Structure effects on electrocatalysts. Oxygen reduction on Te-modified Pt(111) surfaces: Site-blocking vs electronic effects

In this work, the oxygen reduction reaction (ORR) on tellurium-modified Pt(111) surfaces has been studied. Adsorption of Te adatoms on Pt(111) progressively shifts toward less positive values of both the ORR reaction onset and the half-wave potential in 0.1M HClO₄ for 0 < θ_Te < 0.25. However, at θ_Te > 0.25, the ORR activity increases relative to the one at θ_Te < 0.25, but remains lower than that on clean Pt(111). Results were analyzed in light of simulations of kinetic currents as a function of θ_Te, calculated by employing a simple mean field model including both site blocking and electronic effects. Inside this framework, experimental data are best explained by considering that oxygenated Te species inhibit the ORR by either negatively modifying adsorption energies of reaction intermediates or combined site-blocking and electronic effects. A redox ORR catalysis due to redox properties of Te adatoms is discarded. Contrarily, in 0.05M H₂SO₄, a positive catalytic effect has been found, interpreted in terms of a competitive adsorption–desorption mechanism involving the replacement of adsorbed sulfate by Te adatoms. On the other hand, despite the strong site-blocking effect on H_ads and OH_ads adsorption by Te adatoms, it appears that the reduced Te–Pt(111) adlayer does not inhibit the reaction, suggesting different active sites for H_ads and OH_ads adsorption and for the rate-determining step of the ORR mechanism.