Fluorine- and Nitrogen-Codoped MoS₂ with a Catalytically Active Basal Plane.

Area of Science:

• Materials Science
• Catalysis
• Surface Chemistry

Background:

• Two-dimensional molybdenum disulfide (2D MoS₂) is a promising platinum alternative for hydrogen evolution reaction (HER) catalysis.
• Currently, only the edge sites of 2D MoS₂ are considered catalytically active, while the basal planes remain inert.
• Activating the basal plane is crucial for significantly enhancing HER activity.

Purpose of the Study:

• To activate the inert basal planes of 2D MoS₂ for improved HER catalysis.
• To investigate the synergistic effects of nitrogen and fluorine codoping on MoS₂ basal plane activation.
• To explore the potential of nitrogen as a tunable catalytic site within the MoS₂ basal plane.

Main Methods:

• First-principles calculations were employed to investigate the electronic and catalytic properties of codoped MoS₂.
• Synthesis of fluorine- and nitrogen-codoped MoS₂ (NF-MoS₂) materials.
• Experimental evaluation of HER activity for pure MoS₂, N-doped MoS₂, and NF-MoS₂ catalysts.

Main Results:

• First-principles calculations confirmed that nitrogen doping in the basal plane of fluorine- and nitrogen-codoped MoS₂ (NF-MoS₂) creates new, tunable active sites.
• The synthesized NF-MoS₂ catalyst demonstrated significantly enhanced HER activity compared to pure MoS₂.
• The HER activity of NF-MoS₂ was substantially higher than that of N-doped MoS₂, highlighting the synergistic effect of codoping.

Conclusions:

• The inert basal planes of 2D MoS₂ can be effectively activated through synergistic nitrogen and fluorine codoping.
• NF-MoS₂ presents a novel and highly active catalyst for the hydrogen evolution reaction.
• This study offers a new strategy for enhancing catalyst performance via chemical codoping for HER applications.