Electronic-Geometric Pre-Compensation Enables Intermetallic RhSb Bimetallenes for Efficient Nitrite Electroreduction

Area of Science:

• Electrochemistry
• Materials Science
• Catalysis

Background:

• Electrochemical synthesis faces challenges from electrocatalyst deactivation due to intermediate adsorption.
• Linear scaling relationships limit strategies to weaken intermediate binding without affecting desired reactions.

Purpose of the Study:

• To mitigate *NO poisoning in nitrite electroreduction reaction (NO2ERR) using a pre-compensation strategy.
• To reconcile trade-offs between electronic and geometric structures in electrocatalysts.

Main Methods:

• Fabrication of intermetallic RhSb bimetallenes (RhSb IMMs).
• Modulation of Rh active sites' electronic and geometric structures.
• Validation of the pre-compensation strategy in NO2ERR.

Main Results:

• RhSb IMMs demonstrated stable operation (>880 h) with >90% Faradaic efficiency for ammonia (NH3) production.
• Achieved high NH3 yield rate (107.5 g h-1 gcat-1) at -0.3 V (vs. RHE).
• The strategy successfully mitigated *NO poisoning by tuning Rh-Sb interactions.

Conclusions:

• The pre-compensation strategy effectively reconciles electronic and geometric structure trade-offs in catalysis.
• RhSb IMMs offer a promising platform for stable and efficient electrochemical synthesis.
• This approach provides a rational design principle for advanced electrocatalysts.