Ting Zhou1, Lei Wang2, Xingye Huang1, Junjuda Unruangsri3, Hualei Zhang1, Rong Wang1, Qingliang Song1, Qingyuan Yang4, Weihua Li1, Changchun Wang1, Kaito Takahashi5, Hangxun Xu6, Jia Guo7. 1. State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China. 2. Hefei National Laboratory for Physical Sciences at the Microscale, CAS Key Laboratory of Soft Matter Chemistry, University of Science and Technology of China, Hefei, China. 3. Department of Chemistry, Chulalongkorn University, Bangkok, Thailand. 4. State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, China. 5. Institute of Atomic and Molecular Sciences Academia Sinica, Taipei, Taiwan. kt@gate.sinica.edu.tw. 6. Hefei National Laboratory for Physical Sciences at the Microscale, CAS Key Laboratory of Soft Matter Chemistry, University of Science and Technology of China, Hefei, China. hxu@ustc.edu.cn. 7. State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China. guojia@fudan.edu.cn.
Abstract
Two-dimensional covalent organic frameworks (2D COFs) featuring periodic frameworks, extended π-conjugation and layered stacking structures, have emerged as a promising class of materials for photocatalytic hydrogen evolution. Nevertheless, the layer-by-layer assembly in 2D COFs is not stable during the photocatalytic cycling in water, causing disordered stacking and declined activity. Here, we report an innovative strategy to stabilize the ordered arrangement of layered structures in 2D COFs for hydrogen evolution. Polyethylene glycol is filled up in the mesopore channels of a β-ketoenamine-linked COF containing benzothiadiazole moiety. This unique feature suppresses the dislocation of neighbouring layers and retains the columnar π-orbital arrays to facilitate free charge transport. The hydrogen evolution rate is therefore remarkably promoted under visible irradiation compared with that of the pristine COF. This study provides a general post-functionalization strategy for 2D COFs to enhance photocatalytic performances.
Two-dimensional covalent organic frameworks (2Dn class="Chemical">COFs) featuring periodic frameworks, extended π-conjugation and layered stacking structures, have emerged as a promising class of materials for photocatalytic hydrogen evolution. Nevertheless, the layer-by-layer assembly in 2DCOFs is not stable during the photocatalytic cycling in water, causing disordered stacking and declined activity. Here, we report an innovative strategy to stabilize the ordered arrangement of layered structures in 2DCOFs for hydrogen evolution. Polyethylene glycol is filled up in the mesopore channels of a β-ketoenamine-linked COF containing benzothiadiazole moiety. This unique feature suppresses the dislocation of neighbouring layers and retains the columnar π-orbital arrays to facilitate free charge transport. The hydrogen evolution rate is therefore remarkably promoted under visible irradiation compared with that of the pristine COF. This study provides a general post-functionalization strategy for 2DCOFs to enhance photocatalytic performances.
Authors: Adrien P Côté; Annabelle I Benin; Nathan W Ockwig; Michael O'Keeffe; Adam J Matzger; Omar M Yaghi Journal: Science Date: 2005-11-18 Impact factor: 47.728
Authors: Catherine R DeBlase; Katharine E Silberstein; Thanh-Tam Truong; Héctor D Abruña; William R Dichtel Journal: J Am Chem Soc Date: 2013-10-29 Impact factor: 15.419
Authors: Zhiwei Fu; Xiaoyan Wang; Adrian M Gardner; Xue Wang; Samantha Y Chong; Gaia Neri; Alexander J Cowan; Lunjie Liu; Xiaobo Li; Anastasia Vogel; Rob Clowes; Matthew Bilton; Linjiang Chen; Reiner Sebastian Sprick; Andrew I Cooper Journal: Chem Sci Date: 2019-11-21 Impact factor: 9.825