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The aim of the present paper has been to introduce the electron conductive and d-d-interactive individual and composite hypo-d-oxides of the increased altervalent capacity, or their suboxides (Magneli phases), as catalytic supports and therefrom provide: (i) The Strong Metal-Support Interaction (SMSI) effect, and (ii) the Dynamic spillover interactive transfer of primary oxides (M-OH) for further electrode reactions, and thereby advance the overall electrocatalytic activity. The d-band has been pointed out as the bonding, adsorptive and catalytic orbital. In the same context, the phenomenon and significance of the d-d-correlations both in heterogeneous catalysis and electrocatalysis are displayed and inferred. Since hypo-d-oxides feature the exchange membrane properties, the higher the altervalent capacity, the higher the spillover effect. Potentiodynamic experiments have shown that the reversible peak of the primary oxide growth on Pt, Ru and Au supported upon hypo-d-oxides and suboxides becomes distinctly increased in the charge capacity and shifts to remarkably more negative potential values, so that it starts even within the range of H-adatoms desorption, while its reduction extends until and merge with the UPD of hydrogen atoms. With wet tungstenia doped titania supported Pt catalyst in membrane cells these peaks dramatically increase in their charge capacity and reversibly become shrunk with a decreased moisture content in the feeding inert gas mixture, and vice versa. Such distinct potentiodynamic scans, in conjunction with some broaden complementary kinetic electrocatalytic improvements rising from the same hypo-d-oxide and/or suboxide interactive support effects, have been proved to be the best and comparable experimental evidence for the spillover effect of primary oxides.

Interactive supported electrocatalysts and spillover effect in electrocatalysis for hydrogen and oxygen electrode reactions