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Title: Membrane-Organized Chemical Photoredox Systems

This project has three interrelated goals relevant to solar water photolysis, which are to develop: (1) vesicle-organized assemblies for H2 photoproduction that utilize pyrylium and structurally related compounds as combined photosensitizers and cyclic electroneutral transmembrane electron carriers; (2) transmembrane redox systems whose reaction rates can be modulated by light; and (3) homogeneous catalysts for water oxidation. . In area (1), initial efforts to photogenerate H2 from vectorially-organized vesicles containing occluded colloidal Pt and commonly available pyrylium ions as transmembrane redox mediators were unsuccessful. New pyrylium compounds with significantly lower reduction potentials have been synthesized to address this problem, their apparent redox potentials in functioning systems have been now evaluated by using a series of occluded viologens, and H2 photoproduction has been demonstrated in continuous illumination experiments. In area (2), spirooxazine-quinone dyads have been synthesized and their capacity to function as redox mediators across bilayer membranes has been evaluated through continuous photolysis and transient spectrophotometric measurements. Photoisomerization of the spiro moiety to the ring-open mero form caused net quantum yields to decrease significantly, providing a basis for photoregulation of transmembrane redox. Research on water oxidation (area 3) has been directed at understanding mechanisms of catalysis by cis,cis-[(bpy)2Ru(OH2)]2O4+ and related polyimine complexes.more » Using a variety of physical techniques, we have: (i) identified the redox state of the complex ion that is catalytically active; (ii) shown using 18O isotopic labeling that there are two reaction pathways, both of which involve participation of solvent H2O; and (iii) detected and characterized by EPR and resonance Raman spectroscopies new species which may be key intermediates in the catalytic cycle.« less
Publication Date:
OSTI Identifier:
Report Number(s):
DOE Contract Number:
Resource Type:
Technical Report
Research Org:
Washiington State University
Sponsoring Org:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Orgs:
Washington State University
Country of Publication:
United States
14 SOLAR ENERGY; 30 DIRECT ENERGY CONVERSION; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY biomimetic chemistry; dye-sensitized oxidation-reduction; H2 photoproduction; membrane-organized integrated chemical systems; reaction kinetics; water oxidation catalysis.