Computational Modelling of Nitroconversion for Efficient Low-Temperature Electrochemical Synthesis of Ammonia

Daria Stepaniuk^a^,^b, Doreen Mollenhauer^a^,^b^,^c^,^d^,^e

^aInstitute of Physical Chemistry, Justus Liebig University Gießen, Heinrich-Buff-Ring 17, 35392 Gießen Germany.

^bCenter for Materials Research, Justus Liebig University Gießen, Heinrich-Buff-Ring 16, 35392 Gießen Germany.

^cInstitute for Technical and Environmental Chemistry, Friedrich Schiller University Jena, Philosophenweg 7a, 07743 Jena, Germany.

^dHelmholtz Institute for Polymers in Energy Applications Jena (HIPOLE Jena), Lessingstrasse 12-14, 07743 Jena, Germany.

^eHelmholtz-Zentrum Berlin für Materialien und Energie GmbH (HZB), Hahn-Meitner-Platz 1, 14109 Berlin, Germany.

Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS Spring 2025 Conference (MATSUSSpring25)

Interlinking heterogeneous catalysts, mechanisms, and reactor concepts for dinitrogen reduction - #Nitroconversion

Sevilla, Spain, 2025 March 3rd - 7th

Organizers: Roland Marschall, Jennifer Strunk and Dirk Ziegenbalg

Oral, Daria Stepaniuk, presentation 201
DOI: https://doi.org/10.29363/nanoge.matsusspring.2025.201
Publication date: 16th December 2024

The development of the Haber-Bosch process in the early 20th century paved the way for a significant increase in ammonia production, primarily for agricultural and industrial applications. The traditional Haber-Bosch process operates under harsh conditions (high temperature and pressure) with the use of Ru- or Fe-containing catalysts [1]. Despite of the high importance of this process, its harmful impact on the environment requires to find greener alternatives.

The 2D-structures, particularly graphene-based derivatives, attract much attention in the electrochemical catalysis. It was demonstrated that nitrogen-doped graphene C₂N materials exhibits remarkable catalytic activity for N₂ reduction to NH₃ under ambient conditions attributed to their high surface area and tunable electronic structure [2]. Additionally, the presence of the nitrogen-containing functional groups in C₂N materials may serve as active sites for catalyzing nitrogen reduction and hydrogenation reactions [3]. Despite these advances, a deep theoretical understanding of the underlying catalytic mechanisms in C₂N for ammonia synthesis remains underdeveloped, highlighting the need for further exploration in this area.

This work aims to elucidate the most favorable reaction pathway for NH₃ synthesis from N₂ on C₂N catalysts using quantum-chemical calculations. Both pristine and defective C₂N structures are investigated as isolated molecule model systems (in both vacuum and solvent environments) and as extended materials using periodic boundary conditions. We have analyzed associative distal and associative alternative pathways with the different adsorption sides of N₂ molecule with the implementation of computational hydrogen electrode schema [4].Our findings indicate that the distal reaction pathway is energetically favorable on defected C₂N, requiring only an applied potential of < 1 eV. We believe that our results provide valuable insights into the catalytic mechanisms of C₂N and contribute to the development of efficient and sustainable strategies for ammonia synthesis.

References:

[1] Humphreys, J., R. Lan, and S. Tao, Development and Recent Progress on Ammonia Synthesis Catalysts for Haber–Bosch Process. Advanced Energy and Sustainability Research, 2021. 2(1): p. 2000043.

[2] Zhu, S., et al., Theoretical Investigation of Electrocatalytic Reduction of Nitrates to Ammonia on Highly Efficient and Selective g-C2N Monolayer-Supported Single Transition-Metal Atoms. The Journal of Physical Chemistry Letters, 2023. 14(18): p. 4185-4191.

[3] Zhang, Z., X. Huang, and H. Xu, Anchoring an Fe Dimer on Nitrogen-Doped Graphene toward Highly Efficient Electrocatalytic Ammonia Synthesis. Acs Appl Mater Inter, 2021. 13(36): p. 43632-43640.

[4] Skúlason, E., et al., Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations. The Journal of Physical Chemistry C, 2010. 114(42): p. 18182-18197.

Acknowledgements:

This work was conducted within the frame of German Research Foundation (DFG) within priority program “Nitroconversion” (SPP 2370, project number 501491300). The authors gratefully acknowledge the experimental collaborating groups, led by Dr. Daniel Siegmund, Ruhr University, Bochum / Fraunhofer UMSICHT and Prof. Dr. Wolfgang Zeier, University of Münster, Münster.

We acknowledge computational resources provided by the HPC Core Facility and the HRZ of the Justus Liebig University Giessen.

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