Guiding Successive Mo 4 <i>d–</i> S 3 <i>p</i> Orbital Hybridization in MoS ₂ via Dual‐Confinement Engineering for Efficient Pseudocapacitive Storage

ABSTRACT The pseudocapacitive performance of MoS 2 is intrinsically hampered by its poor electronic conductivity and inert basal planes, primarily arising from weak Mo 4 d –S 3 p 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 MoS 2 architecture (denoted as Mn‐EG‐MoS 2 ). Microscopic characterization and theoretical calculations reveal that Mn substitution reconstructs the local Mo–S coordination, enhancing both Mo 4 d –S 3 p and Mn 3 d –S 3 p hybridization, thereby activating the basal plane sites and reinforcing Mo–S–Mn bonding in Mn‐EG‐MoS 2 . Simultaneously, EG incorporation expands the interlayer spacing and promotes dynamic orbital coupling across layers, effectively enhancing electron‐ion transport kinetics. Consequently, the Mn‐EG‐MoS 2 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‐MnO 2 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.