Abstract

Doping foreign atom(s) in metal nanoclusters is an effective strategy to engineer the properties and functionalities of metal nanoclusters. However, until now, to dope Pd atom into Ag nanoclusters remains a huge challenge. Here we develop a one-step rapid method to synthesize the Pd-doped Ag nanocluster with high yield. The prepared Pd₁Ag₂₈ nanocluster was characterized by mass spectroscopy, X-ray photoelectron spectroscopy, X-ray crystallography, fluorescence spectroscopy, ultraviolet–visible absorption spectroscopy and transient absorption spectroscopy. The nanocluster exhibits a perfect face-centered cubic (FCC) kernel structure with a tetrahedron-like shell. Of note, Pd₁Ag₂₈ nanocluster had an unexpectedly long excited-state lifetime of 3.3 microseconds, which is the longest excited-state lifetime for Ag-based nanoclusters so far. Meanwhile, the excellent near-infrared luminescence indicated the nanocluster has the potential in fluorescent bio-imaging. Besides, it was revealed that Pd₁Ag₂₈ nanocluster could be transformed into Au₁Ag₂₈ nanocluster via ion exchange reaction of AuPPh₃Cl with Pd₁Ag₂₈ nanocluster. This work provides an efficient synthetic protocol of alloy nanoclusters and will contribute to study the effect of foreign atom on the properties of metal nanoclusters.

中文翻译：

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Pd 1 Ag 28纳米团簇的一步式快速合成，晶体结构和3.3毫秒长的激发态寿命

抽象的

在金属纳米团簇中掺杂外来原子是一种工程化金属纳米团簇的性质和功能的有效策略。然而，直到现在，将Pd原子掺杂到Ag纳米团簇中仍然是一个巨大的挑战。在这里，我们开发了一种一步式快速方法，以高产率合成掺Pd的Ag纳米团簇。通过质谱，X射线光电子能谱，X射线晶体学，荧光光谱，紫外可见吸收光谱和瞬态吸收光谱对制备的Pd ₁ Ag ₂₈纳米簇进行了表征。纳米团簇具有完美的面心立方（FCC）核结构，并具有类似四面体的壳。值得注意的是Pd ₁ Ag ₂₈纳米团簇的激发态寿命长达3.3微秒，出乎意料的长，这是迄今为止基于Ag的纳米团簇的最长激发态寿命。同时，优异的近红外发光表明该纳米簇具有在荧光生物成像中的潜力。此外，揭示了通过AuPPh ₃ Cl与Pd ₁ Ag ₂₈纳米簇的离子交换反应，可以将Pd ₁ Ag ₂₈纳米簇转变为Au ₁ Ag ₂₈纳米簇。这项工作提供了合金纳米团簇的有效合成方案，并将有助于研究外来原子对金属纳米团簇的性能的影响。