普魯士藍聚合型離子液體修飾電極於電化學分析的開發

The development of Prussian blue - polymerized ionic liquid modified screen - printed carbon electrodes for electrochemical analysis

陳以中(YI-JHUNG CHEN)

指導教授 ： 魏國佐

國立中正大學/理學院/化學暨生物化學系/碩士(2016年)

摘要

本研究主要的目的是利用離子液體作為修飾平台，將普魯士藍 ( Prussian blue, PB)修飾於電極上，開發出製程簡單、快速、且高化學與機械穩定的PB修飾電極。本研究利用兩種方式將PB修飾於網版印刷碳電極上 ( Screen printed carbon electrode, SPCE )後。第一種電極是以電沉積方式製備普魯士藍電極，實驗探討pH值對此電極的氧化還原行為，並進一步以FIA偵測過氧化氫，其校正曲線的線性範圍為10 μM - 5 mM、偵測極限為0.706 µM。
第二種電極為分散式PB電極，以FIA做過氧化氫與乙硫醇酸定量分析，其校正曲線的線性範圍分別為5 μM - 10 mM與5 μM - 2 mM，偵測極限為0.496 µM與0.575 µM。此電極在定量過氧化氫及乙硫醇酸具有不錯的靈敏度，在以FIA做連續偵測分析物測試時，也顯示出此電極高穩定度與不錯的再現性，實際應用於檢測燙髮劑中TGA含量，有不錯回收率，顯示此電極不易受基質影響 ( matrix effect )。
為了解決普魯士藍PB電極偵測乙硫醇酸時電位太大的問題，開發第三種電極為銅赤血鹽 ( Copper hexacyanoferrate, CuHCF )修飾電極。此電極可偵測不同硫醇分子，以FIA定量TGA，其線性範圍為2 μM - 2 mM、偵測極限為0.185 µM。

關鍵字

普魯士藍 ； 離子液體 ； 連續注射分析法 ； 乙硫醇酸

並列摘要

This research is to use ionic liquid as the platform for the modification of screen printed carbon electrodes ( SPCEs ) with Prussian blue. The focus is to develop a fast and easy process for the electrode modification to create the electrodes having high chemical and mechanical stability, such that a mass production of the modified electrodes can be established.
For the first method, an ionic liquid was prepared and coated to the SPCE to become a film and form ePB -PMIL-SPCE electrode. Then we explored the redox behavior of the electrode in different pH value and the characteristic of and evaluated the performance of electrode by FIA.
For the second approach, the PB powder was used to prepare ionic liquid composite electrode, dPB-PIL-SPCE. We then employed dPB -PMIL-SPCE to do quantitative analysis of hydrogen peroxide and thioglycolic acid by FIA. The linear range of the calibration curve is respectively 5 μM - 10 mM and 5 μM - 2 mM, the limit of detection ( LOD ) is 0.496 μM and 0.575 μM. The dPB-PIL-SPCE has good sensitivity in detection of hydrogen peroxide and thioglycolic acid. The electrode has great stability and reproducibility in FIA. This process is a simple and fast approach for modified electrodes and is suitable for mass-production.
To solve the problem of PB modified electrode requires a high potential to detect thioglycolic acid , we made copper hexacyanoferrate - ionic liquid modified electrode ( CuHCF-PIL-SPCE). This electrode can detect different thiols and was used to do quantitative analysis of TGA by FIA. The linear range of the calibration curve is 2 μM - 2 mM, the limit of detection ( LOD ) is 0.185 μM.

並列關鍵字

Prussian blue ； ionic liquid ； flow injection analysis ； thioglycolic acid

參考文獻

1. Brown, J., Observations and Experiments upon the Foregoing Preparation. By Mr. John Brown, Chymist, FRS. Philosophical Transactions 1724, 33 (381-391), 17-24.

2. Neff, V. D., Electrochemical oxidation and reduction of thin films of Prussian Blue. J. Electrochem. Soc. 1978, 125 (6), 886-887.

3. Buser, H.; Schwarzenbach, D.; Petter, W.; Ludi, A., The crystal structure of Prussian blue: Fe4 [Fe (CN) 6] 3. xH2O. Inorg. Chem. 1977, 16 (11), 2704-2710.

4. Lee, S.-H.; Huh, Y.-D., Preferential Evolution of Prussian Blue's Morphology from Cube to Hexapod. Bull. Korean Chem. Soc 2012, 33, 1078-1080.

5. Mortimer, R. J.; Rosseinsky, D. R., Iron hexacyanoferrate films: spectroelectrochemical distinction and electrodeposition sequence of'soluble'(K+-containing) and'insoluble'(K+-free) Prussian Blue, and composition changes in polyelectrochromic switching. J. Chem. Soc., Dalton Trans. 1984, (9), 2059-2062.