Mechanistic Insights into Light-Alkane Formation from Photoexcited Uranyl complexes
4 affiliations
- 1CNRS UMR, Institut Polytechnique de Paris, Route de Saclay, Palaiseau Cedex, France, 91128
- 2Laboratoire de Physique et Chimie des Nano-Objets, CNRS & INSA
- 3Université Paul Sabatier
- 4chemistry, Laboratoire de chimie, ENS de Lyon, UMR 5182, Lyon, France, F-69342
Abstract
This work describes a uranyl-catalysed photo-induced methodology for generating methane from acetic acid. The reaction proceeds in water as the only solvent, with roughly 10 vol % acetic acid — a composition mimicking ommercial vinegar — and only 1 mol % of UO 2 (NO 3 ) 2 , a by-product of the nuclear fuel cycle. The mechanism underlying this transformation was examined in detail through luminescence measurements, EPR spectroscopy, isotope-labelling experiments, and speciation studies. DFT calculations show that the process involves an unstable intermediate, U V O 2 + -AcOH template, which is prompt to disproportionation into inactive U IV and appears to be responsible for the low TON, which is reported. However, the speciation studies also suggest that the equatorial environment of UO 2 2+ would stabilize this UV intermediate and therefore influence the CH 4 production as well as decreasing the potential additional competitive paths, leading to greater selectivity.
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BibTeX
@misc{assendjee2026mechanistic,
title = {{Mechanistic Insights into Light-Alkane Formation from Photoexcited Uranyl complexes}},
author = {Eachann Assendjee and Thayalan Rajeshkumar and Lhoussain Khrouz and Yoann Fréroux and Cyrille Monnereau and Olivier Maury and Laurent Maron and grégory Nocton and grégory Danoun},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008899/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008899/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Mechanistic Insights into Light-Alkane Formation from Photoexcited Uranyl complexes
AU - Eachann Assendjee
AU - Thayalan Rajeshkumar
AU - Lhoussain Khrouz
AU - Yoann Fréroux
AU - Cyrille Monnereau
AU - Olivier Maury
AU - Laurent Maron
AU - grégory Nocton
AU - grégory Danoun
PY - 2026
DA - 2026/09/16
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008899/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008899/v1
AB - This work describes a uranyl-catalysed photo-induced methodology for generating methane from acetic acid. The reaction proceeds in water as the only solvent, with roughly 10 vol % acetic acid — a composition mimicking ommercial vinegar — and only 1 mol % of UO 2 (NO 3 ) 2 , a by-product of the nuclear fuel cycle. The mechanism underlying this transformation was examined in detail through luminescence measurements, EPR spectroscopy, isotope-labelling experiments, and speciation studies. DFT calculations show that the process involves an unstable intermediate, U V O 2 + -AcOH template, which is prompt to disproportionation into inactive U IV and appears to be responsible for the low TON, which is reported. However, the speciation studies also suggest that the equatorial environment of UO 2 2+ would stabilize this UV intermediate and therefore influence the CH 4 production as well as decreasing the potential additional competitive paths, leading to greater selectivity.
ER -