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.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC9321024PMC
http://dx.doi.org/10.1002/anie.202201610DOI Listing

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