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
- Resource Relation:
- Conference: GRI basic research contractor's review meeting on gaseous fuel synthesis from inorganic resources, Chicago, IL, USA, 16 Oct 1985; Other Information: Paper copy only, copy does not permit microfiche production
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CATALYSTS
PHOTOCHEMICAL REACTIONS
RESEARCH PROGRAMS
COPPER COMPLEXES
NICKEL COMPLEXES
PORPHYRINS
LASER SPECTROSCOPY
RAMAN SPECTROSCOPY
SPECTRA
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
COMPLEXES
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
360603* - Materials- Properties
400500 - Photochemistry