JPS6076661A - Carbon electrode for electrochemical analysis - Google Patents
Carbon electrode for electrochemical analysisInfo
- Publication number
- JPS6076661A JPS6076661A JP18550683A JP18550683A JPS6076661A JP S6076661 A JPS6076661 A JP S6076661A JP 18550683 A JP18550683 A JP 18550683A JP 18550683 A JP18550683 A JP 18550683A JP S6076661 A JPS6076661 A JP S6076661A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- carbon electrode
- cpz
- oxidation
- treatment
- 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.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Electrochemical Coating By Surface Reaction (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は炭素電極を用いた電気化学分析方法に関するも
ので、特にグラッシーカーｙｊぐン電極の表面を酸化処
理することによシ著しく感度を向上させることに成功し
たグラッシーカーボン軍極に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrochemical analysis method using a carbon electrode. In particular, the present invention relates to an electrochemical analysis method using a carbon electrode. This is about carbon military poles.
サイクリックポルタンメトリーに代表される電極を用い
た電気化学分析方法は、比軟的ｍ１単な操作により酸化
性、還元性を有する物質を遣択的に検出し得るため各軸
の試料の分析に用いられているが、微蓄の業物の定量や
？ｅＩＪ速液体クロマトグラフィーの検出法としてＦｉ
ｇｉあるいは再現性か不充分であったため実用化に至っ
ていない火１１（である。このため感度を向上させるだ
めの方法の一つとして蜜、極を化学修飾し電極表面の性
質を積極的圧変える方向でいくつかの提案がなされてい
ることは周知の通シである。Electrochemical analysis methods using electrodes, such as cyclic portammetry, can selectively detect substances with oxidizing and reducing properties by a simple operation of specific soft m1. It is used for quantifying small amounts of karma? Fi as a detection method for eIJ fast liquid chromatography
It has not been put into practical use due to insufficient gi or reproducibility.For this reason, one of the methods to improve sensitivity is to chemically modify the electrode surface and actively change the properties of the electrode surface. It is well known that several proposals have been made in this direction.
本発明の目的は電気化学分析装置に使用されるカーがン
電極の表面処理、特にグラッシーカーボン電極の表面酸
化によって感度の著しく向上した電気化学分析方法を提
供することであり、特にそのための電極を提供すること
である。An object of the present invention is to provide an electrochemical analysis method in which the sensitivity is significantly improved by surface treatment of carbon electrodes used in electrochemical analyzers, particularly by surface oxidation of glassy carbon electrodes. It is to provide.
本発明者達は燐酸、クエン畿゛、酒石酸、酊酸等の緩衝
液を用いて表面耐′化処理を施したグラッシーカーボン
電極を用いてクロルゾロマシンの測定を行ったところ、
表面酸化如、 ３ｊｉ＋をしなかった電極に比較して著
しく感度の向上することを知見し、クロルゾロマシン以
外の物質にもこの方法が有効でを・ることを確認しイ本
発明に至り達したものである。The present inventors measured chlorzoromacin using a glassy carbon electrode whose surface had been subjected to a surface resistance treatment using a buffer solution such as phosphoric acid, citric acid, tartaric acid, orxic acid.
They found that surface oxidation significantly improves sensitivity compared to electrodes without 3ji+, and confirmed that this method is effective for substances other than chlorzolomasin, leading to the present invention. This is what I did.
すなわち、本発明は陽極酸化処理を飾したグラッシーカ
ーボン’ＲＥ ＠ｔ、 ｆｔ用いること全特徴とする電
気化学分析方法に関するもので、前処理溶液として燐絃
、クエン臥、泗石敞、酢酸、グリシン等の緩衝液４−用
いてグラッシーカーボン電極の表面を酸化処理する仁と
だけで未処理のグラッシー力−日−ン電極を使用した場
合に比べて１００倍もの感度の向上をもたらし得るもの
である。本発明のグラッシーカーボン電極を使用し得る
電気イ１１学分析方法の稙知には各軸のものがあげられ
るか、一般的にポーラログラフ、定電位電解法等が多い
。定電位′醒、解決は比較電極（飽和カロメル電極など
）に対して作動電極（目的とする反応が起る電極）の電
位を一定に保って電解する方法であり、この方法は作動
電様の電位を任急に設定することによって、作動’ｉｆ
ｆ、極に起る反応を分析対象にあわせて規制できるため
、柚々の共存物質下での分離、定量に適しており、電解
生成物は重量法、電拓分析法などで定ｈＩされ、電解残
液はポーラログラフイーや原子吸光法など４ｍ々の様器
分析法で分析される。第１図は定１３；位電解法に利用
されるポテンショスタットの一例を示すもので、図中、
１は作ｍ電便、２は比較電極、３は対極、４は電５池、
５．５′は増幅器、６．６’は電圧計、７は電位設定器
、８は電流計である。本発明者達は第２図に示したよう
な実験装置を使用した。図中、１゜２．３．４はそれぞ
れ第１図と同一のものでポテンショスタット系統を示す
。第２図に示した装置によシ本発明のグラッシーカーボ
ン電極を使用した電気化学分析法の一例を以下に示す。That is, the present invention relates to an electrochemical analysis method characterized by using glassy carbon 'RE@t, ft decorated with anodizing treatment, and the pretreatment solution includes phosphor, citric acid, silica, acetic acid, and glycine. Oxidizing the surface of a glassy carbon electrode using a buffer solution such as 4-4 can improve sensitivity by a factor of 100 compared to using an untreated glassy carbon electrode. . The electrical analysis methods that can use the glassy carbon electrode of the present invention include those for each axis, and in general, there are many methods such as polarography and constant potential electrolysis. The solution to constant potential is to conduct electrolysis by keeping the potential of the working electrode (the electrode where the desired reaction occurs) constant relative to the reference electrode (such as a saturated calomel electrode). By setting the potential at will, actuation'if
f. Since the reaction occurring at the pole can be regulated according to the target of analysis, it is suitable for separation and quantification in the presence of coexisting substances, and the electrolyzed product can be determined by gravimetric method, electroplating analysis method, etc. The residual electrolyte will be analyzed using a 4-m-long porosity analysis method such as polarography or atomic absorption spectrometry. Figure 1 shows an example of a potentiostat used in the constant 13° position electrolysis method.
1 is a made electric mail, 2 is a comparison electrode, 3 is a counter electrode, 4 is a battery 5,
5.5' is an amplifier, 6.6' is a voltmeter, 7 is a potential setting device, and 8 is an ammeter. The inventors used an experimental apparatus as shown in FIG. In the figure, 1.degree.2.3.4 are the same as in FIG. 1, respectively, and indicate the potentiostat system. An example of an electrochemical analysis method using the glassy carbon electrode of the present invention using the apparatus shown in FIG. 2 is shown below.
実施例 クロルプロマジン（ｃｐｚ）の定ｔＣＰｚの定
量はサイクリックポルタンメトリー法でＣＰＺの酸化ピ
ーク電流値を測定することによって行なった。グラッシ
ー力−？ン電極はアルミナ（粒子径０３μｍ）で鏡面状
に研励し、これを前処理用支持塩浴液中で任意の電位（
＋１゜３〜＋２． ＯＶ□、５ＣＥ）で定電位電解処理
を行なうことにより表面酸化処理電極を調製した。この
結果、グラッシー力−４？ン電極に表面酸化処理を施す
ことによ、６ｃｐｚＬ７）ｙ化電流値が著しく増大する
ことが誌められた（第３図）。電流増大効果はグラッシ
ーカーボン電極の処理条件にょシ大きく異なシ、前処理
溶液として詐取、クエン酸、酒石酸、 ＃販、グリシン
の各緩衝液を用い、加電圧ならびに処理時間を変えて電
解処理を行なった結果、０．１Ｍ、ｐｌｉ６．５の燐酸
緩衝液中で＋１．６Ｖ、１０分間の処理を行なった場合
にｃＰｚノ欧化電流値の最大値が得られた。この時のｃ
Ｐｚの酸化電流値は未処理電極（表面研胎のみ）の電極
を用いた場合（涼４しＩＡ）に比較して約１００倍大き
く、ＣＰＺの検出限外ｔよ２Ｘ１０””ＭＫ達した。擾
ｆＣＣＰＺ 磁度５ Ｘ １０−’ Ｍ 〜５ Ｘ ｌ
０−５Ｍの範囲において′電流値とｃｐｚ 斜度との
間に面側性が酩められた（第４図Ｂ）。また一旦処理さ
れたグラッシーカーボン電＋りは無滴水中に保存するこ
とにより長期間の灰抜使用に耐え、杓現住のめるＣＰｚ
定セｊ結呆が得られることも知られた。 ４
このように次面酸化処３！１８會施されたグラッシーカ
ーボン′東極を使用することによって、従来法よりも著
しく靭皮の向上した電気化学分析法を提供することが可
能となったものである。Example The constant tCPz of chlorpromazine (cpz) was determined by measuring the oxidation peak current value of CPZ using a cyclic portammetry method. Glassy power? The electrode is made of alumina (particle size: 03 μm) polished to a mirror-like surface, and then heated to an arbitrary potential (
+1°3~+2. A surface oxidation-treated electrode was prepared by performing constant potential electrolytic treatment at OV□, 5CE). As a result, Glassy force -4? It was observed that the 6cpzL7) y-oxidation current value increased significantly by subjecting the surface oxidation treatment to the 6cpzL7) electrode (Figure 3). The current increasing effect depends on the treatment conditions of the glassy carbon electrode.The electrolytic treatment was carried out using citric acid, tartaric acid, #sales, and glycine buffers as pretreatment solutions, and varying the applied voltage and treatment time. As a result, the maximum value of the cPz Europeanization current value was obtained when treatment was performed at +1.6 V for 10 minutes in a 0.1 M, pli 6.5 phosphate buffer. c at this time
The oxidation current value of Pz was about 100 times larger than that when using an untreated electrode (surface sensitization only) (cool 4 and IA), and reached the detection limit of CPZ of 2×10""MK.擾fCCPZ Magnetism 5 X 10-' M ~ 5 X l
In the range of 0-5M, there was a plane side effect between the current value and the cpz slope (Fig. 4B). In addition, once treated glassy carbon batteries can withstand long-term ash removal by being stored in drip-free water, making them suitable for CPz use.
