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用于室温下二甲基胺硼烷脱氢反应的可控制粒径的APTES 稳定钌(0)纳米粒子催化剂。

Size-controllable APTS stabilized ruthenium(0) nanoparticles catalyst for the dehydrogenation of dimethylamine-borane at room temperature.

机构信息

Department of Chemistry, Middle East Technical University, 06531, Ankara, Turkey.

出版信息

Dalton Trans. 2012 Jan 14;41(2):590-8. doi: 10.1039/c1dt11290b. Epub 2011 Nov 3.

Abstract

Dimethylamine-borane, (CH(3))(2)NHBH(3), has been considered as one of the attractive materials for the efficient storage of hydrogen, which is still one of the key issues in the "Hydrogen Economy". In a recent communication we have reported the synthesis and characterization of 3-aminopropyltriethoxysilane stabilized ruthenium(0) nanoparticles with the preliminary results for their catalytic performance in the dehydrogenation of dimethylamine-borane at room temperature. Herein, we report a complete work including (i) effect of initial [APTS]/[Ru] molar ratio on both the size and the catalytic activity of ruthenium(0) nanoparticles, (ii) collection of extensive kinetic data under non-MTL conditions depending on the substrate and catalyst concentrations to define the rate law of Ru(0)/APTS-catalyzed dehydrogenation of dimethylamine-borane at room temperature, (iii) determination of activation parameters (E(a), ΔH(#) and ΔS(#)) for Ru(0)/APTS-catalyzed dehydrogenation of dimethylamine-borane; (iv) demonstration of the catalytic lifetime of Ru(0)/APTS nanoparticles in the dehydrogenation of dimethylamine-borane at room temperature, (v) testing the bottlability and reusability of Ru(0)/APTS nanocatalyst in the room-temperature dehydrogenation of dimethylamine-borane, (vi) quantitative carbon disulfide (CS(2)) poisoning experiments to find a corrected TTO and TOF values on a per-active-ruthenium-atom basis, (vii) a summary of extensive literature review for the catalysts tested in the catalytic dehydrogenation of dimethylamine-borane as part of the results and discussions.

摘要

二甲胺硼烷,(CH(3))(2)NHBH(3),被认为是高效储氢的有吸引力的材料之一,而储氢仍是“氢能经济”中的关键问题之一。在最近的一次交流中,我们报道了 3-氨丙基三乙氧基硅烷稳定的零价钌纳米粒子的合成和表征,并初步研究了它们在室温下催化二甲胺硼烷脱氢反应的性能。在此,我们报告了一项完整的工作,包括(i) 初始 [APTS]/[Ru] 摩尔比对钌(0)纳米粒子的尺寸和催化活性的影响,(ii) 在非 MTL 条件下收集广泛的动力学数据,以确定室温下 Ru(0)/APTS 催化的二甲胺硼烷脱氢反应的速率定律,(iii) 确定 Ru(0)/APTS 催化的二甲胺硼烷脱氢反应的活化参数(E(a)、ΔH(#)和ΔS(#));(iv) 证明 Ru(0)/APTS 纳米粒子在室温下催化二甲胺硼烷脱氢的催化寿命,(v) 测试 Ru(0)/APTS 纳米催化剂在室温下催化二甲胺硼烷脱氢的可封装性和可重复使用性,(vi) 定量的二硫化碳(CS(2))中毒实验,以在每个活性钌原子的基础上找到修正的 TTO 和 TOF 值,(vii) 对在催化二甲胺硼烷脱氢反应中测试的催化剂进行广泛文献综述的总结,作为结果和讨论的一部分。

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