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The reduction of an aryl iodide is generally believed to involve a clean-cut two-electron reduction to produce an aryl anion and iodide. This is in contradiction to what is observed if a highly efficient grafting agent, such as an aryldiazonium salt, is employed. The difference in behavior is explained by the much more extreme potentials required for reducing an aryl iodide, which facilitates the further reduction of the aryl radical formed as an intermediate. However, in this study we disclose that electrografting of aryl iodides is indeed possible upon extended voltammetric cycling. This implies that even if the number of aryl radicals left unreduced at the electrode surface is exceedingly small, a functionalization of the surface may still be promoted. In fact, the grafting efficiency is found to increase during the grafting process, which may be explained by the inhibiting effect the growing film exerts on the competing reduction of the aryl radical. The slow buildup of the organic film results in a well-ordered structure as shown by the well-defined electrochemical response from a grafted film containing ferrocenylmethyl groups. Hence, the reduction of aryl iodides allows a precisely controlled, albeit slow, growth of thin organic films.

Bipolar electrochemistry makes various kinds of surface modifications possible by appropriately tuning the applied potential difference. In this study aryl diazonium, iodonium, and sulfonium salts are reductively grafted onto gold surfaces using an excess of hydroquinone to set the anode at a fixed potential. In general, aryl diazonium salts are easier to reduce than the corresponding iodonium salts which, again, are more easily reduced than sulfonium salts. For all three salts grafting is observed at the reductive site of the bipolar electrode, but with distinctly different features due to the different reduction potentials required to facilitate the grafting. Depending on the reduction potentials of the salts relative to that of the grafting agent, that is, the aryl radical, it is possible to create movable band‐like grafted areas by diazonium grafting, expanding bands by iodonium grafting, or optically invisible thin bands by sulfonium grafting. From these findings, a relationship between the grafting behavior and the applied potential difference is deduced.

Development of versatile methods for graphene functionalization is necessary before use in applications such as composites or as catalyst support. In this study, bipolar electrochemistry is used as a wireless functionalization method to graft 4-bromobenzenediazonium on large (10 × 10 mm(2)) monolayer graphene sheets supported on SiO2. Using this technique, transferred graphene can be electrochemically functionalized without the need of a metal support or the deposition of physical contacts. X-ray photoelectron spectroscopy and Raman spectroscopy are used to map the chemical changes and modifications of graphene across the individual sheets. Interestingly, the defect density is similar between samples, independent of driving potential, whereas the grafting density is increased upon increasing the driving potential. It is observed that the 2D nature of the electrode influences the electrochemistry and stability of the electrode compared to conventional electrografting using a three-electrode setup. On one side, the graphene will be blocked by the attached organic film, but the conductivity is also altered upon functionalization, which makes the graphene electrode different from a normal metal electrode. Furthermore, it is shown that it is possible to simultaneously modify an array of many small graphene electrodes (1 × 1 mm(2)) on SiO2.