Density functional study exploring group 13 complexes for methane activation and conversion | Poster Board #2567

Methane is a highly stable molecule, with strong C–H bonds, and hence difficult to activate. Currently, methane conversion occurs via a two-step, indirect process that is energy intensive, expensive, and environmentally unfavorable. Therefore, it is vital to develop a direct, efficient reaction pathway for methane conversion which releases desirable chemicals through the use of catalysts that can effectively activate methane’s strong C-H bonds. Thus, this study explores Group 13 (triel, E) element hydroxide and amide complexes as trivalent metal/metalloid oxide/nitride catalyst models to deduce periodic trends and determine the optimal catalyst/reaction for methane conversion. Density functional theory (DFT) calculations reveal that the thermodynamic and kinetic favorability of reactions involving these triel-based catalysts increases down Group 13 with water-producing reactions being more thermodynamically favorable than methanol-producing reactions. For reactions involving E(OH)x(NH2)3-x, in general, there is a thermodynamic advantage to add methane’s C–H bond to the E–N bond to produce ammonia, but a kinetic advantage for the E–O bond to activate methane. While toxicity concerns would be an issue for thallium-based catalysts, these findings suggest that heavier triel-based metal catalysts – particularly indium-based catalysts – represent a profitable avenue for methane activation and methane functionalization.