Thiolate-Capped Silver Nanoparticles: Discerning Direct Grafting from Sulfidation at the Metal–Ligand Interface by Interrogating the Sulfur Atom - CEA - Commissariat à l’énergie atomique et aux énergies alternatives Accéder directement au contenu
Article Dans Une Revue Journal of Physical Chemistry C Année : 2020

Thiolate-Capped Silver Nanoparticles: Discerning Direct Grafting from Sulfidation at the Metal–Ligand Interface by Interrogating the Sulfur Atom

Yves Joly
Isabelle Michaud-Soret
Aurélien Deniaud

Résumé

Grafting thiol-bearing molecules at the surface of silver nano-particles (AgNPs) is a successful strategy to tune their optical and antibacterial properties. The capping layer generated from self-assembly of the ligands at the nanoparticle surface determines the range of possible applications of the resulting material. In particular, direct grafting of the thiol heads to surface Ag(I) can occur, with various hybridizations of the S atom, sp versus sp 3. Alternatively, a passivating Ag 2 S layer can form. We make use of S K-edge X-ray absorption near edge structure (XANES) and synchrotron-based X-ray photoelectron spectroscopy (XPS) to probe the metal−ligand interface in different thiol-capped AgNPs. The use of cryogenic conditions for XAS analyses reveals a peculiar spectral signature for thiolates chemisorbed on the AgNPs surface, unambiguously distinguished from that of Ag 2 S. Ab initio simulations of XANES spectra and XPS analyses are used to predict the grafting mode, suggesting that different ligand architectures promote slightly different proportions of sp/sp 3 sites, and a dramatic variability in the stability of the nanomaterial that can evolve toward either self-assembly or dissolution of the AgNPs.

Domaines

Matériaux
Fichier principal
Vignette du fichier
JPC_assemblies_revision_unmarked.pdf (871.69 Ko) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)
Loading...

Dates et versions

hal-02906304 , version 1 (24-09-2020)

Identifiants

Citer

Marianne Marchioni, Chiara Battocchio, Yves Joly, Christelle Gateau, Silvia Nappini, et al.. Thiolate-Capped Silver Nanoparticles: Discerning Direct Grafting from Sulfidation at the Metal–Ligand Interface by Interrogating the Sulfur Atom. Journal of Physical Chemistry C, 2020, 124 (24), pp.13467-13478. ⟨10.1021/acs.jpcc.0c03388⟩. ⟨hal-02906304⟩
153 Consultations
435 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More