Investigating the hydrolysis of cryogenically layered molybdenum hexafluoride through a disordered hydrogen-bonded network

Molybdenum hexafluoride (MoF 6 ) is used as a non-radioactive substitute for uranium to study the hydrolysis of metal hexafluorides. Molybdenum hexafluoride gas and water vapor, from the air, were sequentially layered onto a diamond substrate kept at liquid nitrogen temperature using a custom design...

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Published in:Physical chemistry chemical physics : PCCP 2023-01, Vol.25 (4), p.299-2998
Main Authors: McNamara, Louis, Waldron, Abigail, Thomas, Michael, Jones, Willis, O'Rourke, Patrick, Darrell, Simmons, Strange Fessler, K. Alicia
Format: Article
Language:English
Subjects:
Diamonds
Fourier transforms
Hydrofluoric acid
Hydrogen bonding
Hydrolysis
Infrared spectroscopy
Liquid nitrogen
Molybdenum
Substrates
Uranium
Water vapor
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Summary:Molybdenum hexafluoride (MoF 6 ) is used as a non-radioactive substitute for uranium to study the hydrolysis of metal hexafluorides. Molybdenum hexafluoride gas and water vapor, from the air, were sequentially layered onto a diamond substrate kept at liquid nitrogen temperature using a custom designed cryogenic cell with a copper cold finger. Reaction progress was monitored by transmission Fourier Transform Infrared Spectroscopy (FTIR) through the layers and diamond substrate over several hours while allowing the substrate to warm. Changes in the modes in the 500-1000 cm −1 region are tracked as the reaction progresses in order to identify intermediate species. Strong absorption features are also observed in the 1000-3000 cm −1 range, suggesting the presence of ionic dissociation intermediates trapped in a disordered H-bonded network of cryogenic hydrofluoric acid. A possible reaction pathway is proposed and the final hydrolysis product is characterized by FTIR, UV-vis, and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS). Molybdenum hexafluoride (MoF 6 ) is used as a non-radioactive substitute for uranium to study the hydrolysis of metal hexafluorides.
ISSN:1463-9076
1463-9084
DOI:10.1039/d2cp04147b