Asymmetrically Doping a Platinum Atom into a Au-38 Nanocluster for Changing the Electron Configuration and Reactivity in Electrocatalysis
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作者
Liu, Xu; Wang, Endong; Zhou, Meng; Wan, Yan; Zhang, Yuankun; Liu, Haoqi; Zhao, Yue; Li, Jin; Gao, Yi; Zhu, Yan
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刊物名称
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
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年、卷、文献号
2022, 61, 1433-7851
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关键词
Liu, Xu; Wang, Endong; Zhou, Meng; Wan, Yan; Zhang, Yuankun; Liu, Haoqi; Zhao, Yue; Li, Jin; Gao, Yi; Zhu, Yan
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摘要
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 Pt1Au37((SCH2PhBu)-Bu-t)(24) and Pt2Au36((SCH2PhBu)-Bu-t)(24) nanoclusters via controllably doping Pt atoms into the kernels of Au-38((SCH2PhBu)-Bu-t)(24). We reveal that asymmetrical doping of one Pt atom into either of the cores of Au-38((SCH2PhBu)-Bu-t)(24) elevates the relative energy of the HOMO (highest occupied molecular orbital) accompanied by one valence electron loss of Pt1Au37((SCH2PhBu)-Bu-t)(24), compared to Au-38((SCH2PhBu)-Bu-t)(24) with 14 electrons, while symmetrical doping of two Pt atoms into the cores of Au-38((SCH2PhBu)-Bu-t)(24) narrows the HOMO-LUMO gap (LUMO: lowest unoccupied molecular orbital) of Pt2Au36((SCH2PhBu)-Bu-t)(24) with two valence electrons less. Consequently, Pt1Au37((SCH2PhBu)-Bu-t)(24) shows an electron-spin-induced high activity for CO2 electroreduction, whereas Pt2Au36((SCH2PhBu)-Bu-t)(24) is least efficient and Au-38((SCH2PhBu)-Bu-t)(24) has a decent performance.
