Density Functional Theory Study of Synergistic Gas Sensing Using an Electrically Conductive Mixed Ligand Two-Dimensional Metal–Organic Framework

Two-dimensional conductive metal–organic frameworks (2D-cMOFs) have been adopted in electrochemical sensing applications owing to their superior electrical conductivity and large surface area. Here, we performed a density functional theory (DFT) analysis to study the synergistic impact of introducing a secondary organic ligand to the 2D-cMOF system. In this study, cobalt-hexaiminobenzene (Co-HIB) and cobalt-2,3,6,7,10,11-hexaiminotriphenylene (Co-HITP) were combined to form a mixed ligand MOF named, Co-HIB-HITP. A DFT-level comparative study was designed to access stability, synergistic gas adsorption capability, and gas adsorption mechanism, important factors in sensing material development. A potential energy surface calculation predicted the structural stability of Co-HIB-HITP at larger interlayer displacements around 3.6–4.2 Å regions along the ab-plane than its unmixed states, Co-HIB and Co-HITP, indicating the tunability of the stacking mode using the mixed ligand system. Furthermore, the adsorption capabilities toward toxic gases, NH3, H2S, NO, and NO2, were investigated, and Co-HIB-HITP revealed superiority over unmixed 2D-cMOFs in H2S and NH3 gas adsorption energies by showing 158 and 170% improvement, respectively. Finally, an electron charge density analysis revealed Co-HIB-HITP’s unique stacking mode and Co-metal density as contributing factors to its gas-selective synergy effect. The AB stacked layers and an intermediate metal density (5.25%) significantly improved the electrostatic interactions with H2S and NH3 by inducing a change in the chemical environment of the gas binding sites. This work proposes the dual-ligand 2D-cMOF as the promising design strategy for the next-generation sensing material.