Title

Mechanistic Study of Continuous Reactive Aromatic Organothiol Adsorption onto Silver Nanoparticles

Document Type

Article

Publication Date

12-9-2013

Publication Source

Journal of Physical Chemistry C

Abstract

Organothiol (R-SH) (OT) adsorption onto silver nanoparticles (AgNPs) in water was studied for a series of aromatic OTs including p-methylbenzenethiol (p-MBT), p-benzenedithiol (p-BDT), and 2-mercaptobenzimidazole (2-MBI). Unlike the common view that OT forms monolayer adsorption on AgNPs, we found that these aromatic OTs continuously reacted with AgNPs through formation of RS–Ag complexes until complete OT or AgNP consumption occurred. The RS–Ag complex can remain on the AgNP surface, converting the AgNPs into core–shell structures. The OT adsorption onto AgNPs occurs predominately through reaction with silver oxide present on the AgNP surfaces before the OT addition or formed from environmental oxygen in the presence of OT. The RS–H protons are completely released when both p-MBT and 2-MBI reacted with AgNP, Ag2O, and AgNO3. However, a substantial fraction of S–H bonds remained intact when p-BDT, the only dithiol used in this work, is adsorbed on AgNPs or reacted independently with Ag2O and AgNO3. The new insights from this work should be important for understanding OT interaction with AgNPs in water and the SERS spectra of the OT adsorbed onto AgNPs.

Inclusive pages

27146–27154

ISBN/ISSN

1932-7447 (print); 1932-7455 (web)

Document Version

Postprint

Comments

The document available for download is the authors' accepted manuscript, provided in compliance with the publisher's policy on self-archiving. Permission documentation is on file. To view the version of record, use the DOI: XXXXXXX

Publisher

American Chemical Society

Volume

117

Peer Reviewed

yes

Issue

51

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