Reactivity of iron carbonyl complexes in a hydrated sodium-Y zeolite matrix and catalysis of the resulting hydride anion HFe/sub 3/(CO)/sub 11//sup -/ for water-gas-shift reaction
Iron carbonyls Fe(CO)/sub 5/, Fe/sub 2/(CO)/sub 9/, and Fe/sub 3/(CO)/sub 12/ have been introduced into a hydrated Na-Y zeolite. Fe(CO)/sub 5/ was only weakly adsorbed on the zeolite. Fe/sub 2/(CO)/sub 9/ and Fe/sub 3/(CO)/sub 12/ were reactive in the hydrated zeolite cages to yield a hydride anion species HFe/sub 3/(CO)/sub 11//sup -/ which was characterized by IR absorption bands at 2044, 1987, 1950, and 1645 cm/sup -1/, UV-vis spectrum at 540 nm, and gas-phase analyses. The red shift of absorption band of the bridging carbonyl indicated ionic interaction of a bridging carbonyl with an Al/sup 3 +/ ion in the zeolite matrix. The formation of the anion species was not observed in a dehydrated Na-Y zeolite, indicating the importance of water or a surface hydroxyl group n the reaction. The reaction course from di- or trinuclear iron carbonyl to the hydride anion has been studied by an ESR technique. Fe/sub 2/(CO)/sub 8//sup -/, Fe(CO)/sub 4//sup -/, and Fe/sub 3/(CO)/sub 11//sup -/ species were detected as intermediates, and reaction schemes have been proposed. The resulting HFe/sub 3/(CO)/sub 11//sup -/ was stable at or below 413 K both in a vacuum or in a CO atmosphere. Above this temperature it was gradually decomposed. Catalytic activity of the HFe/sub 3/(CO)/sub 11//sup -/ species was examined for water-gas-shift reaction at 333-453 K and atmospheric pressure. The activity was very high and comparable to that reported in the homogeneous phase at high pressure. Kinetics and spectroscopic studies indicated that the reaction between HFe/sub 3/(CO)/sub 11//sup -/ and H/sub 2/O would be rate-determining.
- Research Organization:
- Nagasaki Univ., Japan
- OSTI ID:
- 5141968
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:21; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
080104 -- Hydrogen-- Production-- Water Gas Processes
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
ALKALI METALS
CARBONYLS
CATALYSIS
CATALYTIC EFFECTS
CHEMICAL PREPARATION
COMPLEXES
DATA
ELEMENTS
ENERGY
EXPERIMENTAL DATA
FLUIDS
FUEL GAS
FUELS
GAS FUELS
GASES
HIGH TEMPERATURE
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
INFRARED SPECTRA
INORGANIC ION EXCHANGERS
INTERMEDIATE BTU GAS
ION EXCHANGE MATERIALS
IRON COMPLEXES
MATERIALS
MEDIUM TEMPERATURE
METALS
MINERALS
NUMERICAL DATA
SHIFT PROCESSES
SODIUM
SPECTRA
SURFACE PROPERTIES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
ULTRAVIOLET SPECTRA
VISIBLE SPECTRA
WATER GAS
ZEOLITES