An Xingda, Kays Joshua C, Lightcap Ian V, Ouyang Tianhong, Dennis Allison M, Reinhard Björn M
Center for Sustainable Energy, University of Notre Dame, Notre Dame, Indiana 46556, United States.
ACS Nano. 2022 Apr 26;16(4):6813-6824. doi: 10.1021/acsnano.2c01706. Epub 2022 Mar 29.
Excited, or "hot" charge carrier generation and transfer driven by the decay of localized surface plasmon resonances (LSPRs) are key steps in plasmonic photocatalysis. Hybrid structures that contain both metal and semiconductor building blocks facilitate the extraction of reactive charge carriers and their utilization for photoelectrocatalysis. Additional functionality arises from hybrid structures that combine noble metal nanostructures with semiconductor components, such as chalcopyrite (CuFeS) nanocrystals (NCs), which by themselves support quasistatic resonances. In this work, we use a hybrid membrane to integrate Au nanorods (NRs) with a longitudinal LSPR at 745 nm and CuFeS NCs with a resonance peak at 490 nm into water-stable nanocomposites for robust and bifunctional photocatalysis of oxygen and hydrogen evolution reactions in a wavelength-dependent manner. Excitation of NRs or NCs in the nanocomposite correlates with increased hydrogen or oxygen evolution, respectively, consistent with a light-driven electron transfer between the metal and semiconductor building blocks, the direction of which depends on the wavelength. The bifunctional photoreactivity of the nanocomposite is enhanced by Cu(I)/Cu(II)-assisted catalysis on the surface of the NCs.
由局域表面等离子体共振（LSPR）衰减驱动的激发态或“热”电荷载流子的产生与转移是等离子体光催化的关键步骤。包含金属和半导体构建块的混合结构有助于活性电荷载流子的提取及其在光电催化中的利用。将贵金属纳米结构与半导体组分（如黄铜矿（CuFeS）纳米晶体（NCs））相结合的混合结构会产生额外的功能，黄铜矿纳米晶体本身支持准静态共振。在这项工作中，我们使用一种混合膜将具有745 nm纵向LSPR的金纳米棒（NRs）与具有490 nm共振峰的CuFeS NCs整合到水稳定的纳米复合材料中，以实现对氧气和氢气析出反应的稳健且双功能的光催化，且该光催化具有波长依赖性。纳米复合材料中NRs或NCs的激发分别与氢气或氧气析出的增加相关，这与金属和半导体构建块之间的光驱动电子转移一致，其转移方向取决于波长。纳米复合材料的双功能光反应性通过NCs表面的Cu(I)/Cu(II)辅助催化得到增强。
