A new aspect of heterogeneous catalysis: Highly reactive cis-(NO)2 dimer and Eley–Rideal mechanism for NO–CO reaction on a Co-dimer/γ-alumina catalyst

摘要: Abstract A catalytic aspect, ‘surface NO reactions assisted by gas phase CO molecules’ on a Co2+-ensemble/γ-Al2O3 catalyst, was elucidated successive density functional theory (DFT) calculations Co2+-dimer/γ-Al2O3 model surface. Unique cis-(NO)2 dimeric species formed due to specific alignment of the unoccupied orbitals Co2+-dimer, whose vibrational frequencies were almost identical those for conventional gem-dinitrosyl species. The showed much higher reactivity with than species, through 2π∗–2π∗ bonding between two adsorbates. Detailed DFT reaction pathways indicated an Eley–Rideal mechanism unusually large reactive cross-section.