Solid-state NMR and first-principle calculations reveal the structure and dynamics of Li-N-H materials
6 affiliations
- 1Magnetic Resonance Research Center, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, Nijmegen, Netherlands, 6525 AJ
- 2Theoretical & Computational Chemistry, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, Nijmegen, Netherlands, 6525 AJ
- 3Institute of Science and Technology Austria, Am Campus 1, Klosterneuburg, Austria, 3400
- 4Department of Solid State Chemistry, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, Nijmegen, Netherlands, 6525 AJ
- 5Department of Physics
- 6University of Warwick
Abstract
Lithium-nitrogen-hydrogen (Li-N-H) materials are promising for hydrogen storage, solid-state batteries, and lithium-mediated ammonia synthesis, yet their local structures and proton dynamics remain poorly understood because of compositional disorder and limited sensitivity of conventional diffraction methods. Here, we combine multinuclear solid-state nuclear magnetic resonance spectroscopy (1H, 7Li, 14N, and 15N ssNMR) with first-principles calculations to resolve the atomic environments and dynamics of Li3N, LiNH2, and Li1+xNH2-x (. 7Li NMR and density functional theory calculations identify distinct lithium sites in coexisting α- and β-Li3N phases and in tetragonal LiNH2. 1H and 15N NMR, together with 1H-detected 14N spectroscopy, reveal two distinct domains in synthesized lithium-rich Li1+xNH2-x that are not resolved by laboratory X-ray diffraction. Comparison with calculated NMR parameters assigns these domains to LiNH2 and Li2NH, respectively. Variable-temperature 1H-1H exchange spectroscopy shows that correlations between the two domains arise predominantly from spin diffusion rather than interdomain proton exchange, indicating nanoscale structural heterogeneity within a solid solution. Local proton motion occurs within the Li2NH environment and is restricted in the LiNH2 domains. These results establish a molecular-level relationship between local structure and proton mobility in Li-N-H materials, providing insights relevant to hydrogen storage, solid-state batteries, and ammonia synthesis.
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BibTeX
@misc{luo2026solidstate,
title = {{Solid-state NMR and first-principle calculations reveal the structure and dynamics of Li-N-H materials}},
author = {Ruipeng Luo and Jennifer S. Gómez and Tom Speelman and Benjamin Tatman and Paul Tinnemans and Dinu Iuga and Gilles A. de Wijs and Arno P. M. Kentgens and Evan Wenbo Zhao},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010120/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010120/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Solid-state NMR and first-principle calculations reveal the structure and dynamics of Li-N-H materials
AU - Ruipeng Luo
AU - Jennifer S. Gómez
AU - Tom Speelman
AU - Benjamin Tatman
AU - Paul Tinnemans
AU - Dinu Iuga
AU - Gilles A. de Wijs
AU - Arno P. M. Kentgens
AU - Evan Wenbo Zhao
PY - 2026
DA - 2026/10/08
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010120/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010120/v1
AB - Lithium-nitrogen-hydrogen (Li-N-H) materials are promising for hydrogen storage, solid-state batteries, and lithium-mediated ammonia synthesis, yet their local structures and proton dynamics remain poorly understood because of compositional disorder and limited sensitivity of conventional diffraction methods. Here, we combine multinuclear solid-state nuclear magnetic resonance spectroscopy (1H, 7Li, 14N, and 15N ssNMR) with first-principles calculations to resolve the atomic environments and dynamics of Li3N, LiNH2, and Li1+xNH2-x (. 7Li NMR and density functional theory calculations identify distinct lithium sites in coexisting α- and β-Li3N phases and in tetragonal LiNH2. 1H and 15N NMR, together with 1H-detected 14N spectroscopy, reveal two distinct domains in synthesized lithium-rich Li1+xNH2-x that are not resolved by laboratory X-ray diffraction. Comparison with calculated NMR parameters assigns these domains to LiNH2 and Li2NH, respectively. Variable-temperature 1H-1H exchange spectroscopy shows that correlations between the two domains arise predominantly from spin diffusion rather than interdomain proton exchange, indicating nanoscale structural heterogeneity within a solid solution. Local proton motion occurs within the Li2NH environment and is restricted in the LiNH2 domains. These results establish a molecular-level relationship between local structure and proton mobility in Li-N-H materials, providing insights relevant to hydrogen storage, solid-state batteries, and ammonia synthesis.
ER -