Efficient Tandem Electrocatalytic Nitrate Reduction to Ammonia on Bimodal Nanoporous Ag/Ag-Co across Broad Nitrate Concentrations.

ABSTRACT

Electrocatalytic nitrate (NO3-) reduction reaction (NO3-RR) represents a promising strategy for both wastewater treatment and ammonia (NH3) synthesis. However, it is difficult to achieve efficient NO3-RR on a single-component catalyst due to NO3-RR involving multiple reaction steps that rely on distinct catalyst properties. Here we report a facile alloying/dealloying-driven phase-separation strategy to construct a bimodal nanoporous Ag/Ag-Co tandem catalyst that exhibits a remarkable NO3-RR performance in a broad NO3- concentration range from 5 to 500 mM. In 10 and 50 mM NO3- electrolytes, the NH3 yield rates reach 3.4 and 25.1 mg h-1 mgcat.-1 with corresponding NH3 Faradaic efficiencies of 94.0% and 97.1%, respectively, outperforming most of the reported catalysts under the same NO3- concentration. The experimental results and density functional theory calculations demonstrate that Ag ligaments preferentially reduce NO3- to NO2-, while bimetallic Ag-Co ligaments catalyze the reduction of NO2- to NH3.