Covalent surface modification of single-layer graphene-like BC6N nanosheets with reactive nitrenes for selective ammonia sensing via DFT modeling

Abstract Novel graphene-like nanomaterials with a non-zero bandgap are important for the design of gas sensors. The selectivity toward specific targets can be tuned by introducing appropriate functional groups on their surfaces. In this study, we use first-principles simulations, in the form of density functional theory (DFT), to investigate the covalent functionalization of a single-layer graphitized BC 6 N with azides to yield aziridine-functionalized adducts and explore their possible use to realize ammonia sensors. First, we determine the most favorable sites for physical adsorption and chemical reaction of methylnitrene, arising from the decomposition of methylazide, onto a BC 6 N monolayer. Then, we examine the thermodynamics of the [1 + 2]–cycloaddition reaction of various phenylnitrenes and perfluorinated phenylnitrenes para-substituted with (R = CO 2 H, SO 3 H) groups, demonstrating favorable energetics. We also monitor the effect of the functionalization on the electronic properties of the nanosheets via density of states and band structure analyses. Finally, we test four dBC 6 N to gBC 6 N substrates in the sensing of ammonia. We show that, thanks to their hydrogen bonding capabilities, the functionalized BC 6 N can selectively detect ammonia, with interaction energies varying from −0.54 eV to −1.37 eV, even in presence of competing gas such as CO 2 and H 2 O, as also confirmed by analyzing the change in the electronic properties and the values of recovery times near ambient temperature. Importantly, we model the conductance of a selected substrate alone and in presence of NH 3 to determine its effect on the integrated current, showing that humidity and coverage conditions should be properly tuned to use HO 2 C-functionalized BC 6 N-based nanomaterials to develop selective gas sensors for ammonia.