Highly selective electrocatalytic reduction of nitrate to nitrogen in a chloride ion-free system by promoting kinetic mass transfer of intermediate products in a novel Pd–Cu adsorption confined cathode

The mass transfer on the catalyst surface has a great influence on the selectivity of electrocatalytic nitrate reduction to nitrogen. In this study, a Pd–Cu adsorption confined nickel foam cathode is designed in the absence of both proton exchange membranes and chloride ions. The repulsion of the cathode enables intermediate products such as nitrite to accumulate in the confined region, resulting in an increase in the possibility of a second-order reaction to form nitrogen. The system can obtain more than 92% continuous N2 selectivity when it is used to treat 200 mg L−1 NO3−-N under a current density of 8 mA cm−2, which is not only higher than those of semiconfined and nonconfined systems but also significantly better than the results obtained by Pd–Cu directly modified cathodes prepared by electrodeposition or impregnation. It is found that a high initial nitrate concentration and low current density are more beneficial for the accumulation of intermediates on Pd–Cu catalysts, thus improving the formation of nitrogen. A mechanism study reveals that the intermediates can completely occupy the active sites on the surface of Pd, avoiding the generation of active hydrogen, and therefore inhibiting the first-order reaction to produce ammonia. Moreover, the reducibility of Pd–Cu can also be gradually improved under the function of the cathode so that the system exhibits good stability. This study demonstrates an environmentally friendly and promising method for total nitrogen removal from industrial wastewater with high conductivity. [Display omitted] •A Pd–Cu adsorption confined nickel foam cathode is designed to reduce NO3− to N2.•High and continuous N2 selectivity is achieved in the absence of Cl−.•Intermediates are accumulated in the confined region through cathode repulsion.•N2 generation is boosted by highly efficient mass transfer of intermediates on Pd.•The system exhibited high reducibility and excellent stability.