title: Measurement of the free-energy dependence of interfacial charge-transfer rate constants using ZnO/H2O semiconductor/liquid contacts.
abstract: The dependence of electron-transfer rate constants on the driving force for interfacial charge transfer has been investigated using n-type ZnO electrodes in aqueous solutions. Differential capacitance versus potential and current density versus potential measurements were used to determine the energetics and kinetics, respectively, of the interfacial electron-transfer processes. A series of nonadsorbing, one-electron, outer-sphere redox couples with formal reduction potentials that spanned approximately 900 mV allowed evaluation of both the normal and Marcus inverted regions of interfacial electron-transfer processes. All rate processes were observed to be kinetically first-order in the concentration of surface electrons and first-order in the concentration of dissolved redox acceptors. The band-edge positions of the ZnO were essentially independent of the Nernstian potential of the solution over the range 0.106-1.001 V vs SCE. The rate constant at optimal exoergicity was observed to be approximately 10(-)(16) cm(4) s(-)(1). The rate constant versus driving force dependence at n-type ZnO electrodes exhibited both normal and inverted regions, and the data were well-fit by a parabola generated using classical Marcus theory with a reorganization energy of 0.67 eV. NMR line broadening measurements of the self-exchange rate constants indicated that the redox couples had reorganization energies of 0.64-0.69 eV. The agreement between the reorganization energy of the ions in solution and the reorganization energy for the interfacial electron-transfer processes indicated that the reorganization energy was dominated by the redox species in the electrolyte, as expected from an application of Marcus theory to semiconductor electrodes.
authors.affiliation: Division of Chemistry and Chemical Engineering, Noyes Laboratory, 127-72, California Institute of Technology, Pasadena, California 91125, USA.
authors.forename: Thomas W
authors.initials: TW
authors.lastname: Hamann
authors.forename: Florian
authors.initials: F
authors.lastname: Gstrein
authors.forename: Bruce S
authors.initials: BS
authors.lastname: Brunschwig
authors.forename: Nathan S
authors.initials: NS
authors.lastname: Lewis