Uniform catalytic site in Sn-beta-zeolite determined using X-ray absorption fine structure.
The Sn silicate zeolite, Sn-beta, has been shown to be an efficient, selective heterogeneous catalyst for Baeyer-Villiger oxidations. Using primarily a multishell fit to extended X-ray absorption fine structure (EXAFS) data, we show that the Sn does not randomly insert into the beta-zeolite structure but rather occupies identical, specific, crystallographic sites. These sites are the T5/T6 sites in the six-membered rings. Moreover, the Sn is substituted in pairs on opposite sides of these six-membered rings. We believe that it is the specific, uniform crystallographic location of the Sn in the beta crystal structure that leads to sites with uniform catalytic activity, and consequently to the high chemical selectivity demonstrated for this catalyst. This manifests itself in the almost enzyme-like selectivity of this catalyst in Baeyer-Villiger oxidations. This uniform site distribution of the Sn suggests that there is likely a symbiotic relationship between the structure-directing agent in the zeolite synthesis and the Sn heteroatoms during the framework formation.
Bare
Simon R
SR
UOP LLC, Des Plaines, Illinois 60016, EXAFS Analysis, Bolingbrook, Illinois 60440, USA.
Kelly
Shelly D
SD
Sinkler
Wharton
W
Low
John J
JJ
Modica
Frank S
FS
Valencia
Susana
S
Corma
Avelino
A
Nemeth
Laszlo T
LT
D000042:Absorption; D002384:Catalysis; D008958:Models, Molecular; D014001:Tin / Q000737:chemistry*; D014961:X-Ray Diffraction / Q000379:methods*; D017641:Zeolites / Q000737:chemistry*
D017641:Zeolites; D014001:Tin