An Efficient Copper-Based Redox Shuttle Bearing a Hexadentate Polypyridyl Ligand for DSCs under Low-Light Conditions
An Efficient Copper-Based Redox Shuttle Bearing a Hexadentate Polypyridyl Ligand for DSCs under Low-Light Conditions
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DOI：
10.1021/acsaem.2c00344
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发表时间：
2022-05
影响因子：
6.4
通讯作者：
Anthony Devdass;Jonathon Watson;Eric Firestone;Thomas W. Hamann;J. Delcamp;J. W. Jurss
中科院分区：
文献类型：
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作者：
Anthony Devdass;Jonathon Watson;Eric Firestone;Thomas W. Hamann;J. Delcamp;J. W. Jurss
合成了一种具有六齿配体的铜配合物，并将其作为染料敏化太阳能电池（DSC）器件中的氧化还原梭进行了评价，该器件在弱光条件下表现出优异的性能。已显示Cu基氧化还原梭（RS）在低光条件下表现得非常好;然而，大多数已知的Cu基RS采用双齿吡啶基配体，并且通常需要与这些配体的氮供体相邻的庞大侧翼基团，以防止为了增强电池性能而添加的外源性刘易斯碱（例如4-叔丁基吡啶（TBP））的变形和结合。在没有大体积取代基的情况下，双齿配体易于与TBP进行配体交换。在这种情况下，我们已经开发了一种基于铜的RS与预组织的多齿配体，旨在促进有效的电子转移动力学和高稳定性，通过螯合作用。本文报道的Cu体系[Cu（bpyPY 4）]2+/+由六齿多吡啶基配体bpyPY 4（6，6 ′-bis（1，1-di（pyridine-2-yl）ethyl）-2，2 ′-bipyridine）支撑并在DSC中作为RS进行检测。从X射线晶体学和变温1H NMR研究，bpyPY 4提供了一个动态的协调环境周围的金属中心。循环伏安法和紫外-可见光谱和NMR光谱表明，非配位的吡啶基供体块结合TBP铜。使用[Cu（bpyPY 4）]2+/+作为氧化还原电解质的DSC装置在1个太阳光照（100 mW/cm 2）下给出4.9%的功率转换效率（PCE）值。引人注目的是，当通过荧光灯光源用2400勒克斯（0.5 mW/cm 2）照射时，器件性能增加到11.11%，并且在13500勒克斯（2.10 mW/cm 2）下进一步提高到15.2%PCE。铜氧化还原梭是一个有趣的候选人实施窄带隙敏化剂与低氧化电位，这是重要的高光电流DSC设备。
A Cu complex featuring a hexadentate ligand was synthesized and evaluated as a redox shuttle in dye-sensitized solar cell (DSC) devices, which exhibited excellent performance under low-light conditions. Cu-based redox shuttles (RSs) have been shown to perform remarkably well under low-light conditions; however, most of the known Cu-based RSs employ bidentate pyridyl ligands and often require bulky flanking groups adjacent to the nitrogen donors of these ligands to prevent distortion and binding of exogenous Lewis bases such as 4-tert-butylpyridine (TBP) that are added to enhance cell performance. Without the bulky substituents, the bidentate ligands are susceptible to ligand exchange with TBP. In this context, we have developed a Cu-based RS with a preorganized multidentate ligand designed to facilitate efficient electron transfer kinetics and high stability via the chelate effect. The Cu system, [Cu(bpyPY4)]2+/+, reported here is supported by the hexadentate polypyridyl ligand bpyPY4 (6,6′-bis(1,1-di(pyridine-2-yl)ethyl)-2,2′-bipyridine) and examined as a RS in DSCs. From X-ray crystallography and variable-temperature1H NMR studies, bpyPY4 provides a dynamic coordination environment around the metal center. Cyclic voltammetry and UV–visible and NMR spectroscopy indicate that noncoordinated pyridyl donors block binding of TBP to copper. DSC devices using [Cu(bpyPY4)]2+/+as the redox electrolyte gave a power conversion efficiency (PCE) value of 4.9% under 1 sun illumination (100 mW/cm2). Strikingly, the device performance increased to 11.11% when irradiated with 2400 lux (0.5 mW/cm2) via a fluorescent lamp light source and improved further to 15.2% PCE at 13500 lux (2.10 mW/cm2). The Cu redox shuttle is an intriguing candidate for implementation with narrow band gap sensitizers with low oxidation potentials, which are important for high photocurrent DSC devices.