(701e) Electrocatalytic Interface Engineering with Ionic Liquids
The origin of the effect of water on the progression of the ORR, as well as other elementary electrochemical reactions, is considered to be two-fold: (1) through solvation and hydrogen bonding, H2O stabilizes adsorbed reaction intermediates on the surface to differing degrees. It is found to stabilize *OH by about 0.5 eV and *OOH by 0.25 eV, contributing to the fixed ÎÎGad value9; (2) a mixed *OH-H2O hydrogen bonded structure is found to readily form on metal surfaces where charge redistribution due to the hydrogen bonding increases the binding strength and surface coverage of the *OH10,11,12,13. If strategies can be developed to reduce the binding energy difference between *OH and *OOH and prevent the formation of an ordered water stabilized *OH spectator structure, than the activity and selectivity of multi-intermediate reactions could be potentially maximized.
Here we will present our progress in addressing intermediate scaling for the ORR through the manipulation of metal/electrolyte interface with chemically tailored ionic liquids (IL). The unique ability of IL/organic salts to change the hydration environment and the large chemical library with which to synthesize them from, makes interface tailoring readily accessible. We argue that it is the potential for the manipulation of water interaction with the surface that results in the enhanced ORR activity observed in the presence of IL thin films. Through the testing of well-defined IL/single crystal composite electrodes, we will present a systematic study of the mechanism by which ILs affect the kinetics of the ORR. The insight developed can be applied to other multi-intermediate reactions where the control of water interaction with the catalytic surface and adsorbed intermediate solvation is a viable strategy to approach the breaking of scaling relations.
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