Grafting of Nitrophenyl Groups on Carbon and Metallic Surfaces without Electrochemical Induction

Abstract

The grafting of 4-nitrophenyl groups on carbon or metallic surfaces without externally applied electrochemical induction is described. Clean surfaces of glassy carbon (GC), copper, nickel, iron, and zinc substrates were dipped in a solution of 4-nitrobenzene diazonium tetrafluoroborate salt in acetonitrile. After the modified surfaces were rinsed, they were analyzed by FT-IRRAS, cyclic voltammetry, XPS, and AFM. The main result of this investigation is the spontaneous formation of a multilayer coating without electrochemical induction regardless of the substrate used. Influence of immersion time and of 4-nitrobenzene diazonium tetrafluoroborate salt concentration on the grafting were also investigated.

Covalent modification of graphitic carbon substrates by non-electrochemical methods

“…The first reports of spontaneous attachment of aryl radicals to planar carbon surfaces appeared in 2005 [46,47]. Prior to this time however, the spontaneous modification of carbon blacks by aryl radicals derived from aryldiazonium cation precursors had been patented and used for interesting industrial applications in the manufacturing of inks and toners [48].…”

“…Pinson and co-workers made a detailed investigation of spontaneous grafting from solutions of p-nitrobenzenediazonium tetrafluoroborate onto iron, zinc, copper, nickel and GC [46]. To effect grafting, clean substrates were dipped in deaerated acetonitrile solutions containing 0.1 -10 mM diazonium salt for 1-60 min followed by cleaning by sonication.…”

Shape‐Switchable Azo‐Macrocycles

“…In an electrochemical reduction diazonium salts can be covalently attached to metal, carbon or silicon surfaces. [133][235] [139][236] For a successful subsequent modification by cross coupling reactions a good leaving group for the palladium catalyzed reaction is needed, therefore 4-iodobenzene diazonium salt was chosen for the electroreduction.…”

Raman Characterization of Phenyl-Derivatives: From Primary Amine to Diazonium Salts

“…The rise in popularity of aryl-diazonium salts has further resulted from their efficiency in surface functionalization, where covalently attached coatings on (semi)-conducting materials bear a wide range of functional groups [5][6][7][8][9][10][11][12][13][14]. In addition, the grafting can be accomplished by either chemical (spontaneous grafting), electrochemical, or physical methods [5][6][7][8][9][10][11][12]15].…”

“…In addition, the grafting can be accomplished by either chemical (spontaneous grafting), electrochemical, or physical methods [5][6][7][8][9][10][11][12]15]. Surface functionalization using diazonium salts has thus become one of the most powerful methods for coatings [8,13,14] through linking (bio)molecules [16,17], polymers [18][19][20] or nanoparticles [21].…”