus.
- FIG. 4 shows the measurement results of methane (CH 4 ), ethylene (C 2 H 4 ), and ethane (C 2 H 6 ) by an FID gas chromatograph.
- a Porapak Q separation column was used.
- the FID gas chromatograph shows CH 4 around 1.5 minutes after the start of measurement, C 2 H 4 around 4.5 minutes, and around 6.5 minutes.
- voltage peak values were observed in the time domain corresponding to them. It was confirmed that CH 4 and trace amounts of C 2 H 4 and C 2 H 6 were produced.
- FIG. 4 shows the measurement results of methane (CH 4 ), ethylene (C 2 H 4 ), and ethane (C 2 H 6 ) by an FID gas chromatograph.
- CH 4 methane
- C 2 H 4 ethylene
- ethane C 2 H 6
- FIG. 5 shows measurement results of carbon monoxide (CO) and the like by an FID gas chromatograph.
- a Porapak N separation column was used.
- the valve is controlled according to a preset time sequence, so that the FID gas chromatograph shows CO in the vicinity of 3.2 minutes and CH 4 in the vicinity of 7.2 minutes.
- programmed to be detected As a result, as shown in FIG. 5, a voltage peak value was observed in the time domain corresponding to each. That is, it was confirmed that CO and CH 4 were generated.
- the production of CO, CH 4, and C 2 H 6 was finally confirmed from the analysis result of the product by the catalytic reaction.
- Example 1 The CO 2 reduction current was measured using an electrode consisting only of CP used as the electrode substrate in Example 1. The reduction current of CO 2 was measured using the same method as in Example 1. As a result, no reduction current of CO 2 was observed. That is, the electrode consisting only of CP was inactive to CO 2 reduction. The product of the electrolytic reaction was only hydrogen (H 2 ).
- B 4 C which is a highly durable compound, can electrolytically reduce CO 2 with an overvoltage smaller than that of conventional catalysts. Further, by B 4 C is used as a catalyst for reducing CO 2, CO as a product, that like CH 4 and C 2 H 6 is obtained showed. According to B 4 C, energy-saving CO 2 electroreduction with only a DC power source at room temperature is possible.
- the catalyst used in the method for reducing CO 2 of the present invention can also be applied to a configuration that is more environmentally friendly.
- the method for reducing CO 2 of the present invention can be applied to a method using a solar cell as an external power source.
- a catalyst for reducing CO 2 can be combined with a photocatalyst and developed into a catalyst capable of using solar energy.
- boron carbide is a compound having high durability (B 4 C) is obtained by demonstrating that electrolytic reduction of CO 2 even in a small overpotential than conventional catalyst for reducing CO 2. Boron carbide can generate CH 4 and HCOOH from CO 2 with less energy. That is, the method for reducing CO 2 of the present invention can provide these useful substances at low cost from CO 2 .
