Understanding H2 Evolution from the Decomposition of Dibutylmagnesium Isomers Using in-Situ X-ray Diffraction Coupled with Mass Spectroscopy

Liu, Jian; Schaef, H. Todd; Martin, Paul F.; McGrail, B. Pete; Fifield, Leonard S.

doi:10.1021/acsaem.9b00958

Understanding H₂ Evolution from the Decomposition of Dibutylmagnesium Isomers Using in-Situ X-ray Diffraction Coupled with Mass Spectroscopy

Journal Article · Fri Jun 07 00:00:00 EDT 2019 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.9b00958· OSTI ID:1770577

^[1]; ^[1]; Martin, Paul F. ^[1]; McGrail, B. Pete ^[1]; ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Alkylmagnesium compounds such as dibutylmagnesium can be effectively decomposed to produce MgH₂ and Mg metal for applications such as hydrogen storage, single site catalysis, and powder metallurgy or as the last step of comprehensive processes to produce Mg metal from magnesium salts. For these applications it is important to understand the decomposition reactions of dibutylmagnesium and to quantify its decomposition products. In this study, to avoid interference from air and moisture, an in situ X-ray diffraction (XRD) coupled with mass spectroscopy system was developed to investigate phase changes and released products in real time for the decomposition reactions. For the dibutylmagnesium (MgBu₂^n-n) with two n-butyl groups, transformation to MgH₂ occurred at 250 °C and transformation to Mg metal occurred near 384 °C. The diffraction data suggest the possibility of an intermediate phase with one butyl group formed during the transformation to MgH₂. Decomposition of MgH₂ under vacuum is accelerated by eliminating H₂ from the system as it is evolved. The sec-butyl n-butylmagnesium (MgBu₂^s-n) was observed to decompose at as low as 50 °C, indicating the increased lability of the sec-butyl group in the dibutylmagnesium isomer. Thermogravimetric analysis (TGA) for the MgBu₂^n-n and MgBu₂^s-n loaded in air-free conditions recorded higher than 98% conversion to MgH₂.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1770577

Report Number(s):: PNNL-SA--119043

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 7 Vol. 2; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
alkylmagnesium
decomposition
h2 storage
in situ xrd
magnesium hydride
metals
molecular structure
organic reactions
physical and chemical processes
vacuum

Understanding H2 Evolution from the Decomposition of Dibutylmagnesium Isomers Using in-Situ X-ray Diffraction Coupled with Mass Spectroscopy

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Understanding H₂ Evolution from the Decomposition of Dibutylmagnesium Isomers Using in-Situ X-ray Diffraction Coupled with Mass Spectroscopy