Computational Investigation of Transition Metal Atom-Decorated C₈N₈ Monolayers for Nitrogen Reduction Reaction

Area of Science:

• Materials Science
• Catalysis
• Computational Chemistry

Background:

• Electrocatalytic nitrogen reduction reaction (NRR) offers a sustainable pathway for ammonia synthesis.
• High activity and selectivity in NRR catalysts are essential but challenging to achieve.
• C8N8 monolayers present unique structural and porous properties suitable for single-atom catalyst support.

Purpose of the Study:

• To investigate the catalytic performance of transition metal single-atom-decorated C8N8 monolayers for NRR.
• To identify stable and highly active single-atom catalysts for nitrogen reduction.
• To provide insights into the mechanism of NRR on these novel materials.

Main Methods:

• Comprehensive study using density functional theory (DFT) calculations.
• Screening of 24 transition metal single-atom-C8N8 candidates based on binding and formation energies.
• Analysis of reaction barriers, selectivity, and electronic structures.

Main Results:

• Identified 24 stable single-atom-C8N8 candidates with negative binding and formation energies.
• TiC8N8, MoC8N8, and OsC8N8 demonstrated low reaction barriers (0.67, 0.50, and 0.21 eV, respectively).
• OsC8N8 exhibited superior selectivity and effectively weakened the N≡N bond, facilitating N2 activation.

Conclusions:

• OsC8N8 is a promising candidate for highly active and selective electrocatalytic nitrogen reduction.
• The C8N8 monolayer is an effective support for single-atom catalysts in NRR.
• This study offers valuable guidance for designing advanced electrocatalysts for sustainable ammonia synthesis.