Polyarylether-Based 2D Covalent-Organic Frameworks with In-Plane D-A Structures and Tunable Energy Levels for Energy Storage

Nana Li; Kaiyue Jiang; Fermín Rodríguez-Hernández; Haiyan Mao; Sheng Han; Xiaobin Fu; Jichao Zhang; Chongqing Yang; Changchun Ke; Xiaodong Zhuang

doi:10.1002/advs.202104898

Polyarylether-Based 2D Covalent-Organic Frameworks with In-Plane D-A Structures and Tunable Energy Levels for Energy Storage

Adv Sci (Weinh). 2022 Feb;9(6):e2104898. doi: 10.1002/advs.202104898. Epub 2021 Dec 26.

Authors

Nana Li^{1

2}, Kaiyue Jiang^{2

3}, Fermín Rodríguez-Hernández⁴, Haiyan Mao⁵, Sheng Han^{1

6}, Xiaobin Fu⁷, Jichao Zhang⁸, Chongqing Yang², Changchun Ke⁹, Xiaodong Zhuang²

Affiliations

¹ School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang, 832003, China.
² The Meso-Entropy Matter Lab, School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai, 200240, China.
³ College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, Henan, 450001, China.
⁴ Departamento de Química, Módulo 13, Universidad Autónoma de Madrid, Madrid, 28049, Spain.
⁵ Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA, 94720, USA.
⁶ School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai, 201418, China.
⁷ Department of Molten Salt Chemistry and Engineering, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China.
⁸ Shanghai Synchrotron Radiation Facility, Zhangjiang Laboratory, Shanghai Advanced Research Institute Chinese Academy of Sciences, Shanghai, 201204, China.
⁹ Institute of Fuel Cells, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China.

Abstract

The robust fully conjugated covalent organic frameworks (COFs) are emerging as a novel type of semi-conductive COFs for optoelectronic and energy devices due to their controllable architectures and easily tunable the highest occupied molecular orbital (HOMO) and the lowest occupied molecular orbital (LUMO) levels. However, the carrier mobility of such materials is still beyond requirements due to limited π-conjugation. In this study, a series of new polyarylether-based COFs are rationally synthesized via a direct reaction between hexadecafluorophthalocyanine (electron acceptor) and octahydroxyphthalocyanine (electron donor). These COFs have typical crystalline layered structures, narrow band gaps as low as ≈0.65 eV and ultra-low resistance (1.31 × 10^-6 S cm^-1 ). Such COFs can be composed of two different metal-sites and contribute improved carrier mobility via layer-altered staking mode according to density functional theory calculation. Due to the narrow pore size of 1.4 nm and promising conductivity, such COFs and electrochemically exfoliated graphene based free-standing films are fabricated for in-plane micro-supercapacitors, which demonstrate excellent volumetric capacitances (28.1 F cm^-3 ) and excellent stability of 10 000 charge-discharge cycling in acidic electrolyte. This study provides a new approach toward dioxin-linked COFs with donor-acceptor structure and easily tunable energy levels for versatile energy storage and optoelectronic devices.

Keywords: band gap; covalent-organic frameworks; hexadecafluorophthalocyanine; micro-supercapacitors; polyarylether.

Abstract

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