Dual In Situ Laser Techniques Underpin the Role of Cations in Impacting Electrocatalysts

Understanding the electrode/electrolyte interface is crucial for optimizing electrocatalytic performances. Here, we demonstrate that the nature of alkali metal cations can profoundly impact the oxygen evolution activity of surface-mounted metal–organic framework (SURMOF) derived electrocatalysts, which are based on NiFe(OOH). In situ Raman spectroscopy results show that Raman shifts of the Ni−O bending vibration are inversely proportional to the mass activities from Cs⁺ to Li⁺. Particularly, a laser-induced current transient technique was introduced to study the cation-dependent electric double layer properties and their effects on the activity. The catalytic trend appeared to be closely related to the potential of maximum entropy of the system, suggesting a strong cation impact on the interfacial water layer structure. Our results highlight how the electrolyte composition can be used to maximize the performance of SURMOF derivatives toward electrochemical water splitting.