凯发

Hereby,we describe a fast and versatile method to functionalize high-quality graphene with organic molecules by exploiting the synergetic effect of supramolecular and covalent chemistry [1-3]. Towards this goal, we designed and synthesized a molecule comprising a long aliphatic chain and an aryl diazonium salt. These molecules are self-assembled from solution onto graphene, forming an ordered monolayer. Then, the sample is transferred into water, to hinder both the structural reorganization within the monolayer and the molecular desorption (Fig. 1). An electrochemical stimulus is used to transform the diazonium head-group into a radical capable of grafting covalently to graphene. During covalent grafting in water the molecules retain the ordered packing formed upon self-assembly before the covalent linkage.

Our 2-steps approach is characterized by the independent control over the processes of immobilization of molecules on graphene and their covalent tethering, enabling massive and fast (t<10 sec)covalent functionalization of graphene. This strategy is highly versatile: it can be operated using different solvents and on many carbon-based materials including graphene deposited on silicon, plastic, quartz, as well as glassy carbon and highly oriented pyrolytic graphite.