A sustainable CVD approach for ZrN as a potential catalyst for nitrogen reduction reaction.

In pursuit of developing alternatives for the highly polluting Haber-Bosch process for ammonia synthesis, the electrocatalytic nitrogen reduction reaction (NRR) using transition metal nitrides such as zirconium mononitride (ZrN) has been identified as a potential pathway for ammonia synthesis. In particular, specific facets of ZrN have been theoretically described as potentially active and selective for NRR. Major obstacles that need to be addressed include the synthesis of tailored catalyst materials that can activate the inert dinitrogen bond while suppressing hydrogen evolution reaction (HER) and not degrading during electrocatalysis. To tackle these challenges, a comprehensive understanding of the influence of the catalyst's structure, composition, and morphology on the NRR activity is required. This motivates the use of metal-organic chemical vapor deposition (MOCVD) as the material synthesis route as it enables catalyst nanoengineering by tailoring the process parameters. Herein, we report the fabrication of oriented and facetted crystalline ZrN thin films employing a single source precursor (SSP) MOCVD approach on silicon and glassy carbon (GC) substrates. First principles density functional theory (DFT) simulations elucidated the preferred decomposition pathway of SSP, whereas ab initio molecular dynamics simulations show that ZrN at room temperature undergoes surface oxidation with ambient O2, yielding a Zr-O-N film, which is consistent with compositional analysis using Rutherford backscattering spectrometry (RBS) in combination with nuclear reaction analysis (NRA) and X-ray photoelectron spectroscopy (XPS) depth profiling. Proof-of-principle electrochemical experiments demonstrated the applicability of the developed ZrN films on GC for NRR and qualitatively hint towards a possible activity for the electrochemical NRR in the sulfuric acid electrolyte.

Application of Ion Chromatography for the Reliable Quantification of Ammonium in Electrochemical Ammonia Synthesis Experiments: A Practical Guide.

Assessing novel electrocatalysts for the electrochemical ammonia synthesis (EAS) requires reliable quantitative trace analysis of electrochemically produced ammonia to infer activity and selectivity. This study concerns the development of an ion chromatography (IC) method for quantitative trace analysis of ammonium in 0.1 M sulfuric acid electrolyte, which is applied to EAS gas-diffusion electrode (GDE) experiments with commercial chromium nitride as electrocatalyst. The developed IC method is highly sensitive, versatile, and reliable, achieving a limit of quantification (LOQ) of 6 µg l-1 (6 ppbmol ) ammonium. The impacts of the sample matrix, dilution, and neutralization, as well as contamination, on the quantitative analysis by IC are analyzed. Experimental constraints result in an effective LOQ including dilution of 60 µg l-1 for the determination of ammonium in 0.1 M sulfuric acid electrolyte, owing to necessary sample dilution. The practical guide presented herein is intended to be very relevant for the field of EAS as a guideline and applicable to a broad range of catalyst systems and ion chromatography devices.