JPH0336916B2 - - Google Patents
Info
- Publication number
- JPH0336916B2 JPH0336916B2 JP62167931A JP16793187A JPH0336916B2 JP H0336916 B2 JPH0336916 B2 JP H0336916B2 JP 62167931 A JP62167931 A JP 62167931A JP 16793187 A JP16793187 A JP 16793187A JP H0336916 B2 JPH0336916 B2 JP H0336916B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon dioxide
- electrode
- dioxide gas
- polymer
- layer
- 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.)
- Expired - Lifetime
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 80
- 239000001569 carbon dioxide Substances 0.000 claims description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 28
- 238000006722 reduction reaction Methods 0.000 claims description 27
- 229920001940 conductive polymer Polymers 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 239000004332 silver Substances 0.000 claims description 15
- 229910052702 rhenium Inorganic materials 0.000 claims description 14
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 150000002910 rare earth metals Chemical class 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 claims description 7
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- RMMXTBMQSGEXHJ-UHFFFAOYSA-N Aminophenazone Chemical compound O=C1C(N(C)C)=C(C)N(C)N1C1=CC=CC=C1 RMMXTBMQSGEXHJ-UHFFFAOYSA-N 0.000 claims 2
- 229930188006 polyphyllin Natural products 0.000 claims 1
- 239000007789 gas Substances 0.000 description 29
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
- 238000005868 electrolysis reaction Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- -1 saturated sodium chloride saturated calomel Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003411 electrode reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000008055 phosphate buffer solution Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- BATLCPREIURHFV-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Re+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Re+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] BATLCPREIURHFV-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、二酸化炭素ガス（以下CO2）を電解
還元するための二酸化炭素ガス還元用電極に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a carbon dioxide gas reduction electrode for electrolytically reducing carbon dioxide gas (hereinafter referred to as CO 2 ).
［従来の技術］
CO2の水溶液での電解還元反応は、水素イオン
還元反応より電極反応が起こりにくく、より負電
位で生起するため、一部の非水溶媒を除いては直
接電極で還元することができず、非常に困難であ
つた。[Conventional technology] In the electrolytic reduction reaction in an aqueous solution of CO 2 , the electrode reaction is less likely to occur than in the hydrogen ion reduction reaction, and it occurs at a more negative potential. Therefore, with the exception of some non-aqueous solvents, reduction is performed directly at the electrode. It was extremely difficult.
［発明が解決しようとする問題点］
本発明の目的は、水溶液中のCO2還元用電極を
提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to provide an electrode for reducing CO 2 in an aqueous solution.
［問題点を解決するための手段及び作用］
この問題点を解決するために、本発明の二酸化
炭素ガス還元用電極は、二酸化炭素ガスを水溶液
中で電解還元する二酸化炭素ガス還元用電極であ
つて、
導電性基体と、該導電性基体の表面を被覆する
導電性重合体層と、該導電性重合体層を被覆し、
二酸化炭素ガスの還元反応に対して触媒機能を発
現する希土類金属あるいは希土類金属錯体からな
る触媒層とを備える。[Means and effects for solving the problem] In order to solve this problem, the electrode for reducing carbon dioxide gas of the present invention is an electrode for reducing carbon dioxide gas that electrolytically reduces carbon dioxide gas in an aqueous solution. a conductive substrate; a conductive polymer layer covering the surface of the conductive substrate;
It includes a catalyst layer made of a rare earth metal or a rare earth metal complex that exhibits a catalytic function for the reduction reaction of carbon dioxide gas.
又、二酸化炭素ガスを水溶液中で電解還元する
二酸化炭素ガス還元用電極であつて、
導電性基体と、該導電性基体の表面を被覆する
導電性重合体層と、該導電性重合体層を被覆する
銀・銅・鉛・錫から選ばれる少なくとも１つの金
属からなる補助触媒層と、該補助触媒層を被覆
し、二酸化炭素ガスの還元反応に対して触媒機能
を発現する希土類金属あるいは希土類金属錯体か
らなる触媒層とを備える。 Further, there is provided an electrode for reducing carbon dioxide gas for electrolytically reducing carbon dioxide gas in an aqueous solution, which comprises a conductive substrate, a conductive polymer layer covering the surface of the conductive substrate, and the conductive polymer layer. An auxiliary catalyst layer made of at least one metal selected from silver, copper, lead, and tin to be coated, and a rare earth metal or rare earth metal that covers the auxiliary catalyst layer and exhibits a catalytic function for the reduction reaction of carbon dioxide gas. and a catalyst layer made of a complex.
