Electric double layers are crucial to energy storage and electrocatalytic device performance. While double layer formation originates in electrostatic interactions, electric double layer properties are governed by a balance of both electrostatic and entropic driving forces. Favorable ion-surface electrostatic interactions attract counterions to charged surfaces to compensate, or "screen," potentials, but the confinement of these same ions from a bulk reservoir to the interface incurs an entropic penalty. Here, we use a dicationic imidazolium ionic liquid and its monovalent analogue to explore how cation valence and entropy influence double layer formation and electrochemical reactivity using CO electroreduction as a model reaction. We find that divalent and monovalent cations display similar CO reduction kinetics but differ vastly in steady-state reactivity due to rapid electrochemically induced precipitation of insulating dicationic (bi)carbonate films. Using surface-enhanced Raman scattering spectroscopy, we find that potential-dependent cation reorientation occurs at similar potentials between the two ionic liquids, but the introduction of a covalent link in the divalent cation imparts a more ordered double layer structure that favors (bi)carbonate precipitation. In mixed monovalent-divalent electrolytes, we find that the divalent cations dominate interfacial properties by preferentially accumulating at surfaces even at very low relative concentrations. Our findings confirm that ion entropy plays a key role in modulating local electrochemical environments. Furthermore, we highlight how double layer properties are sensitive to the properties of counterions that pay the lowest entropic penalty to accumulate at interfaces. Overall, we illustrate that ion entropy provides a new knob to tune reaction microenvironments and unveil how entropy plays a major role in modulating electrochemical reactivity in mixed ion electrolytes.

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http://dx.doi.org/10.1039/d3sm01302bDOI Listing

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