Heavy Metal Effects on the Photovoltaic Properties of Metallocorroles in Dye-Sensitized Solar Cells
Heavy Metal Effects on the Photovoltaic Properties of Metallocorroles in Dye-Sensitized Solar Cells
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DOI：
10.1021/acsaem.0c02427
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发表时间：
2020-12-28
影响因子：
6.4
通讯作者：
Imahori, Hiroshi
中科院分区：
文献类型：
--
作者：
Higashino, Tomohiro;Kurumisawa, Yuma;Imahori, Hiroshi
寻找有效的电荷分离策略是在光伏和光催化装置中实现高效太阳能转换的先决条件。卟啉类化合物，包括卟啉和相关的大环，如酞菁和corrole，是一种多功能配体，可以容纳大多数金属离子的单个金属原子，并且它们的光物理和电化学性质可以通过腔中的金属原子来调节。在此，我们评估了基于Au-III-， (ReO)- o- v -和(OsN)- n - vi -的染料敏化太阳能电池（DSSCs）的光伏性能，这些染料敏化太阳能电池在中间苯基的对位和位上具有COOH锚定基团。基于au - iii -啉的DSSCs的功率转换效率（PCE）为4.2%，显著高于(ReO)- o - v -和(OsN)- n - vi -啉。飞秒时间分辨瞬态吸收测量表明，从激发态注入的电子与系统间交叉竞争，au - iii -对应体的系统间交叉比ReVO-和(OsN)- n - vi -对应体慢。因此，au - iii的高入射光子-电流效率和由此产生的短路电流密度和pce归因于高电子注入效率，因为它比ReVO-和(OsN)- n- vi - coroors更慢的系统间交叉。此外，与para-COOH基团（3.4%）相比，具有元cooh基团的au - iii - corole的PCE（4.2%）更高，这是由XPS测量和理论计算支持的更强的Au-TiO2相互作用所解释的。这些结果表明取代基和金属离子对光伏性能都有很大的影响。总体而言，基于au - iii - corroors的DSSCs在腐蚀基DSSCs中表现出最高的光伏性能。
Finding strategies for effective charge separation is a prerequisite for realizing efficient solar energy conversion in photovoltaic and photocatalytic devices. Porphyrinoids, including porphyrins and related macrocycles such as phthalocyanines and corroles, are versatile ligands that can accommodate a single metal atom for most metal ions, and their photophysical and electro-chemical properties can be tuned by the metal atom in the cavity. Herein, we evaluated the photovoltaic properties of the dyesensitized solar cells (DSSCs) based on Au-III-, (ReO)-O-V-, and (OsN)-N-VI-corroles with COOH anchoring groups at the para- and meta-positions of the meso-phenyl groups. The DSSCs based on Au-III-corroles exhibited a power conversion efficiency (PCE) of 4.2%, which is remarkably higher than those for the (ReO)-O-V- and (OsN)-N-VI-corroles. Femtosecond time-resolved transient absorption measurements have shown that the electron injection from the excited singlet state competes with intersystem crossing, and that intersystem crossing for Au-III-corroles is slower than those for ReVO- and (OsN)-N-VI-corroles. Consequently, the high incident photon-to-current efficiencies and resultant short-circuit current densities and PCEs for Au-III-corroles are attributed to the high electron injection efficiencies owing to the slower intersystem crossing than ReVO- and (OsN)-N-VI-corroles. In addition, the higher PCE for a Au-III-corrole with a meta-COOH group (4.2%) as opposed to a para-COOH group (3.4%) is explained by the stronger Au-TiO2 interactions supported by XPS measurements and theoretical calculations. These results imply that both the substituents and the metal ion have a large influence on the photovoltaic performances. Overall, DSSCs based on the Au-III-corroles were found to exhibit the highest photovoltaic performance among corrole-based DSSCs.