Electrolytic hydrogen evolution reaction (HER) that can be performed efficiently in neutral conditions enables the direct splitting of seawater. However, the sluggish water dissociation kinetics in neutral media severely limits the practical deployment of this technology. Herein, we present a simple strategy to rationally design oxophilic and nucleophilic moieties through the in situ reconstruction of a free-standing bimetallic cobalt-iron phosphate electrode. Through an electrochemical reduction step, the electrode surface undergoes self-reconstruction to generate a thin (oxy)hydroxide layer, enabling a significantly improved HER activity in both buffered electrolyte and natural seawater. Our mechanistic investigations reveal the essential role of oxophilic (oxy)hydroxide species in improving the HER activity of nucleophilic bimetallic phosphate sites. In a buffer electrolyte (pH = 7), the resultant electrocatalyst only requires overpotentials of 97 and 198 mV to deliver a current density of 10 and 100 mA cm-2, respectively, which outperforms that of the Pt benchmark. The in situ reconstruction strategy of active sites within such electrodes brings significant opportunity in developing active electrocatalysts that are capable of direct seawater splitting.
Keywords: (oxy)hydroxide; Co−Fe phosphate; hydrogen evolution reaction; neutral media; seawater; surface reconstruction.