Department of Chemistry, National Taiwan University , Taipei 106, Taiwan.
J Am Chem Soc. 2017 Feb 15;139(6):2224-2233. doi: 10.1021/jacs.6b09080. Epub 2017 Feb 6.
Improvements in the performance of electrocatalysts, along with continuing advances in selective pathway for target reaction, have great potential to offer opportunities in designing competitive reactions especially for using a photophysical process owing to its tunable properties. Herein, we demonstrated a first empirical evidence of suppressing the formation of undesired peroxide intermediate through plasmonic effects, in which plasmonic Ag-Pt bimetallic nanocages were synthesized with an edgeless feature, and a custom-made RDE/RRDE working station was designed to provide unique means by which to in situ realize the plasmon-induced effects toward the target reaction. The edgeless Ag-Pt bimetallic nanocages with hollow interior performed newly plasmon-induced effects, which was characteristic of photodependent nature to suppress the formation of undesired peroxide intermediate. We concluded that the plasmon-induced hot electron transfer governed the suppression of peroxide formation instead of plasmon-induced heating that would cause a negative effect (i.e., increase of peroxide yield), in which the hot electron transfer of Ag nanostructure offered a sufficient energy to populate the antibonding orbital of O as illustrated by in situ X-ray absorption approach. This rapid light-dependent nature corresponding to localized surface plasmon resonance in present nanocages can potentially offer synergetic strategies toward altering the chemical reactions or reaction pathways in various fields.
电催化剂性能的提高，以及目标反应选择性途径的持续进步，为设计竞争性反应提供了机会，特别是由于其可调谐特性，利用光物理过程。在此，我们通过等离子体效应证明了抑制不想要的过氧化物中间体形成的第一个经验证据，其中合成了具有无边缘特征的等离子体 Ag-Pt 双金属纳米笼，并设计了定制的 RDE/RRDE 工作站，提供了一种独特的手段，可原位实现目标反应的等离子体诱导效应。具有空心内部的无边缘 Ag-Pt 双金属纳米笼表现出新的等离子体诱导效应，其特征是光依赖性，可抑制不想要的过氧化物中间体的形成。我们得出结论，等离子体诱导的热电子转移控制了过氧化物形成的抑制，而不是会产生负面影响（即过氧化物产率增加）的等离子体诱导加热，其中 Ag 纳米结构的热电子转移提供了足够的能量来填充 O 的反键轨道，如原位 X 射线吸收方法所示。这种与本纳米笼中局部表面等离子体共振相对应的快速光依赖性，可能为改变各个领域的化学反应或反应途径提供协同策略。
