This work undertakes mechanistic studies of H(+) reduction on a palladium microelectrode in a room temperature ionic liquid. It was found that the electrode was initially in a partially passivated state in [NTf(2)](-) based RTILs and that pre-anodisation of the electrode surface has a dramatic effect on the reversibility of the system, also triggering a change from hydrogen evolution to hydrogen absorption. Theoretical modelling supported the idea of Pd/H formation under these conditions.
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