Primary oxide spillover DL pseudo-capacitance charging and discharging in the light of the first principle theory

Abstract

Due to the irreversible disproportionation of the primary (Pt-OH), into much more stable surface (Pt=O) oxide, all plain (Pt) and non-interactive supported (Pt/C) noble metals, within a wider (more than 600 mVs) potential range between hydrogen and oxygen evolving limits are deprived from the former, and thereby behave partially, but broadly polarizable. Since almost all interactive catalytic hypo-d-oxide supports in wet hydrated state feature continuous and renewable latent storage and spillover of the Pt-OH, such composite catalysts (Pt/WO3,TiO2) enable provided the reversible electrocatalytic properties for the oxygen electrode reactions. Potentiodynamically the latter consists in almost unlimited and reversible DL pseudo-capacitor charging and discharging within the whole potential range in between of oxygen and hydrogen evolving limits. To comfirm such DL properties, based and consisted in the Pt-OH dipole spillover, the rigorous First principle analysis has been carried out and yielded with relevant interrelations of broader significance.