Solution-Phase Activation and Functionalization of Colloidal WS₂ Nanosheets with Ni Single Atoms

Single-atom functionalization of transition-metal dichalcogenide (TMD) nanosheets is a powerful strategy to tune the optical, magnetic, and catalytic properties of two-dimensional materials. In this work, we demonstrate a simple solution-phase method to generate nucleophilic sulfide sites on colloidal WS₂ nanosheets that subsequently serve as ligands for Ni single atoms. These materials can be controllably functionalized with varying amounts of Ni on the surface ranging from 9% to 47% coverage with respect to W. High-resolution scanning transmission electron microscopy coupled to electron energy loss spectroscopy and X-ray absorption spectroscopy indicate that adsorbed Ni species bind as single atoms at low coverage and a mixture of single atoms and multimetallic clusters at high coverage. The Ni single atoms adsorbed on WS₂ show altered electronic properties, and both the electronic perturbation and isolated atom geometry play a role in enhancing the intrinsic catalytic activity of Ni-WS₂ samples for the electrochemical oxygen evolution reaction.