Hydrolytic dehydrogenation of ammonia borane and methylamine borane catalyzed by graphene supported Ru@Ni core-shell nanoparticles

Ru@Ni core-shell nanoparticles (NPs) supported on graphene have been synthesized by one-step in situ co-reduction of aqueous solution of ruthenium (III) chloride, nickel (II) chloride, and graphene oxide (GO) with ammonia borane (AB) as the reducing agent under ambient condition. The as-synthesized NPs exhibit much higher catalytic activity for hydrolytic dehydrogenation of AB than the monometallic, bimetallic alloy (RuNi/graphene), and graphene-free core-shell (Ru@Ni) counterparts. Additionally, the Ru@Ni/graphene NPs facilitate the hydrolysis of AB, with the turnover frequency (TOP) value of 340 mol H-2 min(-1) (mol Ru)(-1), which is among the highest value reported on Ru-based NPs so far, and even higher than the reversed Ni@Ru NPs. Furthermore, the as-prepared NPs exert satisfied durable stability and magnetically recyclability for the hydrolytic dehydrogenation of AB and methylamine borane (MeAB). Moreover, this simple synthetic method can be extended to other Ru-based bimetallic core-shell systems for more applications. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

在常温条件下，以氨硼烷（AB）为还原剂，通过一步原位共还原氯化钌（III）、氯化镍（II）和氧化石墨烯（GO）的水溶液，合成了负载在石墨烯上的Ru@Ni核壳纳米粒子（NPs）。所合成的纳米粒子对AB的水解脱氢反应表现出比单金属、双金属合金（RuNi/石墨烯）以及无石墨烯的核壳（Ru@Ni）对应物高得多的催化活性。此外，Ru@Ni/石墨烯纳米粒子促进了AB的水解，其转换频率（TOF）值为340 mol H₂ min⁻¹（mol Ru）⁻¹，这是迄今为止在基于Ru的纳米粒子中所报道的最高值之一，甚至高于反向的Ni@Ru纳米粒子。再者，所制备的纳米粒子对AB和甲胺硼烷（MeAB）的水解脱氢反应具有令人满意的持久稳定性和磁可回收性。而且，这种简单的合成方法可扩展到其他基于Ru的双金属核壳体系以用于更多应用。版权所有（C）2013，氢能出版有限责任公司。由爱思唯尔有限公司出版。保留所有权利。