Capacity enhancement of aqueous borohydride fuels for hydrogen storage in liquids

Schubert, David M.; Neiner, Doinita; Bowden, Mark E.; Whittemore, Sean M.; Holladay, Jamie D.; Huang, Zhenguo; Autrey, Tom

doi:10.1016/j.jallcom.2015.01.063

Cited by 17 publications

(15 citation statements)

References 22 publications

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“…These merits have made NaB 3 H 8 an interesting liquid-phase hydrogen carrier. [45] We have also found that the unsolvated form is not flammable in air.…”

Section: Synthesis and Characterization Of Unsolvated Nab 3 Hmentioning

confidence: 60%

An improved synthesis of unsolvated NaB 3 H 8 and its application in preparing Na 2 B 12 H 12

Chen

et al. 2016

International Journal of Hydrogen Energy

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Octahydrotriborates are potential hydrogen storage materials and chemical vapor deposition precursors to boride films. Their syntheses have been quite challenging, however. In this paper, an improved facile route for the preparation of unsolvated sodium octahydrotriborate (NaB3H8), which is an important precursor to other octahydrotriborates and derivatives, is reported. The key steps in the synthesis involve dispersing Na finely in inert media and preparing fresh tetrahydrofuran (THF)·BH3 at room temperature. High purity unsolvated NaB3H8 can be obtained in tens of grams or more in one batch, depending on the reactor size. Using NaB3H8 as the precursor, sodium dodecaborate (Na2B12H12) has been successfully synthesized. Both octahydrotriborates and dodecaborates have been observed as intermediates during the thermal dehydrogenation of borohydrides, and their facile syntheses would facilitate mechanistic studies on the hydrogen storage of borohydrides, among other potential applications. Disciplines Engineering | Physical Sciences and Mathematics Publication DetailsChen, W., Wu, G., He, T., Li, Z., Guo, Z., Liu, H., Huang, Z. & Chen, P. (2016). An improved synthesis of unsolvated NaB3H8 and its application in preparing Na2B12H12. AbstractOctahydrotriborates are potential hydrogen storage materials and chemical vapor deposition precursors to boride films. Their syntheses have been quite challenging, however. In this paper, an improved facile route for the preparation of unsolvated sodium octahydrotriborate (NaB 3 H 8 ), which is an important precursor to other octahydrotriborates and derivatives, is reported. The key steps in the synthesis involve dispersing Na finely in inert media and preparing fresh tetrahydrofuran (THF)·BH 3 at room temperature. High purity unsolvated NaB 3 H 8 can be obtained in tens of grams or more in one batch, depending on the reactor size. Using NaB 3 H 8 as the precursor, sodium dodecaborate (Na 2 B 12 H 12 ) has been successfully synthesized. Both octahydrotriborates and dodecaborates have been observed as intermediates during the thermal dehydrogenation of borohydrides, and their facile syntheses would facilitate mechanistic studies on the hydrogen storage of borohydrides, among other potential applications.

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“…These merits have made NaB 3 H 8 an interesting liquid-phase hydrogen carrier. [45] We have also found that the unsolvated form is not flammable in air.…”

Section: Synthesis and Characterization Of Unsolvated Nab 3 Hmentioning

confidence: 60%

An improved synthesis of unsolvated NaB 3 H 8 and its application in preparing Na 2 B 12 H 12

Chen

et al. 2016

International Journal of Hydrogen Energy

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“…Another material with greater stability is NaB 3 H 8 , synthesized and investigated by Shore [238]. Schubert [239] noted that the NaB 3 H 8 provided the added advantage of greater solubility of both the starting material and the products, in part due to the formation of a mixture of products upon H 2 release.…”

Section: Liquid Hydridesmentioning

confidence: 99%

“…Very little experimental information about the physical properties (especially thermodynamic properties, e.g. stability) is available in the literature for the complex hydrides [239,244]. Only a few compounds benefiting from their large production are used in chemical processes and have been investigated in more detail (e.g.…”

