Interfacial Evolution on Co-based Oxygen Evolution Reaction Electrocatalysts Probed by Using In Situ Surface-Enhanced Raman Spectroscopy.

Disclosing the roles of reactive sites at catalytic interfaces is of paramount importance for understanding the reaction mechanism. However, due to the difficulties in the detection of reaction intermediates in the complex heterophase reaction system, disentangling the highly convolved roles of different surface atoms remains challenging. Herein, we used CoO x as a model catalyst to study the synergy of Co Td 2+ and Co Oh 3+ active sites in the electrocatalytic oxygen evolution reaction (OER). The formation and evolution of reaction intermediates on the catalyst surface during the OER process were investigated by in situ surface-enhanced Raman spectroscopy (SERS). According to the SERS results in ion-substitution experiments, Co Oh 3+ is the catalytic site for the conversion of OH - to O-O - intermediate species (1140-1180 cm -1 ). CoOOH (503 cm -1 ) and CoO 2 (560 cm -1 ) active centers generated during the OER, at the original Co Td 2+ sites of CoO x , eventually serve as the O 2 release sites (conversion of O-O - intermediate to O 2 ). The mechanism was further confirmed on Co 2+ -Co 3+ layered double hydroxides (LDHs), where an optimal ratio of 1:1.2 (Co 2+ /Co 3+ ) is required to balance O-O - generation and O 2 release. This work highlights the synergistic role of metal atoms at different valence statuses in water oxidation and sheds light on surface component engineering for the rational design of high-performance heterogeneous catalysts.