Density Functional Investigations of Methanol Dehydrogenation on Pd−Zn Surface Alloy

Methanol dehydrogenation on Pd(111) and various Pd-Zn surface alloy films supported on Pd(111) have been investigated using density functional method in combination with periodic slab models. Calculations show that compared to Pd(111) the interaction between CH(3)O and the films is enhanced, whereas that for CH(2)O and CHO is weakened. Zn in top layer facilitates the CH(3)O stability. At variance, the subsurface Zn reduces the interaction of CH(2)O and CHO with the substrate significantly. Addition of Zn promotes the O-H breaking of CH(3)OH and the dehydrogenation of CHO but hinders the dehydrogenation of CH(3)O and CH(2)O. Comparison shows that the third-layer Zn atoms have essentially no effect on the reactions. Our calculations demonstrate that the experimentally observed 360 K desorption peak cannot be originated from CH(2)O adsorbed at flat Pd-Zn alloy surfaces, and it is very likely that CH(2)O combines preferentially with some species before decomposing into CHO during methanol steam reforming if CH(2)O is an intermediate. Finally, we show that the newly proposed relationship between the energy of the initial states and transition states exhibits better correlation than the classical BEP relation.