Investigation and optimization of fuel production using dye-based transition metal complexes as charge-transfer intermediates. Annual report, August 1984-August 1985
Metalloporphyrins offer promising properties for photosensitizing and catalyzing reactions of interest. They provide a unique chemical system for investigations of the basic photophysical processes controlling desired chemistries. Therefore, we have initiated spectroscopic studies of metalloporphyrins in fuel-producing environments, with the goal of determining the factors controlling their photochemical reactivity. Metalloporphyrins perturbed systematically either by structural modifications or by incorporation into various environments were examined by resonance Raman difference spectroscopy, ultraviolet/visible absorption spectroscopy, and other spectroscopic and electrochemical probes. Perturbations on the photosensitizing chromophore resulted in systematic changes in its spectra and its chemical properties. A new theoretical procedure that uses a model of metalloporphyrin electronic states has been applied to quantitatively evaluate systematic differences in the spectra. Efforts to relate metalloporphyrin structure to photochemical activity in an artificial photosynthesis system have begun. For example, the unusually high activity of an anionic tin prophyrin was traced to prevention of formation of inactive complexes by blocking groups attached to the metal. Subsequent studies have shown that blocking groups also prevent aggregation - another inactivating process. Besides this solution system, a number of metalloporphyrin-polymer based systems are being investigated.
- Research Organization:
- Sandia National Labs., Albuquerque, NM (USA)
- DOE Contract Number:
- AC04-76DP00789
- OSTI ID:
- 6144732
- Report Number(s):
- SAND-86-0205C; CONF-8510162-Exc.; ON: DE86006233
- Country of Publication:
- United States
- Language:
- English
Similar Records
Investigation and optimization of fuel production using dye-based transition-metal complexes as charge-transfer intermediates. Annual report, August 1985-April 1987
Method for improving product yields in an anionic metalloporphyrin-based artificial photosynthesis system
Related Subjects
360603* -- Materials-- Properties
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500 -- Photochemistry
CARBOXYLIC ACIDS
CATALYSTS
CHEMICAL REACTIONS
COMPLEXES
COPPER COMPLEXES
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
LASER SPECTROSCOPY
NICKEL COMPLEXES
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PORPHYRINS
RAMAN SPECTROSCOPY
RESEARCH PROGRAMS
SPECTRA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES