US20150096898A1 - Methanol generation device, method for generating methanol, and electrode for generating methanol - Google Patents

Methanol generation device, method for generating methanol, and electrode for generating methanol Download PDF

Info

Publication number
US20150096898A1
US20150096898A1 US14/566,742 US201414566742A US2015096898A1 US 20150096898 A1 US20150096898 A1 US 20150096898A1 US 201414566742 A US201414566742 A US 201414566742A US 2015096898 A1 US2015096898 A1 US 2015096898A1
Authority
US
United States
Prior art keywords
methanol
electrolyte solution
generation device
electrode
cathode electrode
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.)
Abandoned
Application number
US14/566,742
Other languages
English (en)
Inventor
Hiroshi HASHIBA
Masahiro Deguchi
Satoshi Yotsuhashi
Yuka Yamada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Intellectual Property Management Co Ltd
Original Assignee
Panasonic Intellectual Property Management Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Panasonic Intellectual Property Management Co Ltd filed Critical Panasonic Intellectual Property Management Co Ltd
Assigned to PANASONIC INTELLECTUAL PROPERTY MANAGEMENT CO., LTD. reassignment PANASONIC INTELLECTUAL PROPERTY MANAGEMENT CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DEGUCHI, MASAHIRO, HASHIBA, Hiroshi, YAMADA, YUKA, YOTSUHASHI, SATOSHI
Publication of US20150096898A1 publication Critical patent/US20150096898A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • 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
    • C25B3/04—
    • C25B11/0473—
    • 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
    • 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
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/097—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds comprising two or more noble metals or noble metal alloys
    • C25B9/08—
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Definitions

