Nitric monoxide probe molecules are used to characterize the Lewis acid properties of sodium cations and aluminum defect centers in various zeolite materials. The adsorption-desorption behavior of NO probe molecules is studied at different temperatures for Na-A, Na-ZSM-5, H-ZSM-5, and silicalite. Adsorbed NO molecules form paramagnetic adsorption complexes with Lewis acid sites which can be examined by EPR transitions ((Delta)m(S)+/-1) at g approximately 2.0. Otherwise the desorption of NO into the gas phase can be monitored by the typical nine-line EPR spectrum ((Delta)m(J)+/-1) of the (2)Pi(3/2) state at g approximately 0.7776. This gas-phase signal is used to study the overall adsorption-desorption properties of the zeolites in the temperature range 150 K less than or approximately T less than or approximately 300 K. At lower temperatures the probe molecules are adsorbed at the Lewis acid sites inside the nanoporous materials and produce an intensive spectrum at T less than or approximately 110 K. But at intermediate temperatures 110 K less than or approximately T less than or approximately 150 K the NO molecules are adsorbed only for a few hundred picoseconds because the lifetime of the adsorption complexes is limited by the beginning desorption processes. The decreasing lifetime of the adsorption complex with rising temperature results in an increasing homogeneous line broadening of their EPR signals. An analysis of the line-broadening effects provides an opportunity for determining the specific desorption energies E(A)(H-ZSM-5)=(20.2+/-7.3) kJ/mol, E(A)(Na-ZSM-5)=(4.1+/-1.5) kJ/mol, and E(A)(Na-A)=(7.1+/-2.1) kJ/mol for NO probe molecules at sodium cations and aluminum defect centers just below the desorption temperature.
(c) 2002 Elsevier Science (USA).