Effect of Specific Heavy Doping of Silver Atoms into the Icosahedral Au₁₃ on Electronic Structure and Catalytic...

The exploration of specific heavy doping of silver atoms into icosahedral Au₁₃ clusters and their electronic structures and properties has been somewhat limited. Herein, we report two heavily Ag doped nanoclusters, [Au₇Ag₆(C₇H₄NOS)₄(Dppf)₃Cl]⁰ and [Au₇Ag₆(C₇H₄NOS)₃(Dppf)₃Cl](SbF₆) (Au₇Ag₆-0 and Au₇Ag₆-1, respectively) [C₇H₄NOSH = 2-mercaptobenzoxazole, and Dppf = 1,1'-bis(diphenylphosphino)ferrocene]. The electronic structures and superatomic orbitals of nanoclusters were determined by density functional theory (DFT) calculations, and the energy degeneracy of the superatomic orbitals of Au₇Ag₆-1 is higher than that of Au₇Ag₆-0. Transient absorption spectroscopy was performed, revealing that Au₇Ag₆-0 significantly extends the excited-state lifetime. Both nanoclusters were supported on activated carbon for the oxygen reduction reaction. DFT calculations confirm that the catalytic activities mainly stem from the carbon atom of ferrocene rather than the iron atom. This study not only sheds light on the preparation of icosahedral alloy clusters but also provides insights into the regulation of icosahedral superatomic structure and electrocatalytic properties.