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 0.25, the ORR activity increases relative to the one at θTe 0.25, the ORR activity increases relative to the one at θTe < 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 θTe, 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 ...