Asymmetrically Doping a Platinum Atom into a Au Nanocluster for Changing the Electron Configuration and Reactivity in Electrocatalysis.

It is an obstacle to precisely manipulate a doped heteroatom into a desired position in a metal nanocluster. Herein, we overcome this difficulty to obtain Pt Au (SCH Ph Bu) and Pt Au (SCH Ph Bu) nanoclusters via controllably doping Pt atoms into the kernels of Au (SCH Ph Bu) . We reveal that asymmetrical doping of one Pt atom into either of the cores of Au (SCH Ph Bu) elevates the relative energy of the HOMO (highest occupied molecular orbital) accompanied by one valence electron loss of Pt Au (SCH Ph Bu) , compared to Au (SCH Ph Bu) with 14 electrons, while symmetrical doping of two Pt atoms into the cores of Au (SCH Ph Bu) narrows the HOMO-LUMO gap (LUMO: lowest unoccupied molecular orbital) of Pt Au (SCH Ph Bu) with two valence electrons less. Consequently, Pt Au (SCH Ph Bu) shows an electron-spin-induced high activity for CO electroreduction, whereas Pt Au (SCH Ph Bu) is least efficient and Au (SCH Ph Bu) has a decent performance.