［実施例］
第１図に本実施例の二酸化炭素ガス還元用電極
の構成の概念図を示す。本実施例の二酸化炭素ガ
ス還元用電極１０は、基本的に導電性基体１と導
電性重合体層２と触媒層３とから構成される。[Example] FIG. 1 shows a conceptual diagram of the structure of the electrode for reducing carbon dioxide gas of this example. The carbon dioxide gas reduction electrode 10 of this example is basically composed of a conductive substrate 1, a conductive polymer layer 2, and a catalyst layer 3.
第２図に示す三電極セル１５のように、この二
酸化化炭素ガス還元用電極１０を、飽和カロメル
電極質の基準電極１１と白金網の補助電極１２と
共に、過塩素酸ナトリウムやリン酸ナトリウム等
の電解質塩を含む水溶液１７に浸漬して、ポテン
ンシオスタツト装置１３を用いて電位を規制しな
がら電解を行うことによつて、水溶液中のCO2の
還元反応を電極表面で生起する。上記二酸化炭素
ガス還元電極１０で大規模な電解を行い生成物を
集めると、CO2還元生成物はC1化学工業等の原料
として利用できる。又、吹き込み口１６よりCO2
を吹き込みながら、このときの電解電流をＸ−Ｙ
レコーダ１４で測定すれば、CO2の濃度又は分圧
に電流値が比例することからCO2濃度又は分圧を
測定できる。 As in the three-electrode cell 15 shown in FIG. 2, this electrode 10 for reducing carbon dioxide gas is used together with a reference electrode 11 made of a saturated calomel electrode and an auxiliary electrode 12 made of a platinum mesh, such as sodium perchlorate, sodium phosphate, etc. By immersing the electrode in an aqueous solution 17 containing an electrolyte salt and performing electrolysis while regulating the potential using the potentiostat device 13, a reduction reaction of CO 2 in the aqueous solution occurs on the electrode surface. When large-scale electrolysis is performed using the carbon dioxide gas reduction electrode 10 and the products are collected, the CO 2 reduction products can be used as raw materials for C 1 chemical industry, etc. Also, CO 2 from the air inlet 16
While blowing, the electrolytic current at this time is
By measuring with the recorder 14, the CO 2 concentration or partial pressure can be measured because the current value is proportional to the CO 2 concentration or partial pressure.
導電性基体１および導電性重合体層２は電解還
元において水素過電圧が大きいものが好ましく、
さらには酸素還元の過電圧も大きいことが望まし
い。導電性基体１としては、炭素材料、白金、
金、銀、ニツケル等が利用できる。 The conductive substrate 1 and the conductive polymer layer 2 preferably have a large hydrogen overvoltage in electrolytic reduction,
Furthermore, it is desirable that the overvoltage for oxygen reduction is also large. As the conductive substrate 1, carbon material, platinum,
Gold, silver, nickel, etc. can be used.
導電性重合体層２としては、アニリン、ピロー
ル、メチルチオフエン等の電解重合層が特に好ま
しい。 As the conductive polymer layer 2, an electrolytically polymerized layer of aniline, pyrrole, methylthiophene, etc. is particularly preferable.
触媒層には、希土類金属あるいは希土類金属錯
体が望ましく、特にレニウムが望ましい。更に、
補助触媒層８があることが触媒の寿命の点から望
ましく、補助触媒には銀、銅、鉛、錫等が使用さ
れる。 A rare earth metal or a rare earth metal complex is desirable for the catalyst layer, and rhenium is particularly desirable. Furthermore,
The presence of the auxiliary catalyst layer 8 is desirable from the viewpoint of catalyst life, and silver, copper, lead, tin, etc. are used as the auxiliary catalyst.
