Synergistic interaction between a corrugated surface and hydrogen bonding affects selectivity in bond cleaving reaction: A case of coadsorbed hydrazine-OH on Ni(211) system

Investigating how a surface affects first N–H and N–N bond cleaving in hydrazine (N2H4) is a critical step towards designing a selective catalyst. In this study, the first N–H and N–N bond cleaving in hydrazine (N2H4) and hydroxyl (OH) coadsorption system on the Ni(211) surface is investigated using Density Functional Theory (DFT) based calculations. Effects of the vicinal steps and edges in Ni(211) on the H-bond formation and the selectivity of each bond-cleaving reaction are demonstrated. The product of N–H bond cleaving is shown to be less stable than N–N bond cleaving. Nevertheless, the activation energy of N–H bond cleaving is demonstrated to be significantly lower than that of N–N. In an ideal extended periodic system used in this study at specific coverage, the results demonstrate the effect of utilizing a corrugated surface in promoting first N–H bond cleaving instead of N–N.