A density functional theory study on the performance of graphene and N-doped graphene supported Au3 cluster catalyst for acetylene hydrochlorination

Density functional theory (DFT) calculation was used to investigate the mechanism of Au3 clusters, separately supported on pure graphene (Au3/graphene) and one graphitic N-doped graphene (Au3/N-graphene). These supported Au3 clusters were used to catalyze acetylene hydrochlorination. Results show that the graphene supporter could obviously enhance the adsorption of reactants. Also, N-atom doping could broaden the energy gap between the HOMO of graphene and the LUMO of Au3, leading to the significantly attenuated interaction between the Au3 cluster and graphene by more than 19 kcal/mol (1 cal = 4.184 J). The two catalysts possessed extremely similar reaction mechanisms with activation energy values of 23.26 and 23.89 kcal/mol, respectively. The calculated activation barrier declined in the order of Au3 < Au3/N-graphene < Au3/graphene, suggesting that Au3/N-graphene could be a potential catalyst for acetylene hydrochlorination.

Carbon–hydrogen vs. carbon–halogen oxidative addition of chlorobenzene to a cationic iridium(I) system — A density functional theory study

Density functional theory (DFT) is used to explore the competitive C−H and C−Cl oxidative additions (OA) of chlorobenzene to the cationic Ir(I) complex: [(PNP*)IrI]+ [PNP* = 2,6-bis((dimethylphosphino)methyl)pyridine]. Consistent with experimental results, the calculated activation barrier for C−H OA (ΔG‡ = 10.7 kcal mol–1) is lower than that for C−Cl OA (ΔG‡ = 19.7 kcal mol–1). However, the C−Cl OA product is calculated to be thermodynamically preferred as its ΔGo is 14.3 kcal mol–1 below that for the most stable C−H OA product.