実施例 １
(1) BPG電極の作成
ベーサル・プレーン・ピロリテイツク・グラ
フアイト（BPG、ユニオンカーバイト社製）
の板から直径１mm、長さ３mmの円柱を切り出し
て導電性基体１とし、その底面１ａにリード線
４（ウレメツト線、0.1mmφ）を導電性接着剤
６（アミコン社製：Ｃ−850−６）を用いて接
着後、テフロンチユーブ５（内径1.3mm）内に
挿入し、絶縁性接着剤７（株式会社スリーボン
ド製：TB2067）で絶縁してBPG電極を作成し
た。Example 1 (1) Creation of BPG electrode Basal plain pyrolitic graphite (BPG, manufactured by Union Carbide)
A cylinder with a diameter of 1 mm and a length of 3 mm is cut out from the plate to serve as a conductive substrate 1, and a lead wire 4 (Uremet wire, 0.1 mmφ) is attached to the bottom surface 1a with a conductive adhesive 6 (manufactured by Amicon: C-850-6). ) and then inserted into a Teflon tube 5 (inner diameter 1.3 mm) and insulated with an insulating adhesive 7 (manufactured by Three Bond Co., Ltd.: TB2067) to create a BPG electrode.
(2) 導電性重合体層の形成
BPG電極を作用電極とし、飽和塩化ナトリ
ウム飽和カロメル電極（SSCE）を基準電極と
し、白金網を対電極とする三電極式セルを用
い、
10ｍＭ…３メチルチオフエン
0.1M…TBABF4（テトラブチルアンモニウムテ
トラフルオロボレート塩）
を含むアセトニトリル溶液を電解液として、
1.9V vs SSCEで10分間定電位電解を行つて、
導電性重合体層２として約10μｍのポリ（３−
メチルチオフエン）層（以下PMT層）を形成
した。(2) Formation of conductive polymer layer Using a three-electrode cell with a BPG electrode as the working electrode, a saturated sodium chloride saturated calomel electrode (SSCE) as the reference electrode, and a platinum mesh as the counter electrode, 10mM...3-methylthiophene was used. An acetonitrile solution containing 0.1M...TBABF 4 (tetrabutylammonium tetrafluoroborate salt) was used as an electrolyte.
Perform constant potential electrolysis for 10 minutes at 1.9V vs SSCE,
As the conductive polymer layer 2, about 10 μm of poly(3-
methylthiophene) layer (hereinafter referred to as PMT layer) was formed.
(3) 補助触媒の形成
次に上記三電極式セルを用いて、２ｍＭの硝
酸銀を含む水溶液を電解液として、−0.1V vs
SSCEで１分間電解して、補助触媒層８として
銀層をPMT層表面（一部はPMT層内に形成さ
れる）に形成した。(3) Formation of auxiliary catalyst Next, using the above three-electrode cell, an aqueous solution containing 2mM silver nitrate was used as the electrolyte, and −0.1V vs.
Electrolysis was performed using SSCE for 1 minute to form a silver layer as the auxiliary catalyst layer 8 on the surface of the PMT layer (part of which was formed within the PMT layer).
尚、Agの表面濃度PAg＝５×10-5mol／cm2
(4) 触媒層の形成
次に(3)と同様にして、２ｍＭの硝酸レニウム
を含む水溶液を電解液として、−1.0V vs
SSCEで２分間定電位電解を行つて、触媒層３
としてレニウム層を形成した。 Incidentally, the surface concentration of Ag P Ag = 5 × 10 -5 mol/cm 2 (4) Formation of catalyst layer Next, in the same manner as in (3), an aqueous solution containing 2mM rhenium nitrate was used as the electrolyte, and the voltage was set at -1.0V. vs
Perform constant potential electrolysis for 2 minutes with SSCE to remove the catalyst layer 3.
A rhenium layer was formed.
尚、Reの表面濃度PRe＝５×10-5mol／cm2
以上のような工程で、本実施例の二酸化炭素ガ
ス還元用電極１０を作成した。 The electrode 10 for reducing carbon dioxide gas of this example was produced through a process in which the surface concentration of Re was P Re =5×10 −5 mol/cm 2 or higher.
実施例 ２
実施例１と同様にして、BPG電極を作成した
のち、100ｍＭのアニリンと0.5Mの硝酸ナトリウ
ム（PH1.0）を含む電解液中で、1.2V対SSCEで５
分間電解酸化を行い、導電性重合体層としてアニ
リン重合体層を被着した。以降は、実施例１と同
じに銀層レニウム層とを形成した。Example 2 After creating a BPG electrode in the same manner as in Example 1, it was heated at 1.2V vs.
