Abstract
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.