An in situ Al K-edge XAS investigation of the local environment of H+- and Cu+-exchanged USY and ZSM-5 zeolites.
Aluminum coordination in the framework of USY and ZSM-5 zeolites containing charge-compensating cations (NH4+, H+, or Cu+) was investigated by Al K-edge EXAFS and XANES. This work was performed using a newly developed in-situ cell designed especially for acquiring soft X-ray absorption data. Both tetrahedrally and octahedrally coordinated Al were observed for hydrated H-USY and H-ZSM-5, in good agreement with 27Al NMR analyses. Upon dehydration, water desorbed from the zeolite, and octahedrally coordinated Al was converted progressively to tetrahedrally coordinated Al. These observations confirmed the hypothesis that the interaction of water with Brønsted acid protons can lead to octahedral coordination of Al without loss of Al from the zeolite lattice. When H+ is replaced with NH4+ or Cu+, charge compensating species that absorb less water, less octahedrally coordinated Al was observed. Analysis of Al K-edge EXAFS data indicates that the Al-O bond distance for tetrahedrally coordinated Al in dehydrated USY and ZSM-5 is 1.67 angstroms. Simulation of k3chi(k) for Cu+ exchanged ZSM-5 leads to an estimated distance between Cu+ and framework Al atoms of 2.79 angstroms.
Drake
Ian J
IJ
Department of Chemical Engineering, University of California, Berkeley, California 94720-1462, USA.
Zhang
Yihua
Y
Gilles
Mary K
MK
Teris Liu
C N
CN
Nachimuthu
Ponnusamy
P
Perera
Rupert C C
RC
Wakita
Hisanobu
H
Bell
Alexis T
AT
D000535:Aluminum / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D011522:Protons; D013057:Spectrum Analysis / Q000379:methods*; D014965:X-Rays; D017641:Zeolites / Q000737:chemistry*
D011522:Protons; D017641:Zeolites; D003300:Copper; D000535:Aluminum