Surface chemistry of thiomalic acid adsorption on planar gold and gold nanoparticles

The self-assembly of thiomalic acid (TMA) on Au(111) and on preformed Au nanoparticles (AuNPs) protected by weak ligands has been studied by X-ray photoelectron spectroscopy (XPS) and electrochemical techniques. Results show that TMA is adsorbed on the Au(111) surface as thiolate species with a smal...

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Veröffentlicht in:Langmuir : the ACS journal of surfaces and colloids. - 1992. - 30(2014), 7 vom: 25. Feb., Seite 1820-6
1. Verfasser: Azcárate, Julio C (VerfasserIn)
Weitere Verfasser: Addato, María Alejandra Floridia, Rubert, Aldo, Corthey, Gastón, Moreno, Germán S Kürten, Benítez, Guillermo, Zelaya, Eugenia, Salvarezza, Roberto C, Fonticelli, Mariano H
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2014
Zugriff auf das übergeordnete Werk:Langmuir : the ACS journal of surfaces and colloids
Schlagworte:Journal Article Research Support, Non-U.S. Gov't Thiomalates Gold 7440-57-5
Beschreibung
Zusammenfassung:The self-assembly of thiomalic acid (TMA) on Au(111) and on preformed Au nanoparticles (AuNPs) protected by weak ligands has been studied by X-ray photoelectron spectroscopy (XPS) and electrochemical techniques. Results show that TMA is adsorbed on the Au(111) surface as thiolate species with a small amount of atomic sulfur (∼10%) and a surface coverage lower than that found for alkanethiols due to steric factors. The amount of atomic sulfur markedly increases when the TMA is adsorbed on AuNPs by the ligand exchange method. We propose that the atomic sulfur is produced as a consequence of C-S bond cleavage, a process that is more favorable at defective sites of the AuNPs surface. The bond scission is also assisted by the presence of the electron-withdrawing carboxy moiety in the α-position relative to the C-S bond. Moreover, the high local concentration of positively charged species increases the stability of the negatively charged leaving group, leading to a higher amount of coadsorbed atomic sulfur. Our results demonstrate that the terminal functionalities of thiols are conditioning factors in the final structure and composition of the adlayers
Beschreibung:Date Completed 21.10.2014
Date Revised 26.02.2014
published: Print-Electronic
Citation Status MEDLINE
ISSN:1520-5827
DOI:10.1021/la404674m