Surface modification of graphene with functionalized carbenes and their applications in the sensing of toxic gases: a DFT study

Graphene and other 2D materials have gained significant attention in the development of gas sensors. In this study, we employed Density Functional Theory (DFT) to investigate the adsorption properties of diazomethanes (1a–1g) with various functional groups (R = OH (a), OMe (b), OEt (c), OPr (d), CF(3) (e), Ph (f)) on pristine graphene. Furthermore, we explored the adsorption behavior of activated carbenes (2a–2g) generated from the decomposition of diazomethanes on graphene, as well as the functionalized graphene derivatives (3a–3g) resulting from [2 + 1] cycloaddition reactions between (2a–2g) and graphene. The interaction between these functionalized derivatives (3a–3g) and toxic gases was also investigated. Our results revealed that carbenes exhibited a stronger affinity for graphene compared to diazomethanes. The adsorption energy of esters (3b, 3c, and 3d) on graphene decreased relative to compound 3a, while 3e exhibited increased adsorption energy due to the electron-withdrawing effect of fluorine atoms. Additionally, the adsorption energy of phenyl and nitrophenyl groups (3f and 3g) decreased due to their π-stacking interaction with graphene. Importantly, all functionalized derivatives (3a–3g) demonstrated favorable interactions with gases. Notably, the derivative 3a, acting as a hydrogen bonding donor, exhibited superior performance. Furthermore, modified graphene derivatives exhibited the highest adsorption energy with NO(2) gas, highlighting their potential for selective NO(2) sensing applications. These findings contribute to the understanding of gas-sensing mechanisms and the design of novel graphene-based sensor platforms.