D. Goldfarb et al., CHARACTERIZATION OF IRON IN ZEOLITES BY X-BAND AND Q-BAND ESR, PULSEDESR, AND UV-VISIBLE SPECTROSCOPIES, Journal of the American Chemical Society, 116(14), 1994, pp. 6344-6353
The local structure of Fe sites in a series of ferrisilicate and ferri
aluminosilicate zeolites (Fe-sodalite (FeSOD), Fe-L (FeL), Fe-faujasit
e (FeFAU), FeZSM5, and Fe-mazzite (FeMAZ)) in which iron was incorpora
ted during zeolite synthesis was studied by X- and Q-band ESR, electro
n spin echo detected ESR (ED-ESR), electron spin echo envelope modulat
ion (ESEEM), and diffuse reflectance UV-vis spectroscopies. Samples we
re investigated as a function of Fe content and after variable-tempera
ture dehydration and rehydration. Transitions characteristic of tetrah
edrally coordinated Fe3+ were observed in the diffuse reflectance spec
tra of all Fe zeolites except for FeFAU. A strong g = 2 signal was obs
erved in the ESR spectra of all the Fe zeolites whereas a g = 4.3 sign
al was observed only for the FeFAU, FeZSM5, and FeMAZ samples. Compari
son between X- and Q-band spectra indicates that only one type of Fe3 site is present in Fe-sodalite. Thus, neither the traditional assignm
ent of the ESR signals of iron in the zeolite framework to a g = 4.3 s
ignal nor some more recently proposed assignments could fully account
for all the present results. We conclude that Fe3+ can be incorporated
into framework sites in significant amounts in FeSOD, FeL, FeZSM5, an
d FeMAZ and probably also in FeFAU and that in each case framework Fe3
+ exhibits a g = 2 ESR signal. Since extraframework Fe3+ can also show
a g = 2 signal, its appearance does not provide evidence for framewor
k substitution unless combined with other physical or chemical methods
. Furthermore, the absence of the g = 4.3 signal in the ESR spectrum d
oes not exclude the possibility of framework substitution in zeolites.
Fe-faujasite was found to have significantly more extraframework Fe3 than the other Fe zeolites studied. Combined ESR, ED-ESR, and ESEEM o
n Fe-faujasite that was subjected to dehydration/rehydration cycling s
how that phases with ''aggregates'' of Fe ions are generated either by
dislodged framework Fe3+ and/or by migration of extraframework Fe3+.