  • the present disclosure relates to a methanol generation device, a method for generating methanol, and an electrode for generating methanol.
  • Japanese Patent Application laid-open Publication No. 2000-254508A Japanese Patent Application laid-open Publication No. Hei 1-313313A, U.S. Pat. No. 5,234,768, Japanese Patent Application laid-open Publication No. 2004-176129A, and Y. Hori, “Modern Aspects of Electrochemistry”, 2008, vol. 42, p.p. 89-189 disclose a method for reducing carbon dioxide.
  • Japanese Patent Application laid-open Publication No. 2000-254508A and Japanese Patent Application laid-open Publication No. Hei 1-313313A disclose a method for reducing carbon dioxide using a gas phase reaction performed under high temperature.
  • U.S. Pat. No. 5,234,768 discloses a method for reducing carbon dioxide electrochemically using a phthalocyanine metal complex.
  • the present invention provides a methanol generation device for generating methanol by reducing carbon dioxide, comprising:
  • an anode electrode disposed in the container so as to be in contact with the electrolyte solution
  • an external power supply for applying a voltage so that a potential of the cathode electrode is negative with respect to a potential of the anode electrode
  • the cathode electrode includes a region of Cu 1-x Au x (0 ⁇ x ⁇ 1);
  • the anode electrode includes a region of a metal or a metal compound.
  • the present invention provides a methanol generation device having high methanol generation efficiency.
  • FIG. 1A shows a schematic view of a methanol generation device according to the present disclosure.
  • FIG. 1B shows a schematic view of a methanol generation device according to the present disclosure.
  • FIG. 1C shows a schematic view of a methanol generation device according to the present disclosure.
  • FIG. 2 is a graph showing results of the inventive example 1 and the comparative examples 1-2.
  • FIG. 1A-FIG . 1 C each show a schematic view of a methanol generation device for generating methanol by reducing carbon dioxide.
  • a methanol generation device 10 comprises a container 11 , a cathode electrode 12 , an anode electrode 13 , and an external power supply 14 . As shown in FIG. 1A , the methanol generation device 10 may have a voltage measurement device 15 and a current measurement device 16 , each of which is used to monitor how carbon dioxide is reduced.
  • An electrolyte solution 17 is stored in the container 11 .
  • the electrolyte solution 17 is a potassium chloride aqueous solution, a sodium chloride aqueous solution, a sodium hydrogen carbonate aqueous solution, or a sodium sulfate aqueous solution.
  • a potassium chloride aqueous solution or a sodium chloride aqueous solution is desirable. It is desirable that the electrolyte solution 17 has a concentration of not less than 0.05 mol/L and not more than 5.0 mol/L.
  • the cathode electrode 12 has CuAu which is a copper-gold alloy.
  • copper is referred to as “Cu” and gold is referred to as “Au”.
  • CuAu has a composition formula of Cu 1-x Au x (where 0 ⁇ x ⁇ 1).
  • CuAu is in a state of a solid solution or an intermetallic compound.
  • the solid solution means an alloy in which the elements constituting the alloy are randomly mixed at the atomic level.
  • the intermetallic compound means a compound in which the elements constituting the compound are arranged regularly at the atomic level.
  • An example of a method for fabricating CuAu in the state of the solid solution is a vacuum melting method or an arc melting method.
  • the value of x in the composition formula Cu 1-x Au x represents the composition ratio of Au to Cu, both of which constitute CuAu. It is desirable that the value of x is not less than 0.001 and not more than 0.10. In particular, it is more desirable that the value of x is not less than 0.005 and not more than 0.05.
  • CuAu which constitutes the cathode electrode 12 may contain elements other than Cu and Au, as long as the crystalline structure of CuAu is free from disturbance.
  • CuAu fabricated by a vacuum melting method or an arc melting method may contain impurities at a normally acceptable level. The crystalline structure can be observed, for example, by conducting an X-ray diffraction measurement.
  • the cathode electrode 12 may be composed only of CuAu; however, the cathode electrode 12 may have a stacked structure having a CuAu layer and a substrate for supporting the CuAu layer.
  • the cathode electrode 12 is a stacked structure obtained by forming a CuAu thin film on the substrate formed of glass or glassy carbon.
  • the cathode electrode 12 may be formed by arranging a lot of CuAu fine particles on a conductive substrate.
  • the cathode electrode 12 is not limited, as long as the cathode electrode 12 is capable of reducing carbon dioxide and generating methanol.
  • the cathode electrode 12 is in contact with the electrolyte solution 17 . More accurately, CuAu contained in the cathode electrode 12 is in contact with the electrolyte solution 17 . As long as CuAu is in contact with the electrolyte solution 17 , only a part of the cathode electrode 12 has to be immersed in the electrolyte solution 17 .
  • the anode electrode 13 has a conductive material.
  • a conductive material is carbon, platinum, gold, silver, copper, titanium, iridium oxide, or an alloy thereof.
  • the conductive material is not limited, as long as the conductive material is not decomposed through the oxidation reaction of the conductive material itself.
  • the oxidation reaction of water performed in the anode electrode 13 is independent of the reduction reaction of carbon dioxide performed in the cathode electrode 12 .
  • the material of the anode electrode 13 does not have an influence on the reaction performed on the cathode electrode 12 .
  • the anode electrode 13 is also in contact with the electrolyte solution 17 . More accurately, the conductive material included in the anode electrode 13 is in contact with the electrolyte solution 17 . As long as the conductive material is in contact with the electrolyte solution 17 , only a part of the anode electrode 13 has to be immersed in the electrolyte solution 17 .
