Formation of the V center on H-type zeolites with thermal treatment

The effect of thermal treatment on H-MCM-22 and H-ZSM-5 zeolites was investigated using the electron spin resonance technique. A six-line signal (denoted as A, g = 2.048, A = 22. 15 G) was detected on H-MCM-22 after He purging at high temperatures, whose intensities increased with the treating temperature. The same signal was also found on H-ZSM-5 zeolites with different crystal sizes. The paramagnetic center was identified as a V center, namely, a hole of an electron trapped on an oxygen atom bonding to a nearby aluminum atom. These signals appeared only on a dealuminated sample or a sample concomitantly with dealumination. The formation of the hole might involve an electron transferring from the lattice oxygen to a nonframework aluminum species, and the hyperfine splitting is caused by the interaction between the electron hole locating on the p orbit of oxygen and the framework aluminum bonding with the oxygen. The signal disappeared after the sample was exposed to air or oxygen at room temperature. However, the process was reversible. A new set of signals (denoted as B, g(1) = 2.008, g(2) = 2.003, g(3) = 1.9985) was observed after oxygen adsorption on the H-MCM-22 pretreated with He at 973 K or He purging at 973 K on the H-MCM-22 pretreated with oxygen at 813 K, which was attributed to the O- species.