Asymmetrically Doping a Platinum Atom into a Au38 Nanocluster for Changing the Electron Configuration and Reactivity in Electrocatalysis

Abstract 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 1 Au 37 (SCH 2 Ph t Bu) 24 and Pt 2 Au 36 (SCH 2 Ph t Bu) 24 nanoclusters via controllably doping Pt atoms into the kernels of Au 38 (SCH 2 Ph t Bu) 24 . We reveal that asymmetrical doping of one Pt atom into either of the cores of Au 38 (SCH 2 Ph t Bu) 24 elevates the relative energy of the HOMO (highest occupied molecular orbital) accompanied by one valence electron loss of Pt 1 Au 37 (SCH 2 Ph t Bu) 24 , compared to Au 38 (SCH 2 Ph t Bu) 24 with 14 electrons, while symmetrical doping of two Pt atoms into the cores of Au 38 (SCH 2 Ph t Bu) 24 narrows the HOMO–LUMO gap (LUMO: lowest unoccupied molecular orbital) of Pt 2 Au 36 (SCH 2 Ph t Bu) 24 with two valence electrons less. Consequently, Pt 1 Au 37 (SCH 2 Ph t Bu) 24 shows an electron‐spin‐induced high activity for CO 2 electroreduction, whereas Pt 2 Au 36 (SCH 2 Ph t Bu) 24 is least efficient and Au 38 (SCH 2 Ph t Bu) 24 has a decent performance.