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Environmental effects on photoinduced electron transfer reactions

Technical Report ·
OSTI ID:6228809

Photoinduced electron transfer reactions between an electronically excited photosensitizer molecule and a reversible electron acceptor capable of hydrogen production were studied to determine the possible utility of these reactions in solar energy conversion systems. The influence of charged macromolecules on the forward and back electron-transfer reaction between oppositely charged initial photoproducts, the photosensitizer zinc tetra(4-N-methyl pyridinium) porphyrin (ZnP/sup +4/) and the neutral electron acceptor, propyl viologen sulfonate (PVS/sup 0/), has been investigated using continuous photolysis and flash photolysis techniques. Flash photolysis experiments have been performed to study the effect of anionic polyelectrolyte poly(styrene sulfonate) (PSS) on the photoreaction between ZnP/sup +4/ and PVS/sup 0/. These experiments show that all bimolecular rate constants involving PSS-bound ZnP/sup +4/ are decreased by a factor for 40-100. A kinetic model has been developed that describes the transient absorbance behavior of ZnP/sup +4//PVS/sup 0//colloidal silica photolysis systems in which scavenging of PVS/sup -/ by residual O/sub 2/ occurs. Flash photolysis experiments confirmed that alumina-modified silica particles are significantly more effective than unmodified silica sols in neutral pH media at decreasing the rate of back-reaction between ZnP/sup +4/ and PVS/sup -/. 25 refs., 32 figs., 5 tabs.

Research Organization:
Lawrence Berkeley Lab., CA (USA)
DOE Contract Number:
AC03-76SF00098
OSTI ID:
6228809
Report Number(s):
LBL-20817; ON: DE86006445
Country of Publication:
United States
Language:
English