Pristine graphene covalent functionalization with aromatic aziridines and their application in the sensing of volatile amines – an ab initio investigation

Food quality is of paramount importance for public health safety. For instance, fish freshness can be assessed by sensing the volatile short chain alkylamines produced by spoiled fish. Functionalized graphene is a good candidate for the design of gas sensors for such compounds and therefore of interest as the basic material in food quality sensor devices. To shed theoretical insight in this direction, in the present work we investigate via first-principles density functional theory (DFT) simulations: (i) graphene functionalization via aziridine appendages and (ii) the adsorption of short chain alkylamines (methylamine MA, dimethylamine DMA, and trimethylamine TMA) on the chemically functionalized graphene sheets. Optimal geometries, adsorption energies, and projected density of states (PDOS) are computed using a DFT method. We show that nitrene reactive intermediates, formed by thermal or photo splitting of arylazides – p-carboxyphenyl azide (1a), p-carboxyperfluorophenyl azide (1b), and p-nitrophenyl azide (1c) – react with graphene to yield functionalized derivatives, with reaction energies >−1.0 eV and barriers of the order of 2.0 eV, and open a ∼0.3 to 0.5 eV band gap which is in principle apt for applications in sensing and electronic devices. The interaction between the amines and functionalized graphene, as demonstrated from the calculations of charge density differences showing regions of charge gain and others of charge depletion between the involved groups, occurs through hydrogen bonding with interaction energies ranging from −0.04 eV to −0.76 eV, and induce charge differences in the system, which in the case of p-carboxyperfluorophenyl azide (1b) are sizeable enough to be experimentally observable in sensing.