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含银 BEA 型纳米沸石中费米秒瞬态吸收光谱研究的热电子光动力学。

Hot-Electron Photodynamics in Silver-Containing BEA-Type Nanozeolite Studied by Femtosecond Transient Absorption Spectroscopy.

机构信息

Univ. Lille, CNRS, UMR 8516, LASIRE-Laboratoire de Spectroscopie pour les Interactions, la Réactivité et l'Environnement, 59000, Lille, France.

Normandie Université, Laboratoire Catalyse et Spectrochimie (LCS) ENSICAEN, UNICAEN, CNRS, 6 boulevard Maréchal Juin, Caen, 14050, France.

出版信息

Chemphyschem. 2020 Dec 14;21(24):2634-2643. doi: 10.1002/cphc.202000822. Epub 2020 Nov 23.

DOI:10.1002/cphc.202000822
PMID:33078874
Abstract

Silver cations were introduced in nanosized BEA-type zeolite containing organic template by ion-exchange followed by chemical reduction towards preparation of photoactive materials (Ag -BEA). The stabilization of highly dispersed Ag nanoparticles with a size of 1-2 nm in the BEA zeolite was revealed. The transient optical response of the Ag-BEA samples upon photoexcitation at 400 nm was studied by femtosecond absorption. The photodynamic of the hot electrons was found to depend on the sample preparation. The lifetime of the hot electrons in the Ag-BEA samples containing small Ag nanoparticles (1-2 nm) is significantly shortened in comparison to bear Ag nanoparticles with a size of 10 nm. While for the larger Ag nanoparticles, the energy absorbed in the conduction band is decaying by electron-phonon coupling into the metal lattice, the high surface-to-volume ratio of the small Ag nanoparticles favors the dissipation of the energy of the hot electrons from the metal nanoparticles (Ag ) towards the zeolitic micro-environment. This finding is encouraging for further applications of Ag-containing zeolites in photocatalysis and plasmonic chemistry.

摘要

银离子通过离子交换被引入含有有机模板的纳米 BEA 型沸石中,然后通过化学还原制备光活性材料(Ag-BEA)。在 BEA 沸石中稳定高度分散的尺寸为 1-2nm 的 Ag 纳米粒子。通过飞秒吸收研究了在 400nm 光激发下 Ag-BEA 样品的瞬态光学响应。发现光动力热电子的动力学取决于样品的制备。与尺寸为 10nm 的 Ag 纳米粒子相比,含有小尺寸(1-2nm)Ag 纳米粒子的 Ag-BEA 样品中热电子的寿命明显缩短。而对于较大的 Ag 纳米粒子,吸收在导带中的能量通过电子-声子耦合衰减到金属晶格中,小 Ag 纳米粒子的高表面积与体积比有利于将热电子的能量从金属纳米粒子(Ag)耗散到沸石微环境中。这一发现为在光催化和等离子体化学中进一步应用含银沸石提供了希望。

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