Department of Chemical and Biomolecular Engineering, University of Pennsylvania, 311A Towne Building, 220 South 33rd Street, Philadelphia, Pennsylvania 19104, USA.
J Am Chem Soc. 2010 Feb 3;132(4):1402-9. doi: 10.1021/ja909131k.
A methodology is described for the preparation of Pd@CeO(2) core-shell nanostructures that are easily dispersible in common organic solvents. The method involves the synthesis of Pd nanoparticles protected by a monolayer of 11-mercaptoundecanoic acid (MUA). The carboxylic groups on the nanoparticle surfaces are used to direct the self-assembly of a cerium(IV) alkoxide around the metal particles, followed by the controlled hydrolysis to form CeO(2). The characterization of the nanostructures by means of different techniques, in particular by electron microscopy, allowed us to demonstrate the nature of core-shell systems, with CeO(2) nanocrystals forming a shell around the MUA-protected Pd core. Finally, an example of the use of these nanostructures as flexible precursors for the preparation of heterogeneous catalysts is reported by investigating the reactivity of Pd@CeO(2)/Al(2)O(3) nanocomposites toward CO oxidation, water-gas shift (WGS), and methanol steam reforming reactions. Together with CO adsorption data, these observations suggest the accessibility of the Pd phase in the nanocomposites.
介绍了一种制备 Pd@CeO(2)核壳纳米结构的方法,该纳米结构在常见有机溶剂中具有良好的分散性。该方法涉及通过 11-巯基十一酸(MUA)单层保护合成 Pd 纳米颗粒。纳米颗粒表面的羧酸基团用于引导 Ce(IV)烷氧化物在金属颗粒周围自组装,然后进行控制水解以形成 CeO(2)。通过不同技术,特别是电子显微镜,对纳米结构进行的表征使我们能够证明核壳体系的性质,其中 CeO(2)纳米晶体在 MUA 保护的 Pd 核周围形成壳。最后,通过研究 Pd@CeO(2)/Al(2)O(3)纳米复合材料对 CO 氧化、水汽变换(WGS)和甲醇蒸汽重整反应的反应性,报告了这些纳米结构作为制备多相催化剂的柔性前体的用途示例。结合 CO 吸附数据,这些观察结果表明纳米复合材料中 Pd 相的可及性。