title: Observation of the marcus inverted region of electron transfer reactions at a liquid/liquid interface.
abstract: Scanning electrochemical microscopy was used to probe the influence of a driving force on the heterogeneous electron transfer (ET) processes at the externally polarized water/1,2-dichloroethane interface. Being a part of the driving force, the Galvani potential difference at the interface, Deltaowphi, can be quantitatively controlled in a wide range, allowing the precise measurements of the rate constants of the ET reactions. Two opposite systems were chosen in this work. One was 5,10,15,20-tetraphenyl 21H,23H-porphyrin zinc (ZnPor, O)/Fe(CN)64- (W), and the other was TCNQ (O)/Fe(CN)63- (W). For both systems studied, the relations between the rate constant and the Deltaowphi were of parabolic shape; that is, the rate constants increased initially with the Deltaowphi until reaching a maximum and then decreased steadily as the Deltaowphi increased further. This is in accordance with the prediction of the Marcus theory. To our knowledge, this is the first report that the Marcus inverted region can be observed electrochemically at an unmodified liquid/liquid interface with only one redox couple at each phase. The effect of the concentrations of the organic supporting electrolyte has also been discussed in detail.
authors.affiliation: State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry of the Chinese Academy of Sciences, Changchun 130022, China.
authors.forename: Peng
authors.initials: P
authors.lastname: Sun
authors.forename: Fei
authors.initials: F
authors.lastname: Li
authors.forename: Yong
authors.initials: Y
authors.lastname: Chen
authors.forename: Meiqin
authors.initials: M
authors.lastname: Zhang
authors.forename: Zhiquan
authors.initials: Z
authors.lastname: Zhang
authors.forename: Zhao
authors.initials: Z
authors.lastname: Gao
authors.forename: Yuanhua
authors.initials: Y
authors.lastname: Shao