JPS58160860A - Electrode for use in electrochemical examination and analysis - Google Patents
Electrode for use in electrochemical examination and analysisInfo
- Publication number
- JPS58160860A JPS58160860A JP4341482A JP4341482A JPS58160860A JP S58160860 A JPS58160860 A JP S58160860A JP 4341482 A JP4341482 A JP 4341482A JP 4341482 A JP4341482 A JP 4341482A JP S58160860 A JPS58160860 A JP S58160860A
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- electrode
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- diamond
- ions
- implanted
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Analysing Materials By The Use Of Radiation (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
本発ｕＡＵ電気化学的試験・分析用電極に関し、詳しく
にイオン注入にょる導電性ダイヤモンドから成る電気化
学的試験・分析用の’ｉｔ極を提供することな目的とす
る。[Detailed Description of the Invention] Regarding the uAU electrochemical test/analysis electrode of the present invention, it is specifically an object of the present invention to provide an 'it electrode for electrochemical test/analysis made of conductive diamond by ion implantation. .
電気化学的試験・分析用の指示電極としては、目的とす
る＃存物質に対しては電気化学反応性を南し、浴媒や支
持電解−に対してはより安定な電極材料であることが要
求される。このことから、化学的に安定な賞金風、例え
ば白金、金、水銀、Ｌ・よび非金織で碑電体で必る脚素
材（グラファイト、］苧イロリティック・グラファイト
、グラシーカ−カン等）がこれまで良く用いられている
。As an indicator electrode for electrochemical testing and analysis, it is necessary to use an electrode material that has low electrochemical reactivity toward the target substance and is more stable toward bath media and supporting electrolytes. required. For this reason, chemically stable materials such as platinum, gold, mercury, L, and non-gold woven leg materials (graphite, iriolitic graphite, glassy carcan, etc.), which are necessary for inscriptions, have been developed. It has been used well so far.
これらの電極を評価する上では、（１１溶媒に対する安
定性、例えば、水浴猷に対しては、電解による水素発生
および＃巣発生（または、金属の溶出）の生じない電ｔ
１／領域（安定′亀位領破と呼ぶ）の広さ、（２Ｉその
電位領域における残余電流（ノイズと艶なされるーく−
スミ流）の低さが本喪な目安となる。こ＼で１１１の安
定電位領域の広さは、より広範囲の酸化還元電位を有す
る物質の電極反応試験、並びにそれらの電気化学分析を
可能にすることな意味し、（２）の残余電流の低さは、
より高精度、尚６紋な分析を可能とし、栴現性に優れた
測定を可能とするものである。In evaluating these electrodes, (11) stability against solvents, for example, for water baths, it is important to
1/width of the region (referred to as the stability region), (2I residual current in that potential region (noise and polished area)
A low score (Sumi style) is a good indicator of honmo. The wide stable potential region of 111 means that it enables electrode reaction tests of substances with a wider range of redox potentials as well as their electrochemical analysis, and (2) low residual current. Well,
This makes it possible to perform more precise and detailed analysis, and to perform measurements with excellent reproducibility.
本発明者等は、ダイヤモンドが絶縁材料ではあるが硬さ
、緻密さ、平面性、耐蝕性などの表面性状の安定性の非
常に優れた物性を有することに着目し、それらの物性を
損なわずに導電性を付加することにより電気化学的試験
・分析用の′に１極として利用できるのではないかと考
え、鋭意開発研究な拭みた。その結果、イオン注入によ
りダイヤモンドの表層に導電性を付加したダイヤモンド
電極が、＾Ｕ記した従来の固体電極に比べ漫れた特性を
南−イることを見出した。The present inventors focused on the fact that although diamond is an insulating material, it has very excellent physical properties such as hardness, density, flatness, corrosion resistance, and other stable surface properties. We thought that by adding conductivity to the material, it could be used as a single pole for electrochemical testing and analysis, and we conducted extensive research and development. As a result, they found that a diamond electrode, in which conductivity was added to the surface layer of diamond through ion implantation, had more extensive characteristics than the conventional solid electrode described above.
本発明は上記知艷に基づくものであって、イオン注入に
より導電性を付加したダイヤモンドから成る電気化学的
試験・分析用電極である。The present invention is based on the above-mentioned knowledge, and is an electrode for electrochemical testing and analysis, which is made of diamond which has been made conductive by ion implantation.
