Hydrophobic Periphery Tails of Polyphenylenepyridyl Dendrons Control Nanoparticle Formation and Catalytic Properties

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• 作者：Nina V. Kuchkina ; David Gene Morgan ; Athanasia Kostopoulou ; Alexandros Lappas ; Konstantinos Brintakis ; Bethany S. Boris ; Ekaterina Yu. Yuzik-Klimova ; Barry D. Stein ; Dmitri I. Svergun ; Alessandro Spilotros ; Mikhaill G. Sulman ; Linda Zh. Nikoshvili ; Esther M. Sulman ; Zinaida B. Shifrina ; Lyudmila M. Bronstein
• 刊名：Chemistry of Materials
• 出版年：2014
• 出版时间：October 14, 2014
• 年：2014
• 卷：26
• 期：19
• 页码：5654-5663
• 全文大小：734K
• ISSN：1520-5002

文摘

Here we report control of iron oxide and palladium nanoparticle (NP) formation via stabilization with polyphenylenepyridyl dendrons of the second and third generations with dodecyl periphery. These nanomaterials are developed as magnetically recoverable catalysts. To accurately assess the influence of the dodecyl exterior for the same dendron generation, we also designed a second generation dendron with partial dodecyl periphery. For all dendrons studied, the multicore iron oxide mesocrystals were formed, the sizes and morphology of which were controlled by the dendron generation. Analysis of the static and dynamic magnetic properties, in combination with transmission electron microscopy observations, demonstrate that magnetism is sensitive on the structure-directing capabilities of the type of the dendron which was employed for the mesocrystal stabilization. Close proximity of single cores in such multicore mesocrystals promotes the coupling of the neighboring magnetic moments, thus boosting their magnetization and allowing easy crossover between superparamagnetic and ferrimagnetic behaviors at room temperature. The particularly dramatic role of the dendron structure was also witnessed via the Pd NP formation, which was found to depend on both the dendron generation and its dodecyl periphery. In the case of the catalyst based on the second generation dendron with full dodecyl periphery, no Pd NPs were observed by TEM indicating that these species are of a subnanometer size and are not visible on or near the iron oxide NPs. For the catalyst based on the second generation dendron with partial dodecyl periphery, hydrogen reduction leads to much larger Pd NPs (2.7 nm) due to an unimpeded exchange of Pd species between dendrons and nondense dendron coating with asymmetrical dendrons. The third generation dendron with full dodecyl periphery allows nearly monodisperse 1.2 nm Pd NPs in the shells of iron oxide mesocrystals and the best catalytic properties in selective hydrogenation of dimethylethynylcarbinol. This study suggests a robust approach to control NP formation in magnetically recoverable catalysts for a wide variety of catalytic reactions using dendrons combining rigidity and flexibility in one molecule.