Exploring the impact of substrates while tailoring ZrN film properties relevant for nitrogen reduction reaction

Jean Pierre Glauber^a^,^b, Jorit Obenlüneschloß^b, Ji Liu^c, Julian Lorenz^d, Sebastian Bragulla^d^,^e, Björn Müller^f, Michael Wark^f, Corinna Harms^d, Michael Nolan^c, Anjana Devi^a^,^b^,^g

^aLeibniz Institute for Solid State and Materials Research, Helmholtzstr. 20, 01069 Dresden, Germany

^bInorganic Materials Chemistry, Ruhr University Bochum, Universitätsstraße 150, 44801 Bochum, Germany

^cTyndall National Institute, University College Cork, Lee Maltings, Dyke Parade, T12 R5CP Cork, Irelands

^dInstitute of Engineering Thermodynamics, German Aerospace Center (DLR), Carl-von-Ossietzky-Str. 15, 26129 Oldenburg, Germany

^eInstitute of Building Energetics, Thermal Engineering and Energy Storage, University of Stuttgart, Pfaffenwaldring 31, 70569 Stuttgart, Germany

^fInstitute of Chemistry, Carl von Ossietzky University Oldenburg, Carl-von-Ossietzky-Str. 9-11, 26129 Oldenburg, Germany

^gChair of Materials Chemistry, TU Dresden, Bergstr. 66, 01069 Dresden, 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

Poster, Jean Pierre Glauber, 619
Publication date: 16th December 2024

Numerous material systems have been proposed as potential catalysts for the electrocatalytic nitrogen reduction reaction (NRR), including noble metals^[1], transition metal nitrides (TMNs)^[2], oxides^[3] and sulfides^[4]. TMNs exhibit great potential for electrocatalysis, as they feature high electrical conductivities and superior chemical stability.^[5] Among them, the mononitrides of Zr, V, Cr and Nb have been theoretically described as active and stable NRR catalysts under typical electrochemical conditions, provided they are grown in a facetted manner.^[6] To realize facetted growth, metalorganic chemical vapor deposition (MOCVD) is the method of choice, as it allows for precise tuning of materials properties by variation of the process parameters, while enabling moderate process conditions and large-scale fabrication. Since the reactants undergo surface reactions during the MOCVD process, the choice of substrate and its properties such as orientation, crystallinity, composition, lattice parameters, surface energy, have a significant influence on the growth characteristics and the grown material.

In the case of rock salt ZrN, the (100) orientation is preferred for the NRR because it has been theoretically predicted to exhibit higher stability and selectivity compared to the (111) and (220) facets. To experimentally prove this, we developed a MOCVD process to deposit ZrN along the (100) plane using an ammonia-free single source precursor (SSP) approach.^[7] The facet-favored growth was obtained on Si(100) substrates and the thin film properties were investigated by complementary characterization methods including X-ray diffraction (XRD), Rutherford backscattering spectrometry combined with nuclear reaction analysis (RBS/NRA), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). To investigate the electrocatalytic NRR performance, the process had to be transferred to a conductive substrate with limited activity for the competing hydrogen evolution reaction (HER). Therefore, a systematic screening of conductive substrates including glassy carbon (GC), fluorine-doped tin oxide (FTO/glass), stainless steel (316L), and titanium was performed to investigate the influence of the MOCVD growth characteristics. These findings are important for future development of other NRR catalysts by MOCVD such as VN or composite material systems such as Ru/MoS₂.^[8]

References:

[1] H.-M. Liu, S.-H. Han, Y. Zhao, Y.-Y. Zhu, X.-L. Tian, J.-H. Zeng, J.-X. Jiang, B.Y. Xia, Y. Chen, J. Mater. Chem. A, 2018, 6 3211–3217.

[2] X. Yang, J. Nash, J. Anibal, M. Dunwell, S. Kattel, E. Stavitski, K. Attenkofer, J.G. Chen, Y. Yan, B. Xu, J. Am. Chem. Soc. 2018, 140, 13387–13391.

[3] Z. Sun, R. Huo, C. Choi, S. Hong, T.-S. Wu, J. Qiu, C. Yan, Z. Han, Y. Liu, Y.-L. Soo, Y. Jung, Nano Energy 2019, 62, 869–875.

[4] P.-Y. Liu, K. Shi, W.-Z. Chen, R. Gao, Z.-L. Liu, H. Hao, Y.-Q. Wang, Appl. Catal. B-Environ. 2021, 287, 119956.

[5] Luo, Q.; Lu, C.; Liu, L.; Zhu, M., Green Energy & Environ. 2023 8 (2), 406.

[6] Y. Abghoui, A. L. Garden, J. G. Howalt, T. Vegge and E. Skúlason, ACS Catal. 2016, 6, 635-646.

[7] J.-P. Glauber, J. Lorenz, J. Liu, B. Müller, S. Bragulla, A. Kostka, D. Rogalla, M. Wark, M. Nolan, C. Harms and A. Devi, Dalton transactions, 2024, 53, 15451–15464.

[8] B. H. R. Suryanto, D. Wang, L. M. Azofra, M. Harb, L. Cavallo, R. Jalili, D. R. G. Mitchell, M. Chatti and D. R. MacFarlane, ACS Energy Lett., 2019, 4, 430–435.

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