- CO 2 reduction treatment technology using boron carbide (a method of reducing CO 2 and an electrochemical cell used in the method) is also effective as a CO 2 reduction technology for global warming countermeasures. In the future, this CO 2 reduction treatment technology can be expected as a method for reusing resources with less environmental impact by combining with photocatalyst technology and solar power generation technology.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
Abstract
Description
電気化学セルを用意する工程(a)、ここで、
前記電気化学セルは、作用極、対極、および槽を具備し、
前記槽は電解液を蓄えており、
前記作用極は炭化硼素を含有し、
前記電解液は二酸化炭素を含有し、
前記作用極は前記電解液に接しており、
前記対極は前記電解液に接しており、および
前記作用極および前記対極に負の電圧および正の電圧をそれぞれ印加し、前記二酸化炭素を還元する工程(b)。
二酸化炭素を還元するために用いられる電極であって、炭化硼素を含有する、電極。
二酸化炭素を還元する触媒であって、炭化硼素を含有する、触媒。
0.3mmの厚さを有する導電性カーボンペーパー(CP)が、電極基板として準備された。CP上に、1μmの平均粒径を有する炭化硼素粒子(B4C粒子、純度:99.9%)が、約1×107個/cm2の分布密度で担持された。このようにして、本実施例に係る触媒が作製された。この触媒を用いて、CO2の電気化学的な還元反応が行われた。図2は、今回の測定に用いられた電気化学セルの構造模式図を示す。この電気化学セルは、作用極21、参照極22および対極23を備えた三極セルであった。このセルでは、作製された本実施例に係る触媒が、作用極21に用いられた。参照極22には、銀/塩化銀電極(Ag/AgCl電極)が用いられた。対極23には、白金電極(Pt電極)が用いられた。この三極セルに対して、ポテンショスタット24で電位を掃引することにより、CO2の還元反応の評価が行われた。電解液27には、0.1M(0.1mol/L)の炭酸水素カリウム水溶液(KHCO3水溶液)が用いられた。また、作用極21と対極23との間は、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25で仕切られていた。CO2ガスは、セル内に配置されたガス導入管26を用いて電解液27中にバブリングさせることによって、電解液27中に導入された。
(1)最初に、窒素(N2)ガスが200ml/minの流量で電解液27中に30分間流されて、N2ガスのバブリング状態が保持された。溶液中のCO2が排除された状態で電位が掃引されて、反応電流-電解電圧曲線(C-V曲線)が描かれた。
(2)次に、配管がCO2ガスに切り替えられた。CO2ガスが、同じく200ml/minの流量で電解液27中に30分間流されて、CO2ガスのバブリング状態が保持された。電解液27がCO2で飽和した状態で電位が掃引されて、CO2存在下でのC-Vの曲線が描かれた。
状態(1)(電解液27からCO2が追い出された状態)と状態(2)(電解液27がCO2で飽和した状態)との間で、C-V曲線の差分がとられた。この差分により、CO2の還元による反応電流(以下、還元電流)が評価された。図3は、その結果を示す。この図においては、電流値(縦軸)が負となる状態が、CO2の還元反応が起こっていることを示している。図3に示されるように、本実施例による実験の結果、銀/塩化銀電極(Ag/AgCl電極)に対する電位Eが-1.0V付近で、反応電流がゼロからマイナスに推移した。すなわち、B4C粒子を有する触媒では、銀/塩化銀電極(Ag/AgCl電極)を基準に、約-1.0Vの印加電圧下でCO2の還元電流が観測された。これは、標準水素電極において、約-0.8Vで還元が始まっていることを意味する。一方、本測定系を用いて、B4Cの代わりにCu単体を有する触媒を用いて、CO2の還元実験が行われた。その結果、CO2の還元反応を得るためには、-1.1Vよりも大きな印加電圧が必要であった。この結果は、B4CがCO2還元時の過電圧の低減に有効であることを示す。
実施例1において電極基板として用いられたCPのみからなる電極を用いて、CO2の還元電流が測定された。CO2の還元電流は、実施例1と同様の方法を用いて測定された。その結果、CO2の還元電流は観測されなかった。すなわち、CPのみからなる電極は、CO2の還元に対して不活性であった。電解反応による生成物は、水素(H2)のみであった。
Claims (4)
- 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:
電気化学セルを用意する工程(a)、ここで、
前記電気化学セルは、作用極、対極、および槽を具備し、
前記槽は電解液を蓄えており、
前記作用極は炭化硼素を含有し、
前記電解液は二酸化炭素を含有し、
前記作用極は前記電解液に接しており、
前記対極は前記電解液に接しており、および
前記作用極および前記対極に負の電圧および正の電圧をそれぞれ印加し、前記二酸化炭素を還元する工程(b)。 - 請求項1の方法であって、
工程(b)においてメタン、エチレン、エタン、および蟻酸からなる群から選択される少なくとも1種の化合物が生成する。 - 請求項1の方法であって、
前記槽は固体電解質膜を具備し、
前記固体電解質は、前記作用極および前記対極との間に挟まれている。 - 請求項1の方法であって、
前記電気化学セルは管を具備し、
前記管の一端は、前記電解液の内部に配置されており、
前記工程(b)において、前記管から前記二酸化炭素が前記電解液に供給される。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2011800024513A CN102471902A (zh) | 2010-04-26 | 2011-04-07 | 还原二氧化碳的方法 |
JP2011524039A JP4907745B2 (ja) | 2010-04-26 | 2011-04-07 | 二酸化炭素を還元する方法 |
