黏土修飾電極於近幾年受到極大的重視，然而將黏土應用於光閥與生
物感測之研究卻相當少。本篇論文將利用黏土的多孔性、催化性、吸附性
、離子交換性、以及表面積等特點作為電極修飾劑，進而應用於光整流與
葡萄糖感測。 根據EDX 光譜分析，
大部分黏土礦物如蒙特石(Mont. K10) 含鐵量極為豐富，且於大部分多鐵
黏土中的 Fe3+ 和 Fe2+ 具有電化學活性，隨 pH 下降而增大。此外，多
鐵黏土修飾電極具有光活性，在不同pH 環境下，可產生不同的光電效應
。例如當黏土電極表面存在2-pyridylcarboxylic acids (( ab,max 260
nm)時，可將特定波長如260 nm的光訊轉換成交流電子訊號。其訊號的感
應具有相當好的再現性，且感應時間(T90)低於10 秒。
另一方面，利用多鐵性黏土製備而成的化學修飾電極亦可應用於過氧化氫
的催化反應，例如將Mont. K10黏土與Ru(CN)64- 進行錯合反應後，可在
黏土表面上製成一高活性修飾電極材料 Fe4[Ru(CN)6]3 (Ruthenium
purple)。其不僅可催化過氧化氫之分解，更可應用於葡萄糖感測。

本論文利用薄層電極(Thin-Layer Electrocell)及ErCi' 反應機制，確定
Fe4[Ru(CN)6]3 與過氧化氫的反應速率常數 (kf) 約為183(M-1s-1)，且
其催化分解效率隨 pH 值增加而降低。同時，我們也利用此一電極材料對
維他命C 進行偵測；實驗顯示其反應速率常數約為30(M-1s-1)。
受到多鐵黏土對過氧化氫的催化啟示，本論文也嘗試利用Ruthenium
purple 黏土修飾電極來發展葡萄糖感測器。研究顯示Ruthenium purple
黏土修飾電極不僅可對葡萄糖進行偵測(電位約為0.18 V vs. SCE)更可達
到10-5 M的偵測極限。同時，此電極並可免於維他命C或尿酸，或是氧氣
之干擾。

Although clay modified electrodes have been explored and
utilized for a great number of research, the applications of
clays in optical rectification or chemical sensing are
relatively rare. In this thesis, we are conducting a series of
fundamental studies on the photochemical and electrochemical
properties for iron-rich clay minerals and for the potential
applications associated with them.

The first part of this thesis is mainly focusing on the optical
rectifications with iron-rich clay modified electrodes.
According to EDX spectroscopy, clay montmorillonite K10 and KSF
as well as many others are highly aboundant in iron. These iron
species are found electrochemically avtive, e.g., the cathodic
or anodic current increases with the decrease in pH. As well ,
they are also photo-sensitive. Under illumination with 1<420 nm,
the current is significsntly enhanced, whereas under 1>420 nm,
almosno photoactivity is observed. Once the clay electrodes are
incorporated with proton-transfer agents like
2-pyridylcarboxylic acids, the mononic photocurrent originally
revealed from the clay electrodes can be rectified into an ac
pattern, which makes the 260-nm signal distinguishable from the
ambient light. The photoresponses are quite reproducibleand the
T90 is less than 10 seconds.

In the second part, the clay electrodes are further modified
with ruthenium(II) hexacyanide to produce ruthenium purple
(denoted clay/RP)on the clay surface. These clay/RP modified
electrodes show a remarkable ability in chemical sensing, like
in hydrogen peroxide, ascorbatre, and glucose. In the
theoretical section, we successfully treat the EC' mechanisms
with the thin-layer electrocell model to interprete the
voltammetric responses recorded with these electrodes in the
presence or in the absence of bstrates. Resolving from the
model, the pseudo-first orderheterogeneous rate constant for the
reaction of ruthenium purple with H2O2 is 183 M-1s-1, and about
30 M-1s-1 with ascorbate.

Suggested by the catalytic effects of ruthenium purple on the
sensing of hydrogen peroxide, we further modified these clay/RP
electrodes with glucose oxidase for glucose sensing. Under
E=0.18 V vs. SCE, we successfully tranduct the concentration of
glucose into electric response. The response can be extented to
a wide range of glucose concentration, and more amazingly,
almost no interference form oxygen or ascorbate is observed.
Although clay modified electrodes have been explored and