Stimulated Electrocatalytic Hydrogen Evolution Activity of MOF‐Derived MoS(2) Basal Domains via Charge Injection through Surface Functionalization and Heteroatom Doping

The design of MoS(2)‐based electrocatalysts with exceptional reactivity and robustness remains a challenge due to thermodynamic instability of active phases and catalytic passiveness of basal planes. This study details a viable in situ reconstruction of zinc–nitrogen coordinated cobalt–molybdenum disulfide from structure directing metal–organic framework (MOF) to constitute specific heteroatomic coordination and surface ligand functionalization. Comprehensive experimental spectroscopic studies and first‐principle calculations reveal that the rationally designed electron‐rich centers warrant efficient charge injection to the inert MoS(2) basal planes and augment the electronic structure of the inactive sites. The zinc–nitrogen coordinated cobalt–molybdenum disulfide shows exceptional catalytic activity and stability toward the hydrogen evolution reaction with a low overpotential of 72.6 mV at −10 mA cm(−2) and a small Tafel slope of 37.6 mV dec(−1). The present study opens up a new opportunity to stimulate catalytic activity of the in‐plane MoS(2) basal domains for enhanced electrochemistry and redox reactivity through a “molecular reassembly‐to‐heteroatomic coordination and surface ligand functionalization” based on highly adaptable MOF template.