Robust Electrografting on Self-Organized 3D Graphene Electrodes

Philippe Fortgang 1 Teddy Tite 2, 3 Vincent Barnier 4, 5, 6 Nedjla Zehani 1 Chiranjeevi Maddi 2, 3 Florence Lagarde 7 A.-S. Loir 2, 3 Nicole Jaffrezic-Renault 7 Christophe Donnet 2, 3 Florence Garrelie 2, 3 Carole Chaix 7
1 ISA - Institut des Sciences Analytiques
2 LHC - Laboratoire Hubert Curien [Saint Etienne]
3 Université de Lyon
4 MPI-ENSMSE - Département Mécanique physique et interfaces
5 SMS-ENSMSE - Centre Science des Matériaux et des Structures
6 LGF-ENSMSE - Laboratoire Georges Friedel
7 Interfaces & biosensors - Interfaces & biocapteurs
ISA - Institut des Sciences Analytiques
Abstract : Improving graphene-based electrode fabrication processes and developing robust methods for its functionalization are two key research routes to develop new high-performance electrodes for electrochemical applications. Here, a self-organized three-dimensional (3D) graphene electrode processed by pulsed laser deposition with thermal annealing is reported. This substrate shows great performance in electron transfer kinetics regarding ferrocene redox probes in solution. A robust electrografting strategy for covalently attaching a redox probe onto these graphene electrodes is also reported. The modification protocol consists of a combination of diazonium salt electrografting and click chemistry. An alkyne-terminated phenyl ring is first electrografted onto the self-organized 3D graphene electrode by in situ electrochemical reduction of 4-ethynylphenyl diazonium. Then the ethynylphenyl-modified surface efficiently reacts with the redox probe bearing a terminal azide moiety (2-azidoethyl ferrocene) by means of Cu-I-catalyzed alkyne-azide cycloaddition. Our modification strategy applied to 3D graphene electrodes was analyzed by means of atomic force microscopy, scanning electron microscopy, Raman spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy (XPS). For XPS chemical surface analysis, special attention was paid to the distribution and chemical state of iron and nitrogen in order to highlight the functionalization of the graphene-based substrate by electrochemically grafting a ferrocene derivative. Dense grafting was observed, offering 4.9 X 10(-10) mol cm(-2) surface coverage and showing a stable signal over 22 days. The electrografting was performed in the form of multilayers, which offers higher ferrocene loading than a dense monolayer on a flat surface. This work opens highly promising perspectives for the development of self-organized 3D graphene electrodes with various sensing functionalities.
Keywords : NANOCOMPOSITES AZIDE KINETICS ELECTROCHEMISTRY THIN-FILM CARBON self-organized 3D graphene diazonium electrografting ferrocene X-ray photoelectron spectroscopy SINGLE-LAYER GRAPHENE 3-DIMENSIONAL GRAPHENE CLICK CHEMISTRY DIAZONIUM FUNCTIONALIZATION
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Journal articles
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https://hal-emse.ccsd.cnrs.fr/emse-01496461
Contributor : Géraldine Fournier-Moulin <>
Submitted on : Monday, March 27, 2017 - 3:22:18 PM
Last modification on : Sunday, April 28, 2019 - 2:15:27 PM

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Philippe Fortgang, Teddy Tite, Vincent Barnier, Nedjla Zehani, Chiranjeevi Maddi, et al.. Robust Electrografting on Self-Organized 3D Graphene Electrodes. ACS Applied Materials & Interfaces, Washington, D.C. : American Chemical Society, 2016, 8 (Issue : 2), pp.1424-1433. ⟨10.1021/acsami.5b10647 ⟩. ⟨emse-01496461⟩

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