Density functional theory calculations of the hydrazine decomposition mechanism on the planar and stepped Cu(111) surfaces

摘要: We have investigated the adsorption of hydrazine (N2H4) and its reactivity on terraces steps Cu(111) surfaces by first-principles calculations in order to gain insight into decomposition mechanism. different possibilities for N–N N–H bond cleavage any intermediate states analysing reaction barrier energies each elementary step. found that dehydrogenation via scission is neither energetically nor kinetically favourable flat stepped surfaces, but prefers form NH2via decoupling with an activation energy below 1 eV. The NH2 molecule reacts fairly easily co-adsorbed NH3 as well N2Hx (x = 1–4) abstracting hydrogen produce N2 molecules both surfaces. also all intermediates except NNH prefer breaking most likely dissociation pathway, where amide imide produced can be hydrogenated presence hydrogen. only intermediate, which dissociate a highly exothermic process after overcoming small energy. studied production H2 recombination ad-atoms which, considering energies, particularly favoured under conditions moderate temperatures. Our results agree experiments suggesting N2H4 adsorbs dissociatively copper above ∼300 K leading N2, H2. In general, lower coordination lead higher than surface. Furthermore, show influence step edge atoms very intra- intermolecular mechanisms. They increase existing species reaction.