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ABSTRACT: The anomalous stability of magic-number metal clusters has been associated with closed geometric and electronic shells and the opening of HOMO-LUMO gaps. Despite this enhanced stability, magic-number clusters are known to decay and react in the condensed phase to form other products. Improving our understanding of their decay mechanisms and developing strategies to control or eliminate cluster instability is a priority, to develop a more complete theory of their stability, to avoid studying mixtures of clusters produced by the decay of purified materials, and to enable technology development. Silver clusters are sufficiently reactive to facilitate the study of the ambient temporal stability of magic-number metal clusters and to begin to understand their decay mechanisms. Here, the solution phase stability of a series of silver:glutathione (Ag:SG) clusters was studied as a function of size, pH and chemical environment. Cluster stability was found to be a non-monotonic function of size. Electrophoretic separations showed that the dominant mechanism involved the redistribution of mass toward smaller sizes, where the products were almost exclusively previously known cluster sizes. Optical absorption spectra showed that the smaller clusters evolved toward the two most stable cluster sizes. The net surface charge was found to play an important role in cluster stabilization although charge screening had no effect on stability, contrary to DLVO theory. The decay mechanism was found to involve the loss of Ag(+) ions and silver glutathionates. Clusters could be stabilized by the addition of Ag(+) ions and destabilized by either the addition of glutathione or the removal of Ag(+) ions. Clusters were also found to be most stable in near neutral pH, where they had a net negative surface charge. These results provide new mechanistic insights into the control of post-synthesis stability and chemical decay of magic-number metal clusters, which could be used to develop design principles for synthesizing specific cluster species.
Nanoscale 02/2013; · 5.91 Impact Factor
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ABSTRACT: Mass spectrometry has played a key role in identifying the members of a series of gold clusters, which has enabled the development of magic-number cluster theory. The successes of the gold cluster system have yet to be repeated in another metal cluster system, however. Silver clusters in particular have proven to be challenging due to their relative instability compared with gold clusters. Using the well-characterized gold nanocluster, Au(25)(SG)(18), we present optimized electrospray ionization mass spectrometry (ESI-MS) instrumental parameters for the maximal transmission of the intact cluster. Parameters shown to have the largest effect on intact cluster transmission/detection include trap and transfer collision energy, source temperature, and cone gas flow rate. Herein we describe a general strategy to acquire mass spectra of fragile metal clusters with reliable mass assignments. By also optimizing sample solution conditions, high-quality ESI mass spectra of a prototypical silver:glutathione (Ag:SG) cluster were obtained without significant fragmentation. By using gentle conditions and solution conditions designed to stabilize the clusters, fragmentation was dramatically reduced and mass spectra with isotopic resolution were measured. Using this strategy, we have made the first formula assignment for a ligand-protected Ag cluster of Ag(32)(SG)(19).
Analytical Chemistry 05/2012; 84(12):5304-8. · 5.86 Impact Factor
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ABSTRACT: Plasmonic films have become important for many applications including photonics, energy conversion, and chemical sensing, but the fabrication of these films often requires special equipment, great care, and skill. Colloidal metal nanoparticles offer an alternative as they have been shown to self-assemble into highly-ordered monolayer films by the simple and inexpensive technique of drop casting. Using this technique, we fabricated wafer-scale films of highly-ordered 6 nm Au nanoparticles and evaluated them as candidates for plasmonic applications. These colloidal films were found to support uniform and high-quality plasmon modes over the entire area of the wafer. A combination of microscopy and spectroscopy was used to evaluate and correlate the structural and optical qualities of the films. Electron and atomic force microscopy showed that the nanoscale structure of the films was compact and highly ordered, with few defects or bilayers. Spectroscopic ellipsometry showed that the majority of the film was optically quite uniform with some bilayer patches and voids. These were subsequently confirmed by microscopy. Optical analysis of the thin film showed a prominent plasmon resonance band across the entire wafer. The plasmon frequency was quite insensitive to the presence of voids or bilayers. The width of the plasmon band was more sensitive to bilayers, however, and was found to be as much as 15% wider than in monolayer regions. These results indicate that self-assembled colloidal thin films should be suitable for large-scale plasmonic applications.
Thin Solid Films 519(18):6077-6084. · 1.89 Impact Factor
