Institute of New Energy Material Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Chemistry College, Nankai University, Tianjin, 300071, China.
Dalton Trans. 2012 Jan 21;41(3):871-5. doi: 10.1039/c1dt11567g. Epub 2011 Nov 14.
Promoted hydrogen release from ammonia borane (NH(3)BH(3), AB) with mannitol (C(6)H(8)(OH)(6), MA) additive is reported. It is found that for the MA/2AB sample, the dehydrogenation temperature is lowered by ~25 °C compared to that of neat AB, the liberation of undesired byproduct borazine is suppressed, and the released ammonia can be removed by using anhydrous MgCl(2) as absorber. The analyses of Raman, Fourier transform infrared spectroscopy and (11)B nuclear magnetic resonance spectroscopy demonstrate the breaking of B-N, B-H and O-H bonds and the formation of B-O bonds for the dehydrogenation process of MA/2AB. These results suggest a solid-state dehydrogenation reaction between AB and MA: the B-H(δ-) bonds in AB and the O-H(δ+) bonds in MA combine with each other to release H(2). Furthermore, the use of the perfect -OH carrier MA as additive leads to a straightforward understanding of the improved dehydrogenation of AB under the effect of hydroxyl groups in the solid state.
报道了甘露醇(C(6)H(8)(OH)(6),MA)添加剂促进氨硼烷(NH(3)BH(3),AB)释放氢气。结果发现,对于 MA/2AB 样品,与纯 AB 相比,脱氢温度降低了约 25°C,抑制了不期望的副产物硼烷的释放,并且可以使用无水 MgCl(2)作为吸收剂去除释放的氨。拉曼、傅里叶变换红外光谱和(11)B 核磁共振光谱分析表明,MA/2AB 脱氢过程中 B-N、B-H 和 O-H 键断裂,B-O 键形成。这些结果表明 AB 和 MA 之间存在固态脱氢反应:AB 中的 B-H(δ-)键和 MA 中的 O-H(δ+)键相互结合释放出 H(2)。此外,使用完美的-OH 载体 MA 作为添加剂,可直接理解在固态下羟基对 AB 脱氢的促进作用。