Does the Oxygen Evolution Reaction follow the classical OH*, O*, OOH* path on single atom catalysts?

The Oxygen Evolution Reaction (OER) is a key part of water splitting. On metal and oxide surfaces it usually occurs via formation of three intermediates, M(OH), M(O), and M(OOH) (also referred to as OH*, O*, and OOH* species where * indicates a surface site). The last step consists of O2 release. So far, it has been generally assumed that the same path occurs on single atom catalysts (SACs). However, the chemistry of SACs may differ substantially from that of extended surfaces and is reminiscent of that of coordination compounds. This raises the question of whether on SACs the OER follows the classical mechanism or not. Using a DFT approach, we studied a set of 30 SACs made by ten metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Pd and Pt) anchored on three widely used 2D carbon-based materials, graphene, nitrogen doped graphene and carbon nitride. In none of the cases examined the most favourable reaction path is the conventional one. In fact, in all cases other intermediates with higher stabilities form: M(OH)2, M(O)(OH), M(O)2, and M(O2) (OH* OH*, O* OH*, O* O*, O2* according to standard nomenclature). Therefore, the common assumption that on SACs the OER proceeds via formation of OH*, O*, and OOH* intermediates is not verified. Predictions of new catalysts based on the screening of large number of potential structures can lead to completely incorrect conclusions if these additional intermediates are not taken into consideration.(c) 2022 Elsevier Inc. All rights reserved.