Yurderi Mehmet, Top Tuba, Bulut Ahmet, Kanberoglu Gulsah Saydan, Kaya Murat, Zahmakiran Mehmet
Nanomaterials and Catalysis Research Group, Department of Chemistry, Van Yuzuncu Yil University, 65080 Van, Turkey.
Department of Chemical Engineering and Applied Chemistry, Atilim University, 06836 Ankara, Turkey.
Inorg Chem. 2020 Jul 20;59(14):9728-9738. doi: 10.1021/acs.inorgchem.0c00965. Epub 2020 Jun 26.
Hydrazine borane (HB; NHBH) has been considered to be one of the most promising solid chemical hydrogen storage materials owing to its high hydrogen capacity and stability under ambient conditions. Despite that, the high purity of hydrogen production from the complete dehydrogenation of HB stands as a major problem that needs to be solved for the convenient use of HB in on-demand hydrogen production systems. In this study, we describe the development of a new catalytic material comprised of bimetallic Ni@Ir core-shell nanoparticles (NPs) supported on OMS-2-type manganese oxide octahedral molecular sieve nanorods (Ni@Ir/OMS-2), which can reproducibly be prepared by following a synthesis protocol including (i) the oleylamine-mediated preparation of colloidal Ni@Ir NPs and (ii) wet impregnation of these ex situ synthesized Ni@Ir NPs onto the OMS-2 surface. The characterization of Ni@Ir/OMS-2 has been done by using various spectroscopic and visualization techniques, and their results have revealed the formation of well-dispersed Ni@Ir core-shell NPs on the surface of OMS-2. The catalytic employment of Ni@Ir/OMS-2 in the dehydrogenation of HB showed that Ni@Ir/OMS-2 exhibited high dehydrogenation selectivity (>99%) at complete conversion with a turnover frequency (TOF) value of 2590 h at 323 K, which is the highest activity value among all reported catalysts for the complete dehydrogenation of HB. Furthermore, the Ni@Ir/OMS-2 catalyst enables facile recovery and high stability against agglomeration and leaching, which make it a reusable catalyst in the complete dehydrogenation of HB. The studies reported herein also include the collection of wealthy kinetic data to determine the activation parameters for Ni@Ir/OMS-2-catalyzed dehydrogenation of HB.
硼烷肼(HB;NHBH)因其高储氢容量和在环境条件下的稳定性,被认为是最具潜力的固态化学储氢材料之一。尽管如此,HB完全脱氢制氢的高纯度问题仍是其在按需制氢系统中便捷应用所需解决的主要问题。在本研究中,我们描述了一种新型催化材料的开发,该材料由负载在OMS - 2型锰氧化物八面体分子筛纳米棒(Ni@Ir/OMS - 2)上的双金属Ni@Ir核壳纳米颗粒(NPs)组成,可通过如下合成方案重复制备:(i)油胺介导制备胶体Ni@Ir NPs;(ii)将这些非原位合成的Ni@Ir NPs湿法浸渍到OMS - 2表面。通过各种光谱和可视化技术对Ni@Ir/OMS - 2进行了表征,结果表明在OMS - 2表面形成了分散良好的Ni@Ir核壳NPs。Ni@Ir/OMS - 2在HB脱氢反应中的催化应用表明,在323 K下,Ni@Ir/OMS - 2在完全转化时表现出高脱氢选择性(>99%),周转频率(TOF)值为2590 h⁻¹,这是所有报道的用于HB完全脱氢的催化剂中最高的活性值。此外,Ni@Ir/OMS - 2催化剂易于回收,对团聚和浸出具有高稳定性,这使其成为HB完全脱氢反应中的可重复使用催化剂。本文报道的研究还包括收集丰富的动力学数据,以确定Ni@Ir/OMS - 2催化HB脱氢反应的活化参数。