Effects of a conductive support on the bonding of oxygen containing molecules to transition metal oxide surfaces

Conventional oxygen electrocatalysts are expensive for industrial use. Transition metal oxides (TMOs), as a more economical option, have emerged as an alternative to potentially replace conventional precious metal catalysts. However, many experimental studies have suggested that although a few of the TMOs supported by conductive substrates are stable under electrocatalytic conditions, their performances are far from the industrial level, especially in the acidic oxygen reduction reaction (ORR). At present, their ORR and also oxygen evolution reaction (OER) performances are still not well understood. In this study, we analyze the effects of the support on ORR/OER adsorbate binding to TMO catalysts. We show that for wide bandgap TMOs (e.g., ZrO₂ and HfO₂), the use of a metal support leads to a marked enhancement of the adsorbate binding strengths due to a significant induced electron charge gain in the adsorbates, and a considerable up-shift in the ORR/OER adsorbate binding scaling relation. Meanwhile, these support-induced effects are significant even with relatively thick TMO layers on a thin metal substrate, requiring a large thickness cutoff to eliminate the influence. In contrast, the metal-like TMOs (e.g., PdO₂ and SnO₂) are less affected by the metal support. This study suggests that the thickness of the TMO layer can be used to tune the adsorption properties of electronegative adsorbates and thus provides an interesting new design option for oxygen electrocatalysis.