Department of Chemistry, Duke University, 124 Science Drive, Box 90354, Durham, North Carolina 27708, USA.
ACS Nano. 2011 Aug 23;5(8):6119-27. doi: 10.1021/nn201161m. Epub 2011 Jul 15.
Reduction of Pd ions by hydroquinone in the presence of gold nanoparticles and polyvinylpyrrolidone resulted in the formation of nanoflowers with a Au core and Pd petals. Addition of HCl to the synthesis halted the reduction by hydroquinone and enabled the acquisition of snapshots of the nanoflowers at different stages of growth. TEM images of the reaction after 10 s show that the nanoflower morphology resulted from the homogeneous nucleation of Pd clusters in solution and their subsequent attachment to gold seeds coated with a thin (0.8 ± 0.1 nm) shell of Pd. UV-visible spectra also indicate Pd clusters formed in the early stages of the reaction and disappeared as the nanoflowers grew. The speed at which this reaction can be halted is useful not only for producing a variety of bimetallic nanostructures with precisely controlled dimensions and morphologies but also for understanding the growth mechanism of these structures. The ability of the AuPd core-shell structure to catalyze the Suzuki coupling reaction of iodobenzene to phenylboronic acid was probed and compared against the activity of Pd nanocubes and thin-shelled AuPd core-shell nanoparticles. The results of this study suggest that Suzuki coupling was not affected by the surface structure or subsurface composition of the nanoparticles, but instead was primarily catalyzed by molecular Pd species that leached from the nanostructures.
在金纳米粒子和聚乙烯吡咯烷酮存在的情况下,氢醌将 Pd 离子还原,形成具有 Au 核和 Pd 花瓣的纳米花。向合成物中添加 HCl 会阻止氢醌的还原,并能够获取纳米花在不同生长阶段的快照。反应 10 秒后的 TEM 图像表明,纳米花形态是由于溶液中 Pd 团簇的均匀成核及其随后附着在涂有薄(0.8 ± 0.1nm)Pd 壳的金种子上而产生的。紫外-可见光谱也表明,Pd 团簇在反应的早期阶段形成,随着纳米花的生长而消失。这种反应可以停止的速度不仅对于生产具有精确控制尺寸和形态的各种双金属纳米结构非常有用,而且对于理解这些结构的生长机制也非常有用。还探测了 AuPd 核壳结构对碘苯与苯硼酸的 Suzuki 偶联反应的催化作用,并与 Pd 纳米立方体和薄壳 AuPd 核壳纳米粒子的活性进行了比较。这项研究的结果表明,Suzuki 偶联反应不受纳米粒子的表面结构或次表面组成的影响,而是主要由从纳米结构中浸出的分子 Pd 物种催化。