  • the methanol generation device 10 may have a tube 18 in the container 11 . Carbon dioxide may be supplied through the tube 18 to the electrolyte solution 17 . One end of the tube 18 is immersed in the electrolyte solution 17 .
  • a methanol generation device 100 may comprise a solid electrolyte membrane 19 in the container 11 .
  • the solid electrolyte membrane 19 divides the electrolyte solution 17 into an anode-side electrolyte solution 17 L and a cathode-side electrolyte solution 17 R.
  • the solid electrolyte membrane 19 divides the inside of the container 11 into an anode container for storing the anode-side electrolyte solution 17 L and a cathode container for storing the cathode-side electrolyte solution 17 R.
  • the solid electrolyte membrane 19 prevents the anode-side electrolyte solution 17 L and the cathode-side electrolyte solution 17 R from being mixed with each other. Since the solid electrolyte membrane 19 allows passage of protons therethrough, the solid electrolyte membrane 19 connects the cathode-side electrolyte solution 17 R with the anode-side electrolyte solution 17 L electrically.
  • An example of the solid electrolyte membrane 19 is a Nafion membrane available from Du Pont. The reason why the electrolyte solution 17 is divided using the solid electrolyte membrane 19 will be described later.
  • a methanol generation device 200 may comprise a reference electrode 20 near the cathode electrode 12 .
  • the reference electrode 20 is in contact with the cathode-side electrolyte solution 17 R.
  • the reference electrode 20 is used for measuring the electric potential of the cathode electrode 12 and is connected to the cathode electrode 12 through the voltage measurement device 15 .
  • An example of the reference electrode 20 is a silver/silver chloride electrode (hereinafter, referred to as “Ag/AgCl electrode”).
  • the methanol generation device may be placed under room temperature and atmospheric pressure.
  • a voltage is applied to the cathode electrode 12 using the external power supply 14 so that the voltage is negative with respect to the potential of the anode electrode 13 .
  • a voltage exceeding a threshold for establishing the methanol generation reaction has to be applied using the external power supply 14 .
  • the threshold varies depending on the interval between the cathode electrode 12 and the anode electrode 13 , the materials constituting the cathode electrode 12 and the anode electrode 13 , and the concentration of the electrolyte solution 17 . It is desirable that the threshold is not less than 2.5 volts.
  • the potential of the cathode electrode 12 with respect to the potential of the reference electrode 20 may vary depending on the materials of the reference electrode 20 . It is desirable that the potential of the cathode electrode 12 with respect to the potential of the reference electrode 20 is not more than ⁇ 1.7 volts.
  • the cathode-side electrolyte solution 17 R and the anode-side electrolyte solution 17 L are preferably separated from each other using the solid electrolyte membrane 19 .
  • a cathode electrode formed of CuAu according to the inventive example 1 was fabricated below.
  • the composition of the CuAu plate was confirmed using an X-ray diffractometer. As a result, no peak of Au in the state of the elementary substance was observed. The formation of CuAu in which Au was dissolved in Cu was observed.
  • the cathode electrode according to the inventive example 1 was fabricated.
  • the methanol generation device shown in FIG. 1C was fabricated using the above-mentioned cathode electrode. The elements of the methanol generation device are described below.
  • Cathode electrode CuAu (Composition formula: Cu 0.9833 Au 0.0167 )
  • Electrode interval approximately 8 centimeters
  • Anode-side electrolyte solution potassium hydrogen carbonate aqueous solution having a concentration of 0.5 mol/L
  • Cathode-side electrolyte solution potassium chloride aqueous solution having a concentration of 0.5 mol/L
  • Solid electrolyte membrane Nafion membrane (available from Du Pont, Trade name: Nafion 117)
  • Carbon dioxide was supplied through a tube to the cathode-side electrolyte solution by bubbling the cathode-side electrolyte solution using a carbon dioxide gas for thirty minutes (carbon dioxide flow rate: 200 milliliters/minute).
  • the container was sealed. Subsequently, a voltage was applied using a potentiostat so that the potential of the cathode electrode was negative with respect to the potential of the anode electrode. The value of the applied voltage was controlled using the potentiostat so that the potential of the cathode electrode with respect to the potential of the reference electrode was ⁇ 1.9 volts.
  • the production amount of methanol per 1000 seconds of the electrolysis period was 3.1 ⁇ 10 ⁇ 7 mol/cm 2 .
  • the electrolysis period is equal to the period for which the voltage was applied to the cathode electrode using the external power supply.
  • the faraday efficiency of the methanol generation in the inventive example 1 was calculated. As a result, the calculated faraday efficiency was 1.42%. Note that the faraday efficiency means a ratio of the charge amount used for the generation of the reaction product to the charge amount used for all the reactions.
  • the faraday efficiency is calculated in accordance with the following formula:
  • Table 1 shows the comparison of the methanol generation amounts obtained in the inventive examples 1-7 and the comparative examples 1-2.
  • the generation amount of methanol generated in the inventive example 1 is set to be 100%.
  • Each of the generation amounts of methanol generated in the inventive examples 2-7 and the comparative examples 1-2 is indicated relatively.
  • the present disclosure provides a novel device and a novel method for generating methanol as the reduction product of carbon dioxide by using the cathode electrode having CuAu.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US14/566,742 2013-06-28 2014-12-11 Methanol generation device, method for generating methanol, and electrode for generating methanol Abandoned US20150096898A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2013-135820 2013-06-28
JP2013135820 2013-06-28
PCT/JP2014/003077 WO2014208026A1 (ja) 2013-06-28 2014-06-10 メタノール生成装置、メタノールを生成する方法及びメタノール生成用電極

