Guiding Successive Mo 4d–S 3p Orbital Hybridization in MoS₂ via Dual-Confinement Engineering for Efficient Pseudocapacitive Storage

The pseudocapacitive performance of MoS₂ is intrinsically hampered by its poor electronic conductivity and inert basal planes, primarily arising from weak Mo 4d–S 3p orbital hybridization. Herein, we present a dual-confinement strategy that simultaneously modulates orbital hybridization via lattice-confined Mn doping and interlayer-confined ethylene glycol (EG), yielding a Mn- and EG-co-engineered MoS₂ architecture (denoted as Mn-EG-MoS₂). Microscopic characterization and theoretical calculations reveal that Mn substitution reconstructs the local Mo–S coordination, enhancing both Mo 4d–S 3p and Mn 3d–S 3p hybridization, thereby activating the basal plane sites and reinforcing Mo–S–Mn bonding in Mn-EG-MoS₂. Simultaneously, EG incorporation expands the interlayer spacing and promotes dynamic orbital coupling across layers, effectively enhancing electron-ion transport kinetics. Consequently, the Mn-EG-MoS₂ electrode delivers a high areal capacitance of 757.5 mF cm⁻² at 5 mA cm⁻² and good cycling stability. Furthermore, asymmetric supercapacitors assembled with a PVP-MnO₂ cathode achieve a high energy density of 164.00 µWh cm⁻² at 9.77 mW cm⁻², superior cycling stability retaining 90.06% of their initial capacitance after 5000 cycles at 30 mA cm⁻², and robust mechanical flexibility. This work establishes an effective design strategy by tuning orbital-level interactions via dual-confinement engineering for developing high-performance layer-structured materials.