Lanthanide-doped MoS2 with enhanced oxygen reduction activity and biperiodic chemical trends

Abstract

Molybdenum disulfide has broad applications in catalysis, optoelectronics, and solid lubrication, where lanthanide (Ln) doping can be used to tune its physicochemical properties. The reduction of oxygen is an electrochemical process important in determining fuel cell efficiency, or a possible environmental-degradation mechanism for nanodevices and coatings consisting of Ln-doped MoS₂. Here, by combining density-functional theory calculations and current-potential polarization curve simulations, we show that the dopant-induced high oxygen reduction activity at Ln-MoS₂/water interfaces scales as a biperiodic function of Ln type. A defect-state pairing mechanism, which selectively stabilizes the hydroxyl and hydroperoxyl adsorbates on Ln-MoS₂, is proposed for the activity enhancement, and the biperiodic chemical trend in activity is found originating from the similar trends in intraatomic 4f–5d6s orbital hybridization and interatomic Ln–S bonding. A generic orbital-chemistry mechanism is described for explaining the simultaneous biperiodic trends observed in many electronic, thermodynamic, and kinetic properties.

Oxygen reduction reaction plays a key role in many applications of MoS₂-based materials. Here, using first-principles simulations, the authors find the enhanced oxygen-reduction activity with a biperiodic chemical trend on the lanthanide-doped MoS₂.