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In Situ Synchronized SERS-SEIRAS Unveils Cation-Regulated Interfacial Water and Intermediates in the Oxygen Reduction
Xiao-Xuan Huang1, Yao-Hui Wang1, Jianmin Su1
1College of Materials, State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, College of Chemistry and Chemical Engineering, College of Energy, and College of Physical Science and Technology, Xiamen University, Xiamen, China.
None:
Interfacial water plays a crucial yet poorly understood role in the alkaline oxygen reduction reaction (ORR) by modulating the adsorption of oxygen intermediates and mediating proton-coupled electron transfer (PCET). However, the lack of techniques to dynamically correlate interfacial water with adsorbed intermediates makes it difficult to elucidate the mechanism governing the evolution of intermediate species. Here, we report a synchronized, site-consistent SERS-SEIRAS platform that tracks interfacial water and surface-adsorbed species (OOHad and OHad) in real time during cation-dependent ORR. Our results show that decreasing cation hydration energy induces the formation of an interfacial water layer with weak hydrogen bonding, low orientation constraints, and high dynamic flexibility, which diminishes its interactions with OOHad and OHad. This structure enhances water and oxygen transport and weakens OHad solvation, thereby reducing OHad coverage and accelerating the final PCET step. Our results reveal how cations reshape the interfacial hydrogen-bond network to control ORR kinetics. More broadly, this work demonstrates the power of multi-spectroscopic coupling for probing dynamic electrocatalytic interfaces and offers a strategy for improving catalyst performance via electrolyte and interface engineering.
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