Interfacial hydrophobic/hydrophilic reaction fields significantly affect various reactions at the electrode surface. The hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR) have been investigated on single crystal Pt electrodes modified with hydrophobic/hydrophilic cations and anion-exchange copolymers in alkaline solutions. In alkali metal hydroxide solutions, Pt (110) exhibits the highest HER/HOR activity in the low-index planes of Pt. On the low-index planes of Pt, the hydrophilicity of the alkali metal cation in the supporting electrolyte activates the HER/HOR depending on its hydration energy. Hydrophilic cations at the interface facilitate the extraction of hydrogen from the hydrated water. The modification of anion-exchange copolymers with a hydrophobic skeleton on Pt (110) further enhanced the HER/HOR activity. The hydrogen bonding network formed around the hydrophobic species facilitated the mobility of water molecules and the OH− as the reactant/product of the HER/HOR. Appropriately forming hydrophilic and hydrophobic reaction fields at the interface improved the HER/HOR activity.
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