A First-Principles Study of Nitric Oxide Electroreduction on Transition Metal Monolayers Supported on Mo₂N

Area of Science:

• Materials Science
• Electrochemistry
• Catalysis

Background:

• Electrochemical NO reduction reaction (NORR) is a dual-functional process for NO removal and ammonia synthesis.
• Developing efficient electrocatalysts is crucial for NORR applications.

Purpose of the Study:

• To systematically evaluate the NORR catalytic activity of transition metal (TM) monolayers on Mo2N.
• To identify promising NORR candidates and understand the underlying electronic structure-activity relationships.

Main Methods:

• Density Functional Theory (DFT) calculations were employed.
• Systematic evaluation of transition metal monolayers (Ni, Cu, Pd, Ag, Pt, Au) supported on Mo2N.
• Analysis of electronic structure, including d-band center (εd) and electron donation/backdonation mechanisms.

Main Results:

• CuML/Mo2N, AgML/Mo2N, PtML/Mo2N, and AuML/Mo2N exhibited promising NORR activity with low limiting potentials.
• Electronic structure tuning at the atomic level promoted NO adsorption and activation.
• The d-band center (εd) was identified as a key screening indicator for NORR activity.

Conclusions:

• A clear electronic structure-activity relationship was established for NORR on TMML/Mo2N catalysts.
• These findings provide a design principle for novel 2D electrocatalysts for NORR.
• The study contributes to the theoretical understanding and practical application of 2D materials in catalysis.