Finding Key Factors for Efficient Water and Methanol Activation at Metals, Oxides, MXenes, and Metal/Oxide Interfaces

[Image: see text] Activating water and methanol is crucial in numerous catalytic, electrocatalytic, and photocatalytic reactions. Despite extensive research, the optimal active sites for water/methanol activation are yet to be unequivocally elucidated. Here, we combine transition-state searches and electronic charge analyses on various structurally different materials to identify two features of favorable O–H bond cleavage in H(2)O, CH(3)OH, and hydroxyl: (1) low barriers appear when the charge of H moieties remains approximately constant during the dissociation process, as observed on metal oxides, MXenes, and metal/oxide interfaces. Such favorable kinetics is closely related to adsorbate/substrate hydrogen bonding and is enhanced by nearly linear O–H–O angles and short O–H distances. (2) Fast dissociation is observed when the rotation of O–H bonds is facile, which is favored by weak adsorbate binding and effective orbital overlap. Interestingly, we find that the two features are energetically proportional. Finally, we find conspicuous differences between H(2)O/CH(3)OH and OH activation, which hints toward the use of carefully engineered interfaces.