N-Doped CrS₂ Monolayer as a Highly-Efficient Catalyst for Oxygen Reduction Reaction: A Computational Study

Searching for low-cost and highly-efficient oxygen reduction reaction (ORR) catalysts is crucial to the large-scale application of fuel cells. Herein, by means of density functional theory (DFT) computations, we proposed a new class of ORR catalysts by doping the CrS₂ monolayer with non-metal atoms (X@CrS₂, X = B, C, N, O, Si, P, Cl, As, Se, and Br). Our results revealed that most of the X@CrS₂ candidates exhibit negative formation energy and large binding energy, thus ensuring their high stability and offering great promise for experimental synthesis. Moreover, based on the computed free energy profiles, we predicted that N@CrS₂ exhibits the best ORR catalytic activity among all considered candidates due to its lowest overpotential (0.41 V), which is even lower than that of the state-of-the-art Pt catalyst (0.45 V). Remarkably, the excellent catalytic performance of N@CrS₂ for ORR can be ascribed to its optimal binding strength with the oxygenated intermediates, according to the computed linear scaling relationships and volcano plot, which can be well verified by the analysis of the p-band center as well as the charge transfer between oxygenated species and catalysts. Therefore, by carefully modulating the incorporated non-metal dopants, the CrS₂ monolayer can be utilized as a promising ORR catalyst, which may offer a new strategy to further develop eligible electrocatalysts in fuel cells.