PtMCH2+脱氢反应活性相对论密度泛函理论的研究.pdfVIP

Relativistic Density Functional Study on the Dehydrogenation Reactivity of PtMCH2 + (M=Cu, Ag, Au, Pt) toward NH3 1 Fei Xia Jian Chen Zexing Cao* Department of Chemistry, Xiamen University Xiamen, P. R. China 361005 zxcao@ Abstract The reactivity of bimetallic species PtMCH2+(M=Pt, Cu, Ag, Au) toward NH3 has been explored by the relativistic density functional approach. Calculated results reveal that the Dehydrogenation reactivity of PtMCH2+(M=Cu, Ag, Au, Pt) strongly depends on their lower-energy reactive precursors. The coexistence of the closed- and unclosed-triangular structures as precursors to distinct dehydrogenation channels for PtMCH2+(M=Cu, Ag, Au) make them exhibit similar reactivity. Predicted free energies of the reaction ΔG° reasonably agree with the experimental ratio of the product. Keywords: DFT Calculation ; PtMCH2+; Dehydrogenation reactivity. 1 Introduction The large-scale industrial synthesis of hydrogen cyanide lies on the Degussa process. Recently, a gas-phase model for the C-N bond coupling mediated by platinum has been proposed [1]. It has been shown that the metal cation carbene PtCH2+ [2,3] play a crucial role in the C-N bond formation. To explore the cooperative effect of bimetallic clusters on the catalytic process, Koszinowski et al. extended their investigations from mononuclear metal ion Pt+ to dinuclear metal ion clusters