Rearrangement Energy for Electron Transfer at Semiconductor/Electrolyte Interface

1984 ◽  
Vol 131 (8) ◽  
pp. 1832-1838
Author(s):  
Kenkichiro Kobayashi ◽  
Masasuke Takata ◽  
Shoichi Okamoto ◽  
Mitsunori Sukigara
Keyword(s):  
Electron Transfer ◽  
Electrolyte Interface ◽  
Rearrangement Energy

Surface polaron states on single-crystal rutile TiO2 nanorod arrays enhancing charge separation and transfer

2020 ◽  
Vol 49 (42) ◽  
pp. 15054-15060
Author(s):  
Qimeng Yang ◽  
Heng Zhu ◽  
Yanghui Hou ◽  
Duanduan Liu ◽  
Huang Tang ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Single Crystal ◽  
Charge Separation ◽  
Nanorod Arrays ◽  
Rutile Tio2 ◽  
Electron Transfer Pathway ◽  
Tio2 Nanorod ◽  
Electrolyte Interface ◽  
Tio2 Nanorod Arrays

Polaron states on single-crystal TiO2 photoanodes provide an important electron transfer pathway at the electrode–electrolyte interface.

The dependence of the rate of electrochemical charge transfer on the electric field at the metal-electrolyte interface

1972 ◽  
Vol 25 (2) ◽  
pp. 231 ◽  
Author(s):  
DB Matthews
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Potential Energy ◽  
Electric Field ◽  
Electric Fields ◽  
Potential Energy Curves ◽  
Energy Curve ◽  
Electrolyte Interface ◽  
Activated State ◽  
Wide Range

Electric fields at the metal-electrolyte interface are very high (of the order of 107 V/cm) and one intuitively expects that these fields should have a profound influence on the movement of charged species such as ions and electrons at the interface. Qualitatively, such field effects manifest themselves as deviations from linearity of Tafel plots or as a dependence of the symmetry factor on electrode potential. It is shown that Gurney's potential energy curve representation of charge transfer reactions yields only small changes in β over a wide range of potential, with the anharmonic (Morse) curves showing smaller changes than the harmonic (parabolic) curves. Superposition of the double layer electric field on these potential energy curves increases the curvature of the Tafel plots, but the effect is still not very large, being within the limits of uncertainty in determining the correct form of the potential energy curves. The effect of electric field on electron transfer is considered both from the viewpoint of change in electron transfer distance arising from a dependence of coordinates of the activated state on potential and from the viewpoint of a direct effect on the electron transfer barrier (analogous to field electron emission). The field emission effects are found to be even less than the effects of the field on the proton transfer potential energy barrier.

The Absence of a Marcus Inversion Region for Electron Transfer at the Metal-Redox Electrolyte Interface

1994 ◽  
Vol 47 (12) ◽  
pp. 2171 ◽  
Author(s):  
D Matthews
Keyword(s):  
Electron Transfer ◽  
Potential Energy ◽  
Electron Distribution ◽  
Distribution Functions ◽  
Rate Distribution ◽  
Inversion Region ◽  
Redox Electrolyte ◽  
Electrolyte Interface ◽  
Metal Redox ◽  
Nuclear Configuration

The theory of electron transfer at the metal- redox electrolyte interface is described by starting with the work of Gurney and incorporating that of Gerischer and Marcus. This GGM model brings together diverse approaches to the description of electron transfer at electrodes. The electron transfer is described in terms of nuclear configuration potential energy diagrams, electronic configuration potential energy diagrams, electron distribution functions and rate distribution functions. The distinction between microscopic energies and macroscopic (thermodynamic) energies is made and the concept of the Fermi level of the redox electrolyte is clarified. The model of identical parabolas is used for the nuclear configuration diagrams and this is shown to lead to Gaussian electron distribution functions for the redox electrolyte. The rate distribution is obtained from the overlap between occupied and unoccupied states of the metal and redox electrolyte. Integration of the rate distribution gives the rate which is calculated as a function of the electrode potential for various values of the reorganization energy λ. It is shown that the variation of symmetry factor β is small for high λ and that the Tafel plots do not show significant decrease in rate at high overpotentials in the anomalous or inversion region. The Tafel plots for charge transfer (mass transfer is assumed to be fast at all potentials) tend to a limiting value with only a small decrease at high overpotential. This contrasts with the prediction based on nuclear configuration potential energy curves and is attributed to the fact that the overlap is between a Gaussian and a Fermi function rather than between two Gaussians, the latter being the case for homogeneous reactions.

Free Energy and Temperature Dependence of Electron Transfer at the Metal-Electrolyte Interface

Science ◽  
1991 ◽  
Vol 251 (4996) ◽  
pp. 919-922 ◽  
Author(s):  
C. E. D. CHIDSEY
Keyword(s):  
Electron Transfer ◽  
Free Energy ◽  
Temperature Dependence ◽  
Electrolyte Interface

scholarly journals Electron Transfer at the Metal Oxide/Electrolyte Interface: A Simple Methodology for Quantitative Kinetics Evaluation

2018 ◽  
Vol 122 (24) ◽  
pp. 12761-12770 ◽  
Author(s):  
Iban Azcarate ◽  
Cyrille Costentin ◽  
Christophe Methivier ◽  
Christel Laberty-Robert ◽  
Alexis Grimaud
Keyword(s):  
Electron Transfer ◽  
Metal Oxide ◽  
Electrolyte Interface ◽  
Oxide Electrolyte

Molecular-dynamics model for electron transfer at the electrode-electrolyte interface

1988 ◽  
Vol 38 (16) ◽  
pp. 11704-11710 ◽  
Author(s):  
J. W. Halley ◽  
Joseph Hautman
Keyword(s):  
Molecular Dynamics ◽  
Electron Transfer ◽  
Dynamics Model ◽  
Electrolyte Interface
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