Effects of Ionic Interferents on Electrocatalytic Nitrate Reduction: Mechanistic Insight

Nitrate, a prevalent water pollutant, poses substantial public health concerns and environmental risks. Electrochemical reduction of nitrate (eNO₃RR) has emerged as an effective alternative to conventional biological treatments. While extensive lab work has focused on designing efficient electrocatalysts, implementation of eNO₃RR in practical wastewater settings requires careful consideration of the effects of various constituents in real wastewater. In this critical review, we examine the interference of ionic species commonly encountered in electrocatalytic systems and universally present in wastewater, such as halogen ions, alkali metal cations, and other divalent/trivalent ions (Ca²⁺, Mg²⁺, HCO₃^-/CO₃^2-, SO₄^2-, and PO₄^3-). Notably, we categorize and discuss the interfering mechanisms into four groups: (1) loss of active catalytic sites caused by competitive adsorption and precipitation, (2) electrostatic interactions in the electric double layer (EDL), including ion pairs and the shielding effect, (3) effects on the selectivity of N intermediates and final products (N₂ or NH₃), and (4) complications by the hydrogen evolution reaction (HER) and localized pH on the cathode surface. Finally, we summarize the competition among different mechanisms and propose future directions for a deeper mechanistic understanding of ionic impacts on eNO₃RR.