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

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 O-2 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.

Automated summary

This study investigates the electronic properties and catalytic performances of 2D transition-metal tellurides for oxygen reduction reaction (ORR) through density functional theory simulations. The results show that the activation of ORR depends on the partially filled p(z) state of active Te atoms, which can accept and donate electrons similarly to Pt atoms. The study proposes the p(z)-band center as an effective descriptor for telluride catalysts' performance and predicts promising 2D transition-metal tellurides for ORR.