添加叔丁醇钾对Mg(NH2)2-2LiH体系储氢性能的影响
Effect of Potassium tert-Butoxide on Hydrogen Storage Properties of Mg(NH2)2-2LiH System
作者单位E-mail
冯文钦 中国计量大学材料与化学学院, 杭州 310018  
李超 中国计量大学材料与化学学院, 杭州 310018
硅材料国家重点实验室, 浙江大学材料科学与工程学院, 杭州 310027 
lichao@cjlu.edu.cn 
刘凯元 中国计量大学材料与化学学院, 杭州 310018  
蔡明源 中国计量大学材料与化学学院, 杭州 310018  
范美强 中国计量大学材料与化学学院, 杭州 310018 fanmeiqiang@126.com 
摘要: 叔丁醇钾(C4H9OK)的添加显著改善了Mg(NH22-2LiH体系的储氢性能。添加0.08 mol C4H9OK的Mg(NH22-2LiH-0.08C4H9OK样品表现出最佳储氢性能。该样品的起始放氢温度仅为70℃,较Mg(NH22-2LiH原始样品降低了60℃;130℃完全放氢后,该样品可在50℃开始吸氢,较原始样品降低了50℃。Mg(NH22-2LiH-0.08C4H9OK样品可在150℃的等温条件下50min内迅速放出质量分数3.82%的氢气,完全放氢后可在120℃的等温条件下50 min内快速吸收质量分数4.11%的氢气,表现出良好的吸放氢动力学性能。C4H9OK的添加降低了样品放氢反应的表观活化能和反应焓变,改善了放氢反应的动力学和热力学性能,从而降低了放氢反应温度。进一步的放氢反应机理研究发现,在180℃之前,C4H9OK对Mg(NH22-2LiH体系的放氢起催化改性作用;温度继续升高后,C4H9OK将会分解并参与放氢反应最终生成Li3K(NH24
关键词: 储氢材料  氨基物  叔丁醇钾  动力学  催化改性  反应机理
基金项目: 国家自然科学基金(No.51501175)和浙江省杰出青年基金(No.LQ16E010001)资助。
Abstract: The hydrogen storage properties of Mg(NH2)2-2LiH system were significantly enhanced by adding a small amount of potassium tert-butoxide (C4H9OK). The 0.08 mol C4H9OK-added sample (Mg(NH2)2-2LiH-0.08C4H9OK) showed optimum hydrogen storage performances. The on-set dehydrogenation temperature of Mg(NH2)2-2LiH-0.08C4H9OK sample was only 70℃, which was 60℃ lower than that of pristine Mg(NH2)2-2LiH sample. After fully dehydrogenated at 130℃, the Mg(NH2)2-2LiH-0.08C4H9OK sample begined to absorb hydrogen at 50℃, which was 50℃ lower than the pristine sample. At 150℃, mass ratio of 3.82% of hydrogen can be rapidly released from the Mg(NH2)2-2LiH-0.08C4H9OK sample within 50 min. The fully dehydrogenated Mg(NH2)2-2LiH-0.08C4H9OK sample could absorb mass ratio of 4.11% hydrogen at 120℃ within 50 min. Adding C4H9OK decreases the dehydrogenation activation energy and reaction enthalpy of the Mg(NH2)2-2LiH system, and enhances the hydrogen desorption kinetic and thermodynamic properties. Mechanistic investigations indicate that C4H9OK acts catalytically to enhance the dehydrogenation properties before 180℃, then it participates in the reaction to generate Li3K(NH2)4 by further increasing the operating temperature.
Keywords: hydrogen storage materials  amide  potassium tert-butoxide  kinetics  catalytic modification  reaction mechanisms
投稿时间:2021-02-25 修订日期:2021-04-26
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冯文钦,李超,刘凯元,蔡明源,范美强.添加叔丁醇钾对Mg(NH2)2-2LiH体系储氢性能的影响[J].无机化学学报,2021,37(6):1097-1105.
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