Interfacial Electronic Synergism in Cobalt‐Doped MoS₂‐COF Heterostructures for Energy‐Efficient Hydrazine‐Assisted Hydrogen Production

Hydrazine oxidation (HzOR) assisted hydrogen production offers a promising alternative to energy-intensive and sluggish oxygen evolution reaction (OER), improving its efficiency. However, its practical implementation demands the development of advanced electrocatalysts capable of overcoming intrinsic kinetic and charge transfer limitations. Herein, the study reports a hybrid catalyst by anchoring a β-ketoenamine linked covalent organic framework (TpPa-1) on vertically aligned Co-doped MoS₂ cuboids, enabling enhanced hydrazine-assisted hydrogen evolution reaction (HER). The molecularly engineered heterostructure leverages interfacial electronic synergism to enhance charge delocalization and interfacial conductivity, thereby improving electrocatalytic performance. The hybrid catalyst exhibits low overpotentials of 43 mV for the HER and 88 mV for the HzOR at 10 mA cm^-2. Combined experimental and theoretical analyses reveal that Co doping activates MoS₂, while TpPa-1 integration enhances charge delocalization and interfacial conductivity through electronic synergism. This work presents a robust strategy for molecular-level interface engineering to enable efficient, bifunctional hydrogen production, establishing a foundation for the broader application of hybrid electrocatalysts.