Inhibited interlayer electron transfer in metal ion linked multilayers on mesoporous metal oxide films
Inhibited interlayer electron transfer in metal ion linked multilayers on mesoporous metal oxide films
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介孔金属氧化物薄膜上金属离子连接多层膜中层间电子转移的抑制
DOI：
10.1016/j.jpap.2021.100088
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发表时间：
2022
影响因子：
--
通讯作者：
Hanson, Kenneth
中科院分区：
文献类型：
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作者：
Arcidiacono, Ashley;Robb, Alex J.;Masitas, Rafael A.;Salpage, Sahan R.;McLeod, Grace M.;Chen, Jiaqi;Ogunsolu, Omotola O.;Roper, Michael G.;Hanson, Kenneth
在金属氧化物表面上掺入染料-电子供体基序是提高染料再生速率、减缓复合和改善整体染料敏化器件性能的常见策略。在这里，我们使用锌离子连接的多层组装的染料（N3）和钴聚吡啶电子供体（Co）的TiO 2作为替代传统的共价连接的染料供体系统。使用UV-Vis和ATR-IR监测TiO 2-N3-Zn-共多层膜的形成，并且我们引入电感耦合等离子体质谱作为量化光谱遮蔽的分子如Co的表面负载的手段。有趣的是，与最初的意图相反，Co电子供体的加入阻碍了染料敏化器件的几乎每一个性能指标。瞬态吸收测量表明，Co对N3+的电子转移和Co对N3+的电子转移对N3+的激发态猝灭分别慢于本征激发态的衰减和复合.我们认为，金属离子连接的架构所施加的几何限制，足以减缓电子转移，使钴是有效地惰性在这个大会。虽然这种双层没有改善器件性能，但这些见解可以指导新的设计策略，这些策略将改善性能和/或将用于不需要电子转移但需要自旋和/或磁矩通信的其他应用中。
The incorporation of dye-electron donor motifs on metal oxide surfaces is a common strategy to increase dye regeneration rate, slow recombination, and improve overall dye-sensitized device performance. Here we used zinc ion linked multilayer assembly of a dye (N3) and a cobalt polypyridyl electron donor (Co) on TiO2as an alternative to traditional covalently linked dye-donor systems. The formation of the TiO2-N3-Zn-Comultilayer was monitored using UV–Vis and ATR-IR and we introduced inductively coupled plasma mass spectrometry as a means of quantifying the surface loading of spectroscopically obscured molecules likeCo. Interestingly, and contrary to the original intent, the addition ofCoelectron donor impeded the dye-sensitized device in nearly every performance metric. Transient absorption measurements indicate that both excited state quenching ofN3byCoandCotoN3+electron transfer are slower than the intrinsic excited state decay and recombination, respectively. We suggest that the geometric restriction imposed by the metal ion linked architecture sufficiently slows electron transfer such thatCois effectively inert in this assembly. While this bilayer did not improve device performance, these insights may guide new design strategies that will improve performance and/or will be of use in other applications where electron transfer is not desired but say communication of spin and/or magnetic moment is needed.