Potential of nanostructured carbon materials for iodine detection in realistic environments revealed by first-principles calculations

In the context of effective detection of iodine species (I2, CH3I) formed in nuclear power plants and nuclear fuel reprocessing facilities, we perform a comparative study of the potential sensing performance of four expectedly promising 2D materials (8-Pmmn borophene, BC3, C3N, and BC6N) towards the iodine-containing gases and, with the view of checking selectivity, towards common inhibiting gases in the containment atmosphere (H2O and CO), applying methods of dispersion-corrected density functional theory with periodic boundary conditions. A covalent bond is formed between the CO molecule and boron in BC3 or in 8-Pmmn borophene, compromising the anticipated applicability of these materials for iodine detection. The presence of nitrogen atoms in BC6N-2 prevents the formation of a covalent bond with CO; however, the closeness of adsorption energies for all the four gases studied does not distinguish this material as specifically sensitive to iodine species. Finally, the energies of adsorption on C3N yield a significant and promising discrimination between the adsorption energies of (I2, CH3I) vs. (CO, H2O), revealing possibilities for this material's use as an iodine sensor. The conclusions are supported by simulations at finite temperature; underlying electronic structures are also discussed.