S. Takahashi et al., FORMATION OF A METHOXY-MODIFIED INTERLAYER SURFACE VIA THE REACTION BETWEEN METHANOL AND LAYERED PEROVSKITE HLANB2O7-CENTER-DOT-XH(2)O, Inorganic chemistry, 34(20), 1995, pp. 5065-5069
The reactions between methanol (CH3OH, CH3OD, CD3OD, (CH3OH)-C-13) and
layered HLaNb2O7 . xH(2)O were investigated. X-ray powder diffraction
(XRD) analysis showed that a peak corresponding to the basal spacing
of HLaNb2O7 . H2O (1.05 nm) disappeared and a new peak appeared at 1.1
8 nm. Carbon-13 NMR spectra revealed the presence of two environments
of the methyl group; the broad 67 ppm signal is ascribed to the rigid
species located in the interlayer space, and the 50 ppm signal is ascr
ibed to mobile methanol on the external surface. The amount of the lat
ter species was negligibly small. Deuterium NMR spectra revealed the p
resence of a Pake doublet with an effective quadrupole coupling consta
nt (QCC) of 47 kHz and an asymmetry factor (eta) of zero, indicating t
hat the CD3O group was rigidly bound to the interlayer surface. In add
ition, when both CD3OD and CH3OD were used, no signal corresponding to
the OD group was observed. Hence, although XRD results can be interpr
eted as intercalation of methanol, the H-2 NMR results indicate that m
ethanol was dissociatively adsorbed to the interlayer surface. The obs
erved very high thermal stability of the methyl group is consistent wi
th methoxy formation. The structure of the product is discussed on the
basis of the results with larger n-alcohols.