ABSTRACT
This paper reports a novel procedure using nanosomes, made of bola-hydroxyl and mercapto-palmitic acids, for the production of gold clusters with robust luminescent emissions and very large Stokes shifts. It shows that these results cannot be explained by the currently accepted mechanism based on ligand-to-metal charge transfer absorptions involving electron-rich ligands attached to the cluster core. Exhaustive characterization of the cluster samples using Mass Spectrometry, HR-TEM/STEM, XPS, EXAFS, and steady-state and time-resolved luminescence allows to deduce that a mixture of two cluster sizes, having non-closed shell electronic configurations, are firstly generated inside the nanosome compartments due to the difference in bonding strength of the two types of terminal groups in the fatty acids. This initial bimodal cluster size distribution slowly evolves into very stable, closed-shell Au cluster complexes (Au6-Au16 and Au5-Au14) responsible for the observed luminescent properties. The very small (≈1.2 nm) synthesized cluster complexes are water soluble and suitable to be used for the conjugation of biomolecules (through the terminal COO(-) groups) making these systems very attractive as biomarkers and offering, at the same time, a novel general strategy of fabricating stable atom-level quantum dots with large Stokes shifts of great importance in many sensor applications.
ABSTRACT
Ni-W nanostructured coatings electrodeposited on steel by galvanostatic pulses were functionalized by tetraethoxysilane (TEOS) and octadecyltrichlorosilane (OTS) in a two-step procedure. A silica-rich layer is formed by the reaction of TEOS with the metal coating surface oxides, which allows a further reaction with OTS forming a hydrocarbon-silica outer network. This mixed silane layer provides hydrophobicity and improves the corrosion behavior of the Ni-W surface coatings without modifying their excellent mechanical properties.
ABSTRACT
Reductive electrodesorption has been used to produce "naked" gold nanoparticles (AuNPs) 3 nm in size on HOPG from different thiolate-capped AuNPs. The clean AuNPs transform the electrocatalytic inert HOPG into an active surface for hydrogen peroxide electroreduction, causing a lowering of the cathodic overpotential of 0.25 V with respect to the Au(111) surface. Compared to the plain gold substrates, the nanostructures promote only a slight increase in the hydrogen evolution reaction. In a second modification step a â¼1 nm thick melanin-iron coating is electrochemically formed around the AuNPs. This ultrathin melanin-iron coating largely improves the catalytic activity of the bare AuNPs for both hydrogen peroxide electroreduction and hydrogen evolution reaction. This strategy, which integrates electrochemistry and nanotechnology, can be applied to the preparation of efficient "naked" AuNPs and organic-iron capped AuNPs catalysts.
Subject(s)
Gold/chemistry , Graphite/chemistry , Melanins/chemistry , Nanostructures/chemistry , Nanostructures/ultrastructure , Catalysis , Macromolecular Substances/chemistry , Materials Testing , Molecular Conformation , Particle Size , Surface PropertiesABSTRACT
Perturbed-angular correlation, x-ray absorption, and small-angle x-ray scattering spectroscopies were suitably combined to elucidate the local structure of highly diluted and dispersed InOx species confined in the porous of the ZSM5 zeolite. This novel approach allow us to determined the structure of extremely nanosized In-O species exchanged inside the 10-atom-ring channel of the zeolite, and to quantify the amount of In2O3 crystallites deposited onto the external zeolite surface.