It is also known that certain results can be obtained. 4 By using glassy carbon 'Tokyoku' which has been subjected to 3.18 subsurface oxidation treatments in this way, it has become possible to provide an electrochemical analysis method with significantly improved bast compared to conventional methods. It is.
第１図は定電位電解法に利用される鱈？テンショスタッ
トの説明図、＠２図は本発明に使用した装置の説明図、
第３図は１．０Ｘ１０ ＭＣＰＺをサイクリ、クボルワ
ンメトリーによシ測定した結果を示すもので０．１ Ｍ
燐酸緩衝液中でＡは＋１．６Ｖ、１０分間、Ｂは同５分
間、Ｃは０分間電他処理したものである。縞４図は表面
酸化処理電極によるＣＰｚの検゛−縁を示したものでＡ
は未処理のものを、Ｉｌｊ：燐酸緩衝液中で＋１，６Ｖ
、１０分間処理したものを示す。
１・・・作動電極 ５，５′・・増幅器２０．６比較電
極 ６．６””電圧計
３・・・対極 ７・・・電位設定器
４ ・・・篭 池 Ｂ ・・・ 電流ｊ干出 願 人
日本分光工業株式会社
代 理 人 丸 山 辛 雄
第 ２ 図
第 Ｌ 図
第 ３ 図
第４図Figure 1 shows cod used in constant potential electrolysis method. An explanatory diagram of the tensionostat, Figure @2 is an explanatory diagram of the device used in the present invention,
Figure 3 shows the results of measuring 1.0X10 MCPZ by cyclic and Kuboruwanometry.
In a phosphate buffer, A was subjected to voltage treatment at +1.6 V for 10 minutes, B for 5 minutes, and C for 0 minutes. Figure 4 shows the detection edge of CPz using the surface oxidized electrode.
is the untreated one, Ilj: +1,6V in phosphate buffer
, those treated for 10 minutes are shown. 1... Working electrode 5,5'... Amplifier 20.6 Reference electrode 6.6'' Voltmeter 3... Counter electrode 7... Potential setting device 4... Basket B... Current j dry applicant
JASCO Corporation Agent Shino Maruyama Figure 2 Figure L Figure 3 Figure 4
Claims (1)
化学分析用グラッシーカーーζン電極。A glassy carn electrode for electrochemical analysis characterized by anodized surface treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18550683A JPS6076661A (en) | 1983-10-04 | 1983-10-04 | Carbon electrode for electrochemical analysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18550683A JPS6076661A (en) | 1983-10-04 | 1983-10-04 | Carbon electrode for electrochemical analysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6076661A true JPS6076661A (en) | 1985-05-01 |
Family
ID=16171968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18550683A Pending JPS6076661A (en) | 1983-10-04 | 1983-10-04 | Carbon electrode for electrochemical analysis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6076661A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996023215A1 (en) * | 1995-01-26 | 1996-08-01 | Universiteit Gent - Vakgroep Textielkunde | Sensor electrode for continuous measurement of hydrogen peroxide concentration |
| EP1055926A3 (en) * | 1999-05-28 | 2001-11-14 | Kabushiki Kaisha Meidensha | Electrochemical assay using an electroconductive diamond-coated electrode, and electrochemical assay system based thereon |
| CN104677973A (en) * | 2015-03-13 | 2015-06-03 | 武汉工程大学 | Method for measuring octyl phenol by virtue of electrochemical sensor |
-
1983
- 1983-10-04 JP JP18550683A patent/JPS6076661A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996023215A1 (en) * | 1995-01-26 | 1996-08-01 | Universiteit Gent - Vakgroep Textielkunde | Sensor electrode for continuous measurement of hydrogen peroxide concentration |
| BE1009053A5 (en) * | 1995-01-26 | 1996-11-05 | Universiteit Gent Vakgroep Tex | MEASURING PROBE SUITABLE FOR CONTINUED TO MEASURE HYDROGEN CONCENTRATION IN A bleaching bath. |
| EP1055926A3 (en) * | 1999-05-28 | 2001-11-14 | Kabushiki Kaisha Meidensha | Electrochemical assay using an electroconductive diamond-coated electrode, and electrochemical assay system based thereon |
| CN104677973A (en) * | 2015-03-13 | 2015-06-03 | 武汉工程大学 | Method for measuring octyl phenol by virtue of electrochemical sensor |
| CN104677973B (en) * | 2015-03-13 | 2017-04-26 | 武汉工程大学 | Method for measuring octyl phenol by virtue of electrochemical sensor |
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