Abstract
Zeolites and microporouos materials continue to attract attention as novel hosts for photochemical reactions. Zeolities are attractive because of their ability to selectivity exchange and incorporate species within the void spaces and interconnecting channels, providing a spatial arrangement of molecules. Our research has primarily focused on intrazeolitic electron transfer from excited Ru(bpy)32+ in supercages of zeolite Y to a series of bipyridinium ions. In the Ru(bpy)32+ viologen-zeolite Y samples, the slowing of the back electron transfer from the bipyridinium radical cation to Ru(bpy)32+ allows for charge propagation via self exchange between diquat molecules. This provides an opportunity for permanent charge separation. When the migrating charge on the diquat radical within the zeolite reaches the surface, it can be transferred to a neutral viologen (PVS) in solution, resulting in permanent charge separation. The advantage of long-lived charge separation can be exploited for useful chemistry if suitable catablysts can be assembled on the zeolities. We have studied Ru(bpy)2 as water oxdiation catalysts. We have demonstrated that synthesis of RuO2 fibers on a zeolite via thermal decomposition of Ru3(CO)12 leads to the most active water decomposition catalyst reported to date. Because of the extensive interest of photochemical water reduction to H2, much is known about catalytic systems usin gone electron catalyst, and even more importantly, that no reaction of viologen occurred with H2 over this catalyst. The present challenge is to incorporate all these elements of the system into an architecture and we are examining zeolite membranes for this purpose.