Encapsulation of tetracarbonyl(trimethylstannyl)cobalt in NaY zeolite. Reactivity and alloy cluster formation
- Purdue Univ., West Lafayette, IN (United States)
A bimetallic precursor route toward the encapsulation of subnanometer tin-transition metal alloy clusters in zeolites is presented. The intrazeolite chemistry and thermal stability of Me[sub 3]SnCo(CO)[sub 4] in NaY zeolite were studied with X-ray absorption spectroscopy (Sn, Co edge EXAFS) and in-situ FTIR/TPD-MS techniques. In the NaY host, the intact precursor is physically adsorbed from hexane solution into the dehydrated zeolite cages at room temperature without further chemical reaction. Symmetry changes of the Co(CO)[sub 4] moiety indicate interaction of the CO ligands with the Na[sup +] ions of the zeolite framework. The intrazeolite complex in NaY is accessible to external reactants and undergoes carbonyl substitution with PMe[sub 3] at the cobalt center. The encaged organometallic complex is stable up to about 90[degrees]C and then decomposes by loss of CO ligands and rearrangement of the Sn-Co structure, resulting in metal clusters with bridging carbonyl ligands. At about 300[degrees]C, all CO is removed, and very small tin-cobalt alloy clusters are formed as detected with EXAFS spectroscopy. This process is also observed in porosity measurements showing successive recovery of free volume on CO removal. 39 refs., 11 figs., 2 tabs.
- DOE Contract Number:
- AS05-80ER10742
- OSTI ID:
- 6605378
- Journal Information:
- Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:46; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
ADSORPTION
ALKANES
ALLOYS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CATALYSTS
CHALCOGENIDES
CHEMICAL REACTIONS
COBALT COMPLEXES
COMPILED DATA
COMPLEXES
DATA
DECOMPOSITION
ENCAPSULATION
HEXANE
HYDROCARBONS
INFORMATION
INORGANIC ION EXCHANGERS
ION EXCHANGE MATERIALS
LIGANDS
MATERIALS
MINERALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
SILICATE MINERALS
SOLID CLUSTERS
SORPTION
SPECTROSCOPY
TIN COMPLEXES
TRANSITION ELEMENT COMPLEXES
X-RAY SPECTROSCOPY
ZEOLITES