Observation of H2 Evolution and Electrolyte Diffusion on MoS2 Monolayer by In Situ Liquid‐Phase Transmission Electron Microscopy

Unit‐cell‐thick MoS2 is a promising electrocatalyst for the hydrogen evolution reaction (HER) owing to its tunable catalytic activity, which is determined based on the energetics and molecular interactions of different types of HER active sites. Kinetic responses of MoS2 active sites, including the reaction onset, diffusion of the electrolyte and H2 bubbles, and continuation of these processes, are important factors affecting the catalytic activity of MoS2. Investigating these factors requires a direct real‐time analysis of the HER occurring on spatially independent active sites. Herein, the H2 evolution and electrolyte diffusion on the surface of MoS2 are observed in real time by in situ electrochemical liquid‐phase transmission electron microscopy (LPTEM). Time‐dependent LPTEM observations reveal that different types of active sites are sequentially activated under the same conditions. Furthermore, the electrolyte flow to these sites is influenced by the reduction potential and site geometry, which affects the bubble detachment and overall HER activity of MoS2. In situ electrochemical liquid‐phase transmission electron microscopy (LPTEM) facilitates real‐time observation of the H2 evolution reaction (HER) on MoS2 monolayer. Time‐series LPTEM shows sequential activation, H2 bubble formation, and electrolyte flow on different types of catalytic active sites. Directionality of H2 bubbling and competitive wetting between the bubbles and electrolyte on catalyst surface significantly affect the HER activity of the active sites.