Self-Assembled Bilayers on Nanocrystalline Metal Oxides: Exploring the Non-Innocent Nature of the Linking Ions.
Self-Assembled Bilayers on Nanocrystalline Metal Oxides: Exploring the Non-Innocent Nature of the Linking Ions.
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纳米晶金属氧化物上的自组装双层：探索连接离子的非无辜性质。
DOI：
10.1021/acs.langmuir.7b01964
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Kenneth Hanson
中科院分区：
文献类型：
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作者：
Jamie C Wang;Kyle Violette;O. Ogunsolu;Seda Cekli;E. Lambers;Hadi M. Fares;Kenneth Hanson
纳米晶金属氧化物膜上的自组装双层膜是一种越来越流行的调制染料-半导体界面上电子和能量转移的策略。迄今为止，大部分工作都依赖于ZrII和ZnIV连接离子来组装薄膜。在本报告中，我们证明了几种不同的阳离子（CdII, CuII, FeII, LaIII， MnII和SnIV）不仅可以有效地生成双层组装体，而且对薄膜的稳定性和光物理性质有深远的影响。ZrIV离子双层膜在TiO2和ZrO2上均表现出最高的光稳定性。尽管金属离子对染料的吸收/发射能量和氧化电位的影响很小，但由CuII、FeII和MnII组成的双分子膜表现出明显的激发态猝灭。激发态猝灭降低了电子注入率，但对于CuII和MnII双分子层，也显著减缓了电子转移动力学。
Self-assembled bilayers on nanocrystalline metal oxide films are an increasingly popular strategy for modulating electron and energy transfer at dye-semiconductor interfaces. A majority of the work to date has relied on ZrII and ZnIV linking ions to assemble the films. In this report, we demonstrate that several different cations (CdII, CuII, FeII, LaIII, MnII, and SnIV) are not only effective in generating the bilayer assemblies but also have a profound influence on the stability and photophysical properties of the films. Bilayer films with ZrIV ions exhibited the highest photostability on both TiO2 and ZrO2. Despite the metal ions having a minimal influence on the absorption/emission energies and oxidation potentials of the dye, bilayers composed of CuII, FeII, and MnII exhibit significant excited-state quenching. The excited-state quenching decreases the electron injection yield but also, for CuII and MnII bilayers, significantly slows the back electron transfer kinetics.