以下、実施例により本発明な眸しく説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
イオン注入装ｖ（２θθＫｅＶ 、イ＃−’＃ｉ ：
ＲＦ型又はニールセン型）を用い、５×ダ×２ ｍの
ダイヤモンド試別に、チタン（４８ｒｔ＋ ）、アルゴ
ン４０ ＋
（Ａｒ ）、チッ素（Ｎ）、（Ｎ２）％アルミニラｂ（
”、４／＋）、１ｌｌ（”Ｏ” ）％ 亜鉛（６４Ｚｎ
）、ヒ素（＾Ｓ ）のイオンを注入した。各々の注入に
用いた物質及び実施条件を表／に示す。Ion implantation device v (2θθKeV, i#-'#i:
RF type or Nielsen type), titanium (48rt+), argon 40+ (Ar), nitrogen (N), (N2)% alumina b(
”, 4/+), 1ll (“O”)% Zinc (64Zn
), arsenic (^S) ions were implanted. The materials used for each injection and the operating conditions are shown in Table/.
表 ／
表−はイオン注入したダイヤモンドの抵抗率と注入時の
電流値を示す。Table / Table - shows the resistivity of ion-implanted diamond and the current value during implantation.
表 −
図／は抵抗率とイオン注入電の依存性を示すグラフであ
る。Table - Figure/ is a graph showing the dependence of resistivity and ion implantation charge.
表−および図／からも明らかなように１イオン糧に＠係
なくいずれも抵抗率龜注入蓄に依存し、注入蓋がｌ〜Ｊ
Ｘ ／ ０１′イオン／♂ 以上ではソ一定（飽和値
）となり、その時の抵抗率値は／〜Ｓ×７０−１２鋼で
Ｔｏシ、導電性を有している。As is clear from the table and figure, the resistivity depends on the injection storage irrespective of the ion source, and the injection lid is
At X/01' ions/♂ or more, the value becomes constant (saturation value), and the resistivity value at that time is /~Sx70-12 steel, which has conductivity.
上［ｉＣで得られた２４電性ダイヤモ／ドのうち、アル
ゴンイオン（＾、＋ ）と亜鉛イオン（Ｚｎ” ）を壮
大したダイヤモンド電極（Ｄｌａ −ＡｒおよびＤｌａ
−Ｚｎ と略記）【選択し、これらと従来のグラシー
カ−が／電４ｋ（ａｃ と給配ンについて、０．７Ｍ
（ＩｌＩＣ＃ナトリウム水浴液中でベース電流を比軟測
定した結果、図−を得た。Above [Among the 24-electrode diamonds obtained by iC, diamond electrodes (Dla-Ar and Dla
-Zn) [Selected, these and conventional glass seeker / electric 4k (ac and distribution, 0.7M
(As a result of specific softness measurement of base current in IlIC# sodium water bath solution, Figure - was obtained.
１コ中、正の加電圧で見られる電流の増加偽夛は、水の
電解に伴う酸素発生、負の加電圧での電流増加但）ｔま
水素抛生に対応する。この結果、特にυ１ａ−Ｚｎ ｆ
よ＠）の電Ｆｔ、増加が看るしく少なく、また、千ｔｌ
ｉｆｔｔｉ（±／Ｖの安定亀位愉域）でのペース電流（
恢余亀ａ）も小きく電気化学的試験・分析用の指示電極
として優れていることが解る。In this case, the increase in current seen at a positive applied voltage corresponds to the generation of oxygen accompanying water electrolysis, and the increase in current at a negative applied voltage, however, corresponds to the production of hydrogen. As a result, especially υ1a−Zn f
The increase in electricity Ft of Yo@) is noticeably small, and the increase in electric Ft is noticeably small.
Pace current at ifti (stable range of ±/V) (
It can be seen that the a) is also small and excellent as an indicator electrode for electrochemical testing and analysis.
次に、これらの１１極を用い、代表的な電極反応性ｆ６
存物質である（ Ｆｓ” （ＣＮ） 、 ）４−におけ
るＰ”ａ （ｆｌ ＃Ｐａ（Ｉｌ＋ｔの反応性について
比較した結果を図３に示す。同図は！；ｒｒＭ Ｋ４
（Ｆｎ（ＣＮ） ４ ） を含む０．７Ｍ硫酸ナトリ
ウム水浴液を用いて測定したサイク１ノック・がルクモ
グラムである。Ｄｌａ −ＺｎとＤｉａ −Ａｒ Ｆｉ
ｌ”！ソ等しい反応性を示す。ＧＣでは波高値がや＼高
いが、酸化（１，Ｍｌ）および還元（１＜θ）における
電流ピーク間の電位差（ΔＥ）ｔｌ、ダイヤモンド電極
に比べＧＣで大きく、ダイヤモンド電極ｌ極において反
応の可逆性（反応速度）が＾いことを示している。Next, using these 11 electrodes, a typical electrode reactivity f6
Figure 3 shows the results of a comparison of the reactivity of P''a (fl #Pa(Il+t) in (Fs'' (CN), )4-, which is an existing substance.
