Advancing carbon capture research thanks to 17O-labeling of MOFs

Research will be carried out at the Institut Charles Gerhardt (ICGM, UMR5253) of the University of Montpellier
(https://www.icgm.fr/), within the MISOTOP research group (https://www.misotoplab.org/). The ICGM is internationally
renowned for its expertise in materials science, with an excellent support for advanced studies on their synthesis and
characterization. The MISOTOP group is fully equipped for 17O isotopic labeling (with 7 ball-mills for mechanochemistry, and UV-lamps for photochemical reactions), and for the analysis of the enriched compounds (including by mass spectrometry and solid-state NMR).

Project description
With the increase in CO2 concentration in the atmosphere, there is an urgent need to reduce our emissions and
develop means to capture this gas in an efficient and durable way. A wide variety of materials have been tested and studied
for this purpose, including porous compounds like zeolites and MOFs (Metal-Organic Frameworks). However, to help
understand and further optimize the properties of these materials, it appears necessary to analyze their structure in more
depth, including at the atomic scale. The general purpose of this project is to participate to the development of advanced
NMR-based techniques for studying the structure of MOFs currently being developed for CO2 capture. The focus will be set
on helping analyze in depth the local environment of the oxygen atoms present in the ligands which make up these MOFs,
using 17O NMR. Indeed, the role of the ligands is central in defining the overall structure of the material, but also, in some
cases, the reactivity which can take place within the pores, upon incorporation of small molecules.
To date, oxygen-17 NMR has only been used in a small number of cases for the investigation of MOFs, due to the
very poor natural abundance of 17O (only 0.04 %). Therefore, in this project, the objectives will be:
- to develop novel efficient 17O-enrichment schemes of ligands which are commonly used in MOFs, by using
synthetic techniques like mechanochemistry or photochemistry,1,2
- to characterize the labeled ligands by a variety of analytical techniques (to evaluate their enrichment level),
including mass spectrometry and 17O solid state NMR;
- to use these labeled ligands for the preparation and analyses of a selection of 17O-enriched MOFs.

Research environment
Research will be carried out at the Institut Charles Gerhardt (ICGM, UMR5253) of the University of Montpellier
(https://www.icgm.fr/), within the MISOTOP research group (https://www.misotoplab.org/). The ICGM is internationally
renowned for its expertise in materials science, with an excellent support for advanced studies on their synthesis and
characterization. The MISOTOP group is fully equipped for 17O isotopic labeling (with 7 ball-mills for mechanochemistry,
and UV-lamps for photochemical reactions), and for the analysis of the enriched compounds (including by mass
spectrometry and solid-state NMR).
On a daily basis, the recruited student will work under the supervision of Drs Thomas-Xavier Métro and Danielle
Laurencin. He/she will also have the opportunity to interact with the team of researchers, engineers, and students involved
in this study both locally (in Montpellier), and at the national level, notably with the groups of Dr F. Pourpoint in Lille and
Prof C. Gervais in Paris.

Application procedure
This project is funded by the French national research funding agency (ANR). The starting date for the internship
is planned for early 2026. To apply, send a CV, motivation letter, and the names of 2 references to both Drs Thomas-Xavier
Métro and Danielle Laurencin. Candidacies will
be examined until the position gets filled.

References
(1) Métro, T.-X.; Gervais, C.; Martinez, A.; Bonhomme, C.; Laurencin, D. Unleashing the Potential of 17O NMR Spectroscopy Using
Mechanochemistry. Angew. Chem. Int. Ed. 2017, 56 (24), 6803–6807. https://doi.org/10.1002/anie.201702251.
(2) Doussot, A.; Bakaï, M.-F.; Fouquet, E.; Hermange, P. Ex Situ Generation of 18O2 and 17O2 from Endoperoxides for *O-Labeling and
Mechanistic Studies of Oxidations by Dioxygen. Org. Lett. 2023, 25 (25), 4661–4665. https://doi.org/10.1021/acs.orglett.3c01487.
NB: Image of MOF-74 taken from reference : Xiao, T.; Liu, D. The Most Advanced Synthesis and a Wide Range of Applications of MOF-74 and Its
Derivatives. Microporous Mesoporous Mater. 2019, 283, 88–103. https://doi.org/10.1016/j.micromeso.2019.03.002.

In this project, the recruited student will be in charge of:
- to develop novel efficient 17O-enrichment schemes of ligands which are commonly used in MOFs, by using
synthetic techniques like mechanochemistry or photochemistry,1,2
- to characterize the labeled ligands by a variety of analytical techniques (to evaluate their enrichment level),
including mass spectrometry and 17O solid state NMR;
- to use these labeled ligands for the preparation and analyses of a selection of 17O-enriched MOFs.