Understanding potential over-oxidation reactionsi.e. further oxidation of the product methanolis also an important consideration for the overall reaction selectivity. For this reason, we further studied the activation of methanol on the active site MO. The catalytic cycle is depicted in Figure , starting with formation of the active species MO from the reaction of M and N2O as above. The adsorption energy of CH3OH onto the MO site is -31.3 kJ/mol (HSE06; for PBE -36.5 kJ/mol). As expected, this is more exothermic (approximately 23 kJ/mol) than CH4 adsorption at the same site, as methanol exhibits a dipole moment. Once adsorbed, two relevant pathways were investigated: C-H activation or O-H activation. For the activation of the C-H bond of methanol, we find an activation energy of +20.1 kJ/mol (HSE06; for PBE +82.7 kJ/mol) via the transition structure 2 TS CH (see also Table ). The reaction energy to the product radical ΔE(CH3OH@MO→CH2OH@Fe(OH)2) is +9.9 kJ/mol (HSE06; for PBE +71.5 kJ/mol). The energy diagram is plotted in Figure . As in the methane oxidation step, the differences in reaction energies between PBE and HSE06 are large. Overall, a smaller activation energy is observed for the C-H activation of methanol than for the C-H activation of methane, as expected.