Isotope-Labeling Inspired Lattice-Inherited Rhenium Single-Atom Regulating Local Electronic Microenvironment of Dual-Phase MoS₂/MoP Nanotubes for Accelerated Sulfur Redox Kinetics.

Abstract

Simultaneously regulating the local electronic microenvironment of dual phases in heterostructures remains a significant challenge. Herein, we propose a lattice-inherited single-atom strategy to construct Re-doped MoS₂/MoP dual phases, where Re atoms remain atomically dispersed throughout the MoS₂ to MoP transformation. This strategy enables concurrent regulation of the diffusion of MoS₂ and catalytic MoP phases, thereby overcoming the intrinsic adsorption, diffusion, and catalytic limitations of individual phases in conventional dual-phase heterostructures. DFT calculations reveal that, in Re-MoS₂, Re incorporation induces reconfiguration of surface S 3p orbitals, weakening Li-S orbital overlap and lowering Li⁺ diffusion barrier. In Re-MoP, unpaired delocalized electrons upshift the d-band center and strengthen interfacial charge coupling, thereby accelerating polysulfide redox kinetics. Meanwhile, the dual-phase distribution of Re atoms enhances the built-in electric field, promoting directional polysulfide migration toward catalytic domains. Structurally, the constructed hetero-nanotube catalysts, featuring ultrathin Re-doped MoS₂/MoP coaxially encapsulating carbon nanotubes, ensure intimate face-to-face contact and efficient electron transport. The cell exhibits remarkable cycling stability (0.035% decay over 1000 cycles at 5 C) and achieves a high areal capacity of 9.16 mAh cm^-2 at 10.59 mg cm^-2 sulfur loading. This work opens a new avenue for enhancing heterostructure synergistic effects, extending beyond Li-S batteries to other multi-electron-transfer systems.