鐵鉑氯化物與鈰鉑氯化物與釩鉑氯化物薄膜修飾電極的電化學特性以及電催化反應研究

The Characterization and Electrocatalytic Properties of Iron hexachloroplatinate and Cerium hexachloroplatinate and Vanadium hexachloroplatinate Film Modified Electrodes

林高慧(Kao-Hui Lin)

指導教授 ： 陳生明

國立臺北科技大學/工程學院/化學工程所/碩士(2005年)

https://doi.org/10.6841/NTUT.2005.00142

摘要

本研究主要分為三部分討論。鐵鉑氯化物(FePtCl6)薄膜是在KCl溶液中混合Fe2+和PtCl62-所製備而成。本實驗使用電化學石英晶體微天平(EQCM)、旋轉環－碟電極(RRDE)、紫外光/可見光吸收光譜、快速截止流動分光光譜法(Stopped-flow spectroscopy)及循環伏安法來研究鐵鉑氯化物薄膜的沉積與薄膜成長之機制，也可以觀察到鐵鉑氯化物薄膜具有一對氧化還原對。鐵鉑氯化物薄膜的沉積是在KCl（pH＝3）溶液下，PtIVCl62-還原成PtIICl64-，以及Fe3+ 還原成Fe2+。接著Fe2+跟PtIICl64-及PtIVCl62-發生化學反應所產生的。鐵鉑氯化物薄膜對NAD+和血紅素(hemoglobin)具有電催化還原反應，並使用循環伏安法及旋轉環－碟電極(RRDE)研究NAD+的電化學性質。
鈰鉑氯化物(CePtCl6)薄膜是在KCl溶液中混合Ce3+和PtCl62-所製備而成。本實驗使用電化學石英晶體微天平(EQCM)、旋轉環－碟電極(RRDE)、紫外光/可見光吸收光譜、快速截止流動分光光譜法(Stopped-flow spectroscopy)、計時安培法(chronoamperometry)及循環伏安法來研究鈰鉑氯化物薄膜的沉積與薄膜成長之機制。鈰鉑氯化物薄膜的沉積是在KCl（pH＝3）溶液下，PtIVCl62-還原成PtIICl64-，接著Ce3+跟PtIICl64-及PtIVCl62-發生化學反應所產生的。鈰鉑氯化物薄膜對NAD+、L-cystine、SO52- 和S4O62-具有電催化還原活性，並使用計時安培法研究鈰鉑氯化物薄膜對NAD+的電催化反應。
兩種型式薄膜，釩以及釩/氧化釩鉑氯化物薄膜是在KCl溶液中混合V2+和PtCl62-並透過不同電位掃描製備而成。第一種型式薄膜即釩鉑氯化物薄膜，具有一對氧化還原對的特性。第二種型態薄膜即混合釩/氧化釩鉑氯化物薄膜，具有兩對氧化還原對的特性。薄膜的沉積是在KCl（pH＝3）溶液下，PtIVCl62-還原成PtIICl64-，以及V3+ 還原成V2+。接著V2+跟PtIICl64-及PtIVCl62-發生化學反應所產生的。本實驗使用電化學石英晶體微天平(EQCM)、旋轉環－碟電極(RRDE)、紫外光/可見光吸收光譜、快速截止流動分光光譜法(Stopped-flow spectroscopy)、計時安培法(chronoamperometry)及循環伏安法來研究釩鉑氯化物薄膜的沉積與薄膜成長之機制。並且釩鉑氯化物薄膜對NAD+、S2O82-、SO52- 和S4O62-具有電催化還原活性。