Electrolytic oxidation was carried out for a minute to deposit an aniline polymer layer as a conductive polymer layer. Thereafter, a silver layer and a rhenium layer were formed in the same manner as in Example 1.
実施例 ３
導電性重合体層を、１ｍＭのメソーテトラアミ
ノポリフイリンと10ｍＭのNaCl4とを含むアセト
ニトリル電解液中で、1.8V対SSCEで60分間電解
して形成した。以降は、実施例１と同様にして銀
層とレニウム層とを形成した。Example 3 A conductive polymer layer was formed by electrolysis at 1.8 V vs. SSCE for 60 minutes in an acetonitrile electrolyte containing 1 mM meso-tetraaminopolyphyllin and 10 mM NaCl4 . Thereafter, a silver layer and a rhenium layer were formed in the same manner as in Example 1.
実施例 ４
導電性重合体層を、100ｍＭの１，２−ジアミ
ノベンゼンと0.5Mの硝酸ナトリウム（PH1.0）と
を含む電解液中で、−0.8Vから1.2V対SSCEの範
囲で50ｍＶ／secの掃引速度で30分間走査して形
成した。以降は、実施例１と同様にして銀層とレ
ニウム層とを形成した。Example 4 A conductive polymer layer was electrolyzed in an electrolyte containing 100 mM 1,2-diaminobenzene and 0.5 M sodium nitrate (PH 1.0) at 50 mV/50 mV in the range of -0.8 V to 1.2 V vs. SSCE. It was formed by scanning for 30 minutes at a sweep speed of sec. Thereafter, a silver layer and a rhenium layer were formed in the same manner as in Example 1.
比較例 １〜４
レニウム層を形成しない以外は、実施例１〜４
と同様にして、二酸化炭素ガス還元用電極を作製
した。Comparative Examples 1 to 4 Examples 1 to 4 except that no rhenium layer was formed.
In the same manner as above, an electrode for reducing carbon dioxide gas was prepared.
比較例 ５〜８
銀層を形成しない以外は、実施例１〜４と同様
にして二酸化炭素ガス還元用電極を作製した。Comparative Examples 5 to 8 Carbon dioxide gas reduction electrodes were produced in the same manner as Examples 1 to 4, except that no silver layer was formed.
実験例 １
実施例１〜４で作製した二酸化炭素ガス還元用
電極１０をPH7.4のリン酸塩緩衝溶液に浸漬し、
前述の三電極式セルを用いて、電流−電位特性を
測定した。その結果をそれぞれ第３図〜第６図に
示す。Experimental Example 1 The carbon dioxide gas reduction electrode 10 prepared in Examples 1 to 4 was immersed in a phosphate buffer solution of PH7.4,
Current-potential characteristics were measured using the three-electrode cell described above. The results are shown in FIGS. 3 to 6, respectively.
窒素ガスで脱ガスした場合に比較して、二酸化
炭素ガスが存在する溶液では−0.7V以下の電位
で還元電流が増大することから、本実施例の電極
は二酸化炭素ガスの還元反応に対して触媒として
作用することがわかつた。 Compared to the case of degassing with nitrogen gas, in a solution containing carbon dioxide gas, the reduction current increases at a potential of -0.7V or less, so the electrode of this example is effective against the reduction reaction of carbon dioxide gas. It was found that it acts as a catalyst.
また、比較例１〜４に示すレニウム層を形成し
ない構成の電極ではCO2に対する触媒作用が極め
て弱く、（導電性基体／導電性重合体層／銀層／
レニウム層）構成の電極において、この作用が顕
著となることがわかつた。 In addition, in the electrodes having a structure in which no rhenium layer is formed as shown in Comparative Examples 1 to 4, the catalytic effect on CO 2 is extremely weak (conductive substrate/conductive polymer layer/silver layer/
It was found that this effect is remarkable in electrodes having a rhenium layer structure.
更に、比較例５〜８に示した銀層を形成しない
構成の電極では、２〜３回の電解で活性が失活す
ることがわかつた。 Furthermore, it was found that the activity of the electrodes shown in Comparative Examples 5 to 8, which did not form a silver layer, was deactivated after 2 to 3 electrolysis cycles.
