Chen Lu-Ning, Li Hui-Qi, Yan Meng-Wen, Yuan Chao-Fan, Zhan Wen-Wen, Jiang Ya-Qi, Xie Zhao-Xiong, Kuang Qin, Zheng Lan-Sun
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
Pen-Tung Sah Institute of Micro-Nano Science and Technology, Xiamen University, Xiamen, 361005, China.
Small. 2017 Sep;13(33). doi: 10.1002/smll.201700683. Epub 2017 Jul 4.
Functional nanoparticles encapsulated within metal-organic frameworks (MOFs) as an emerging class of composite materials attract increasing attention owing to their enhanced or even novel properties caused by the synergistic effect between the two functional materials. However, there is still no ideal composite structure as platform to systematically analyze and evaluate the relation between the enhanced catalytic performance of composites and the structure of MOF shells. In this work, taking RhCoNi ternary alloy nanoflowers, for example, first the RhCoNi@MOF composite catalysts sheathed with different structured MOFs via a facile self-sacrificing template process are successfully fabricated. The structure type of MOF shells is easily adjustable by using different organic molecules as etchant and coordination reagent (e.g., 2,5-dihydroxyterephthalic acid or 2-methylimidazole), which can dissolve out the Co or Ni element in the alloy template in a targeted manner, thereby producing ZIF-67(Co) or MOF-74(Ni) shells accordingly. With the difference between the two MOF shells in the aperture sizes, the as-prepared two RhCoNi@MOF composites preform distinct size selectivity during the alkene hydrogenation. This work would help us to get more comprehensive understanding of the intrinsic role of MOFs behind the enhanced catalytic performance of nanoparticle@MOF composites.
封装在金属有机框架(MOF)中的功能纳米粒子作为一类新兴的复合材料,由于两种功能材料之间的协同效应所产生的增强甚至新颖的性能而受到越来越多的关注。然而,目前仍没有理想的复合结构作为平台来系统地分析和评估复合材料增强的催化性能与MOF壳层结构之间的关系。在这项工作中,以RhCoNi三元合金纳米花为例,首先通过简便的自牺牲模板法成功制备了包覆有不同结构MOF的RhCoNi@MOF复合催化剂。通过使用不同的有机分子作为蚀刻剂和配位试剂(例如2,5-二羟基对苯二甲酸或2-甲基咪唑),可以轻松调节MOF壳层的结构类型,它们能够有针对性地溶解合金模板中的Co或Ni元素,从而相应地生成ZIF-67(Co)或MOF-74(Ni)壳层。由于两种MOF壳层在孔径大小上存在差异,所制备的两种RhCoNi@MOF复合材料在烯烃氢化过程中表现出明显不同的尺寸选择性。这项工作将有助于我们更全面地理解MOF在纳米粒子@MOF复合材料增强催化性能背后所起的内在作用。