title: Theoretical ONIOM2 study on pyridine adsorption in the channels and intersection of ZSM-5.
abstract: The structures of the acid sites in the channels and intersections of H-, Li-, and Na-ZSM-5 (ZSM = zeolite socony mobil) and their interactions with pyridine molecule have been computed by using three corresponding models containing 22 tetrahedral sites. The calculated adsorption energies of pyridine in the intersection regions of H-, Li-, and Na-ZSM-5 are 197.0, 172.5, and 122.3 kJ/mol, respectively, in good agreement with the respective experimental values of 200 +/- 5, 155-195, and 120 kJ/mol, while those in the straight and sinusoidal channels are much smaller (157.9 and 127.6, 152.2 and 149.4, and 150.4 and 109.9 kJ/mol, respectively). These indicate that the most probable adsorption site for pyridine in ZSM-5 is the acidic site located in the intersection region. The structural parameters of the adsorption complexes show that the acidic proton in the three models of H-ZSM-5 has been transferred to the nitrogen of pyridine, while in alkali cation-exchanged ZSM-5, the coordination of the alkali cation to the nitrogen atom of pyridine dominates the overall interaction. In addition, the adsorption complexes were further stabilized by the long-range electrostatic interaction between the positively charged pyridine hydrogen atoms and the negatively charged lattice oxygen atoms of the zeolite framework. In the intersection regions of H-, Li-, and Na-ZSM-5, the coordination energy of the charge-compensating cation to the pyridine nitrogen amounts to 58, 60, and 68% of the total adsorption energy, respectively, while another 42, 40, and 32%, respectively, is due to long-range electrostatic interactions. This indicates that the zeolite lattice framework surrounding the adsorption site has important contributions to the adsorption energy of the pyridine molecule.
authors.affiliation: State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, Taiyuan 030001, P. R. China.
authors.forename: Shuping
authors.initials: S
authors.lastname: Yuan
authors.forename: Wei
authors.initials: W
authors.lastname: Shi
authors.forename: Bingrui
authors.initials: B
authors.lastname: Li
authors.forename: Jianguo
authors.initials: J
authors.lastname: Wang
authors.forename: Haijun
authors.initials: H
authors.lastname: Jiao
authors.forename: Yong-Wang
authors.initials: YW
authors.lastname: Li