Adsorption and Reaction of C₂H₄ and O₂ on a Nanosized Gold Cluster: A Computational Study

We have investigated the adsorption and reaction mechanisms of C₂H₄ and O₂ catalyzed by a Au₃₈ nanoparticle based on periodic density-functional theory (DFT) calculations. The configurations of the adsorption of C₂H₄/Au₃₈, O₂/Au₃₈, and O/Au₃₈ as well as the coadsorption of C₂H₄–O₂/Au₃₈ were predicted. The calculation results show that C₂H₄, O₂, and O are preferably bound at top (T), bridge (B), and hexagonal (h) sites with adsorption energies of −0.66, −0.99, and −3.93 eV, respectively. The detailed reaction mechanisms for ethylene epoxidation on the Au₃₈ nanoparticle has been illustrated using the nudged elastic band (NEB) method. The oxidation process takes place via the Langmuir–Hinshelwood (LH) mechanism to generate ethylene oxide and acetaldehyde. The overall reaction of C₂H₄ + O₂ + Au₃₈ → ethylene oxide + O/Au₃₈ is exothermic by 2.20–2.40 eV whereas those are 3.03–3.08 eV for the production of acetaldehyde and O/Au₃₈. The nature of the interaction between the adsorbate and gold nanocluster has been analyzed by the detailed electronic local density of states (LDOS) to understand the high catalytic activity of the gold nanoclusters