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), Vol. 90:21
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
08 HYDROGEN
CARBONYLS
ACTIVATION ENERGY
CHEMICAL PREPARATION
HYDRIDES
IRON COMPLEXES
SHIFT PROCESSES
CATALYTIC EFFECTS
SODIUM
SURFACE PROPERTIES
ZEOLITES
CATALYSIS
EXPERIMENTAL DATA
HIGH TEMPERATURE
INFRARED SPECTRA
MEDIUM TEMPERATURE
ULTRAVIOLET SPECTRA
VISIBLE SPECTRA
WATER GAS
ALKALI METALS
COMPLEXES
DATA
ELEMENTS
ENERGY
FLUIDS
FUEL GAS
FUELS
GAS FUELS
GASES
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ION EXCHANGERS
INTERMEDIATE BTU GAS
ION EXCHANGE MATERIALS
MATERIALS
METALS
MINERALS
NUMERICAL DATA
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
080104 - Hydrogen- Production- Water Gas Processes