DFT Studies on Dehydrogenation Mechanism of Methane Activated by Gas-phase Niobium Cations

Abstract

Abstract: Density functional calculations were employed to investigate the quintet, triplet and singlet energies of methane direct- or inserted- dehydrogenation by gas-phase Nb⁺ as well as the influence of spin-inversion on the reaction mechanism. The results indicate that the inserted-dehydrogenation mechanism is more favorable than the direct-dehydrogenation. The minimum energy reaction path is thought to be related to the spin flip from 2S+1＝5 to 3, which decreases the activation barrier of methane-dehydrogenation significantly. The formed intermediate HNbCH⁺₃ is transformed into(H₂)NbCH⁺₂ via a four-centered transition state, and the final product is the triplet NbCH⁺₂+H₂. The rate determined step of reaction is the dehydrogenation of (H₂)NbCH⁺₂. In addition, the reactivities of gas-phase group V cations(V⁺, Nb⁺ and Ta⁺) towards the dehydrogenation of methane were also discussed.

Key words: DFT, Methane, Dehydrogenation, Nb

CLC Number:

O641

TrendMD:

LI Jian-Hui, XIA Wen-Sheng, WAN Hui-Lin. DFT Studies on Dehydrogenation Mechanism of Methane Activated by Gas-phase Niobium Cations[J]. Chem. J. Chinese Universities, doi: .

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DFT Studies on Dehydrogenation Mechanism of Methane Activated by Gas-phase Niobium Cations

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