Abstract
The zeolite-catalyzed conversion of DME into chemicals is considered environmentally friendly in industry. The periodic density functional theory, statistical thermodynamics, and the transition state theory are used to study some possible parallel reactions about the hydrogen-bonded DME over zeolite ferrierite. The following are the key findings: (1) the charge separation probably leads to the conversion of a hydrogen-bonded DME into a dimethyl oxonium ion (i.e., DMO(+) or (CH(3))(2)OH(+)) with a positive charge of about 0.804 e; (2) the methylation of DME, CH(3)OH, H(2)O, and CO by DMO(+) at the T2O6 site of zeolite ferrierite shows the different activated internal energy (∆E(≠)) ranging from 18.47 to 30.06 kcal/mol, implying the strong methylation ability of DMO(+); (3) H-abstraction by DMO(+) is about 3.94-15.53 or 6.57-18.16 kcal/mol higher than DMO(+) methylation in the activation internal energy; (4) six DMO(+)-mediated reactions are more likely to occur due to the lower barriers, compared to the experimental barrier (i.e., 39.87 kcal/mol) for methyl acetate synthesis; (5) active intermediates, such as (CH(3))(3)O(+), (CH(3))(2)OH(+), CH(3)CO(+), CH(3)OH(2)(+), and CH(2)=OH(+), are expected to appear; (6) DMO(+) is slightly weaker than the well-known surface methoxy species (ZO-CH(3)) in methylation; and (7) the methylated activity declines in the order of DME, CH(3)OH, H(2)O, and CO, with corresponding rate constants at 463.15 K of about 3.4 × 10(4), 1.1 × 10(2), 0.18, and 8.2 × 10(-2) s(-1), respectively.