以上のことから、レニウムがCO2の触媒として
作用し、銀がその補助触媒として作用しているこ
とが明らかとなつた。 From the above, it has become clear that rhenium acts as a CO 2 catalyst, and silver acts as an auxiliary catalyst.
実験例 ２
実施例１〜４で作成した二酸化炭素ガス還元用
電極１０のリン酸塩緩衝液（PH7.4）中における
電流−電圧特性を、実験例１と同様の三電極セル
を用いて測定した。電流−電圧特性（例、第３
図、第６図）の二酸化炭素ガスの還元電位（対飽
和塩化ナトリウムカロメル電極：SSCE）は、約
−0.9V（３メチルチオフエン／銀／レニウム）、−
0.75V（１，２アミベンゼン／銀／レニウム）に
あつた。Experimental Example 2 The current-voltage characteristics of the carbon dioxide gas reduction electrode 10 prepared in Examples 1 to 4 in a phosphate buffer solution (PH7.4) were measured using the same three-electrode cell as in Experimental Example 1. did. Current-voltage characteristics (e.g., 3rd
The reduction potential (versus saturated sodium chloride calomel electrode: SSCE) of carbon dioxide gas (Fig. 6) is approximately -0.9V (3 methylthiophene/silver/rhenium), -
It was 0.75V (1,2-amibenzene/silver/rhenium).
以上のことから、本実施例の二酸化炭素ガス還
元用電極１０は、二酸化炭素を還元する触媒とし
て作用する。 From the above, the carbon dioxide gas reducing electrode 10 of this embodiment acts as a catalyst for reducing carbon dioxide.
したがつて、C1化学分野での触媒として、こ
の二酸化炭素ガス還元用電極１０が適用できるこ
とがわかつた。 Therefore, it has been found that this carbon dioxide gas reduction electrode 10 can be applied as a catalyst in the field of C1 chemistry.
以上述べてきたように、本実施例の二酸化炭素
ガス還元用電極は、
(a) 水溶液中で、O2やH2の影響を受けることな
く、CO2を電解還元することができる。 As described above, the carbon dioxide gas reduction electrode of the present example is capable of (a) electrolytically reducing CO 2 in an aqueous solution without being affected by O 2 or H 2 ;
(b) 電極の構成が簡単であるため、大量生産が可
能である。(b) Since the electrode structure is simple, mass production is possible.
(c) CO2（ガス）の電解還元の電流効果が高いた
め（95％以上）、電極反応生成物（COと考えら
れる）をC1化学工業のピユアな原料として利
用できる。(c) Due to the high current efficiency of electrolytic reduction of CO 2 (gas) (over 95%), the electrode reaction product (considered to be CO) can be used as a pure raw material in the C 1 chemical industry.
尚、本実施例では、補助触媒層として銀層を、
触媒層としてレニウム層を代表させて説明した
が、前述した如く、触媒層は他の希土類金属ある
いはその錯体でもよく、補助触媒層には銅、鉛、
錫等が使用されてもよい。 In this example, a silver layer was used as an auxiliary catalyst layer.
Although the rhenium layer has been described as a representative catalyst layer, as mentioned above, the catalyst layer may be other rare earth metals or their complexes, and the auxiliary catalyst layer may include copper, lead, etc.
Tin or the like may also be used.
［発明の効果］
本発明により、水溶液中のCO2還元用の二酸化
炭素ガス還元用電極を提供できる。[Effects of the Invention] According to the present invention, an electrode for reducing carbon dioxide gas for reducing CO 2 in an aqueous solution can be provided.
詳細には、
(1) 電極の構成が簡単であるため、大量生産が可
能である。 In detail, (1) The structure of the electrode is simple, so mass production is possible.
(2) CO2（ガス）の電解還元の電流効果が高いた
め（95％以上）、電極反応生成物をC1化学工業
のピユアな原料として利用できる。(2) Because the current effect of electrolytic reduction of CO 2 (gas) is high (more than 95%), the electrode reaction product can be used as a pure raw material in the C 1 chemical industry.
