Reaction mechanism of methyl nitrite dissociation during co catalytic coupling to dimethyl oxalate: A density functional theory study

Dissociation of methyl nitrite is the first step during CO catalytic coupling to dimethyl oxalate followed by hydrogenation to ethyl glycol in a typical coal to liquid process. In this work, the first-principle calculations based on density functional theory were performed to explore the reaction mechanism for the non-catalytic dissociation of methyl nitrite in the gas phase and the catalytic dissociation of methyl nitrite on Pd(111) surface since palladium supported on alpha-alumina is the most effective catalyst for the coupling. For the non-catalytic case, the calculated results show that the CH₃O-NO bond will break with a bond energy of 1.91 eV, and the produced CH₃O radicals easily decompose to formaldehyde, while the further dissociation of formaldehyde in the gas phase is difficult due to the strong C-H bond. On the other hand, the catalytic dissociation of methyl nitrite on Pd(111) to the adsorbed CH₃O andNOtakes place with a small energy barrier of 0.03 eV. The calculated activation energies along the proposed reaction pathways indicate that (i) at lowcoverage, a successive dehydrogenation of the adsorbed CH₃O to CO and H is favored while (ii) at high coverage, hydrogenation of CH₃O to methanol and carbonylation of CH₃O to methyl formate are more preferred. On the basis of the proposed reaction mechanism, two meaningfulways are proposed to suppress the dissociation of methyl nitrate during the CO catalytic coupling to dimethyl oxalate.