(Fn(CN) 4 ) is measured using a 0.7 M sodium sulfate aqueous bath solution. Dla-Zn and Dia-Ar Fi
The peak value is slightly higher in GC, but the potential difference (ΔE)tl between the current peaks in oxidation (1, Ml) and reduction (1<θ) is smaller in GC than in the diamond electrode. This is large, indicating that the reversibility (reaction rate) of the reaction is high at the diamond electrode.
また、浴液中のカドミウムイオンを電析させ、さらにそ
れを島田させる過程を繰返させるサイクリックＮｋｌム
メトリ−（ＳＱ ｍＶＳ−’１．ｘｓ℃で銅１ｊ達）の
結果は、ダイヤモンド電極、特にＯｂ蟲−Ｚｎ にお
いて、電流−電圧曲縁の゛＾現性か高く、ｔｒ出したカ
ドミウムの電極表面での吸蔵等、６堝性を低下させる嶽
因の少ないことが酩められた。In addition, the results of cyclic Nkl measurement (SQ mVS-'1.xsC, copper 1j reached), in which the process of electrodepositing cadmium ions in the bath liquid and then repeating the Shimada process, show that diamond electrodes, especially Ob In the case of Zn, it was found that the current-voltage curve had a high degree of susceptibility, and there were few causes of deterioration of the conductivity, such as occlusion of truncated cadmium on the electrode surface.
これらの結果は、本発明の１１極が、イオン注入によシ
ダイヤモンド表層の結晶を破壊して非晶質ｌｌ１ｅ集と
した導電性ダイヤモンド電極であｐ１ダイヤモンド表向
の硬さ、緻密さ、平面性、耐蝕性等表面性状の安定性に
優れていることに起因するものと考えられる。These results demonstrate that the 11 electrodes of the present invention are conductive diamond electrodes that are made into amorphous ll1e by destroying the crystals on the diamond surface layer through ion implantation, and the hardness, density, and flatness of the p1 diamond surface are improved. This is thought to be due to the excellent stability of surface properties such as hardness and corrosion resistance.
以上評述し九ように、本発明のイオン注入による導電性
ダイヤモンド電極は、（＋）＊定電位領域の広さ、（Ｉ
ｌ）そこでの残余電流の低さ、（船溶存物質の電極反応
性の＾さ、ＱｖＪ反応ｖｋ返し再塊性の良さ等、電気化
学的試験・分析用指示を極として優れた特性を有する。As described above, the conductive diamond electrode by ion implantation of the present invention has (+)*width of constant potential region, (I
l) It has excellent properties for use in electrochemical testing and analysis, such as low residual current, high electrode reactivity of ship-dissolved substances, and good QvJ reaction vk re-agglomeration properties.
なお、本実施例では、Ｄｌａ−Ｚｎと０１畠Ａ「電極を
例にとって説明し九が、他のイオン槓を注入し次ダイヤ
モンド電極の場合も表コおよび図／からも明らかなよう
に抵抗率１１１は１０−Ωσ＠良でいずれも−Ｊｌｉｌ
縦の導電性を有しているので、亀気化字的＃Ａ、ｋ・分
析用指示電極として同軸な特性が得られることは勿論で
ある。In addition, in this example, the explanation will be given using Dla-Zn and 01 Hatake A "electrodes" as an example, but in the case of diamond electrodes as well, the resistivity will change as is clear from Table 1 and Figure 9. 111 is 10-Ωσ@good and both are -Jlil
Since it has vertical conductivity, it goes without saying that coaxial characteristics can be obtained as an indicator electrode for #A, K analysis.
