Breaking the Volcano-Shaped Relationship for Highly Efficient Electrocatalytic Nitrogen Reduction: A Computational...

Area of Science:

• Materials Science
• Electrochemistry
• Computational Chemistry

Background:

• The volcano-shaped relationship, common in electrocatalytic nitrogen reduction (e-NRR), hinders catalyst performance due to competing hydrogenation steps.
• Breaking this relationship is crucial for advancing e-NRR efficiency.

Purpose of the Study:

• To investigate transition-metal doped Cu-based single-atom alloys (TM1-Cu(111)) as catalysts for e-NRR.
• To understand and overcome the volcano-shaped relationship in e-NRR.

Main Methods:

• First-principles calculations were employed to study TM1-Cu(111) catalysts.
• Analysis focused on the activation of N2 and the energetics of hydrogenation steps.

Main Results:

• A strategy was developed to break the volcano-shaped relationship by ensuring strong N2 adsorption and facile final hydrogenation.
• Four catalysts (Re1-Cu(111), W1-Cu(111), Tc1-Cu(111), Mo1-Cu(111)) showed outstanding e-NRR activity with limiting potentials from -0.38 to -0.56 V.
• These catalysts also suppressed the hydrogen evolution reaction and demonstrated long-term stability.

Conclusions:

• The study provides a guideline for breaking the volcano-shaped relationship in e-NRR.
• The identified TM1-Cu(111) catalysts are promising for highly efficient and stable electrocatalytic nitrogen reduction.