Stimulated Electrocatalytic Hydrogen Evolution Activity of MOF‐Derived MoS₂ Basal Domains via Charge Injection through Surface Functionalization and Heteroatom Doping

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.

In Situ Synthesis of Copper Sulfide‐Nickel Sulfide Arrays on Three‐Dimensional Nickel Foam for Overall Water Splitting

“…The CV curves at different scan rates (10, 20, 40, 80, 160, 320 and 640 mV s −1 ) were recorded in the potential window range of −0.1‐+0.2 V Vs. SCE as displayed in (Figure S8a‐b–c). Herein, the current response is obviously due to the charging of the double‐layer and no Faradaic reaction takes place . Further the plot of difference in double‐layer charging current densities (Δ j = j a ‐j c ) Vs. scan rate (Figure S8d) derives the 2C dl value, which is related to the ECSA by definition .…”

Defects Enhance the Electrocatalytic Hydrogen Evolution Properties of MoS2‐based Materials

“…Although much research has sought to regulate the catalytic activity of MoS 2 -based catalysts by heteroatom doping, defects are difficult to introduce by this method. [62][63][64][65][66] The type and amount of dopant and the doped material (MoS 2 or carbon supports) greatly affect catalytic performance, and need to be further explored to ensure full control of heteroatom doping to generate defects.…”

微纳结构过渡金属化合物能源转化电催化剂研究进展

“…Transition metal sulfides have shown unique physicochemical properties and a significantly enhanced conductivity compared with metal oxides, which make them promising candidates for many electrochemical applications [56][57][58][59][60][61][62][63]. Due to the higher electronegativity, the S sites in the sulfides can withdraw electrons from the metals and then act as efficient active sites for reactant adsorption and activation [64].…”