Lin Lu, Zhang Tong, Liu Haiou, Qiu Jieshan, Zhang Xiongfu
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, P. R. China.
Nanoscale. 2015 May 7;7(17):7615-23. doi: 10.1039/c5nr00257e.
Controllable encapsulation of nanoparticles with metal organic frameworks (MOFs) has been an efficient way to impart the unique chemical and physical properties of the nanoparticles to metal organic frameworks and create new types of multifunctional MOF core-shell materials with enhanced properties. Here, a novel ZnO support-induced encapsulation strategy is reported to efficiently fabricate a Pd/ZnO@ZIF-8 core-shell catalyst, with Pd/ZnO as the core and ZIF-8 as the shell. The novel synthesis procedure involves first loading Pd nanoparticles onto the surface of the ZnO microsphere to form a Pd/ZnO core and then coating the core with a layer of defect-free ZIF-8 shell via ZnO-induced in situ ZIF-8 growth to obtain the Pd/ZnO@ZIF-8 core-shell catalyst. It was crucial that the ZIF-8 was in situ formed from the ZnO core in an ethanol solution only containing 2-methylimidazole under mild conditions. This strategy allowed for the growth of ZIF-8 right on the surface of Pd/ZnO via the reaction between ZnO and the 2-methylimidazole ligands, and thus avoided the random deposition of ZIF-8 crystals on the Pd/ZnO core as in the case of the conventional ZIF-8 synthesis solution. Furthermore, use of ethanol as the solvent also favored achievement of the well-defined Pd/ZnO@ZIF-8 structure, since the ethanol solution of 2-methylimidazole was able to keep the balance between ZnO dissolution and ZIF-8 formation. The as-prepared Pd/ZnO@ZIF-8 core-shell microsphere as an efficient catalyst displayed excellent performance in terms of size-selectivity, stability and anti-poisoning in the liquid hydrogenations of alkenes.
用金属有机框架材料(MOF)对纳米颗粒进行可控封装,是一种将纳米颗粒独特的化学和物理性质赋予金属有机框架材料,并制备具有增强性能的新型多功能MOF核壳材料的有效方法。在此,报道了一种新颖的氧化锌载体诱导封装策略,用于高效制备Pd/ZnO@ZIF-8核壳催化剂,其中Pd/ZnO为核,ZIF-8为壳。这种新颖的合成方法首先将钯纳米颗粒负载到氧化锌微球表面形成Pd/ZnO核,然后通过氧化锌诱导原位生长ZIF-8,在核上包覆一层无缺陷的ZIF-8壳,从而获得Pd/ZnO@ZIF-8核壳催化剂。至关重要的是,ZIF-8是在温和条件下仅含2-甲基咪唑的乙醇溶液中由氧化锌核原位形成的。该策略通过氧化锌与2-甲基咪唑配体之间的反应,使ZIF-8直接在Pd/ZnO表面生长,并避免了常规ZIF-8合成溶液中ZIF-8晶体在Pd/ZnO核上的随机沉积。此外,使用乙醇作为溶剂也有利于实现明确的Pd/ZnO@ZIF-8结构,因为2-甲基咪唑的乙醇溶液能够在氧化锌溶解和ZIF-8形成之间保持平衡。所制备的Pd/ZnO@ZIF-8核壳微球作为一种高效催化剂,在烯烃液相加氢反应中表现出优异的尺寸选择性、稳定性和抗中毒性能。