Nanoconfinement of Molecular Magnesium Borohydride Captured in a Bipyridine-Functionalized Metal–Organic Framework

Schneemann, Andreas; Wan, Liwen F.; Lipton, Andrew S.; Liu, Yi-Sheng; Snider, Jonathan L.; Baker, Alexander A.; Sugar, Joshua D.; Spataru, Catalin D.; Guo, Jinghua; Autrey, Tom S.; Jørgensen, Mathias; Jensen, Torben R.; Wood, Brandon C.; Allendorf, Mark D.; Stavila, Vitalie

doi:10.1021/acsnano.0c03764

Title: Nanoconfinement of Molecular Magnesium Borohydride Captured in a Bipyridine-Functionalized Metal–Organic Framework

Journal Article · Mon Jul 13 00:00:00 EDT 2020 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.0c03764· OSTI ID:1658692

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^[2]; Lipton, Andrew S. ^[3];

^[4]; Snider, Jonathan L. ^[1];

^[2]; Sugar, Joshua D. ^[1]; Spataru, Catalin D. ^[1];

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^[3]; Jørgensen, Mathias ^[5];

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Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Sandia National Lab. (SNL-CA), Livermore, CA (United States); Aarhus Univ. (Denmark)
Aarhus Univ. (Denmark)

The lower limit of metal hydride nanoconfinement is demonstrated through the coordination of a molecular hydride species to binding sites inside the pores of a metal–organic framework (MOF). Magnesium borohydride, which has a high hydrogen capacity, is incorporated into the pores of UiO-67bpy (Zr$$_6$$O$$_4$$(OH)$$_4$$(bpydc)$$_6$$ with bpydc$$^{2–}$$ = 2,2'-bipyridine-5,5'-dicarboxylate) by solvent impregnation. The MOF retained its long-range order, and transmission electron microscopy and elemental mapping confirmed the retention of the crystal morphology and revealed a homogeneous distribution of the hydride within the MOF host. Notably, the B-, N-, and Mg-edge XAS data confirm the coordination of Mg(II) to the N atoms of the chelating bipyridine groups. $$In situ^{11}$$B MAS NMR studies helped elucidate the reaction mechanism and revealed that complete hydrogen release from Mg(BH$$_4$$)$$_2$$ occurs as low as 200 °C. Sieverts and thermogravimetric measurements indicate an increase in the rate of hydrogen release, with the onset of hydrogen desorption as low as 120 °C, which is approximately 150 °C lower than that of the bulk material. Furthermore, density functional theory calculations support the improved dehydrogenation properties and confirm the drastically lower activation energy for B–H bond dissociation.

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Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program; German Research Foundation (DFG); Danish National Research Foundation; Danish Council for Independent Research, Technology and Production; USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC52-07NA27344; SCHN 1539/1-1; NA-0003525; AC02-05CH11231; DNRF93; 4181-00462; AC04-94AL85000

OSTI ID:: 1658692

Alternate ID(s):: OSTI ID: 1639073; OSTI ID: 1775403

Report Number(s):: LLNL-JRNL-799365; SAND-2020-6480J; 1002094

Journal Information:: ACS Nano, Vol. 14, Issue 8; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 26 works

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