1H solid-state nuclear magnetic resonance study of the mobility of the tetrapropylammonium template in a purely siliceous MFI-type zeolite.
Dynamics of tetrapropylammonium (TPA) cation occluded during the synthesis in a siliceous MFI zeolite is investigated by 1H broad-line nuclear magnetic resonance (NMR) methods. Second moments M2, spin-lattice relaxation times T1 and T1 rho are measured in a large temperature domain. To al comparison, similar measurements are also reported in bulk tetrapropylammonium bromide (TPABr). Whereas methyl reorientation at low temperature and tumbling of the cation in the plastic phase are observed in crystalline TPABr in accordance with published studies, a new slower motion which could not be identified is observed below the phase transition. Such a motion is much more clearly shown by the existence of a minimum of T1 rho in a quenched sample. Our measurements in the zeolite demonstrate that the TPA template exhibits a larger and more complex mobility below 378 K. Beyond the fast methyl reorientation, the results disclose a motion which probably involves the entire propyl arms inside the channels. So the zeolite framework seems to make such a kind of motion easier. On the contrary, even at 450 K, the highest temperature investigated, the tumbling which would necessitate exchange of the propyl arms between the channels is not observed. A slow motion, responsible for a decrease of T1 rho above 350 K, could not be identified. While a simple correlation time is sufficient to describe the relaxation time dependences in TPABr, a distribution (such as Williams-Watts) is required to account for those in the zeolite.
Gougeon
R
R
Laboratoire de Matériaux Minéraux (URA-CNRS 428), Ecole Nationale Supérieure de Chimie de Mulhouse, France.
Chezeau
J M
JM
Meurer
B
B
D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008958:Models, Molecular; D011522:Protons; D000644:Quaternary Ammonium Compounds; D013696:Temperature; D017641:Zeolites
D011522:Protons; D000644:Quaternary Ammonium Compounds; C052377:tetrapropylammonium; D017641:Zeolites