Anti‐galvanic reaction (AGR) not only defies classic galvanic theory but is a promising method for tuning the compositions, structures, and properties of noble‐metal nanoparticles. Employing AGR for the preparation of alloy nanoparticles has recently received great interest. Herein, we report an unprecedented alloying mode by way of AGR, in which foreign atoms induce structural transformation of the mother nanoparticles and enter the nanoparticles in a non‐replacement fashion. A novel, active‐metal‐doped, gold nanoparticle was synthesized by this alloying mode, and its structure resolved. A CdSH motif was found in the protecting staples of the bimetal nanoparticle. DFT calculations revealed that the Au₂₀Cd₄(SH)(SR)₁₉ nanoparticle is a 8e superatom cluster. Furthermore, although the Cd‐doping does not essentially alter the absorption spectrum of the mother nanocluster, it distinctly enhances the stability and catalytic selectivity of the mother nanoclusters.

中文翻译：

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通过抗电反应的第四种合金化模式

抗电反应（AGR）不仅违背了经典的电学理论，而且还是一种用于调节贵金属纳米粒子的组成，结构和性能的有前途的方法。最近，采用AGR制备合金纳米颗粒受到了广泛的关注。在本文中，我们报道了一种通过AGR前所未有的合金化模式，其中外来原子诱导了母体纳米颗粒的结构转变，并以不可替代的方式进入纳米颗粒。通过这种合金化方式合成了一种新型的，掺杂有活性金属的金纳米粒子，并且其结构得以解析。在双金属纳米颗粒的保护钉中发现了CdSH基序。DFT计算表明，Au ₂₀ Cd ₄（SH）（SR）₁₉纳米粒子是8e超原子簇。此外，尽管Cd掺杂并没有本质上改变母纳米团簇的吸收光谱，但它明显增强了母纳米团簇的稳定性和催化选择性。