第１図は本実施例の二酸化炭素ガス還元用電極
の構造を示す概念図、第２図は三電極式セルおよ
び電解装置（ポテンシオスタツト）を示す図、第
３図〜第６図は実施例１〜４の二酸化炭素ガス還
元用電極の実験結果を示す図である。
図中、１……導電性基体、１ａ……底面、２…
…導電性重合体層、３……触媒層、４……リード
線、５……テフロンチユーブ、６……導電性接着
剤、７……絶縁性接着剤、８……補助触媒層であ
る。
Figure 1 is a conceptual diagram showing the structure of the electrode for reducing carbon dioxide gas in this example, Figure 2 is a diagram showing the three-electrode cell and electrolyzer (potentiostat), and Figures 3 to 6 are the actual results. It is a figure which shows the experimental result of the electrode for carbon dioxide gas reduction of Examples 1-4. In the figure, 1... conductive substrate, 1a... bottom surface, 2...
... conductive polymer layer, 3 ... catalyst layer, 4 ... lead wire, 5 ... Teflon tube, 6 ... conductive adhesive, 7 ... insulating adhesive, 8 ... auxiliary catalyst layer.
Claims (1)
酸化炭素ガス還元用電極であつて、 導電性基体と、 該導電性基体の表面を被覆する導電性重合体層
と、 該導電性重合体層を被覆し、二酸化炭素ガスの
還元反応に対して触媒機能を発現する希土類金属
あるいは希土類金属錯体からなる触媒層とを備え
ることを特徴とする二酸化炭素ガス還元用電極。 ２ 前記導電性重合体層は、アニリン重合体、
１，２−ジアミノベンゼン重合体、メチルチオフ
エン重合体、ピロール重合体、ポリフイリン類重
合体、アミノピレン重合体から選ばれる層である
ことを特徴とする特許請求の範囲第１項記載の二
酸化炭素ガス還元用電極。 ３ 前記希土類金属はレニウムであることを特徴
とする特許請求の範囲第１項記載の二酸化炭素ガ
ス還元用電極。 ４ 二酸化炭素ガスを水溶液中で電解還元する二
酸化炭素ガス還元用電極であつて、 導電性基体と、 該導電性基体の表面を被覆する導電性重合体層
と、 該導電性重合体層を被覆する銀、銅、鉛、錫か
ら選ばれる少なくとも１つの金属からなる補助触
媒層と、 該補助触媒層を被覆し、二酸化炭素ガスの還元
反応に対して触媒機能を発現する希土類金属ある
いは希土類金属錯体からなる触媒層とを備えるこ
とを特徴とする二酸化炭素ガス還元用電極。 ５ 前記導電性重合体層は、アニリン重合体、
１，２−ジアミノベンゼン重合体、メチルチオフ
エン重合体、ピロール重合体、ポリフイリン類重
合体、アミノピレン重合体から選ばれる層である
ことを特徴とする特許請求の範囲第４項記載の二
酸化炭素ガス還元用電極。 ６ 前記希土類金属はレニウムであることを特徴
とする特許請求の範囲第４項記載の二酸化炭素ガ
ス還元用電極。[Scope of Claims] 1. An electrode for reducing carbon dioxide gas by electrolytically reducing carbon dioxide gas in an aqueous solution, comprising: a conductive substrate; a conductive polymer layer covering the surface of the conductive substrate; and the conductive substrate. 1. An electrode for reducing carbon dioxide gas, comprising: a catalyst layer comprising a rare earth metal or a rare earth metal complex that exhibits a catalytic function for a reduction reaction of carbon dioxide gas; 2 The conductive polymer layer includes an aniline polymer,
The carbon dioxide gas reduction according to claim 1, characterized in that the layer is selected from a 1,2-diaminobenzene polymer, a methylthiophene polymer, a pyrrole polymer, a polyphyllin polymer, and an aminopyrene polymer. electrode. 3. The electrode for reducing carbon dioxide gas according to claim 1, wherein the rare earth metal is rhenium. 4. An electrode for reducing carbon dioxide gas that electrolytically reduces carbon dioxide gas in an aqueous solution, comprising: a conductive substrate; a conductive polymer layer covering the surface of the conductive substrate; and a conductive polymer layer covering the surface of the conductive substrate. an auxiliary catalyst layer made of at least one metal selected from silver, copper, lead, and tin; and a rare earth metal or rare earth metal complex that coats the auxiliary catalyst layer and exhibits a catalytic function for the reduction reaction of carbon dioxide gas. An electrode for reducing carbon dioxide gas, comprising a catalyst layer consisting of: 5 The conductive polymer layer includes an aniline polymer,
