Asymmetrically Doping a Platinum Atom into a Au<sub>38</sub> Nanocluster for Changing the Electron Configuration and Reactivity in Electrocatalysis
Xu Liu, Endong Wang, Meng Zhou, Yan Wan, Yuankun Zhang, Haoqi Liu, Yue Zhao, Jin Li, Yi Gao, Yan Zhu
Abstract
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.