Atomic‐Scale Structurally Locked 1T / 2H ‐ MoS 2 / ZnS Z‐Scheme Heterojunctions for Prolonged Charge Kinetics and Dual‐Functional Photocatalysis

The simultaneous realization of high‐efficiency solar‐to‐hydrogen conversion and robust environmental remediation is fundamentally constrained by the redox paradox and rapid carrier recombination in conventional heterojunctions. Herein, we report a carefully engineered 0D/2D 1T/2H‐MoS 2 /ZnS Z‐scheme heterojunction featuring an atomic‐scale structurally locked interface. The metallic 1T‐phase of MoS 2 was strategically integrated as a multifunctional electronic actuator, facilitating a seamless charge‐transfer bridge between ZnS and MoS 2 . The optimized 0.3MoS 2 /ZnS composite delivered an exceptional dual‐functional performance, exhibiting a cumulative hydrogen evolution of 2210.33 μmol g −1 cat (approx. 45 times higher than pristine MoS 2 ) and achieving 100% degradation of high‐concentration Malachite Green (50 mg L −1 ) within 180 min. Advanced kinetic investigations via IMVS and time‐resolved photoluminescence unveiled an ultrafast extraction–delayed recombination paradigm, where the recombination lifetime (τ rec ) was dramatically prolonged to 0.396 s, representing a competitive performance among reported sulfide‐based photocatalysts. Electron paramagnetic resonance and DFT calculations confirmed that the superior activity originates from a direct Z‐scheme pathway empowered by the electronic hybridization of Zn 3d/S 3p and Mo 4d orbitals at the intimate interface. Furthermore, the 0.3MoS 2 /ZnS catalyst demonstrated remarkable photostability and phase integrity, with the metastable 1T phase effectively preserved over 50 h of continuous operation. This work establishes a sophisticated kinetic and thermodynamic framework for designing metallic‐phase‐mediated Z‐scheme architectures for integrated solar energy conversion and ecological restoration.