關鍵字

鐵鉑氯化物 ； 鈰鉑氯化物 ； 釩鉑氯化物 ； 薄膜修飾電極 ； 菸鹼醯胺腺嘌呤二核苷酸 ； 血紅素 ； 半胱胺酸 ； 電催化

並列摘要

Iron hexachloroplatinate (FePtCl6) films have been prepared by mixing Fe2+ and PtCl62- ions in an aqueous KCl solution. The electrochemical quartz crystal microbalance (EQCM), rotating ring-disk electrode, UV–visible absorption spectroscopy, stopped-flow kinetic method and cyclic voltammetry were used to study the deposition and growth mechanism of the iron hexachloroplatinate films. The electrochemical and EQCM properties of the films indicated that a single redox process was confined to the immobilized iron hexachloroplatinate films. The deposition of an iron hexabromoplatinate film occured when PtIVCl62- was electrochemically reduced to PtIICl64- and Fe3+ to Fe2+. In the aqueous KCl pH 3.0 solution, PtIVCl62- was electrochemically reduced to PtIICl64- and the Fe2+ reacted with the PtIICl64- and PtIVCl62- species. The electrocatalytic reduction properties of NAD+, and hemoglobin were determined using the iron hexachloroplatinate films. The electrocatalytic and electrochemical reactions of NAD+ with an iron hexabromoplatinate film was investigated using the rotating ring-disk electrode method.
Cerium hexachloroplatinate (CePtCl6) films have been prepared by mixing Ce3+ and PtCl62- ions in an aqueous KCl pH 3.0 solution. The deposition of a cerium hexachloroplatinate film occured when PtIVCl62- was electrochemically reduced to PtIICl64- and Ce4+ to Ce3+.The electrochemical quartz crystal microbalance (EQCM), UV–visible absorption spectroscopy, stopped-flow kinetic method, chronoamperometry and cyclic voltammetry techniques were used to study the deposition and growth mechanism of the cerium hexachloroplatinate films. The electrochemical properties of this film indicated that a single redox process was confined to the immobilized cerium hexachloroplatinate films. In the aqueous KCl pH 3.0 solution, PtIVCl62- was electrochemically reduced to PtIICl64- and the Ce3+ reacted with the PtIICl64- and PtIVCl62-species. The reversibility of the cerium (III) hexachloroplatinate film during cycling and with changing frequency has been found good, and the Ce3+ ion exchange obviously occurred in the redox couples. The electrocatalytic reduction properties of NAD+, L-cystine, SO52- and S4O62- were determined using the cerium hexachloroplatinate films. The electrocatalysis and electrochemical reactions of NAD+ with cerium hexachloroplatinate film was measured by chronoamperometry using the rotating disk electrodes.
Two types film of vanadium hexachloroplatinate (VPtCl6) and vanadium oxide hexachloroplatinate films have been prepared directly from the mixing of V2+ and PtCl62- ions in an aqueous KCl pH 3.0 solution over different scanning potential ranges. The cyclic voltammogram of the growing type I film (assigned as a vanadium hexachloroplatinate film) is characterized by one redox couple and the type II film(assigned as a hybrid film of vanadium oxide hexachloroplatinate film and vanadium hexachloroplatinate film) exhibits two redox couples and both films were confined to the immobilized film when transferred to a pH = 3.0 aqueous solution. The deposition of a vanadium hexachloroplatinate film occured when PtIVCl62- was electrochemically reduced to PtIICl64- and V3+ to V2+. The electrochemical quartz crystal microbalance (EQCM), UV–visible absorption spectroscopy, stopped-flow kinetic method, chronoamperometry and cyclic voltammetry techniques were used to study the deposition and growth mechanism of the vanadium hexachloroplatinate films. The reversibility of the vanadium (II/III) hexachloroplatinate film during cycling and with changing frequency has been found good, and the V2+ ion exchange obviously occurred in the redox couples. The electrocatalytic reduction properties of NAD+, SO52- and S4O62- were determined using the vanadium hexachloroplatinate films. The electrochemical reactions of V3+ with vanadium hexachloroplatinate film was measured by chronoamperometry using the rotating disk electrodes.

並列關鍵字

Iron hexachloroplatinate ； Cerium hexachloroplatinate ； Vanadium hexachloroplatinate ； Film ； EQCM ； NAD+ ； Electrocatalysis

參考文獻

5 R. F. Lane, A. T. Hubbard and J. Phys. Chem., 77 (1973) 1401.

6 C. R. Martin; Rhoades, T. A., Ferguson and J. A. Anal. Chem., 54 (1982) 1639.

7 C. S. Cha and Chen, J., Liu, P. F. Electroanal. Chem., 345 (1993) 463.

8 L. M. Siperko and T. Kuwana, J. Electrochem. Soc., 130 (1983) 396.

9 S.-M. Chen, C.-M. Chan, J. Electroanal. Chem., 543 (2003), 161.