Discovery of the potential of minimum mass for platinum electrodes

Langmuir. 2011 Apr 5;27(7):4220-6. doi: 10.1021/la200153n. Epub 2011 Mar 14.


Electrochemical quartz-crystal nanobalance (EQCN) analysis of the behavior of Pt in aqueous H(2)SO(4) reveals that the interfacial mass reaches a minimum, the potential of minimum mass (E(pmm)), at 0.045 V. A similar behavior is observed for Pt in aqueous HClO(4) and NaOH. E(pmm) is a new parameter describing the electrochemical interface. The value of E(pmm) coincides with the completion of the saturation layer of electroadsorbed H (H(UPD)) and the commencement of H(2)(g) generation or H(2)(g) electro-oxidation. The value of E(pmm) and the structure of the Pt/electrolyte interface are discussed in terms of the interactions of the anions H(3)O(+), H(UPD), H(OPD), and H(2)O with Pt. The layer of H(UPD) embedded in the Pt surface lattice minimizes the surface dipole-water dipole and surface charge-water dipole interactions, thus reduces the wetting ability of Pt. Consequently, the discharge of H(3)O(+) in the electrolytic formation of H(2)(g) or the dissociative adsorption of H(2)(g) that precedes its electro-oxidation to H(3)O(+) proceed easily on Pt, because the species do not have to displace H(2)O molecules. Effective and inexpensive non-platinum electrocatalysts for the electrolytic H(2)(g) generation in water electrolyzers or H(2)(g) electro-oxidation in polymer electrolyte membrane fuel cells should mimic the interfacial behavior of Pt by minimizing the interaction of H(2)O molecules with the electrode.