The performance of many advanced catalytic systems depends not only on the size and composition but also on the specific shape of the metal nanoparticles (NPs) from which they are assembled. In turn, the shape of colloidal NPs depends on the specific capping agent involved in their synthesis, though the mechanism is still poorly understood. Here, supported by electrochemical experiments, FTIR spectra and DFT calculations, on well-defined surfaces, we show how a specific capping agent determines the shape of colloidal NPs.Solvated citrate can become simultaneously adsorbed on the Pt(111) surface through three dehydrogenated carboxylic groups, each one of them in bidentate configuration. On the other basal planes, citrate is adsorbed through only two of them. For this reason, under the synthesis conditions, citrate is more favorably adsorbed on the Pt(111) than on the other two basal planes of platinum. This adsorption behavior explains why colloidal platinum NPs of tetrahedral and octahedral shape are produced when citrate is used as the capping agent in water. The mechanism for citrate would also operate determining the shape of other pure fcc metals and can inspire the engineering of future capping agents.

The highly packed cetyltrimethylammonium bromide bilayer on the surface of gold nanorods synthesized by the seed-mediated procedure hampers the complete ligand exchange under experimental conditions that preserves the stability of the dispersions.

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Adsorbed amino acids can modulate the behavior of metal nanoparticles in advanced applications. Using a combination of electrochemical experiments, FTIR spectroscopy, and DFT calculations, glutamate species interacting with the Au(111) surface in solution are here investigated. Electrochemical results indicate that the adsorption behavior depends on the solution pH (which controls the glutamate ionization) and on the charge of the surface. Glutamate adsorption starts at potentials slightly negative to the potential of zero charge. The thermodynamic analysis of these results indicates that two electrons are exchanged per molecule, implying that both carboxylic groups become deprotonated upon adsorption. The FTIR spectra reveal that carboxylate groups are bonded to the surface in a bidentate configuration (with both oxygen atoms attached to the surface).Plausible adsorbed configurations, consistent with the whole of these insights, were found using DFT. Moreover, it was observed that glutamate oxidation only takes place when the surface is oxidized, which suggests that this oxidation process involves the transfer of an oxygen group to the molecule, though, according to the FTIR spectra, the main chain remains intact.