Li Zhuoyao, Zhang Chengyu, Sheng Huixiang, Wang Jin, Zhu Yameng, Yu Liuyingzi, Wang Junjie, Peng Qiming, Lu Gang
Key Laboratory of Flexible Electronics, School of Flexible Electronics (Future Technologies), and Institute of Advanced Materials, Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816, PR China.
National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, PR China.
ACS Appl Mater Interfaces. 2022 Aug 24;14(33):38302-38310. doi: 10.1021/acsami.2c08327. Epub 2022 Aug 9.
Localized surface plasmon resonance (LSPR) has been demonstrated to be highly effective in the initialization or acceleration of chemical reactions because of its unique optical properties. However, because of the ultrashort lifetime (fs to ps) of plasmon-generated hot carriers, the potential of LSPR in photochemical reactions has not been fully exploited. Herein, we demonstrate an acceleration of the plasmon-mediated reduction of -nitrothiophenol (PNTP) molecules on the surface of silver nanoparticles (AgNPs) with in situ Raman spectroscopy. -Mercaptophenylboronic acid (PMPBA) molecules coadsorbed on AgNP surfaces act as a molecular cocatalyst in the plasmon-mediated reaction, resulting in a boosting of the PNTP reduction. This boosting is attributed to the improved transfer and separation of the plasmon-generated hot carriers at the interface of the AgNPs and coadsorbed PMPBA molecules. Our finding provides a highly simple, cost-effective, and highly effective strategy to promote plasmonic photochemistry by introducing a molecular cocatalyst, and this strategy can be extended to promote various plasmon-mediated reactions.
由于其独特的光学性质，局域表面等离子体共振（LSPR）已被证明在化学反应的引发或加速方面非常有效。然而，由于等离子体产生的热载流子的超短寿命（飞秒到皮秒），LSPR在光化学反应中的潜力尚未得到充分利用。在此，我们通过原位拉曼光谱证明了银纳米颗粒（AgNP）表面上等离子体介导的对硝基硫酚（PNTP）分子还原反应的加速。共吸附在AgNP表面的巯基苯硼酸（PMPBA）分子在等离子体介导的反应中作为分子助催化剂，导致PNTP还原反应得到增强。这种增强归因于在AgNP与共吸附的PMPBA分子界面处等离子体产生的热载流子的转移和分离得到改善。我们的发现提供了一种非常简单、经济高效且有效的策略，即通过引入分子助催化剂来促进等离子体光化学，并且该策略可以扩展到促进各种等离子体介导的反应。
