Exploitation of the Large‐Area Basal Plane of MoS₂ and Preparation of Bifunctional Catalysts through On‐Surface Self‐Assembly

Abstract The development of nonprecious electrochemical catalysts for water splitting is a key step to achieve a sustainable energy supply for the future. Molybdenum disulfide (MoS₂) has been extensively studied as a promising low‐cost catalyst for hydrogen evolution reaction (HER), whereas HER is only catalyzed at the edge for pristine MoS₂, leaving a large area of basal plane useless. Herein, on‐surface self‐assembly is demonstrated to be an effective, facile, and damage‐free method to take full advantage of the large ratio surface of MoS₂ for HER by using multiscale simulations. It is found that as supplement of edge sites of MoS₂, on‐MoS₂ M(abt)₂ (M = Ni, Co; abt = 2‐aminobenzenethiolate) owns high HER activity, and the self‐assembled M(abt)₂ monolayers on MoS₂ can be obtained through a simple liquid‐deposition method. More importantly, on‐surface self‐assembly provides potential application for overall water splitting once the self‐assembled systems prove to be of both HER and oxygen evolution reaction activities, for example, on‐MoS₂ Co(abt)₂. This work opens up a new and promising avenue (on‐surface self‐assembly) toward the full exploitation of the basal plane of MoS₂ for HER and the preparation of bifunctional catalysts for overall water splitting.