Patterning edge-like defects and tuning defective areas on the basal plane of ultra-large MoS2 monolayers toward the hydrogen evolution reaction.

The catalytic sites of MoS₂ monolayers towards hydrogen evolution are well known to be vacancies and edge-like defects. However, it is still very challenging to control the position, size, and defective areas on the basal plane of MoS₂ monolayers by most of the defect-engineering routes. In this work, the fabrication of etched arrays on ultra-large supported and free-standing MoS₂ monolayers using a focused ion beam (FIB) is reported for the first time. By tuning the Ga⁺ ion dose, it is possible to confine defects near the etched edges or spread them over ultra-large areas on the basal plane. The electrocatalytic activity of the arrays toward the hydrogen evolution reaction (HER) was measured by fabricating microelectrodes using a new method that preserves the catalytic sites. We demonstrate that the overpotential can be decreased up to 290 mV by assessing electrochemical activity only at the basal plane. High-resolution transmission electron microscopy images obtained on FIB patterned freestanding MoS₂ monolayers reveal the presence of amorphous regions and X-ray photoelectron spectroscopy indicates sulfur excess in these regions. Density-functional theory calculations enable identification of catalytic defect sites. Our results demonstrate a new rational control of amorphous-crystalline surface boundaries and future insight for defect optimization in MoS₂ monolayers. [ABSTRACT FROM AUTHOR]