Dey Ananta, Mendalz Amal, Wach Anna, Vadell Robert Bericat, Silveira Vitor R, Leidinger Paul Maurice, Huthwelker Thomas, Shtender Vitalii, Novotny Zbynek, Artiglia Luca, Sá Jacinto
Department of Chemistry-Ångström, Physical Chemistry division, Uppsala University, Box 532, 751 20, Uppsala, Sweden.
Paul Scherrer Institut, CH-5232, Villigen PSI, Switzerland.
Nat Commun. 2024 Jan 10;15(1):445. doi: 10.1038/s41467-024-44752-y.
Plasmonic systems convert light into electrical charges and heat, mediating catalytic transformations. However, there is ongoing controversy regarding the involvement of hot carriers in the catalytic process. In this study, we demonstrate the direct utilisation of plasmon hot electrons in the hydrogen evolution reaction with visible light. We intentionally assemble a plasmonic nanohybrid system comprising NiO/Au/[Co(1,10-Phenanthrolin-5-amine)(HO)], which is unstable at water thermolysis temperatures. This assembly limits the plasmon thermal contribution while ensuring that hot carriers are the primary contributors to the catalytic process. By combining photoelectrocatalysis with advanced in situ spectroscopies, we can substantiate a reaction mechanism in which plasmon-induced hot electrons play a crucial role. These plasmonic hot electrons are directed into phenanthroline ligands, facilitating the rapid, concerted proton-electron transfer steps essential for hydrogen generation. The catalytic response to light modulation aligns with the distinctive profile of a hot carrier-mediated process, featuring a positive, though non-essential, heat contribution.
等离子体系统将光转化为电荷和热量，介导催化转化。然而，关于热载流子是否参与催化过程仍存在争议。在本研究中，我们展示了在可见光驱动的析氢反应中对等离子体热电子的直接利用。我们特意组装了一种等离子体纳米杂化系统，该系统由NiO/Au/[Co(1,10-菲咯啉-5-胺)(HO)]组成，在水热分解温度下不稳定。这种组装方式限制了等离子体的热贡献，同时确保热载流子是催化过程的主要贡献者。通过将光电催化与先进的原位光谱相结合，我们可以证实一种反应机制，其中等离子体诱导的热电子起着关键作用。这些等离子体热电子被导向菲咯啉配体，促进了对氢气生成至关重要的快速、协同的质子-电子转移步骤。对光调制的催化响应与热载流子介导过程的独特特征相符，其具有正向但非必需的热贡献。