Section: Liquid Hydridesmentioning

confidence: 99%

Complex and liquid hydrides for energy storage

et al. 2016

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The research on complex hydrides for hydrogen storage was initiated by the discovery of Ti as a hydrogen sorption catalyst in NaAlH 4 by Boris Bogdanovic in 1996. A large number of new complex hydride materials in various forms and combinations have been synthesized and characterized, and the knowledge regarding the properties of complex hydrides and the synthesis methods has grown enormously since then. A significant portion of the research groups active in the field of complex hydrides is collaborators in the International Energy Agreement Task 32. This paper reports about the important issues in the field of complex hydride research, i.e. the synthesis of borohydrides, the thermodynamics of complex hydrides, the effects of size and confinement, the hydrogen sorption mechanism and the complex hydride composites as well as the properties of liquid complex hydrides. This paper is the result of the collaboration of several groups and is an excellent summary of the recent achievements.

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“…B. darin, dass NaB 3 H 8 eine deutlich höhere Stabilität und Löslichkeit in Wasser besitzt als NaBH 4 , weshalb mit NaB 3 H 8 sehr viel konzentriertere homogene Lösungen erhalten werden können . Auch die Hydrolyseprodukte von NaB 3 H 8 , verschiedene Polyborate, sind relativ gut in Wasser löslich, wodurch die Bildung von unlöslichen Niederschlägen im Verlauf der Hydrolyse vermindert wird . Somit ist NaB 3 H 8 bei der hydrolytischen H 2 ‐Freisetzung weit effizienter als NaBH 4 , wobei eine Regenerierung von B 3 H 8 − aus den Polyborat‐Hydrolyseprodukten bislang noch erreicht werden konnte.…”

Section: Borverbindungen Als Wasserstoffspeichermaterialienunclassified

Bor in energiebezogenen Prozessen und Anwendungen

et al. 2020

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Direkt an der Grenze zwischen Metallen und Nichtmetallen angesiedelt, nimmt das Element Bor eine einzigartige Position im Periodensystem ein. Diese besondere Stellung ermöglicht eine enorme Vielfalt an chemischen Reaktionen und Anwendungen. Auch in Hinblick auf die stetig steigende Nachfrage an erneuerbaren und sauberen Energien bzw. energieeffizienten Prozessen ist das Element Bor mehr und mehr in den Fokus der energiebezogenen Forschung gerückt und umfasst mittlerweile Bereiche wie 1) die Aktivierung und Synthese kleiner energiereicher Moleküle, 2) die Speicherung von chemischer und elektrischer Energie und 3) die Umwandlung von elektrischer Energie zu Licht. Diese Anwendungen basieren hierbei auf den besonderen Eigenschaften des Elements Bor, d. h. vor allem auf dessen Elektronenmangel in Verbindung mit der Gegenwart eines unbesetzten p‐Orbitals, was die Ausbildung unzähliger Verbindungen mit gezielt beeinflussbaren chemischen und physikalischen Eigenschaften ermöglicht. So erreicht Bor beispielsweise mit vier kovalenten Bindungen und einer negativen Ladung relativ einfach ein Elektronenoktett, wodurch die Verbindungsklasse der Boratanionen zugänglich wird, welche eine außergewöhnlich hohe chemische und elektrochemische Stabilität aufweisen. Besonders hervorzuheben ist in diesem Zusammenhang die synthetisch wertvolle Klasse der schwach‐koordinierenden Anionen. Dieser Aufsatz soll die Bedeutung von Borverbindungen für energiebezogene Prozesse und Anwendungen verdeutlichen und fasst die Fortschritte der letzten Jahre auf diesem Gebiet zusammen.

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Capacity enhancement of aqueous borohydride fuels for hydrogen storage in liquids

Cited by 17 publications

References 22 publications

An improved synthesis of unsolvated NaB 3 H 8 and its application in preparing Na 2 B 12 H 12

An improved synthesis of unsolvated NaB 3 H 8 and its application in preparing Na 2 B 12 H 12

Complex and liquid hydrides for energy storage

Bor in energiebezogenen Prozessen und Anwendungen

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