Chemically Stable Polyarylether-Based Metallophthalocyanine Frameworks with High Carrier Mobilities for Capacitive Energy Storage
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 butmore »
- Authors:
-
[6];
[7];
[3];
[2];
[8];
[9];
[1]
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
- Shanghai Jiao Tong Univ. (China). The meso-Entropy Matter Lab.
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Clark Atlanta University, Atlanta, GA (United States)
- Univ. of California, Berkeley, CA (United States)
- Shanghai Jiao Tong Univ. (China). Frontiers Science Center for Transformative Molecules, In-situ Center for Physical Science, Center of Hydrogen Science; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; China Univ. of Geosciences, Beijing (China)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA); National Natural Science Foundation of China (NSFC)
- OSTI Identifier:
- 1833994
- Grant/Contract Number:
- AC02-05CH11231; 51973114; 21720102002
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 143; Journal Issue: 42; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Covalent organic frameworks; Thin films; Electrical properties; Carrier dynamics; Electrical conductivity
Citation Formats
Yang, Chongqing, Jiang, Kaiyue, Zheng, Qi, Li, Xinle, Mao, Haiyan, Zhong, Wenkai, Chen, Cheng, Sun, Bing, Zheng, Haimei, Zhuang, Xiaodong, Reimer, Jeffrey A., Liu, Yi, and Zhang, Jian. Chemically Stable Polyarylether-Based Metallophthalocyanine Frameworks with High Carrier Mobilities for Capacitive Energy Storage. United States: N. p., 2021.
Web. doi:10.1021/jacs.1c08265.
Yang, Chongqing, Jiang, Kaiyue, Zheng, Qi, Li, Xinle, Mao, Haiyan, Zhong, Wenkai, Chen, Cheng, Sun, Bing, Zheng, Haimei, Zhuang, Xiaodong, Reimer, Jeffrey A., Liu, Yi, & Zhang, Jian. Chemically Stable Polyarylether-Based Metallophthalocyanine Frameworks with High Carrier Mobilities for Capacitive Energy Storage. United States. https://doi.org/10.1021/jacs.1c08265
Yang, Chongqing, Jiang, Kaiyue, Zheng, Qi, Li, Xinle, Mao, Haiyan, Zhong, Wenkai, Chen, Cheng, Sun, Bing, Zheng, Haimei, Zhuang, Xiaodong, Reimer, Jeffrey A., Liu, Yi, and Zhang, Jian. Thu .
"Chemically Stable Polyarylether-Based Metallophthalocyanine Frameworks with High Carrier Mobilities for Capacitive Energy Storage". United States. https://doi.org/10.1021/jacs.1c08265. https://www.osti.gov/servlets/purl/1833994.
@article{osti_1833994,
title = {Chemically Stable Polyarylether-Based Metallophthalocyanine Frameworks with High Carrier Mobilities for Capacitive Energy Storage},
author = {Yang, Chongqing and Jiang, Kaiyue and Zheng, Qi and Li, Xinle and Mao, Haiyan and Zhong, Wenkai and Chen, Cheng and Sun, Bing and Zheng, Haimei and Zhuang, Xiaodong and Reimer, Jeffrey A. and Liu, Yi and Zhang, Jian},
abstractNote = {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},
journal = {Journal of the American Chemical Society},
number = 42,
volume = 143,
place = {United States},
year = {Thu Oct 07 00:00:00 EDT 2021},
month = {Thu Oct 07 00:00:00 EDT 2021}
}
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