Controlling CH2 dissociation on Ru(0001) through surface site blocking by adsorbed hydrogen
2014
Kirsch, Harald | Zhao, Xunhua | Ren, Zefeng | Levchenko, Sergey V. | Wolf, Martin | Campen, R Kramer
Understanding the relative stability of CHx species on surfaces is necessary for mechanistic description of much important catalytic chemistry. Here, we experimentally quantify the barrier of the reaction CH2→CH+H on Ru(0001) in UHV and find an activation energy, 65±6kJ/mol, that is >4× higher than previous computational results with 0, 1, or 2 coadsorbed H atoms per CH2, i.e. 16kJ/mol. Employing density functional theory calculations, we show that this disagreement can be reconciled if 3 coadsorbed H atoms per CH2 are present in our experiment. We further demonstrate, by calculating the surface phase diagram for one carbon species on Ru(0001) as a function of H2 chemical potential, that the additional hydrogen surface coverage requires non-equilibrium conditions. Such conditions may be important at the high temperatures and pressures of real catalytic systems.
显示更多 [+] 显示较少 [-]