Synthesis gas transformations with heterogeneous iridium and homogeneous rhodium metal complexes
The emphasis of this work has been on the development of homogeneous and heterogeneous catalytic systems capable of the indirect transformation of H{sub 2} and CO into chemicals under mild reaction conditions. Supported iridium carbonyl and aluminum chloride were investigated in an attempt to heterogenize an analogous homogeneous catalyst. The presence of aluminum chloride was found to lead to cluster interactions resulting in a system capable of selective reduction of carbon monoxide under mild reaction conditions. When a gaseous mixture of H{sub 2}, CO, and HCl was passed over the supported cluster at 125 C, methyl chloride, methane, carbon dioxide and water were observed as major products. Unlike the homogeneous analog, only trace C{sub 2} products were detected. Infrared spectroscopy was used to investigate the preparation of the deposited clusters as well as the iridium species formed on the support during reaction. The second study involved the investigation of a rhodium carboxylate triphenylphosphine complex which was found to be an active, homogeneous hydroformylation catalyst. The system selectively produced more of the linear aldehyde than the branched. The product selectivity was found to depend upon the amount of phosphine present. Spectroscopic studies supported that a bis(triphenylphosphine)rhodium(I) trifluoroacetate carbonyl species was the active catalyst. Comparative studies with other rhodium carboxylate complexes and hydroformylation catalysts showed that the perfluorocarboxylate complexes exhibited greater activity.
- Research Organization:
- Florida Univ., Gainesville, FL (USA)
- OSTI ID:
- 6918984
- Resource Relation:
- Other Information: Thesis (Ph. D.)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
CARBON MONOXIDE
HYDROGENATION
METHANATION
IRIDIUM
CATALYTIC EFFECTS
RHODIUM
ALDEHYDES
ALUMINIUM CHLORIDES
CARBON DIOXIDE
CATALYST SUPPORTS
CHEMICAL PREPARATION
CHEMICAL REACTION YIELD
COMPARATIVE EVALUATIONS
HETEROGENEOUS CATALYSIS
HOMOGENEOUS CATALYSIS
HYDROCHLORIC ACID
INFRARED SPECTRA
IRIDIUM COMPLEXES
METHANE
METHYL CHLORIDE
MIXTURES
RHODIUM COMPLEXES
SYNTHESIS
SYNTHESIS GAS
WATER
ALKANES
ALUMINIUM COMPOUNDS
CARBON COMPOUNDS
CARBON OXIDES
CATALYSIS
CHALCOGENIDES
CHEMICAL REACTIONS
CHLORIDES
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINE COMPOUNDS
COMPLEXES
DISPERSIONS
ELEMENTS
FLUIDS
GASES
HALIDES
HALOGEN COMPOUNDS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROCARBONS
HYDROGEN COMPOUNDS
INORGANIC ACIDS
METALS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PLATINUM METALS
SPECTRA
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENTS
YIELDS
010408* - Coal
Lignite
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