First-principles analysis of the C-N bond scission of methylamine on Mo-based model catalysts.

The C-N bond breaking of methylamine on clean, carbon (nitrogen, oxygen)-modified Mo(100) [denoted as Mo(100) and Mo(100)-C(N,O), respectively], Mo(2)C(100), MoN(100), and Pt(100) surfaces has been investigated by the first-principles density functional theory (DFT) calculations. The results show that the reaction barriers of the C-N bond breaking in CH(3)NH(2) on Mo(100)-C(N,O) are higher than that on clean Mo(100). The calculated energy barrier can be correlated linearly with the density of Mo 4d states at the Fermi level after the adsorption of CH(3)NH(2) for those surfaces. Moreover, the DFT results show that the subsurface atom, e.g., carbon, can reduce the reaction barrier. In addition, We noticed that the activation energies for the C-N bond breaking on Mo(2)C(100) and MoN(100) are similar to that on Pt(100), suggesting that the catalytic properties of the transition metal carbides and nitrides for C-N bond scission of CH(3)NH(2) might be very similar to the expensive Pt-group metals.