Synthesis of Ni-Ru Alloy Nanoparticles and Their High Catalytic Activity in Dehydrogenation of Ammonia Borane
Synthesis of Ni-Ru Alloy Nanoparticles and Their High Catalytic Activity in Dehydrogenation of Ammonia Borane
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DOI：
10.1002/chem.201200292
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发表时间：
2012-06-01
影响因子：
4.3
通讯作者：
Ma, Dongling
中科院分区：
文献类型：
--
作者：
Chen, Guozhu;Desinan, Stefano;Ma, Dongling
我们报告的合成和表征新的NixRu 1-x（x=0.560.74）合金纳米粒子（NPs）和它们的催化活性，在氨硼烷水解过程中的氢释放。通过湿化学方法使用三乙基硼氢化锂快速还原油胺中的Ni 2+和Ru 3+前体来获得合金NP。采用TEM、XRD、EDX、XPS等测试手段对合金进行了表征。我们发现，所制备的NiRu合金纳米颗粒表现出优异的催化活性的氨硼烷水解反应的氢释放。所有NiRu合金NP，特别是Ni0.74Ru0.26样品，都优于类似尺寸的单一Ni和Ru NP，甚至Ni@Ru核-壳NP的活性。Ni0.74Ru0.26合金催化剂的水解活化能测定为约37 kJ？mol-1.这个值是相当低的测量值monten-Ni（类似于70千焦？mol-1）和Ru NPs（49 kJ？mol-1），Ni@Ru（44 kJ？mol-1），并且也低于文献中报道的大多数含贵金属的纳米颗粒的值。因此，通过将Ru与相对便宜的金属Ni合金化，获得了Ru在氨硼烷脱氢中的催化活性的显著改善。
We report the synthesis and characterization of new NixRu1-x (x=0.560.74) alloy nanoparticles (NPs) and their catalytic activity for hydrogen release in the ammonia borane hydrolysis process. The alloy NPs were obtained by wet-chemistry method using a rapid lithium triethylborohydride reduction of Ni2+ and Ru3+ precursors in oleylamine. The nature of each alloy sample was fully characterized by TEM, XRD, energy dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). We found that the as-prepared NiRu alloy NPs exhibited exceptional catalytic activity for the ammonia borane hydrolysis reaction for hydrogen release. All NiRu alloy NPs, and in particular the Ni0.74Ru0.26 sample, outperform the activity of similar size monometallic Ni and Ru NPs, and even of Ni@Ru core-shell NPs. The hydrolysis activation energy for the Ni0.74Ru0.26 alloy catalyst was measured to be approximately 37 kJ?mol-1. This value is considerably lower than the values measured for monometallic Ni (similar to 70 kJ?mol-1) and Ru NPs (49 kJ?mol-1), and for Ni@Ru (44 kJ?mol-1), and is also lower than the values of most noble-metal-containing bimetallic NPs reported in the literature. Thus, a remarkable improvement of catalytic activity of Ru in the dehydrogenation of ammonia borane was obtained by alloying Ru with a Ni, which is a relatively cheap metal.