In situ evolution of electrocatalysts for enhanced electrochemical nitrate reduction under realistic conditions

Electrochemical nitrate reduction to ammonia (ENRA) is gaining attention for its potential in water remediation and sustainable ammonia production, offering a greener alternative to the energy-intensive Haber-Bosch process. Current research on ENRA is dedicated to enhancing ammonia selectively and productivity with sophisticated catalysts. However, the performance of ENRA and the change of catalytic activity in more complicated solutions (i.e., nitrate-polluted groundwater) are poorly understood. Here we first explored the influence of Ca²⁺ and bicarbonate on ENRA using commercial cathodes. We found that the catalytic activity of used Ni or Cu foam cathodes significantly outperforms their pristine ones due to the <i>in situ</i> evolution of new catalytic species on used cathodes during ENRA. In contrast, the nitrate conversion performance with nonactive Ti or Sn cathode is less affected by Ca²⁺ or bicarbonate because of their original poor activity. In addition, the coexistence of Ca²⁺ and bicarbonate inhibits nitrate conversion by forming scales (CaCO₃) on the <i>in situ</i>-formed active sites. Likewise, ENRA is prone to fast performance deterioration in treating actual groundwater over continuous flow operation due to the presence of hardness ions and possible organic substances that quickly block the active sites toward nitrate reduction. Our work suggests that more work is required to ensure the long-term stability of ENRA in treating natural nitrate-polluted water bodies and to leverage the environmental relevance of ENRA in more realistic conditions.