Bayles Aaron, Tian Shu, Zhou Jingyi, Yuan Lin, Yuan Yigao, Jacobson Christian R, Farr Corbin, Zhang Ming, Swearer Dayne F, Solti David, Lou Minghe, Everitt Henry O, Nordlander Peter, Halas Naomi J
Department of Chemistry, Rice University, Houston, Texas 77005, United States.
Laboratory for Nanophotonics, Rice University, Houston, Texas 77005, United States.
ACS Nano. 2022 Apr 26;16(4):5839-5850. doi: 10.1021/acsnano.1c10995. Epub 2022 Mar 16.
Plasmon-induced photocatalysis is a topic of rapidly increasing interest, due to its potential for substantially lowering reaction barriers and temperatures and for increasing the selectivity of chemical reactions. Of particular interest for plasmonic photocatalysis are antenna-reactor nanoparticles and nanostructures, which combine the strong light-coupling of plasmonic nanostructures with reactors that enhance chemical specificity. Here, we introduce Al@TiO core-shell nanoparticles, combining earth-abundant Al nanocrystalline cores with TiO layers of tunable thickness. We show that these nanoparticles are active photocatalysts for the hot electron-mediated H dissociation reaction as well as for hot hole-mediated methanol dehydration. The wavelength dependence of the reaction rates suggests that the photocatalytic mechanism is plasmonic hot carrier generation with subsequent transfer of the hot carriers into the TiO layer. The Al@TiO antenna-reactor provides an earth-abundant solution for the future design of visible-light-driven plasmonic photocatalysts.
等离子体激元诱导光催化是一个迅速受到越来越多关注的课题，因为它有潜力大幅降低反应势垒和温度，并提高化学反应的选择性。对于等离子体激元光催化而言，特别值得关注的是天线 - 反应器纳米颗粒和纳米结构，它们将等离子体激元纳米结构的强光耦合与增强化学特异性的反应器结合在一起。在此，我们介绍了Al@TiO核壳纳米颗粒，它将储量丰富的Al纳米晶核与厚度可调的TiO层结合在一起。我们表明，这些纳米颗粒对于热电子介导的H解离反应以及热空穴介导的甲醇脱水反应都是活性光催化剂。反应速率的波长依赖性表明，光催化机制是等离子体激元热载流子的产生，随后热载流子转移到TiO层中。Al@TiO天线 - 反应器为未来可见光驱动的等离子体激元光催化剂的设计提供了一种储量丰富的解决方案。
