通过扫描光电化学显微镜研究超分子光敏剂-二氧化钛薄膜系统的光诱导电子转移

doi:10.13208/j.electrochem.2218005

摘要/Abstract

摘要：

在基于TiO₂的光阳极上枝接电荷转移通道仍然是太阳能到化学转换技术的一个迫切瓶颈。尽管进行了大量的尝试，但TiO₂作为有前途的光阳极材料仍然受到电荷传输动力学迟缓的影响。因此，一种组装策略涉及将金属卟啉基光敏剂分子（MP）轴向配位嫁接到表面改性的TiO₂纳米棒（TiO₂NRs）光阳极上，形成复合MP/TiO₂ NRs光电极。正如预期的那样，与单独的TiO₂NR和MPA/TiO₂ NRs光电极相比，所得到的独特的MPB/TiO₂ NRs光电极具有明显提高的光电流密度。采用扫描光电化学显微镜（SPECM）和强度调制光电流光谱（IMPS）系统地评估了MP/TiO₂ NRs光电极的连续光激发电子转移（PET）动力学信息。通过数据拟合发现，在光照条件下，MPB/TiO₂ NRs的光电子转移速率（k_eff）常数比纯TiO₂ NRs高2.6倍左右。MPB/TiO₂ NRs的高动力学常数是由于D-A结构的共轭分子MPB可以有效地加速分子内电子转移，以及促进电子在新型电荷转移通道中参与I₃^-到I^-的还原反应。本研究展示的结果有望为研究人工光合作用电荷转移过程的机制和构建高效的光电极提供一些启发。

关键词: 光敏剂, TiO₂纳米棒, 扫描光电化学显微镜, 光激发电子转移

Abstract:

Crafting charge transfer channels at titanium dioxide (TiO₂) based photoanodes remain a pressing bottleneck in solar-to-chemical conversion technology. Despite the tremendous attempts, TiO₂ as the promising photoanode material still suffers from sluggish charge transport kinetics. Herein, we propose an assembly strategy that involves the axial coordination grafting metalloporphyrin-based photosensitizer molecules (MP) onto the surface-modified TiO₂ nanorods (NRs) photoanode, forming the composite MP/TiO₂ NRs photoelectrode. As expected, the resulted unique MP_B/TiO₂ NRs photoelectrode displays significantly improved photocurrent density as compared to TiO₂ NRs alone and MP_A/TiO₂ NRs photoelectrode. Scanning photoelectrochemical microscopy (SPECM) and intensity modulated photocurrent spectroscopy (IMPS) were employed to systematically evaluate the continuous photoinduced electron transfer (PET) dynamics for MP/TiO₂ NRs photoelectrode. According to the data fitting, it is found that the photoelectron transfer rate (k_eff) constant for the MP_B/TiO₂ NRs is about 2.6 times higher than that for the pure TiO₂ NRs under light irradiation. The high kinetic constant for the MP_B/TiO₂ NRs was ascribed to that the conjugated molecules MP_B of D-A structure can effectively accelerate intramolecular electrons transfer as well as promote electrons taking part in the reduction reaction of I₃^-to I^-in the novel charge transfer channel. The results demonstrated in this study are expected to shed some light on investigating the mechanism in the charge transfer process of artificial photosynthesis and constructing efficient photoelectrodes.

Key words: photosensitizer, TiO₂ nanorods, Scanning photoelectrochemical microscopy, photoexcited electron transfer

张生雅, 姚敏, 王泽, 刘天娇, 张蓉芳, 叶慧琴, 冯彦俊, 卢小泉. 通过扫描光电化学显微镜研究超分子光敏剂-二氧化钛薄膜系统的光诱导电子转移[J]. 电化学（中英文）, 2023, 29(6): 2218005.

Sheng-Ya Zhang, Min Yao, Ze Wang, Tian-Jiao Liu, Rong-Fang Zhang, Hui-Qin Ye, Yan-Jun Feng, Xiao-Quan Lu. Scanning Photoelectrochemical Microscopic Study in Photoinduced Electron Transfer of Supramolecular Sensitizers-TiO₂ Thin Films Systems[J]. Journal of Electrochemistry, 2023, 29(6): 2218005.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.2218005

https://electrochem.xmu.edu.cn/CN/Y2023/V29/I6/2218005

图/表 8

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