Please use this identifier to cite or link to this item: http://dx.doi.org/10.18419/opus-14973
Authors: Glauber, Jean-Pierre
Lorenz, Julian
Liu, Ji
Müller, Björn
Bragulla, Sebastian
Kostka, Aleksander
Rogalla, Detlef
Wark, Michael
Nolan, Michael
Harms, Corinna
Devi, Anjana
Title: A sustainable CVD approach for ZrN as a potential catalyst for nitrogen reduction reaction
Issue Date: 2024
metadata.ubs.publikation.typ: Zeitschriftenartikel
metadata.ubs.publikation.seiten: 15451-15464
metadata.ubs.publikation.source: Dalton transactions 53 (2024), S. 15451-15464
URI: http://nbn-resolving.de/urn:nbn:de:bsz:93-opus-ds-149929
http://elib.uni-stuttgart.de/handle/11682/14992
http://dx.doi.org/10.18419/opus-14973
ISSN: 1477-9234
1477-9226
Abstract: 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.
A versatile CVD process for growing facetted ZrN layers as a potential catalyst for electrochemical reduction of nitrogen to ammonia.
Appears in Collections:04 Fakultät Energie-, Verfahrens- und Biotechnik

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