The carbon dioxide gas reduction according to claim 4, characterized in that the layer is selected from a 1,2-diaminobenzene polymer, a methylthiophene polymer, a pyrrole polymer, a polyphylline polymer, and an aminopyrene polymer. electrode. 6. The electrode for reducing carbon dioxide gas according to claim 4, wherein the rare earth metal is rhenium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62167931A JPS6415388A (en) | 1987-07-07 | 1987-07-07 | Electrode for reducing gaseous carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62167931A JPS6415388A (en) | 1987-07-07 | 1987-07-07 | Electrode for reducing gaseous carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6415388A JPS6415388A (en) | 1989-01-19 |
| JPH0336916B2 true JPH0336916B2 (en) | 1991-06-03 |
Family
ID=15858712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62167931A Granted JPS6415388A (en) | 1987-07-07 | 1987-07-07 | Electrode for reducing gaseous carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6415388A (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3009703B2 (en) * | 1990-05-02 | 2000-02-14 | 正道 藤平 | Electrode catalyst for carbon dioxide gas reduction |
| US8313634B2 (en) * | 2009-01-29 | 2012-11-20 | Princeton University | Conversion of carbon dioxide to organic products |
| JP5707773B2 (en) * | 2009-09-14 | 2015-04-30 | 株式会社豊田中央研究所 | Composite photoelectrode and photoelectrochemical reaction system |
| US8845877B2 (en) | 2010-03-19 | 2014-09-30 | Liquid Light, Inc. | Heterocycle catalyzed electrochemical process |
| US8721866B2 (en) | 2010-03-19 | 2014-05-13 | Liquid Light, Inc. | Electrochemical production of synthesis gas from carbon dioxide |
| US8845878B2 (en) | 2010-07-29 | 2014-09-30 | Liquid Light, Inc. | Reducing carbon dioxide to products |
| US9090976B2 (en) | 2010-12-30 | 2015-07-28 | The Trustees Of Princeton University | Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction |
| WO2012137344A1 (en) * | 2011-04-08 | 2012-10-11 | トヨタ自動車株式会社 | Device for generating mixed gas |
| WO2013031065A1 (en) | 2011-08-29 | 2013-03-07 | パナソニック株式会社 | Method for reducing carbon dioxide |
| ES2555473T3 (en) * | 2012-05-02 | 2016-01-04 | Haldor Topsøe A/S | Procedure for the production of chemical compounds from carbon dioxide |
| US8845876B2 (en) | 2012-07-26 | 2014-09-30 | Liquid Light, Inc. | Electrochemical co-production of products with carbon-based reactant feed to anode |
| US10329676B2 (en) | 2012-07-26 | 2019-06-25 | Avantium Knowledge Centre B.V. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
| US9175407B2 (en) | 2012-07-26 | 2015-11-03 | Liquid Light, Inc. | Integrated process for producing carboxylic acids from carbon dioxide |
| US8858777B2 (en) | 2012-07-26 | 2014-10-14 | Liquid Light, Inc. | Process and high surface area electrodes for the electrochemical reduction of carbon dioxide |
| US9873951B2 (en) | 2012-09-14 | 2018-01-23 | Avantium Knowledge Centre B.V. | High pressure electrochemical cell and process for the electrochemical reduction of carbon dioxide |
| JP6202886B2 (en) * | 2013-05-31 | 2017-09-27 | 株式会社東芝 | Photochemical reactor and thin film |
| JP6497276B2 (en) * | 2015-08-28 | 2019-04-10 | 株式会社豊田中央研究所 | Coating agent and method for producing catalyst-carrying electrode |
| US20230083041A1 (en) * | 2019-04-01 | 2023-03-16 | The Regents Of The University Of California | Electrochemical conversion |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5782485A (en) * | 1980-11-12 | 1982-05-22 | Matsushita Electric Ind Co Ltd | Formation of electrode |
-
1987
- 1987-07-07 JP JP62167931A patent/JPS6415388A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5782485A (en) * | 1980-11-12 | 1982-05-22 | Matsushita Electric Ind Co Ltd | Formation of electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6415388A (en) | 1989-01-19 |
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