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Aspects of artificial photosynthesis. Photosensitized electron transfer across bilayers, charge separation, and hydrogen production in anionic surfactant vesicles

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00400a002· OSTI ID:6293229

Photosensitized electron transfer from tris(2,2'-bipyridine)ruthenium cation, Ru(bpy)/sub 3//sup 2 +/, to methylviologen, MV/sup 2 +/, has been investigated in the presence of negatively charged dihexadecyl phosphate, DHP, surfactant vesicles by steady state photolysis, fluorescence quenching, and nanosecond laser flash photolysis. Four different substrate-surfactant vesicle organizations have been used. In system I, Ru(bpy)/sub 3//sup 2 +/ was attached to the outer and MV/sup 2 +/ was placed onto the inner surfaces of DHP vesicles. In system II, MV/sup 2 +/ was attached to the outer and Ru(bpy)/sub 3//sup 2 +/ to the inner surfaces of DHP vesicles. In system III, both Ru(bpy)/sub 3//sup 2 +/ and MV/sup 2 +/ were localized on the outer surfaces of DHP vesicles. In system IV, both Ru(bpy)/sub 3//sup 2 +/ and MV/sup 2 +/ were localized on the inner surfaces of DHP vesicles. Extremely efficient electron transfers have been observed on the surfaces of surfactant vesicles in systems III and IV. Electron transfer from excited Ru(bpy)/sub 3//sup 2 +/ to MV/sup 2 +/ across the bilayers of vesicles in the presence of externally added EDTA in system I resulted in the formation of reduced methylviologen, MV/sup +/., up to 75% conversion with a quantum efficiency of 2.40 x 10/sup -2/. If additionally approx. 10/sup -5/ M PtO/sub 2/ was entrapped in the interiors of DHP vesicles in system I, MV/sup +/. promptly reformed with concomitant hydrogen evolution. Photolysis of this system leads to the net consumption of only EDTA at very low stoichiometric Ru(bpy)/sub 3//sup 2 +/, MV/sup 2 +/, and PtO/sub 2/ concentrations. Dynamics of these processes have been determined and their relevance to photochemical solar energy conversions is discussed.

Research Organization:
Texas A and M Univ., College Station
OSTI ID:
6293229
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:10; ISSN JACSA
Country of Publication:
United States
Language:
English