A theoretical roadmap for the best oxygen reduction activity in two-dimensional transition metal tellurides

Abstract

Developing highly active and cost-effective electrocatalysts to replace Pt-based catalysts for the sluggish oxygen reduction reaction (ORR) is a major challenge in the commercialization of fuel cells. Although two-dimensional (2D) transition-metal tellurides have recently been proposed as alternative low-cost ORR catalysts, a fundamental study on the origin of the activity is required to further optimize their composition and performance. Herein, we investigated the electronic properties and ORR catalytic performances of a series of exfoliable 2D transition-metal tellurides to uncover the underlying mechanisms by means of density functional theory simulations. Our in-depth analysis shows that the activation of the ORR mainly depends on the partially filled p_z state of active Te atoms, which can simultaneously accept and donate electrons behaving similarly to both the occupied and unoccupied d orbitals of Pt atoms. This results in a linear relationship between the p_z-band center and the adsorption free energies of O₂ and intermediates, indicating that the p_z-band center might be used as an effective descriptor to probe the performance of telluride catalysts. On this basis, we predicted several 2D transition-metal tellurides with promising catalytic performance and reduced precious-metal contents, where NbRhTe₄ reaches the top of the activity volcano with a limiting potential of 0.96 V. This study provides theoretical guidance to design high-performing 2D telluride ORR catalysts, and its principle might be applicable to other electrochemical reactions in 2D chalcogenides.