Metal-Organic Frameworks As Templates for Nanoscale NaAlH 4

Bhakta, Raghunandan K.; Herberg, Julie L.; Jacobs, Benjamin; Highley, Aaron; Behrens, Richard; Ockwig, Nathan W.; Greathouse, Jeffery A.; Allendorf, Mark D.

doi:10.1021/ja904431x

Title: Metal-Organic Frameworks As Templates for Nanoscale NaAlH ₄

Journal Article · Tue Sep 01 00:00:00 EDT 2009 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja904431x· OSTI ID:1113448

Bhakta, Raghunandan K. ^[1]; Herberg, Julie L. ^[2]; Jacobs, Benjamin ^[1]; Highley, Aaron ^[1]; Behrens, Richard ^[1]; Ockwig, Nathan W. ^[2]; Greathouse, Jeffery A. ^[2]; Allendorf, Mark D. ^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Metal-organic frameworks (MOFs) offer an attractive alternative to traditional hard and soft templates for nanocluster synthesis because their ordered crystalline lattice provides a highly controlled and inherently understandable environment. We demonstrate that MOFs are stable hosts for metal hydrides proposed for hydrogen storage and their reactive precursors, providing platform to test recent theoretical predictions that some of these materials can be destabilized with respect to hydrogen desorption by reducing their critical dimension to the nanoscale. With the MOF HKUST-1 as template, we show that NaAlH4 nanoclusters as small as eight formula units can be synthesized. The confinement of these clusters within the MOF pores dramatically accelerates the desorption kinetics, causing decomposition to occur at ~100 °C lower than bulk NaAlH4. However, using simultaneous thermogravimetric modulated beam mass spectrometry, we also show that the thermal decomposition mechanism of NaAlH4 is complex and may involve processes such as nucleation and growth in addition to the normally assumed two-step chemical decomposition reactions.

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Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: W-7405-ENG-48

OSTI ID:: 1113448

Report Number(s):: LLNL-JRNL-413291

Journal Information:: Journal of the American Chemical Society, Vol. 131, Issue 37; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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