Abstract
The polarization effect has been a powerful tool in controlling the morphology of metal nanoparticles. However, a precise investigation of the polarization effect has been a challenging pursuit for a long time, and little has been achieved for analysis at the atomic level. Here the atomic-level analysis of the polarization effect in controlling the morphologies of metal nanoclusters is reported. By simply regulating the counterions, the controllable transformation from Pt1Ag28(S-PhMe2)x(S-Adm)18−x(PPh3)4 (x = 0–6, Pt1Ag28-2) to Pt1Ag24(S-PhMe2)18 (Pt1Ag24) with a spherical configuration or to Pt1Ag28(S-Adm)18(PPh3)4 (Pt1Ag28-1) with a tetrahedral configuration has been accomplished. In addition, the spherical or tetrahedral configuration of the clusters could be reversibly transformed by re-regulating the proportion of counterions with opposite charges. More significantly, the configuration transformation rate has been meticulously manipulated by regulating the polarization effect of the ions on the parent nanoclusters. The observations in this paper provide an intriguing nanomodel that enables the polarization effect to be understood at the atomic level.
Highlights
Metal nanoparticles with different morphologies, such as nanostars, nanorods, nanowires, nano owers, and so on, have all been the subjects of widespread research interest in the past few decades.[1]
The role of counterions in controlling the shape of the nanoparticles has become a subject of particular interest.2b–d a detailed understanding of how potential counterion–metal interactions in uence the generation of corresponding nanoparticles with different morphologies has remained elusive for two main reasons: (i) the reaction process is hard to track, and (ii) the surface chemistry of the nanoparticles is difficult to study at the atomic level.3a These aDepartment of Chemistry, Centre for Atomic Engineering of Advanced Materials, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei 230601, P
Mirkin and co-workers have demonstrated that manipulating (i) the ratio of metal to halide ion, and (ii) the selection of appropriate halide ions could rationally control the morphology of the nanoparticles, under otherwise identical preparation conditions.2d In this context, it is acceptable that the nature of the counterions plays a crucial role in the growth processes of nanoparticles, and the polarization effect of ion-tonanoparticle is among one of the most effective in shape control
Summary
Metal nanoparticles with different morphologies, such as nanostars, nanorods, nanowires, nano owers, and so on, have all been the subjects of widespread research interest in the past few decades.[1] The underlying chemistry is a signi cant in uence on the morphologies of nanoparticles, and on their physicochemical properties, including electrochemical, catalytic, and optical properties.[1] Several reaction factors (e.g., temperature, stirring speed, reactant, counterions and so on) have been proved to have the capability to control the morphology of nanoparticles.[1,2] Amongst these factors, the role of counterions (e.g., halides) in controlling the shape of the nanoparticles has become a subject of particular interest.2b–d a detailed understanding of how potential counterion–metal interactions in uence the generation of corresponding nanoparticles with different morphologies has remained elusive for two main reasons: (i) the reaction process is hard to track, and (ii) the surface chemistry (e.g., metal–ligand interactions) of the nanoparticles is difficult to study at the atomic level.3a These.
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