Operando quantification of ammonia produced from computationally-derived transition metal nitride electro-catalysts

Abstract

Electrochemical reduction of dinitrogen to ammonia is investigated in a micro-reactor flow-cell using thin films of VN, CrN, NbN and ZrN. Chronoamperometry loops are used for ammonia production analysis. Operando ammonia quantification is accomplished in a flow injection analyzer. Results show the effect of presence/absence of N2(g) within both the electrochemical characterization and ammonia production for ZrN. However, no ammonia is detected from studies on CrN. VN and NbN are inactivated upon reacting their N atoms of the surface top layer(s). Results obtained from ammonia measurements, electrochemical impedance spectroscopy analysis, surface stability checks, and surface characterization using X-ray reflectivity, reveal certain trends indicating catalytic behavior for ZrN. However, the concentration of produced ammonia is below the detection limit of the methods devised to analyze the samples from isotope labeling experiments. The onset of ammonia production on ZrN appears to be in close agreement with that predicted previously by computational studies.