Computational Insight into Metallated Graphynes as Single Atom Electrocatalysts for Nitrogen Fixation

Area of Science:

• Materials Science
• Electrochemistry
• Catalysis

Background:

• Sustainable ammonia synthesis is crucial, but efficient catalysts for the electrochemical nitrogen reduction reaction (NRR) are scarce.
• Transition metal-1,3,5-triethynylbenzene (TM-TEB) frameworks present unique atomic and electronic structures for catalysis.

Purpose of the Study:

• To conduct a comprehensive first-principles study of TM-TEB systems for NRR electrocatalyst applications.
• To screen TM-TEB systems for high NRR activity and selectivity, considering hydrogen evolution reaction competition.

Main Methods:

• First-principles calculations were employed to study TM-TEB systems across the first three d-block transition metal series.
• A hierarchical screening strategy evaluated catalytic activity, NRR selectivity, and hydrogen evolution reaction competition.
• Detailed analysis of various NRR pathways on TM-TEB surfaces was performed.

Main Results:

• TM-TEB systems with V, Mo, Tc, W, and Os demonstrated high NRR catalytic activity.
• Mo- and V-TEB specifically showed promising NRR selectivity.
• Analysis provided insights into the catalytic mechanisms on TM-TEB surfaces.

Conclusions:

• TM-TEB systems hold significant potential as electrocatalysts for the NRR.
• This study enhances understanding of TM-TEB materials and encourages further research in catalysis.