Influence of Dye-Coordinated Metal Ions on Electron Transfer Dynamics at Dye–Semiconductor Interfaces
Influence of Dye-Coordinated Metal Ions on Electron Transfer Dynamics at Dye–Semiconductor Interfaces
复制标题
染料配位金属离子对染料半导体界面电子转移动力学的影响
DOI：
10.1021/acsaem.8b01559
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发表时间：
2018
影响因子：
6.4
通讯作者：
Hanson, Kenneth
中科院分区：
文献类型：
--
作者：
Ogunsolu, Omotola O.;Braun, Alexander J.;Robb, Alex J.;Salpage, Sahan R.;Zhou, Yan;Hanson, Kenneth
最大化染料-半导体界面的再生率和最小化复合率对于实现高效的染料敏化太阳能和光电化学电池至关重要。先前已经表明，简单地将金属离子与染料分子的非表面结合的羧酸根配位可以减慢复合速率并增加开路电压。然而，尚不清楚额外的空间效应或金属离子的电荷是否是造成这种行为的原因。在这里，我们使用三种不同的氧化还原介体，(1) I–/I3–、(2) [tris(1,10-phenanthroline)cobalt]3+/2+ 和 (3) [Co(4,4′,4″-三叔丁基-2,2′:6′,2″-三联吡啶)(NCS)3]0/1– 来阐明配位金属离子和介体之间静电相互作用的作用（如果有）决定这些界面电子转移事件。通过结合光谱学、电化学和太阳能电池测量，我们证明虽然静电相互作用可能会影响染料再生速率，但 TiO2(e–) 和氧化介体之间金属离子空间体积的增加可能对整体器件性能产生更强的影响。此外，电化学阻抗谱和强度相关测量表明，金属离子的配位可以减缓介孔氧化物内介体的扩散，这可能对染料敏化器件中多层组件的使用产生影响。
Maximizing regeneration and minimizing recombination rates at dye–semiconductor interfaces is crucial for the realization of efficient dye-sensitized solar and photoelectrosynthesis cells. Previously it has been shown that simply coordinating the metal ion to the nonsurface bound carboxylate groups of a dye molecule can slow recombination rates and increase open-circuit voltages. However, it was unclear if the additional steric effects or charge of the metal ion were the cause of this behavior. Here we use three different redox mediators, (1) I–/I3–, (2) [tris(1,10-phenanthroline)cobalt]3+/2+, and (3) [Co(4,4′,4″-tritert-butyl-2,2′:6′,2″-terpyridine)(NCS)3]0/1–to elucidate the role, if any, of electrostatic interactions between the coordinated metal ion and mediator in dictating these interfacial electron transfer events. Using a combination of spectroscopy, electrochemistry, and solar cell measurements, we demonstrate that while electrostatic interactions may influence dye regeneration rates, for example, increased steric bulk of the metal ion between TiO2(e–) and the oxidized mediator likely has a stronger influence on the overall device performance. Additionally, electrochemical impedance spectroscopy and intensity dependent measurements suggest that the coordination of the metal ion can slow diffusion of the mediators within the mesoporous oxide which could have implications for the use of multilayer assemblies in dye-sensitized devices.
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影响因子：
3.7
作者：
Brennaman, M. Kyle;Gish, Melissa K.;Meyer, Thomas J.
通讯作者：
Meyer, Thomas J.
影响因子：
4.6
作者：
Casarin, Laura;Swords, Wesley B.;Meyer, Gerald J.
通讯作者：
Meyer, Gerald J.
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
发表时间：
2017
期刊：
Langmuir : the ACS journal of surfaces and colloids
影响因子：
--
作者：
Jamie C Wang;Kyle Violette;O. Ogunsolu;Seda Cekli;E. Lambers;Hadi M. Fares;Kenneth Hanson
通讯作者：
Kenneth Hanson
用于有机氧化还原液流电池的聚吡啶铁(II)和钴(II)配合物的电化学表征
影响因子：
2.6
作者：
E. Benazzi;Vito Cristino;Stefano Caramori;L. Meda;Rita Boaretto;C. Bignozzi
通讯作者：
C. Bignozzi
影响因子：
15
作者：
Brady, Matthew D.;Sampaio, Renato N.;Meyer, Gerald J.
通讯作者：
Meyer, Gerald J.