Optical Method for Quantifying the Potential of Zero Charge at the Platinum–water Electrochemical Interface

When an electrode contacts an electrolyte, an interfacial electric field forms. This interfacial field can polarize the electrode’s surface and nearby molecules, but its effect can be countered by an applied potential. Quantifying the value of this countering potential (‘potential of zero charge’ (pzc)) is, however, not straightforward. Here we present an optical method for determining the pzc at an electrochemical interface. Our approach uses phase-sensitive second-harmonic generation to determine the electrochemical potential where the interfacial electric field vanishes at an electrode–electrolyte interface with Pt–water as a model experiment. Our method reveals that the pzc of the Pt–water interface is 0.23 ± 0.08 V versus standard hydrogen electrode (SHE) and is pH independent from pH 1 to pH 13. First-principles calculations with a hybrid explicit–implicit solvent model predict the pzc of the Pt(111)–water interface to be 0.23 V versus SHE and reveal how the interfacial water structure rearranges as the electrode potential is moved above and below the pzc. We further show that pzc is sensitive to surface modification; deposition of Ni on Pt shifts the interfacial pzc in the cathodic direction by ~360 mV. Our work demonstrates a materials-agnostic approach for quantifying the interfacial electrical field and water orientation at an electrochemical interface without requiring probe molecules and confirms the long-held view that the interfacial electric field is more intense during hydrogen electrocatalysis in alkaline than in acid.