US13/276,926 US8617375B2 (en) | 2010-04-26 | 2011-10-19 | Method for reducing carbon dioxide |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-100588 | 2010-04-26 | ||
JP2010100588 | 2010-04-26 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/276,926 Continuation US8617375B2 (en) | 2010-04-26 | 2011-10-19 | Method for reducing carbon dioxide |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011135783A1 true WO2011135783A1 (ja) | 2011-11-03 |
Family
ID=44861112
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/002071 WO2011135783A1 (ja) | 2010-04-26 | 2011-04-07 | 二酸化炭素を還元する方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US8617375B2 (ja) |
JP (1) | JP4907745B2 (ja) |
CN (1) | CN102471902A (ja) |
WO (1) | WO2011135783A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013089112A1 (ja) * | 2011-12-14 | 2013-06-20 | パナソニック株式会社 | 酸塩基反応触媒、ガス拡散電極、及びco2透過装置 |
WO2019181002A1 (ja) * | 2018-03-22 | 2019-09-26 | 株式会社 東芝 | 二酸化炭素電解装置および二酸化炭素電解方法 |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170010073A1 (en) * | 2010-01-15 | 2017-01-12 | Colt Canada Ip Holding Partnership | Networked battle system with heads up display |
KR20150055033A (ko) * | 2012-09-14 | 2015-05-20 | 리퀴드 라이트 인코포레이티드 | 이산화탄소의 전기화학적 환원을 위한 방법 및 고 표면적 전극 |
CN102912374B (zh) * | 2012-10-24 | 2015-04-22 | 中国科学院大连化学物理研究所 | 一种以双极膜为隔膜的电化学还原co2电解池及其应用 |
NL2011354C2 (en) | 2013-08-29 | 2015-03-03 | Univ Leiden | Process for preparing an anode material, an electrochemical cell and a process to convert water. |
US20160270467A1 (en) * | 2015-03-18 | 2016-09-22 | Drake Munson | Slidable magnetic closure for cap |
KR101784452B1 (ko) * | 2016-03-21 | 2017-11-06 | 광운대학교 산학협력단 | 메탄올 자화균 유래 이산화탄소 환원효소를 이용한 이산화탄소의 환원방법 |
WO2018044978A1 (en) * | 2016-08-30 | 2018-03-08 | Harris Mareo Alexander | Illuminating helmet |
JP6672210B2 (ja) * | 2017-03-21 | 2020-03-25 | 株式会社東芝 | 電気化学反応装置と電気化学反応方法 |
CN108660479B (zh) * | 2018-04-29 | 2019-12-10 | 浙江工业大学 | 一种木质素基酚类化合物电催化加氢制取ka油及其衍生物的方法 |
CN111304689B (zh) * | 2018-12-11 | 2022-04-12 | 深圳先进技术研究院 | 一种二硼化钛/碳化硼复合电极及其制备方法与应用 |
CN110117794B (zh) * | 2019-05-21 | 2021-05-18 | 盐城工学院 | 一种电还原co2制甲酸盐的三室型电解池装置及其电解方法 |
CN113680358B (zh) * | 2021-07-13 | 2023-09-12 | 湖南农业大学 | 磷酸银/碳化硼复合光催化剂及其制备方法和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07188961A (ja) * | 1993-12-27 | 1995-07-25 | Hitachi Ltd | 炭酸ガス還元電極および炭酸ガス変換装置 |
JP2001089887A (ja) * | 1999-09-22 | 2001-04-03 | Iwasaki Electric Co Ltd | ダイヤモンド薄膜を用いた電解反応用電極及びそれを用いた二酸化炭素の還元方法 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3514335A (en) * | 1966-12-30 | 1970-05-26 | Gen Electric | Process and apparatus for electrochemically oxidizing alcohol to generate electrical energy |
DD137365A5 (de) | 1976-03-31 | 1979-08-29 | Diamond Shamrock Techn | Elektrode |
US4146438A (en) | 1976-03-31 | 1979-03-27 | Diamond Shamrock Technologies S.A. | Sintered electrodes with electrocatalytic coating |
