美国劳伦斯伯克利国家实验室Jian Zhang团队开发了具有高载流子迁移率的用于电容储能的化学稳定聚芳醚基金属酞菁框架。相关研究成果发表在2021年10月7日出版的《美国化学会杂志》。

共价有机框架（COFs）具有高效的电荷传输和优异的化学稳定性，正在成为光电器件和能源相关应用的一类重要半导体材料。然而，获得此类材料的合成化学有限，并且缺乏对载流子迁移率机制的理解，极大地阻碍了它们的实际应用。

该文中，研究人员报道了三种化学稳定的聚芳醚基金属酞COFs（PAE-PcM，M=Cu，Ni和Co）的合成，以及在溶剂热条件下在不同衬底（即SiO2/Si，ITO，石英）上容易地原位生长其薄膜。研究人员发现，具有范德华层状结构的PAE-PcM-COFs薄膜具有p型半导体特性，其本征迁移率高达～19.4 cm² V^–1 s^–1，碘掺杂后PAE-PcCu薄膜（0.2 s m^–1）的电导率增加了4个数量级。密度泛函理论计算表明，骨架中的载流子输运是各向异性的，沿柱状堆积酞菁的平面外空穴输运更为有利。此外，PAE PcCo的氧化还原行为对其电容性能的贡献最大约为88.5%，从而产生约19μF cm^–2的高比表面积归一化电容。

总的来说，该工作不仅为基于聚芳醚的2D COFs的电子性质提供了基本的理解，而且为其与能量相关的应用铺平了道路。

附：英文原文

Title: Chemically Stable Polyarylether-Based Metallophthalocyanine Frameworks with High Carrier Mobilities for Capacitive Energy Storage

Author: Chongqing Yang, Kaiyue Jiang, Qi Zheng, Xinle Li, Haiyan Mao, Wenkai Zhong, Cheng Chen, Bing Sun, Haimei Zheng, Xiaodong Zhuang, Jeffrey A. Reimer, Yi Liu, Jian Zhang

Issue&Volume: October 7, 2021

Abstract: Covalent organic frameworks (COFs) with efficient charge transport and exceptional chemical stability are emerging as an import class of semiconducting materials for opto-/electronic devices and energy-related applications. However, the limited synthetic chemistry to access such materials and the lack of mechanistic understanding of carrier mobility greatly hinder their practical applications. Herein, we report the synthesis of three chemically stable polyarylether-based metallophthalocyanine COFs (PAE-PcM, M = Cu, Ni, and Co) and facile in situ growth of their thin films on various substrates (i.e., SiO2/Si, ITO, quartz) under solvothermal conditions. We show that PAE-PcM COFs thin films with van der Waals layered structures exhibit p-type semiconducting properties with the intrinsic mobility up to ～19.4 cm2 V–1 s–1 and 4 orders of magnitude of increase in conductivity for PAE-PcCu film (0.2 S m–1) after iodine doping. Density functional theory calculations reveal that the carrier transport in the framework is anisotropic, with the out-of-plane hole transport along columnar stacked phthalocyanine more favorable. Furthermore, PAE-PcCo shows the redox behavior maximumly contributes ～88.5% of its capacitance performance, giving rise to a high surface area normalized capacitance of ～19 μF cm–2. Overall, this work not only offers fundamental understandings of electronic properties of polyarylether-based 2D COFs but also paves the way for their energy-related applications.

DOI: 10.1021/jacs.1c08265

Source: https://pubs.acs.org/doi/10.1021/jacs.1c08265