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 CoOx as a model catalyst to study the synergy of CoTd2+ and CoOh3+ 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, CoOh3+ is the catalytic site for the conversion of OH- to O-O- intermediate species (1140-1180 cm-1). CoOOH (503 cm-1) and CoO2 (560 cm-1) active centers generated during the OER, at the original CoTd2+ sites of CoOx , eventually serve as the O2 release sites (conversion of O-O- intermediate to O2). The mechanism was further confirmed on Co2+-Co3+ layered double hydroxides (LDHs), where an optimal ratio of 1:1.2 (Co2+/Co3+) is required to balance O-O- generation and O2 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.

Automated summary

Understanding the roles of reactive sites at catalytic interfaces is crucial for the understanding of reaction mechanisms. This study investigated the synergy of CoTd2+ and CoOh3+ active sites in the electrocatalytic oxygen evolution reaction (OER) using CoOx as a model catalyst. By employing in situ surface-enhanced Raman spectroscopy (SERS), the formation and evolution of reaction intermediates on the catalyst surface were studied. It was found that CoOh3+ acts as the catalytic site for the conversion of OH- to O-O- intermediate species, while CoOOH and CoO2 active centers generated at the CoTd2+ sites serve as the O2 release sites. These findings shed light on the surface component engineering for the rational design of high-performance heterogeneous catalysts.