Department of Chemistry and Texas Materials Institute, The University of Texas at Austin , 105 East 24th Street, Stop A5300, Austin, Texas 78712-1224, United States.
Langmuir. 2014 Dec 16;30(49):15009-15. doi: 10.1021/la503956h. Epub 2014 Dec 2.
Here we outline a new method for synthesizing fully reduced Pt dendrimer-encapsulated nanoparticles (DENs). This is achieved by first synthesizing Cu DENs of the appropriate size through sequential dendrimer loading and reduction steps, and then galvanically exchanging the zerovalent Cu DENs for Pt. The properties of Pt DENs having an average of 55, 140, and 225 atoms prepared by direct chemical reduction and by galvanic exchange are compared. Data obtained by UV-vis spectroscopy, X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and high-resolution electron microscopy confirm only the presence of fully reduced Pt DENs when synthesized by galvanic exchange, while chemical reduction leads to a mixture of reduced DENs and unreduced precursor. These results are significant because Pt DENs are good models for developing a better understanding of the effects of finite size on catalytic reactions. Until now, however, the results of such studies have been complicated by a heterogeneous mixture of Pt catalysts.
我们在这里概述了一种新的方法来合成完全还原的 Pt 树状大分子包裹的纳米粒子(DENs)。这是通过首先通过顺序的树状大分子负载和还原步骤合成适当尺寸的 Cu DENs,然后通过电置换将零价 Cu DENs 置换为 Pt 来实现的。比较了通过直接化学还原和电置换制备的平均具有 55、140 和 225 个原子的 Pt DENs 的性质。通过紫外可见光谱、X 射线吸收光谱、X 射线光电子能谱和高分辨率电子显微镜获得的数据仅证实了当通过电置换合成时存在完全还原的 Pt DENs,而化学还原会导致还原的 DENs 和未还原的前体的混合物。这些结果是重要的,因为 Pt DENs 是开发更好地理解有限尺寸对催化反应影响的良好模型。然而,到目前为止,这些研究的结果因 Pt 催化剂的不均匀混合物而变得复杂。