A novel niobium (oxy)nitride-BaCe0.7Zr0.1Y0.2O3-δ composite electrode for Proton Ceramic Membrane Reactors (PCMRs)

The necessity to accelerate green and low carbon technologies, to mitigate the pending energetic crisis, potentiates the urgent search for alternative energy transfer methods. In this regard, Proton Ceramic Membrane Reactors (PCMRs) have shown great potential as a clean alternative for both energy production and the electrochemical synthesis of a wide range of chemical products. One of the most important is that of ammonia, where recent literature has demonstrated the potential use of PCMRs to either synthesize this chemical product or to use it as a fuel, and where suitable new electrodes must be developed. Hence, this work investigates the use of niobium (oxy)nitride (NbNxOy) in combination with proton ceramic conducting materials, as a new category of composite electrode for PCMRs applications. To achieve this goal, firstly, the chemical compatibility of the NbNxOy phase with the well-known proton conducting perovskite, yttrium-doped barium cerate (BaCe0.9Y0.1O3-δ, BCY10), was assessed. By X-ray powder diffraction, BaCe0.7Zr0.1Y0.2O3-δ (BCZY712) was shown to be chemically stable with the NbNxOy phase, surviving up to 850 °C, thus, facilitating the production of an electrolyte supported composite electrode film based on BCZY712-NbNxOy (40–60 vol%). Thermogravimetric experiments combined with X-ray diffraction were also made to assess the thermal stability of the NbNxOy material in both N2 and 2 % H2/N2 atmospheres, revealing that NbNxOy decomposes into its parent oxide in N2, while retaining the pure (oxy)nitride phase in the more reducing conditions. The polarization behavior of the BCZY712-NbNxOy composite electrode was evaluated by electrochemical impedance spectroscopy under different gaseous conditions of H2/N2 and NH3 atmospheres. The overall electrode mechanism was tentatively explained by three main steps, including i) proton incorporation/water release or adsorption/desorption of water, ii) gaseous hydrogen adsorption/desorption, and iii) interfacial transfer reaction of either protons or oxygen-ion vacancies. To the best of our knowledge, this is the first work that reports a detailed chemical compatibility study of niobium (oxy)nitride with a protonic ceramic matrix, while also outlining a detailed electrode mechanism under prospective conditions of hydrogenation/de‑hydrogenation of ammonia.