Reversible and Irreversible Redox Series as Probes of Fundamental Aspects of Charge Transfer Across INP, WSe sub 2 , and SNS sub 2 /Acetonitrile Interfaces: Progress Report, May 15, 1986-May 14, 1987

摘要

Kinetics at metal electrode/solution interfaces has been studied for decades and the understanding of electron transfer processes is relatively mature. Despite numerous experimental studies during the past 10 years, many fundamental questions regarding redox processes at semiconductor/liquid junctions, even in the absence of light, remain unanswered. We have attempted to resolve some of these questions by making measurements that are analogous to those that were crucial for detailed understanding of electrochemistry at metals. The key aspects of our semiconductor studies are: (1) use of semiconducting materials and surface preparations that result in reproducible and stable interfacial energetics; (2) using both p- and n-type electrodes with a wide range of doping densities; (3) use of nonaqueous solvents to minimize surface corrosion processes; (4) thorough characterization of the interfacial energetics by measuring the capacitance of the space charge region over the same regions of electrode potential used in voltammetric experiments; and (5) use of substituted metallocenes as solution redox probes in order to insure 1e sup - , outer-sphere reactions with varying reduction potentials yet constant reorganization energies. 22 refs., 3 figs., 2 tabs. (ERA citation 12:016423)