First-principles study of methane dehydrogenation on a bimetallic Cu/Ni(111) surface.

We present density-functional theory calculations of the dehydrogenation of methane and CH(x) (x=1-3) on a Cu/Ni(111) surface, where Cu atoms are substituted on the Ni surface at a coverage of 14 monolayer. As compared to the results on other metal surfaces, including Ni(111), a similar activation mechanism with different energetics is found for the successive dehydrogenation of CH(4) on the Cu/Ni(111) surface. In particular, the activation energy barrier (E(act)) for CH-->C+H is found to be 1.8 times larger than that on Ni(111), while E(act) for CH(4)-->CH(3)+H is 1.3 times larger. Considering the proven beneficial effect of Cu observed in the experimental systems, our findings reveal that the relative E(act) in the successive dehydrogenation of CH(4) plays a key role in impeding carbon formation during the industrial steam reforming of methane. Our calculations also indicate that previous scaling relationships of the adsorption energy (E(ads)) for CH(x) (x=1-3) and carbon on pure metals also hold for several Ni(111)-based alloy systems.