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/003077 Continuation WO2014208026A1 (ja) 2013-06-28 2014-06-10 メタノール生成装置、メタノールを生成する方法及びメタノール生成用電極

Publications (1)

Publication Number Publication Date
US20150096898A1 true US20150096898A1 (en) 2015-04-09

Family

ID=52141398

Family Applications (1)

Application Number Title Priority Date Filing Date
US14/566,742 Abandoned US20150096898A1 (en) 2013-06-28 2014-12-11 Methanol generation device, method for generating methanol, and electrode for generating methanol

Country Status (3)

Country Link
US (1) US20150096898A1 (ja)
JP (1) JP5816803B2 (ja)
WO (1) WO2014208026A1 (ja)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6767202B2 (ja) * 2016-08-23 2020-10-14 古河電気工業株式会社 金属含有ナノ粒子担持電極および二酸化炭素還元装置
KR101839819B1 (ko) 2016-12-13 2018-03-19 서강대학교산학협력단 이산화탄소 환원 장치

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003213472A (ja) * 2002-01-16 2003-07-30 National Institute Of Advanced Industrial & Technology 二酸化炭素の炭化水素ガスへの電気化学的変換用電極
WO2008134871A1 (en) * 2007-05-04 2008-11-13 Principle Energy Solutions, Inc. Production of hydrocarbons from carbon and hydrogen sources
AU2008276180B2 (en) * 2007-07-13 2011-08-04 University Of Southern California Electrolysis of carbon dioxide in aqueous media to carbon monoxide and hydrogen for production of methanol
JP5321218B2 (ja) * 2009-04-21 2013-10-23 株式会社豊田中央研究所 Ｃｏ２電解装置及びｃｏ２電解生成物の製造方法
CN103348040A (zh) * 2011-08-31 2013-10-09 松下电器产业株式会社 还原二氧化碳的方法

Also Published As

Publication number Publication date
JP5816803B2 (ja) 2015-11-18
WO2014208026A1 (ja) 2014-12-31
JPWO2014208026A1 (ja) 2017-02-23

Similar Documents

Publication Publication Date Title
US20180010255A1 (en) Methanol generation device, method for generating methanol, and electrode for generating methanol
EP3358042B1 (en) Electrolysis cell and electrolytic device for carbon dioxide
US8815074B2 (en) Method for reducing carbon dioxide
WO2012046374A1 (ja) 二酸化炭素を還元する方法
KR101468782B1 (ko) 이산화탄소 환원방법 및 이를 이용한 무격막형 이산화탄소 환원장치
EP0390157B1 (en) Electrolysis cell and method of use
Chang et al. Kinetics of oxygen reduction at RuO2-coated titanium electrode in alkaline solution
US9315913B2 (en) Formic acid generation apparatus and method
JP2013129883A (ja) 二酸化炭素を還元する方法
JP6931769B2 (ja) 二酸化炭素を電気化学的に還元し、エチレンを生成する電解装置及び方法
US20150096898A1 (en) Methanol generation device, method for generating methanol, and electrode for generating methanol
US4306950A (en) Process for forming sulfuric acid
JP2017155304A (ja) 二酸化炭素電解装置
Rivera et al. Electrochemical study in acid aqueous solution and ex-situ X-ray photoelectron spectroscopy analysis of metallic rhenium surface
KR102318719B1 (ko) 이산화탄소 환원 장치를 위한 집전체, 이를 포함하는 이산화탄소 환원 장치 및 이를 이용하여 이산화탄소를 환원하는 방법
JP4907748B2 (ja) 二酸化炭素を還元する方法
JP4458362B2 (ja) ヒ素検出用電極、これを用いるセンサー及びヒ素濃度測定方法
WO2012011208A1 (ja) 二酸化炭素を還元する方法
Rethinam et al. Indirect electrooxidation of crotyl and cinnamyl alcohol using a Ni (OH) 2 electrode
Kohlmüller Anodic oxidation of ethylene glycol with noble metal alloy catalysts
JP2019218579A (ja) 化学反応装置及びそれを用いた太陽エネルギー利用システム
KR102481048B1 (ko) 알칼리-옥살산염 전환 전기화학적 공정
Hoare Some Aspects of the Reduction of Oxygen at a Platinum‐Oxygen Alloy Diaphragm
CN110612365B (zh) 电化学制造锗烷的方法
Johnson et al. The anodic oxidation of maleic acid on platinized-platinum

Legal Events

Date Code Title Description
AS Assignment

Owner name: PANASONIC INTELLECTUAL PROPERTY MANAGEMENT CO., LT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HASHIBA, HIROSHI;DEGUCHI, MASAHIRO;YOTSUHASHI, SATOSHI;AND OTHERS;REEL/FRAME:034965/0130

Effective date: 20141106

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION