Improving the efficiency of photo-electrocatalytic cells depends on controlling the rates of interfacial electron transfer to promote the formation of long-lived charge separated states. Ultimately, for efficient catalytic assemblies to see widespread implementation, repeated electron transfer in the absence of charge recombination needs to be realized. In this study, a series of manganese-based transition metal complexes known to undergo charge transfer-induced spin crossover are employed to study how significant increases in inner-sphere reorganization energy affect the rates of interfacial electron transfer. Each complex is characterized by transient spectroscopic and electrochemical methods to calculate the rate of electron transfer to a model chromophore anchored to the surface of a TiO2 film. Likewise, open-circuit voltage decay measurements were used to determine the voltage-dependent lifetime of injected electrons in TiO2 in the presence of each complex. To further characterize the rates of electronic recombination, density functional theory was used to calculate the inner-sphere and outer-sphere reorganization energy for each complex. These calculations were then combined with classical Marcus theory to determine the theoretical rate of back-electron transfer from the TiO2 conduction band. These results show that, in model complexes, a significant reduction in the recombination rate constant is achieved for complexes possessing a significant inner-sphere reorganization energy.
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28 September 2020
Research Article|
September 29 2020
The effect of inner-sphere reorganization on charge separated state lifetimes at sensitized TiO2 interfaces
Special Collection:
65 Years of Electron Transfer
M. C. Kessinger
;
M. C. Kessinger
Department of Chemsitry, Virginia Polytechnic and State University
, Blacksburg, Virginia 24061, USA
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C. Brillhart
;
C. Brillhart
Department of Chemsitry, Virginia Polytechnic and State University
, Blacksburg, Virginia 24061, USA
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V. Vaissier Welborn;
V. Vaissier Welborn
Department of Chemsitry, Virginia Polytechnic and State University
, Blacksburg, Virginia 24061, USA
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A. J. Morris
A. J. Morris
a)
Department of Chemsitry, Virginia Polytechnic and State University
, Blacksburg, Virginia 24061, USA
a)Author to whom correspondence should be addressed: ajmorris@vt.edu
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a)Author to whom correspondence should be addressed: ajmorris@vt.edu
Note: This paper is part of the JCP Special Topic on 65 Years of Electron Transfer.
J. Chem. Phys. 153, 124711 (2020)
Article history
Received:
July 30 2020
Accepted:
September 09 2020
Citation
M. C. Kessinger, C. Brillhart, V. Vaissier Welborn, A. J. Morris; The effect of inner-sphere reorganization on charge separated state lifetimes at sensitized TiO2 interfaces. J. Chem. Phys. 28 September 2020; 153 (12): 124711. https://doi.org/10.1063/5.0023591
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