Thomas Smok, Yang Hu, Saibal Jana, Frank Pammer and Maximilian Fichtner
{"title":"Exploring the chemical and structural change of copper porphyrins upon charging by means of synchrotron X-ray absorption spectroscopy†","authors":"Thomas Smok, Yang Hu, Saibal Jana, Frank Pammer and Maximilian Fichtner","doi":"10.1039/D4YA00242C","DOIUrl":null,"url":null,"abstract":"<p >In response to the growing demand for battery materials, researchers explore alternative resources with a focus on sustainability. Among these, organic electrode materials including porphyrins have emerged as promising candidates due to their advantageous properties, such as rapid charging capabilities and high energy densities. However, despite their potential, the precise charging mechanism of these alternatives remains elusive. To address this gap, our study delved into copper porphyrins, with a primary focus on [5,15-bis(ethynyl)-10,20-diphenylporphinato] copper(<small>II</small>) (CuDEPP). Employing synchrotron X-ray absorption spectroscopy in <em>operando</em> mode, we probed the evolution in chemical and electronic structure of Cu in CuDEPP. Our findings unequivocally demonstrate the participation of copper as a redox center during reversible charge storage, shedding light on its superior electrochemical performance. Furthermore, a combined approach involving extended X-ray absorption fine structure (EXAFS) studies and theoretical calculations provided deeper insights into the observed structural distortion during the charge storage process. Notably, our results support the hypothesis that redox processes, specifically those involving the aromatic porphyrin ring, drive the electrochemical activity of CuDEPP. In summary, our investigation offers important insights into the charging mechanism of copper porphyrins an essential step toward advancing sustainable organic materials for batteries.</p>","PeriodicalId":72913,"journal":{"name":"Energy advances","volume":null,"pages":null},"PeriodicalIF":3.2000,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ya/d4ya00242c?page=search","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Energy advances","FirstCategoryId":"1085","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/ya/d4ya00242c","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
In response to the growing demand for battery materials, researchers explore alternative resources with a focus on sustainability. Among these, organic electrode materials including porphyrins have emerged as promising candidates due to their advantageous properties, such as rapid charging capabilities and high energy densities. However, despite their potential, the precise charging mechanism of these alternatives remains elusive. To address this gap, our study delved into copper porphyrins, with a primary focus on [5,15-bis(ethynyl)-10,20-diphenylporphinato] copper(II) (CuDEPP). Employing synchrotron X-ray absorption spectroscopy in operando mode, we probed the evolution in chemical and electronic structure of Cu in CuDEPP. Our findings unequivocally demonstrate the participation of copper as a redox center during reversible charge storage, shedding light on its superior electrochemical performance. Furthermore, a combined approach involving extended X-ray absorption fine structure (EXAFS) studies and theoretical calculations provided deeper insights into the observed structural distortion during the charge storage process. Notably, our results support the hypothesis that redox processes, specifically those involving the aromatic porphyrin ring, drive the electrochemical activity of CuDEPP. In summary, our investigation offers important insights into the charging mechanism of copper porphyrins an essential step toward advancing sustainable organic materials for batteries.
为满足对电池材料日益增长的需求,研究人员以可持续发展为重点,探索替代资源。其中,有机电极材料--包括卟啉--因其快速充电能力和高能量密度等优势特性而成为前景广阔的候选材料。然而,尽管这些替代材料潜力巨大,但其精确的充电机制仍然难以捉摸。为了填补这一空白,我们的研究深入探讨了铜卟啉,重点是[5,15-双(乙炔基)-10,20-二苯基卟吩]铜(II)(CuDEPP)。我们采用同步辐射 X 射线吸收光谱的操作模式,探究了 CuDEPP 中铜的化学和电子结构的演变。我们的研究结果明确证明了铜在可逆电荷存储过程中作为氧化还原中心的参与,从而揭示了其卓越的电化学性能。此外,通过扩展 X 射线吸收精细结构(EXAFS)研究和理论计算相结合的方法,我们对电荷存储过程中观察到的结构畸变有了更深入的了解。值得注意的是,我们的研究结果支持这样一种假设,即氧化还原过程,特别是涉及芳香族卟啉环的氧化还原过程,驱动了 CuDEPP 的电化学活性。总之,我们的研究为了解卟啉铜的充电机理提供了重要依据--这是向推动可持续有机电池材料发展迈出的重要一步。