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使用基于离子液体的路易斯酸从碱金属硼氢化物中控制释放乙硼烷

Controlled Release of Diborane from Alkali Metal Borohydride using Ionic Liquid-Based Lewis Acids.

作者信息

Kumar Vasudevan Ashvin, Wang Yujie, Biswas Prithwish, Shi Keren, Zachariah Michael R

机构信息

Department of Chemical and Environmental engineering, University of California, Riverside, 900 University avenue, Riverside, CA-92521.

出版信息

Angew Chem Int Ed Engl. 2024 Nov 11;63(46):e202401743. doi: 10.1002/anie.202401743. Epub 2024 Oct 8.

Abstract

Alkali metal borohydrides present a rich source of energy dense materials of boron and hydrogen, however their potential in propellants has been hitherto untapped. Potassium borohydride is a promising fuel with high gravimetric energy density and relatively low sensitivity to air and moisture. Problems arise due to the dehydrogenation of the borohydride on heating with minimal energy release. Common methods to extract both boron and hydrogen by means of borane species involve direct reaction of boron trifluoride species with alkali borohydrides. However, these methods face storage and safety issues due to rapid release of diborane on mixing the reactants. We propose a method of diborane release through controlled release of boron trifluoride by means of a tetrafluoroborate based ionic liquid. The trifluoride is released from the ionic liquid at elevated temperatures and enables safe mixture of the reactants at room temperature. It was found that the reaction between borohydride and boron trifluoride proceeds well above room temperature with potassium borohydride releasing diborane and potassium fluoride. The reaction pathway shows a primary reaction releasing diborane and potassium fluoride and a second less energy efficient step leading to the formation of potassium tetrafluoroborate. A 3D printed propellant formulation was also tested.

摘要

碱金属硼氢化物是硼和氢的高能量密度材料的丰富来源,然而它们在推进剂中的潜力迄今尚未得到开发。硼氢化钾是一种很有前景的燃料,具有高重量能量密度,并且对空气和水分的敏感性相对较低。由于硼氢化物在加热时脱氢且能量释放极少,因此会出现问题。通过硼烷物种提取硼和氢的常用方法涉及三氟化硼物种与碱金属硼氢化物的直接反应。然而,这些方法由于在混合反应物时乙硼烷的快速释放而面临储存和安全问题。我们提出了一种通过基于四氟硼酸盐的离子液体控制释放三氟化硼来释放乙硼烷的方法。三氟化物在升高的温度下从离子液体中释放出来,并能使反应物在室温下安全混合。结果发现,硼氢化物与三氟化硼之间的反应在远高于室温的温度下进行,硼氢化钾释放出乙硼烷和氟化钾。反应途径显示出一个释放乙硼烷和氟化钾的初级反应以及一个能量效率较低的第二步反应,该反应导致四氟硼酸钾的形成。还测试了一种3D打印的推进剂配方。

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