Chloromethoxyl and dichloromethoxyl formation on zeolite ZnY, an in situ NMR and flow reactor study

In situ C-13 and Al-27 MAS NMR and flow reactor studies were used to study the decomposition of dichloromethane and chloroform on zeolite ZnY. The initially formed products were framework-bound chloromethoxyl (from dichloromethane) and dichloromethoxyl (from chloroform) species, analogous to the non-halogenated alkoxyls observed in previous investigations. The principal components of the C-13 chemical shift tensors were: chloromethoxyl, delta(11) = 116 ppm, delta(22) = 79 ppm and delta(33) = 37 ppm; dichloromethoxyl, delta(11) = 128 ppm, delta(22) = 91 ppm and delta(33) = 65 ppm. Formation of both species occurred at 298 K, and each decomposed at 423 K. This decomposition formed HCl which dealuminated the zeolite (as monitored by Al-27 MAS NMR) causing deactivation (flow reactor studies). Further evidence for the destruction of the zeolite was the NMR observation of CO formation, implying incorporation of oxygen from zinc hydroxyl or framework sites. Although ZnY is shown to be unsuitable for catalytic chlorocarbon destruction, the observation of chloromethoxyl and dichloromethoxyl species is significant, and the formation of halogenated alkoxyl species should be considered in future investigations of halocarbon chemistry on oxides and molecular sieves.