Local Structure of Sulfur Vacancies on the Basal Plane of Monolayer MoS2

The nature of the S-vacancy is central to controlling the electronic properties of monolayer MoS2. Understanding the geometric and electronic structures of the S-vacancy on the basal plane of monolayer MoS2 remains elusive. Here, operando S K-edge X-ray absorption spectroscopy shows the formation of clustered S-vacancies on the basal plane of monolayer MoS2 under reaction conditions (H-2 atmosphere, 100-600 degrees C). First-principles calculations predict spectral fingerprints consistent with the experimental results. The Mo K-edge extended X-ray absorption fine structure shows the local structure as coordinatively unsaturated Mo with 4.1 +/- 0.4 S atoms as nearest neighbors (above 400 degrees C in an H-2 atmosphere). Conversely, the 6-fold Mo-Mo coordination in the crystal remains unchanged. Electrochemistry confirms similar active sites for hydrogen evolution. The identity of the S-vacancy defect on the basal plane of monolayer MoS2 is herein elucidated for applications in optoelectronics and catalysis.

Automated summary

This study reveals the presence of clustered S-vacancies on the basal plane of monolayer MoS2 and provides insights into their role in catalytic reactions through in situ X-ray absorption spectroscopy and first-principles calculations.