Electron and energy transfer as probes of interparticle ion-exchange reactions in zeolite Y
- Univ. of Texas, Austin, TX (United States)
Photoinduced electron transfer and energy transfer reactions of tris(2,2[prime]-bipyridyl)ruthenium(II) (Ru(bpy)[sub 3][sup 2+]) with methylviologen (MV[sup 2+]) and tris(2,2[prime]-bipyridyl)osmium(II) (Os(bpy)[sub 3][sup 2+]) ion-exchanged onto/into separate zeolite Y particles were studied by emission spectroscopy. The kinetics of interparticle exchange were probed by observing the quenching of the MLCT excited state of-Ru(bpy)[sub 3][sup 2+] by mobile MV[sup 2+] or OS(bpy)[sub 3][sup 2+] ions. The exchange reactions occur on time scales of seconds to hours, depending on the ionic strength of the surrounding medium. The time-dependent luminescence data were fitted to a dispersed kinetics model, from which average rate constants for the exchange reactions could be extracted. Time constants for interparticle exchange of MV[sup 2+] and Os(bpy)[sub 3][sup 2+] ions, in the range 10[sup 3]-10[sup 5] s at electrolyte concentrations of 0.1-3 mM, are significantly longer than the time scales (10[sup [minus]7]-10[sup 1] s) of most electrochemical and photochemical intrazeolitic reactions involving these and similar electroactive ions. These results argue for reaction mechanisms that invoke intrazeolite electron transfer, rather than exchange of electroactive ions followed by solution-phase electron transfer, in these systems. 25 refs., 6 figs., 1 tab.
- DOE Contract Number:
- FG05-87ER13789
- OSTI ID:
- 5576084
- Journal Information:
- Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 97:33; 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
400400 -- Electrochemistry
400500 -- Photochemistry
CHEMISTRY
COMPLEXES
DATA
ELECTROCHEMISTRY
ELECTRON TRANSFER
EMISSION SPECTROSCOPY
ENERGY TRANSFER
EXPERIMENTAL DATA
INFORMATION
INORGANIC ION EXCHANGERS
ION EXCHANGE
ION EXCHANGE MATERIALS
KINETICS
LUMINESCENCE
MATERIALS
MINERALS
NUMERICAL DATA
OSMIUM COMPLEXES
PHOTOCHEMISTRY
REACTION KINETICS
RUTHENIUM COMPLEXES
SILICATE MINERALS
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
ZEOLITES