Radiation Laboratory and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
ACS Nano. 2010 Dec 28;4(12):7321-30. doi: 10.1021/nn102564x. Epub 2010 Nov 11.
The electrodic behavior of platinum nanoparticles (2.8 nm diameter) and their role in influencing the photocatalytic behavior of CdSe quantum dots (3.4 nm diameter) has been evaluated by confining both nanoparticles together in heptane/dioctyl sulphosuccinate/water reverse micelles. The particles spontaneously couple together within the micelles via micellar exchange processes and thus facilitate experimental observation of electron transfer reactions inside the water pools. Electron transfer from CdSe to Pt is found to occur with a rate constant of 1.22 × 10(9) s(-1). With the use of methyl viologen (MV(2+)) as a probe molecule, the role of Pt in the photocatalytic process is established. Ultrafast oxidation of the photogenerated MV(+•) radicals indicates that Pt acts as an electron sink, scavenging electrons from MV(+•) with a rate constant of 3.1 × 10(9) s(-1). The electron transfer between MV(+•) and Pt, and a drastically lower yield of MV(+•) under steady state irradiation, confirms the ability of Pt nanoparticles to discharge electrons quickly. The kinetic details of photoinduced processes in CdSe-Pt assemblies and the electrodic behavior of Pt nanoparticles provide important information for the development of light energy conversion devices.
通过将两种纳米粒子一起限制在庚烷/二辛基磺基琥珀酸钠/水反胶束中,评估了铂纳米粒子(直径 2.8nm)的电极行为及其在影响 CdSe 量子点(直径 3.4nm)光催化行为中的作用。这些粒子通过胶束交换过程自发地在胶束中耦合在一起,从而便于在水相中观察到电子转移反应。发现 CdSe 向 Pt 的电子转移以 1.22×10(9)s(-1)的速率常数发生。使用甲基紫精(MV(2+))作为探针分子,确定了 Pt 在光催化过程中的作用。光生 MV(+•)自由基的超快氧化表明,Pt 作为电子阱,以 3.1×10(9)s(-1)的速率常数从 MV(+•)中捕获电子。MV(+•)和 Pt 之间的电子转移以及在稳态辐照下 MV(+•)的产量明显降低,证实了 Pt 纳米粒子快速放电电子的能力。CdSe-Pt 组装体中光诱导过程的动力学细节和 Pt 纳米粒子的电极行为为开发光能转换器件提供了重要信息。