KINETIC-STUDY OF ELECTROCATALYTIC REDUCTION OF HYDROGEN-PEROXIDE AT IRON(III) PORPHYRIN MODIFIED GLASSY-CARBON ELECTRODE IN ALKALINE-MEDIUM USING THE ROTATION-SCAN METHOD

Reduction of hydrogen peroxide at a glassy carbon (GC) electrode modified with sigma-bonded pyrrole iron(III) octaethylporphyrin complex, (OEP)Fe(Pyr), was studied by cyclic voltammetry and a rotating disk electrode. In 0.1N NaOH solution, it is shown that such an (OEP)Fe(Pyr)/GC electrode has a significant catalytic activity towards hydrogen peroxide reduction (E(D) = -0.80 V, k = 0.066 cm s(-1)); however, the electrode stability is low. The deactivation is observed when the reaction charge (Q) is passing through the (OEP)Fe(Pyr)/GC disk electrode. A linear rotation scan method is applied to study the kinetic process by determining the disk electrochemical response (i(D)) to rotation rate (omega) at a definite disk potential (E(D)). Considering that the number of adsorbed electroreduced catalyst molecules (Red) varies according to the disk potential, a factor theta(= Gamma(Red)/(Gamma(Red) + Gamma(Ox))) is introduced to describe the electrode surface area fraction for electroreduced species. The obtained Koutecky-Levich equation is applicable whatever the potential is.

APPLICATIONS OF RAPID SCAN SPECTROELECTROCHEMISTRY - DETERMINATION OF HETEROGENEOUS ELECTRON-TRANSFER RATE-CONSTANT OF BILIVERDIN OXIDATION

The rapid scan spectrometer was used to determine the heterogeneous electron transfer rate parameters for the oxidation of Biliverdin in DMF by single potential step thin layer spectroelectrochemical techniques and yielded an average formal heterogeneous electron transfer rate constant K(s, h)0' = 2.45 (+/-0.12) x 10(-4) cm s-1, electrochemical transfer coefficient alpha = 0.694+/-0.008. The oxidation process of Biliverdin was also studied and the formal potential E0 = 0.637 V (vs. Ag/AgCl) was obtained.

高温高压下Z轴水晶的电导率实验研究

电导率测量的过程历经了从直流-交流-阻抗谱的过程，已经为地球物理学家借助于高温高压手段研究固体深部物质电学性质所广泛认同的。本文首先介绍了阻抗谱法测定水晶电导率的实验原理，进而采用该方法在10^-1～10^6Hz的频率范围以及1．0—4．0GPa和823—1073K条件下，借助于YJ-3000t紧装式六面顶高压设备对沿Z轴方向生长的水晶进行了的电导率实验就位测量。实验结果表明：在选择的频率范围，样品的复阻抗的模和相角都对频率具有很强的依赖性；随着温度的升高，电阻迅速降低，电阻率降低，电导率增大；在压力1．0—4．0GPa，其活化焓分别为：0．8548eV、0．8320eV、0．8172eV、0．7834eV，独立于温度的指前因子分别为：1．003S／m、1．778S／m、3．082S／m、6．987S／m，活化焓随着压力的升高而降低，指前因子随着压力的升高而增大。