JPH01313313A (ja) | 1988-06-09 | 1989-12-18 | Nkk Corp | 二酸化炭素の還元方法 |
EP0390157B1 (en) | 1989-03-31 | 2000-01-05 | United Technologies Corporation | Electrolysis cell and method of use |
JP2501576Y2 (ja) | 1990-02-27 | 1996-06-19 | 株式会社豊田自動織機製作所 | 織機における緯糸検出フィ―ラ用反射板の筬羽への取付構造 |
JPH04290526A (ja) | 1991-03-20 | 1992-10-15 | Hitachi Ltd | 炭酸ガス分離再資源化方法 |
JPH04311586A (ja) | 1991-04-09 | 1992-11-04 | Mitsubishi Electric Corp | 二酸化炭素の電解還元装置 |
FR2684091B1 (fr) | 1991-11-21 | 1994-02-25 | Pechiney Recherche | Procede de fabrication de carbures metalliques a grande surface specifique sous balayage de gaz inerte a pression atmospherique. |
JPH06290782A (ja) * | 1993-03-30 | 1994-10-18 | Sanyo Electric Co Ltd | 非水系電解質二次電池 |
US5965004A (en) | 1996-03-13 | 1999-10-12 | Sterling Pulp Chemicals, Ltd. | Chlorine dioxide generation for water treatment |
KR100907214B1 (ko) | 1999-01-12 | 2009-07-10 | 하이페리온 커탤리시스 인터내셔널 인코포레이티드 | 카바이드 및 옥시카바이드계 조성물 및 나노로드 |
JP4167775B2 (ja) | 1999-03-10 | 2008-10-22 | 三井造船株式会社 | 二酸化炭素メタン化用触媒及びその製造方法 |
JP3675793B2 (ja) | 2002-11-27 | 2005-07-27 | 興太郎 小倉 | 二酸化炭素からのエチレンの選択的製造方法 |
US20060141346A1 (en) * | 2004-11-23 | 2006-06-29 | Gordon John H | Solid electrolyte thermoelectrochemical system |
JP2006198570A (ja) | 2005-01-24 | 2006-08-03 | Sumitomo Chemical Co Ltd | 電極触媒の製造方法 |
JP2007125532A (ja) | 2005-11-07 | 2007-05-24 | Toyota Motor Corp | 触媒、支持体担持触媒および燃料電池 |
US20070160899A1 (en) * | 2006-01-10 | 2007-07-12 | Cabot Corporation | Alloy catalyst compositions and processes for making and using same |
US20100258446A1 (en) * | 2009-04-03 | 2010-10-14 | Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada | Systems including nanotubular arrays for converting carbon dioxide to an organic compound |
WO2011067873A1 (ja) | 2009-12-04 | 2011-06-09 | パナソニック株式会社 | 二酸化炭素還元方法、並びに、それに用いる二酸化炭素還元触媒および二酸化炭素還元装置 |
-
2011
- 2011-04-07 CN CN2011800024513A patent/CN102471902A/zh active Pending
- 2011-04-07 WO PCT/JP2011/002071 patent/WO2011135783A1/ja active Application Filing
- 2011-04-07 JP JP2011524039A patent/JP4907745B2/ja active Active
- 2011-10-19 US US13/276,926 patent/US8617375B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07188961A (ja) * | 1993-12-27 | 1995-07-25 | Hitachi Ltd | 炭酸ガス還元電極および炭酸ガス変換装置 |
JP2001089887A (ja) * | 1999-09-22 | 2001-04-03 | Iwasaki Electric Co Ltd | ダイヤモンド薄膜を用いた電解反応用電極及びそれを用いた二酸化炭素の還元方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013089112A1 (ja) * | 2011-12-14 | 2013-06-20 | パナソニック株式会社 | 酸塩基反応触媒、ガス拡散電極、及びco2透過装置 |
WO2019181002A1 (ja) * | 2018-03-22 | 2019-09-26 | 株式会社 東芝 | 二酸化炭素電解装置および二酸化炭素電解方法 |
Also Published As
Publication number | Publication date |
---|---|
US20120031770A1 (en) | 2012-02-09 |
JP4907745B2 (ja) | 2012-04-04 |
US8617375B2 (en) | 2013-12-31 |
JPWO2011135783A1 (ja) | 2013-07-18 |
CN102471902A (zh) | 2012-05-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4907745B2 (ja) | 二酸化炭素を還元する方法 | |
