Liu Xu, Wang Endong, Zhou Meng, Wan Yan, Zhang Yuankun, Liu Haoqi, Zhao Yue, Li Jin, Gao Yi, Zhu Yan
Key Lab of Mesoscopic Chemistry of MOE and Jiangsu Key Lab of Vehicle Emissions Control, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
Interdisciplinary Research Center, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201210, China.
Angew Chem Int Ed Engl. 2022 Aug 1;61(31):e202207685. doi: 10.1002/anie.202207685. Epub 2022 Jun 15.
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.
在金属纳米团簇中将掺杂杂原子精确地操控到期望位置是一个障碍。在此，我们克服了这一困难，通过将Pt原子可控地掺杂到Au(SCH₂PhBu)₄的内核中，获得了Pt₁Au(SCH₂PhBu)₄和Pt₂Au(SCH₂PhBu)₄纳米团簇。我们发现，与具有14个电子的Au(SCH₂PhBu)₄相比，将一个Pt原子不对称地掺杂到Au(SCH₂PhBu)₄的任一内核中会提高HOMO（最高占据分子轨道）的相对能量，同时Pt₁Au(SCH₂PhBu)₄会损失一个价电子；而将两个Pt原子对称地掺杂到Au(SCH₂PhBu)₄的内核中会使具有少两个价电子的Pt₂Au(SCH₂PhBu)₄的HOMO-LUMO能隙（LUMO：最低未占据分子轨道）变窄。因此，Pt₁Au(SCH₂PhBu)₄对CO电还原表现出电子自旋诱导的高活性，而Pt₂Au(SCH₂PhBu)₄效率最低，Au(SCH₂PhBu)₄具有良好的性能。
