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Using Time-Resolved Electrochemical Patterning to Gain Fundamental Insight into Aryl-Radical Surface Modification

Authors

  • Kristian Torbensen,

    1. Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C (Denmark), Fax: (+45) 86196199
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  • Kristoffer Malmos,

    1. Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C (Denmark), Fax: (+45) 86196199
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  • Dr. Frederic Kanoufi,

    Corresponding author
    1. Physio-Chimie des Electrolytes, des Colloides et Sciences Analytiques, ESPCI Paris Tech, CNRS UMR 7195, 10 Rue Vauquelin, 75234 Paris Cedex 05 (France)
    • Physio-Chimie des Electrolytes, des Colloides et Sciences Analytiques, ESPCI Paris Tech, CNRS UMR 7195, 10 Rue Vauquelin, 75234 Paris Cedex 05 (France)
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  • Prof. Dr. Catherine Combellas,

    1. Physio-Chimie des Electrolytes, des Colloides et Sciences Analytiques, ESPCI Paris Tech, CNRS UMR 7195, 10 Rue Vauquelin, 75234 Paris Cedex 05 (France)
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  • Dr. Steen U. Pedersen,

    1. Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C (Denmark), Fax: (+45) 86196199
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  • Prof. Dr. Kim Daasbjerg

    Corresponding author
    1. Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C (Denmark), Fax: (+45) 86196199
    • Department of Chemistry, Aarhus University, Langelandsgade 140, 8000 Aarhus C (Denmark), Fax: (+45) 86196199
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Abstract

Scanning electrochemical microscopy is used to carry out local free-radical grafting at a gold surface through mild oxidation of an aryl hydrazine. The process can be deliberately controlled by creation of a local pH gradient at the tip. Comparison of the experimental results with simulations shows that the radial expansion of the pH profile in which successful grafting can be accomplished increases with increasing generation time of OH and with decreasing initial concentration of the grafting precursor. Furthermore, the radial expansion is faster than the nucleation of the grafting process.

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