Catalytic Water Electrolysis by Co-Cu-W Mixed Metal Oxides: Insights from X-ray Absorption Spectroelectrochemistry

Mixed metal oxides (MMOs) are a promising class of electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Despite their importance for sustainable energy schemes, our understanding of relevant reaction pathways, catalytically active sites, and synergistic effects is rather limited. Here, we applied synchrotron-based X-ray absorption spectroscopy (XAS) to explore the evolution of the amorphous Co-Cu-W MMO electrocatalyst, shown previously to be an efficient bifunctional OER and HER catalyst for water splitting. Ex situ XAS measurements provided structural environments and the oxidation state of the metals involved, revealing Co²⁺ (octahedral), Cu^+/2+ (tetrahedral/square-planar), and W⁶⁺ (octahedral) centers. Operando XAS investigations, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), elucidated the dynamic structural transformations of Co, Cu, and W metal centers during the OER and HER. The experimental results indicate that Co³⁺ and Cu⁰ are the active catalytic sites involved in the OER and HER, respectively, while Cu²⁺ and W⁶⁺ play crucial roles as structure stabilizers, suggesting strong synergistic interactions within the Co-Cu-W MMO system. These results, combined with the Tafel slope analysis, revealed that the bottleneck intermediate during the OER is Co³⁺ hydroperoxide, whose formation is accompanied by changes in the Cu-O bond lengths, pointing to a possible synergistic effect between Co and Cu ions. Our study reveals important structural effects taking place during MMO-driven OER/HER electrocatalysis and provides essential experimental insights into the complex catalytic mechanism of emerging noble-metal-free MMO electrocatalysts for full water splitting.