The confinement effect on the adsorption and reaction mechanism of unsaturated aliphatic, aromatic and heterocyclic compounds on H-ZSM-5 zeolite has been investigated by the four ONIOM methods (MP2:M06-2X), (MP2:B3LYP), (MP2:HF), and (MP2:UFF). The H-ZSM-5 'nanoreactor' porous intersection, where chemical reactions take place, is represented by a quantum cluster of 34 tetrahedral units. Ethene, benzene, ethylbenzene, and pyridine are chosen to represent reactions of various adsorbates of aliphatic, aromatic and heterocyclic compounds. Among the four combined methods, (MP2:M06-2X) outperforms the others. The results confirm that the method that takes weak interactions, especially the van der Waals interaction, into account is essential for describing the confinement effect from the zeolite framework. The effects of the infinite zeolitic framework on the cluster model are also included by a set of point charges generated by the embedded ONIOM model. The energies for the adsorption of ethene, benzene, ethylbenzene, and pyridine on H-ZSM-5 from an embedded ONIOM(MP2:M06-2X) calculation are predicted to be -14.0, -19.8, -24.7, and -48.4 kcal/mol, respectively, which are very close to available experimental observations. The adsorption energy of pyridine agrees well with the experiment data of -47.6 kcal/mol. We also applied the same computational methodology on the systematic investigation of the H/H exchange reaction of benzene and ethylbenzene with the acidic H-ZSM-5 zeolite. The H/H exchange reaction was found to take place in a single concerted step. The calculated apparent activation energies for benzene and ethylbenzene are 12.6 and 4.9 kcal/mol, which can be compared to the experimental estimates of 11.0 and 6.9 kcal/mol, respectively. The confinement effect of the extended zeolite framework has been clearly demonstrated not only to stabilize the adsorption complexes but also to improve their corresponding activation energies to approach the experimental benchmark.

Catalytic conversion of hazardous gases can solve many of the environmental problems caused by them. We performed a density functional theory (DFT) study with the Perdew−Burke−Ernzerhof (PBE) functional to investigate the CO oxidation by using N 2 O as an oxidizing agent over an iron-embedded graphene (Fe-Graphene) catalyst. The N 2 O molecule was first decomposed on the Fe site yielding the N 2 molecule and an Fe−O intermediate, which was an active species for the CO oxidation. The activation energy for the N 2 O decomposition step was predicted to be 8 kcal/mol. According to the population analysis, the graphene acted as both the electron withdrawing and donating support to assist the charge transfer between the Fe atom and the probe molecules, which are important for the reaction. The reaction was found to be less facile when the Fe site was first covered by the CO which has a higher adsorption energy than that of the N 2 O (−10.0 vs −33.6 kcal/mol). The reaction proceeded via a concerted transition structure and required an activation energy of 19.2 kcal/mol when the CO was prior adsorbed. Thus, control of the adsorbing molecules over Fe-Graphene might be a key factor for the activity of the catalyst. With the higher catalytic activities of Fe-embedded graphene compared to other typical catalysts, this may open new avenues in searching for oxidation of CO at an economical cost.

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The reaction mechanisms of the partial oxidation of methane to methanol over FeO/graphene are unraveled using an advanced DFT approach.

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Ethanol, through the utilization of bioethanol as a chemical resource, has received considerable industrial attention as it provides an alternative route to produce more valuable hydrocarbons. Using a density functional theory approach incorporating the M06-L functional, which includes dispersion interactions, a large 34T nanocluster model of Fe-ZSM-5 zeolite in which T is a Si or Al atom is employed to examine both the stepwise and concerted mechanisms of the transformation of ethanol into ethene. For the stepwise mechanism, ethanol dehydration commences from the first hydrogen abstraction of the ethanol OH group to form the ethoxide-hydroxide intermediate with a low activation energy of 17.7 kcal mol(-1). Consequently, the ethoxide-hydroxide intermediate is decomposed into ethene through hydrogen abstraction from the ethoxide methyl carbon to either the OH group of hydroxide or the oxygen of the ethoxide group with high activation energies of 64.8 and 63.5 kcal mol(-1), respectively. For the concerted mechanism, ethanol transformation into the ethene product occurs in a single step without intermediate formation, with an activation energy of 32.9 kcal mol(-1).

The isomerization mechanisms of propene oxide over H-ZSM-5 zeolite have been investigated via the utilization of 5T and 46T cluster models calculated by the B3LYP/6-31G(d,p) and the ONIOM(B3LYP/6-31G(d,p):UFF) methods, respectively. The reactions are considered to proceed through a stepwise mechanism: (1) the epoxide ring protonation, and concurrently the ring-opening, and (2) the 1,2-hydride shift forming the adsorbed carbonyl compound. Because of the asymmetric structure of propene oxide, two different C-O bonds (more or less substituted carbon atom sides) can be broken leading to two different types of products, propanal and propanone. The ring-opening step of these mechanisms is found to be the rate-determining step with an activation barrier of 38.5 kcal/mol for the propanal and of 42.4 kcal/mol for the propanone. Therefore, the propanal is predicted to be the main product for this reaction.

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