The in-situ electrochemical cell was fabricated by depositing a ~10 µm thick room temperature ionic liquid - polymer electrolyte membrane on a screen printed electrode. The cell showed a stable rectangular double layer capacitive behavior both in high vacuum (10-5 Torr) and reactive gaseous environments. We demonstrate the performance of the in-situ electrochemical cell for studying both the intrinsic redox activity and reactive electrochemistry of well-defined ions at EEI. Specifically, we examined the intrinsic redox activity of mixed-addenda Keggin PMoxW12-xO403- (x=0,1,2,3,6,9,12) polyoxometalates. Multi-electron redox activity of stable anionic Keggin POMs that enable transfer of up to 24 electrons while retaining the structure of the cluster makes them attractive systems for studies in catalysis and energy storage.(5, 6) In addition, we examined the oxygen reduction reactivity of bare Pt cluster ions ∼1 nm in diameter produced using magnetron sputtering combined with gas aggregation. Soft landing of bare metal clusters directly onto the cell eliminates the need to use stabilizing ligands or solvent and, therefore, provides a direct route for studying intrinsic electrocatalytic activity.
In summary, the in-situ electrochemical cell combined with mass-selected ion deposition is a powerful approach for studying processes both at model and technologically-relevant EEIs during operating conditions.
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