Fast second order electron transfer reactions coupled to redox protein electrochemistry: Experiment and digital simulation

Chemical modification of metal surfaces by chemisorption provides a versatile method for the production of electrode interfaces which can be selective for the direct electrochemistry of one redox protein over another. The electrochemistry of a mixture of horse heart cytochrome c and spinach plastocyanin has been investigated at gold surfaces made selective for first one and then the other protein. The resulting cyclic voltammetry is quite unusual, containing pre-shoulders to both reduction current and reoxidation current peaks. The results have been interpreted in terms of fast second order electron transfer reactions taking place between the two proteins in homogeneous solution. This rationalisation has been corroborated by an explicit digital simulation of the proposed reaction scheme, using second order RKI. There are three independently variable parameters to the simulation: forward kinetic parameter, reverse kinetic parameter, and concentration ratio of non-electrode-active species to electrode-active species. The simulation has been used to explore a number of interesting trends in these parameters. Five such sequences of simulated cyclic voltammograms are reported, together with peak current and potential data in most cases. Attention is drawn to the possibility for further interesting experimental mixed redox protein electrochemistry at selective surfaces.     

Cyclic chronocoulemetry: Disproportionation and dimerization reactions coupled to electron transfer

An extension of double-potential-step chronocoulemetry to multiple or cyclic techniques has been developed, and its potential applications in the study of coupled chemical reactions in electrochemistry are discussed. Disproportionation and dimerization mechnisms are considered. Wroking curves have been calculated with the use of the finite difference digital simulation method. It is shown that better resolution for disproportionation and dimerization reactions can be obtained with cyclic chronocoulometry than with double-potential-step chronocoulemetry. The method has been experimentally verified measuring the disproportionation reaction U(V) in 1 mol dm^?3 sodium hydrogen carbonate solutions. A rate coefficient of 15.6 dm³ mol^?1 was calculated for this reaction.     

Electrogenerated Chemiluminescence Imaging of Electrocatalysis at a Single Au‐Pt Janus Nanoparticle

Noble metal nanoparticles are promising catalysts in electrochemical reactions, while understanding the relationship between the structure and reactivity of the particles is important to achieve higher efficiency of electrocatalysis, and promote the development of single‐molecule electrochemistry. Electrogenerated chemiluminescence (ECL) was employed to image the catalytic oxidation of luminophore at single Au, Pt, and Au‐Pt Janus nanoparticles. Compared to the monometal nanoparticles, the Janus particle structure exhibited enhanced ECL intensity and stability, indicating better catalytic efficiency. On the basis of the experimental results and digital simulation, it was concluded that a concentration difference arose at the asymmetric bimetallic interface according to different heterogeneous electron‐transfer rate constants at Au and Pt. The fluid slip around the Janus particle enhanced local redox reactions and protected the particle surface from passivation.     

表面电化学和电化学催化研究进展——97'国际电化学联合大会和97'国际表面电化学会议综述

表面电化学和电化学催化研究进展①——９７＇国际电化学联合大会和９７＇国际表面电化学会议综述孙世刚（厦门大学化学系,固体表面物理化学国家重点实验室厦门３６１００５）表面电化学和电化学催化是当前极为活跃的研究领域．这首先得益于近年来各种物理和光谱技术的飞...     

21世纪电化学的若干发展趋势

本文简要回顾 2 0世纪后五十年电化学在理论、实验技术、新现象发现和应用等领域的重要进展 ,提出了 2 1世纪前期电化学的若干发展趋势 ,强调应重视电化学新体系的研究 ,以迎接 2 1世纪能源、材料、生命、信息和环境对电化学技术的挑战     

Electrochemistry of the bis(1,4,7-triazacyclodecane) cobalt(III) complex and its role in the catalytic reduction of hydrogen

The electrochemistry of the bis(1,4,7-triazacyclodecane) cobalt(III) complex at a mercury electrode, HMDE, in aqueous Britton–Robinson buffer solutions was investigated using cyclic voltammetry, double-potential-step chronoamperometry and chronocoulometry. The cyclic voltammetric data were analyzed by digital simulation to confirm and to measure the heterogeneous and homogeneous parameters for the suggested electrode mechanism. Generally, the complex is electrochemically reduced giving rise to two cyclic voltammetric waves. The first wave is a diffusion-controlled reversible wave. It is assigned to the stable Co(III)/Co(II) redox couple. The second one is found to be irreversible and corresponding to a reduction of Co(II) to Co(I) species. The monovalent cobalt, highly unstable, is rapidly protonated, and then forms cobalt hydride. The hydride decomposes to hydrogen molecules and regenerates Co(II) species following a disproportionation pathway. The overall reduction mechanism is concluded to be an EECC kinetics.     

The numerical simulation of vanadium RedOx flow batteries

In this article a theoretical model of a RedOx flow cell (RFC), based on an equation system of fluid dynamics and of electrochemistry, is presented. A numerical algorithm of the solution of the equation system is developed. The results of numerical simulation of processes in the RFC are analyzed and validated in a test cell. The effects of different electrode collectors and current densities on the operation of the RFC are studied.     

固液界面双电层的理论计算模拟

固液界面双电层在电化学中处于核心地位. 如何发展一个理论方法,在该方法的框架下计算双电层的平衡性质和动力学性质一直以来都是理论研究的难点和热点. 本文总结了最近十几年第一性原理计算方法在计算双电层平衡性质和电催化反应的进展,如热力学方法、反应中心模型以及双参考方法. 并进一步详细地阐述了基于周期性均匀介质溶剂化模型 ( DFT/CM-MPB)对于固液界面双电层的研究,该方法能够计算双电层的平衡性质(零电荷电势和微分电容)和表面相图,在此基础上能深入研究基元反应的电荷转移系数,并结合微观动力学推导出宏观的Tafel(电流-电势)曲线. 并列举了该方法对于重要电化学反应(如氢电极反应)的应用实例.     

Microwave‐Assisted Electroanalysis: A Review

Microwave‐assisted electrochemistry is critically discussed with a focus on the fundamental aspects of the processes involved and its applications in electroanalysis. The concept of direct and nondirect heated electrodes is discussed, and simulation work is evaluated. Microwave‐assisted electrochemistry predominantly results in higher current responses (up to 2 magnitudes higher) due to increased temperature and mass transport to the active electrodes. Temperature gradients at microwave‐affected electrodes may exceed 10⁵ K/cm, with temperature hotspots found in the thin diffusion layers set up at ultramicroelectrodes. Research into microwave‐assisted electroanalysis can lead to enhanced capillary electrophoresis detection, improved stripping voltammetry and development of new high temperature methods.