用于材料设计的阴离子氧化还原拓扑化学:钙钛矿及其他

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY
Shunsuke Sasaki*, Simon J. Clarke, Stéphane Jobic and Laurent Cario, 
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引用次数: 0

摘要

拓扑化学是指一种固态反应的总类,在这种反应中,前体和产物的晶体结构显示出很强的隶属关系。各种低维材料通过范德华(vdW)相互作用将客体原子或分子松散地结合在二维板块或一维链之间,从而实现这种逐步的结构转变。这些过程由客体和宿主框架之间的氧化还原反应驱动,其中过渡金属阳离子被广泛用作氧化还原中心。拓扑化学与阳离子氧化还原反应相结合,不仅实现了锂离子二次电池等技术应用,还成为层状过渡金属化合物结构或电子微调的有力工具。近年来,我们一直在追求超越这种阳离子氧化还原拓扑化学的材料设计,而这种拓扑化学大多局限于二维或一维 vdW 系统。为此,我们提出了非 vdW 化合物的新拓扑化学反应,这些化合物由阴离子恰尔原二聚体的二维阵列与氧化还原惰性阳离子主层交替组成。研究发现,这些缩醛二聚体会与外部金属元素发生氧化还原反应,引发(1)这些金属的插入,从而构建二维金属缩醛,或(2)组成缩醛阴离子的脱嵌。从整体上看,这种拓扑化学就像 "拉链",阴离子钙原-钙原键的还原裂解打开了非钒钛材料的空间,从而形成了新颖的层状结构。本视角简要总结了阴离子氧化还原拓扑化学实现独特结构转变的开创性实例,以及这些实例在合成和表征方面面临的挑战。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Anionic Redox Topochemistry for Materials Design: Chalcogenides and Beyond

Anionic Redox Topochemistry for Materials Design: Chalcogenides and Beyond

Anionic Redox Topochemistry for Materials Design: Chalcogenides and Beyond

Topochemistry refers to a generic category of solid-state reactions in which precursors and products display strong filiation in their crystal structures. Various low-dimensional materials are subject to this stepwise structure transformation by accommodating guest atoms or molecules in between their 2D slabs or 1D chains loosely bound by van der Waals (vdW) interactions. Those processes are driven by redox reactions between guests and the host framework, where transition metal cations have been widely exploited as the redox center. Topochemistry coupled with this cationic redox not only enables technological applications such as Li-ion secondary batteries but also serves as a powerful tool for structural or electronic fine-tuning of layered transition metal compounds. Over recent years, we have been pursuing materials design beyond this cationic redox topochemistry that was mostly limited to 2D or 1D vdW systems. For this, we proposed new topochemical reactions of non-vdW compounds built of 2D arrays of anionic chalcogen dimers alternating with redox-inert host cationic layers. These chalcogen dimers were found to undergo redox reaction with external metal elements, triggering either (1) insertion of these metals to construct 2D metal chalcogenides or (2) deintercalation of the constituent chalcogen anions. As a whole, this topochemistry works like a “zipper”, where reductive cleavage of anionic chalcogen–chalcogen bonds opens up spaces in non-vdW materials, allowing the formation of novel layered structures. This Perspective briefly summarizes seminal examples of unique structure transformations achieved by anionic redox topochemistry as well as challenges on their syntheses and characterizations.

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来源期刊
ACS Organic & Inorganic Au
ACS Organic & Inorganic Au 有机化学、无机化学-
CiteScore
4.10
自引率
0.00%
发文量
0
期刊介绍: ACS Organic & Inorganic Au is an open access journal that publishes original experimental and theoretical/computational studies on organic organometallic inorganic crystal growth and engineering and organic process chemistry. Short letters comprehensive articles reviews and perspectives are welcome on topics that include:Organic chemistry Organometallic chemistry Inorganic Chemistry and Organic Process Chemistry.
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