図／は本発明の実施例で得られた抵抗率とイオン注入量
の関係を示すグラフ、図コは本発明の実施例で得られ友
ダイヤモンド’ＩＩＩ極とグラシーカ−がン１１Ｆ極と
のベースｔｆｉを比較測定し九グラフ、図３は本発明の
実施例で得られ九ダイヤモンド°電極とグラジ−カーボ
ン電極とｔ比較測定したヤイクリック・ゲルタモグラム
を示すグラフ。
特許出願人：理化学研死所
馬２図
電極量４Ｊ Ｅ （司陀和りロメル電極）／Ｖ馬３図
電柵電位Ｅ（対飽和カロメル電極）／ＶアFigure / is a graph showing the relationship between resistivity and ion implantation amount obtained in an example of the present invention, and Figure (C) is a graph showing the relationship between the resistivity and ion implantation amount obtained in an example of the present invention. FIG. 3 is a graph showing a Y-Click gel tamogram obtained by comparing tfi with a 9-diamond electrode and a Grazi-carbon electrode obtained in an example of the present invention. Patent applicant: RIKEN Mortuary Uma 2 Electrode amount 4J E (Shidawari Romel electrode) / V Uma 3 Electric fence potential E (vs. saturated calomel electrode) / V A
Claims (1)
ドから成る電気化学的試験・分析用ＩＩ！Ｌ極。 （２１前記のイオンがＡ「 などの不活性がスイオン、
Ｏなとの活性がスイオン、 Ｚｎ などの金属イオン
であることを特徴とする特許請求の範囲第（１１項に記
載の電気化学的試験・分析用電惨。 １３１ 前記のイオン注入量が５×１０１５イオン／
ｃｍ２以上であることを特徴とする特許請求の−ｉ囲第
ｉｌｌ ｉＡに記載の電気化学的試験・分析用１１を極
。[Claims] 01 Electrochemical test/analysis II made of diamond with conductivity added by ion implantation! L pole. (21 The above ion is A", the inert is sion,
Claim No. 11, characterized in that the activity with oxygen is metal ions such as sulfur ions and Zn (electrochemical test/analysis electrolyte according to claim 11). 1015 ions/
11 for electrochemical testing and analysis according to item iA of the claims, characterized in that the electrode has a diameter of cm2 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4341482A JPS58160860A (en) | 1982-03-18 | 1982-03-18 | Electrode for use in electrochemical examination and analysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4341482A JPS58160860A (en) | 1982-03-18 | 1982-03-18 | Electrode for use in electrochemical examination and analysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58160860A true JPS58160860A (en) | 1983-09-24 |
| JPH0222900B2 JPH0222900B2 (en) | 1990-05-22 |
Family
ID=12663060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4341482A Granted JPS58160860A (en) | 1982-03-18 | 1982-03-18 | Electrode for use in electrochemical examination and analysis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58160860A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001203429A (en) * | 2000-01-19 | 2001-07-27 | Japan Fine Ceramics Center | Diamond wiring substrate and its manufacturing method |
| WO2001098766A1 (en) * | 2000-06-21 | 2001-12-27 | Center For Advanced Science And Technology Incubation, Ltd. | Method for determining concentration of xanthin type compound and sensor for use therein |
| WO2002025261A1 (en) * | 2000-09-21 | 2002-03-28 | Center For Advanced Science And Technology Incubation, Ltd. | Diamond electrode for measuring glucose concentration, and measuring method and apparatus employing the same |
| JP2006098281A (en) * | 2004-09-30 | 2006-04-13 | Keio Gijuku | Electrode for electrochemical analysis/measurement, electrochemical analysis/measurement device, and electrochemical analysis/measurement method of inspected material concentration |
| US8338323B2 (en) | 2010-03-09 | 2012-12-25 | Permelec Electrode Ltd. | Electrode for electrochemical reaction and production process thereof |
| WO2013069711A1 (en) | 2011-11-09 | 2013-05-16 | Shinshu University | Electrode for electrochemistry and manufacturing method for the same |
| JP2020150883A (en) * | 2019-03-22 | 2020-09-24 | 国立研究開発法人物質・材料研究機構 | Microbial culture method, microbial culture device, and carbon dioxide reduction device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0718900U (en) * | 1993-09-21 | 1995-04-04 | ターナー色彩株式会社 | Storage case for paints and paints |
-
1982
- 1982-03-18 JP JP4341482A patent/JPS58160860A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001203429A (en) * | 2000-01-19 | 2001-07-27 | Japan Fine Ceramics Center | Diamond wiring substrate and its manufacturing method |
| WO2001098766A1 (en) * | 2000-06-21 | 2001-12-27 | Center For Advanced Science And Technology Incubation, Ltd. | Method for determining concentration of xanthin type compound and sensor for use therein |
| WO2002025261A1 (en) * | 2000-09-21 | 2002-03-28 | Center For Advanced Science And Technology Incubation, Ltd. | Diamond electrode for measuring glucose concentration, and measuring method and apparatus employing the same |
| JP2006098281A (en) * | 2004-09-30 | 2006-04-13 | Keio Gijuku | Electrode for electrochemical analysis/measurement, electrochemical analysis/measurement device, and electrochemical analysis/measurement method of inspected material concentration |
| US8338323B2 (en) | 2010-03-09 | 2012-12-25 | Permelec Electrode Ltd. | Electrode for electrochemical reaction and production process thereof |
| WO2013069711A1 (en) | 2011-11-09 | 2013-05-16 | Shinshu University | Electrode for electrochemistry and manufacturing method for the same |
| JP2020150883A (en) * | 2019-03-22 | 2020-09-24 | 国立研究開発法人物質・材料研究機構 | Microbial culture method, microbial culture device, and carbon dioxide reduction device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0222900B2 (en) | 1990-05-22 |
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