Three-dimensional covalent organic frameworks with pto and mhq-z topologies based on Tri- and tetratopic linkers

Dongyang Zhu; Yifan Zhu; Yu Chen; Qianqian Yan; Han Wu; Chun-Yen Liu; Xu Wang; Lawrence B Alemany; Guanhui Gao; Thomas P Senftle; Yongwu Peng; Xiaowei Wu; Rafael Verduzco

doi:10.1038/s41467-023-38538-x

Three-dimensional covalent organic frameworks with pto and mhq-z topologies based on Tri- and tetratopic linkers

Nat Commun. 2023 May 19;14(1):2865. doi: 10.1038/s41467-023-38538-x.

Authors

Dongyang Zhu^#¹, Yifan Zhu^#², Yu Chen¹, Qianqian Yan², Han Wu³, Chun-Yen Liu¹, Xu Wang⁴, Lawrence B Alemany^{4

5}, Guanhui Gao^{2

4}, Thomas P Senftle¹, Yongwu Peng⁶, Xiaowei Wu⁷, Rafael Verduzco^{8

9}

Affiliations

¹ Department of Chemical and Biomolecular Engineering, Rice University, 6100 Main Street, MS-362, Houston, TX, 77005, USA.
² Department of Materials Science and NanoEngineering, Rice University, 6100 Main Street, MS-325, Houston, TX, 77005, USA.
³ Ganjiang Chinese Medicine Innovation Center, Nanchang, 330000, China.
⁴ Shared Equipment Authority, Rice University, 6100 Main Street, Houston, TX, 77005, USA.
⁵ Department of Chemistry, Rice University, 6100 Main Street, Houston, TX, 77005, USA.
⁶ College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou, 310014, Zhejiang, China.
⁷ Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials, Xiamen Institute of Rare Earth Materials, Fujian Institute of Research on the Structure of Matter, Haixi Institutes, Chinese Academy of Sciences, Xiamen, 361021, China. xmwuxiaowei@fjirsm.ac.cn.
⁸ Department of Chemical and Biomolecular Engineering, Rice University, 6100 Main Street, MS-362, Houston, TX, 77005, USA. rafaelv@rice.edu.
⁹ Department of Materials Science and NanoEngineering, Rice University, 6100 Main Street, MS-325, Houston, TX, 77005, USA. rafaelv@rice.edu.

^# Contributed equally.

Abstract

Three-dimensional (3D) covalent organic frameworks (COFs) possess higher surface areas, more abundant pore channels, and lower density compared to their two-dimensional counterparts which makes the development of 3D COFs interesting from a fundamental and practical point of view. However, the construction of highly crystalline 3D COF remains challenging. At the same time, the choice of topologies in 3D COFs is limited by the crystallization problem, the lack of availability of suitable building blocks with appropriate reactivity and symmetries, and the difficulties in crystalline structure determination. Herein, we report two highly crystalline 3D COFs with pto and mhq-z topologies designed by rationally selecting rectangular-planar and trigonal-planar building blocks with appropriate conformational strains. The pto 3D COFs show a large pore size of 46 Å with an extremely low calculated density. The mhq-z net topology is solely constructed from totally face-enclosed organic polyhedra displaying a precise uniform micropore size of 1.0 nm. The 3D COFs show a high CO₂ adsorption capacity at room temperature and can potentially serve as promising carbon capture adsorbents. This work expands the choice of accessible 3D COF topologies, enriching the structural versatility of COFs.

Abstract

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