Nature Communications · 2016 · 126 citations · 54 references
Natural SciencesChemistryMaterials ScienceMaterials ChemistryPhysical ChemistryTheoretical ChemistryChemical ReactionsCluster ChemistryCoordination ChemistryMetal-ligand BondingNanomaterials SynthesisNanoparticle SynthesisAlloy Composition EffectsCluster Assembling ReactionsElectrospray IonizationElectrospray Ionization CouplingMetal Alloy CompositionMolecular Docking AnalysisNanoparticle Surface ChemistryTransformations
Abstract Ambient, structure- and topology-preserving chemical reactions between two archetypal nanoparticles, Ag 25 (SR) 18 and Au 25 (SR) 18 , are presented. Despite their geometric robustness and electronic stability, reactions between them in solution produce alloys, Ag m Au n (SR) 18 ( m + n =25), keeping their M 25 (SR) 18 composition, structure and topology intact. We demonstrate that a mixture of Ag 25 (SR) 18 and Au 25 (SR) 18 can be transformed to any arbitrary alloy composition, Ag m Au n (SR) 18 ( n =1–24), merely by controlling the reactant compositions. We capture one of the earliest events of the process, namely the formation of the dianionic adduct, (Ag 25 Au 25 (SR) 36 ) 2− , by electrospray ionization mass spectrometry. Molecular docking simulations and density functional theory (DFT) calculations also suggest that metal atom exchanges occur through the formation of an adduct between the two clusters. DFT calculations further confirm that metal atom exchanges are thermodynamically feasible. Such isomorphous transformations between nanoparticles imply that microscopic pieces of matter can be transformed completely to chemically different entities, preserving their structures, at least in the nanometric regime.
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