Evidence of the Grafting Mechanisms of Diazonium Salts on Gold Nanostructures

Type Article
Date 2016-08
Language English
Author(s) Betelu Stephanie1, 2, Tijunelyte Inga3, Boubekeur-Lecaque Leila4, Ignatiadis Ioannis1, 2, Ibrahim Joyce5, Gaboreau Stephane1, 2, Berho Catherine1, 2, Toury Timothee4, Guenin Erwann3, Lidgi-Guigui Nathalie3, Felidj Nordin4, Rinnert EmmanuelORCID6, Lamy De La Chapelle Marc3
Affiliation(s) 1 : Bur Rech Geol & Minieres, Water Environm & Ecotechnol Div, F-45060 Orleans 02, France.
2 : Bur Rech Geol & Minieres, Lab Direct, F-45060 Orleans 02, France.
3 : Univ Paris 13, Sorbonne Paris Cite, CNRS, Lab CSPBAT,UMR7244, 74 Rue Marcel Cachin, F-93017 Bobigny, France.
4 : Univ Paris Diderot, Sorbonne Paris Cite, CNRS, ITODYS,UMR 7086, 15 Rue J-A de Baif, F-75205 Paris 13, France.
5 : Univ Technol Troyes, 12 Rue Marie Curie, F-10000 Troyes, France.
6 : IFREMER, Brittany Ctr, CS10070, Measurements Detect & Sensors Lab, F-29280 Plouzane, France.
Source Journal Of Physical Chemistry C (1932-7447) (Amer Chemical Soc), 2016-08 , Vol. 120 , N. 32 , P. 18158-18166
DOI 10.1021/acs.jpcc.6b06486
WOS© Times Cited 34
Abstract Gold nanostructures (GNS) were chemically functionalized using four different diazonium salts: benzene-diazonium-tetrafluoroborate (DS), 4-decylbenzene-diazonium-tetrafluoroborate (DS-C10H21), 4-carboxybenzene-diazonium-tetrafluoroborate (DS-COOH), and 4-(aminoethyl)-benzene-diazonium-tetrafluoroborate (DS-(CH2)(2)NH2). Effective chemical grafting on GNS was shown by surface-enhanced Raman spectroscopy (SERS); aromatic ring deformations in the range of 1570-1591 cm(-1) are of particular interest. The very strong band observed around 1075 cm(-1), related to CH in-plane bending for mono- and para-substituted benzenes (coupled with ring-N stretching mode), provided further irrefutable evidence of the grafting. SERS enhancement of these two bands ascertains the perpendicular orientation of the aromatic rings on the GNS. X-ray photoelectron spectroscopy (XPS) analyses of chemically grafted flat gold surfaces suggest azophenyl radical pathways when using DS, DS-(CH2)(2)-NH2, or DS-C10H21. It was shown that coating at the interface is the result of a Au-N covalent bond; growth of the layers is via N=N. These XPS results agree with those provided by SERS without excluding the aryl radical pathways. For DS-COOH, the results provided by SERS, XPS, and density functional theory calculations show (i) effective chemical grafting of the GNS via a covalent bond between gold and carboxylate forms and (ii) growth via multilayers in the meta position between aromatic rings through either N=N or C-C bonds.
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Betelu Stephanie, Tijunelyte Inga, Boubekeur-Lecaque Leila, Ignatiadis Ioannis, Ibrahim Joyce, Gaboreau Stephane, Berho Catherine, Toury Timothee, Guenin Erwann, Lidgi-Guigui Nathalie, Felidj Nordin, Rinnert Emmanuel, Lamy De La Chapelle Marc (2016). Evidence of the Grafting Mechanisms of Diazonium Salts on Gold Nanostructures. Journal Of Physical Chemistry C, 120(32), 18158-18166. Publisher's official version : https://doi.org/10.1021/acs.jpcc.6b06486 , Open Access version : https://archimer.ifremer.fr/doc/00350/46139/