JP5017499B2 (ja) | 二酸化炭素を還元する方法 | |
Du et al. | Critical assessment of the electrocatalytic activity of vanadium and niobium nitrides toward dinitrogen reduction to ammonia | |
Hursán et al. | Morphological attributes govern carbon dioxide reduction on N-doped carbon electrodes | |
Garg et al. | Advances and challenges in electrochemical CO 2 reduction processes: an engineering and design perspective looking beyond new catalyst materials | |
Lv et al. | A highly porous copper electrocatalyst for carbon dioxide reduction | |
Zhang et al. | Tailoring the electrochemical production of H2O2: strategies for the rational design of high‐performance electrocatalysts | |
Tsujiguchi et al. | Acceleration of electrochemical CO2 reduction to formate at the Sn/reduced graphene oxide interface | |
Sher Shah et al. | Catalytic oxidation of methane to oxygenated products: recent advancements and prospects for electrocatalytic and photocatalytic conversion at low temperatures | |
JP5386533B2 (ja) | 二酸化炭素還元方法 | |
Ampelli et al. | Electrocatalytic conversion of CO 2 to produce solar fuels in electrolyte or electrolyte-less configurations of PEC cells | |
Martins et al. | In situ decoration of metallic catalysts in flow-through electrodes: application of Fe/Pt/C for glycerol oxidation in a microfluidic fuel cell | |
Luo et al. | Valorizing carbon dioxide via electrochemical reduction on gas‐diffusion electrodes | |
Li et al. | Weak CO binding sites induced by Cu–Ag interfaces promote CO electroreduction to multi-carbon liquid products | |
Zhang et al. | Nickel–nitrogen–carbon molecular catalysts for high rate CO2 electro-reduction to CO: on the role of carbon substrate and reaction chemistry | |
JP5017498B2 (ja) | 二酸化炭素を還元する方法 | |
Pagliaro et al. | Hydrogen production from the electrooxidation of methanol and potassium formate in alkaline media on carbon supported Rh and Pd nanoparticles | |
Wang et al. | Electrooxidation of acetaldehyde on carbon-supported Pt, PtRu and Pt 3 Sn and unsupported PtRu 0.2 catalysts: A quantitative DEMS study | |
Ali et al. | Recent advances in material design and reactor engineering for electrocatalytic ambient nitrogen fixation | |
Pei et al. | Thermo-Electrochemically Induced Dynamic Snδ+/Sn Interface for Direct Bicarbonate Reduction to Formate | |
JP4907748B2 (ja) | 二酸化炭素を還元する方法 | |
WO2011135781A1 (ja) | 二酸化炭素を還元する方法 | |
JP4969702B2 (ja) | 二酸化炭素を還元する方法 | |
Novoselova et al. | Electrochemical CO2 conversion | |
Zhang et al. | L-arginine-etched nickel-silver electrocatalyst for low-potential hydrogen evolution |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180002451.3 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011524039 Country of ref document: JP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11774574 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11774574 Country of ref document: EP Kind code of ref document: A1 |