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有机-无机杂化钙钛矿的熔化

Melting of hybrid organic-inorganic perovskites.

作者信息

Shaw Bikash Kumar, Hughes Ashlea R, Ducamp Maxime, Moss Stephen, Debnath Anup, Sapnik Adam F, Thorne Michael F, McHugh Lauren N, Pugliese Andrea, Keeble Dean S, Chater Philip, Bermudez-Garcia Juan M, Moya Xavier, Saha Shyamal K, Keen David A, Coudert François-Xavier, Blanc Frédéric, Bennett Thomas D

机构信息

Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, UK.

Department of Chemistry, University of Liverpool, Liverpool, UK.

出版信息

Nat Chem. 2021 Aug;13(8):778-785. doi: 10.1038/s41557-021-00681-7. Epub 2021 May 10.

Abstract

Several organic-inorganic hybrid materials from the metal-organic framework (MOF) family have been shown to form stable liquids at high temperatures. Quenching then results in the formation of melt-quenched MOF glasses that retain the three-dimensional coordination bonding of the crystalline phase. These hybrid glasses have intriguing properties and could find practical applications, yet the melt-quench phenomenon has so far remained limited to a few MOF structures. Here we turn to hybrid organic-inorganic perovskites-which occupy a prominent position within materials chemistry owing to their functional properties such as ion transport, photoconductivity, ferroelectricity and multiferroicity-and show that a series of dicyanamide-based hybrid organic-inorganic perovskites undergo melting. Our combined experimental-computational approach demonstrates that, on quenching, they form glasses that largely retain their solid-state inorganic-organic connectivity. The resulting materials show very low thermal conductivities (~0.2 W m K), moderate electrical conductivities (10-10 S m) and polymer-like thermomechanical properties.

摘要

金属有机框架(MOF)家族中的几种有机-无机杂化材料已被证明在高温下能形成稳定的液体。骤冷会导致形成熔融淬火的MOF玻璃,其保留了晶相的三维配位键。这些杂化玻璃具有引人入胜的特性,可能会有实际应用,但到目前为止,熔融淬火现象仍仅限于少数MOF结构。在这里,我们转向有机-无机杂化钙钛矿——由于其离子传输、光电导、铁电和多铁性等功能特性,在材料化学中占据突出地位——并表明一系列基于双氰胺的有机-无机杂化钙钛矿会发生熔化。我们结合实验和计算的方法表明,在淬火时,它们会形成玻璃,在很大程度上保留其固态无机-有机连接性。所得材料显示出非常低的热导率(约0.2 W m⁻¹ K⁻¹)、适度的电导率(10⁻¹⁰ S m⁻¹)和类似聚合物的热机械性能。

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