Substrate-Modulated Reductive Graphene Functionalization

TL;DR

This study reveals that substrate type significantly influences the reactivity of graphene layers during covalent functionalization, with monolayers on SiO2 being more reactive than bilayers, supported by experimental and computational evidence.

Contribution

It demonstrates substrate-dependent reactivity differences in graphene functionalization and explains them through DFT calculations showing lattice strain effects.

Findings

Monolayer graphene on SiO2 shows higher reactivity than bilayers.

Ditopic binding results in more stable products than monotopic.

Substrate nature critically affects the functionalization process.

Abstract

Covalently functionalizing mechanical exfoliated monolayer and bilayer graphenides with {\lambda}-iodanes led to the discovery that the monolayers supported on a SiO2 substrate are considerably more reactive than bilayers as demonstrated by statistical Raman spectroscopy/microscopy. Supported by DFT calculations we show that ditopic addend binding leads to much more stable products than the corresponding monotopic reactions due to much lower lattice strain of the reactions products. The chemical nature of the substrate (graphene versus SiO2) plays a crucial role.14858-14862.