DFT-Based Functionalization of Graphene with Lithium-Modified Groups for Enhanced Hydrogen Detection: Thermodynamic, Electronic, and Spectroscopic Properties.

This study investigates the impact of oxygen-containing functional groups (COO-Li, CO-Li, and O-Li) on the electronic and optical properties of graphene, with a focus on hydrogen sensing applications. Using density functional theory (DFT) calculations, we evaluated the thermodynamic feasibility of the functionalization and hydrogen adsorption processes. The Gibbs free energy changes (ΔG) for the functionalization of pristine graphene were calculated as -1233, -1157, and -1119 atomic units (a.u.) for COO-Li, CO-Li, and O-Li, respectively. These negative values indicate that the functionalization processes are spontaneous (ΔG < 0), with COO-Li being the most thermodynamically favorable. Furthermore, hydrogen adsorption on the functionalized graphene surfaces also exhibited spontaneous behavior, with ΔG values of -1269, -1204, and -1175 a.u., respectively. These results confirm that both functionalization and subsequent hydrogen adsorption are energetically favorable, enhancing the potential of these materials for hydrogen sensing applications. Among the functional groups we simulated, COO-Li exhibited the largest surface area and volume, which were attributed to the high electronegativity and steric influence of the carboxylate moiety. Based on the previously described results, we analyzed the interaction of these functionalized graphene systems with molecular hydrogen. The adsorption of two H