Direct Construction of Isomeric Benzobisoxazole-Vinylene-Linked Covalent Organic Frameworks with Distinct Photocatalytic Properties

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Shengxu Li - , CAS - Ningbo Institute of Material Technology and Engineering (Author)
  • Rui Ma - , CAS - Technical Institute of Physics and Chemistry (Author)
  • Shunqi Xu - , Chair of Molecular Functional Materials (cfaed) (Author)
  • Tianyue Zheng - , CAS - Ningbo Institute of Material Technology and Engineering (Author)
  • Guangen Fu - , CAS - Ningbo Institute of Material Technology and Engineering (Author)
  • Yanling Wu - , CAS - Ningbo Institute of Material Technology and Engineering (Author)
  • Zhongquan Liao - , Fraunhofer Institute for Ceramic Technologies and Systems (Author)
  • Yongbo Kuang - , CAS - Ningbo Institute of Material Technology and Engineering (Author)
  • Yang Hou - , Zhejiang University (Author)
  • Dashuai Wang - , Quzhou University (Author)
  • Petko Stoev Petkov - , Sofia University St. Kliment Ohridski (Author)
  • Kristina Simeonova - , Sofia University St. Kliment Ohridski (Author)
  • Xinliang Feng - , Chair of Molecular Functional Materials (cfaed) (Author)
  • Li Zhu Wu - , CAS - Technical Institute of Physics and Chemistry (Author)
  • Xu Bing Li - , CAS - Technical Institute of Physics and Chemistry (Author)
  • Tao Zhang - , CAS - Ningbo Institute of Material Technology and Engineering (Author)

Abstract

Vinylene/olefin-linked two-dimensional covalent organic frameworks (v-2D-COFs) have emerged as advanced semiconducting materials with excellent in-plane conjugation, high chemical stabilities, and precisely tunable electronic structures. Exploring new linkage chemistry for the reticular construction of v-2D-COFs remains in infancy and challenging. Herein, we present a solid-state benzobisoxazole-mediated aldol polycondensation reaction for the construction of two novel isomeric benzobisoxazole-bridged v-2D-COFs (v-2D-COF-NO1 and v-2D-COF-NO2) with trans and cis configurations of benzobisoxazole. Interestingly, the isomeric benzobisoxazole linkers endow the two v-2D-COFs with distinct optoelectronic and electrochemical properties, ranging from light absorption and emission to charge-transfer properties. When employed as the photocathode, v-2D-COF-NO1 exhibits a photocurrent of up to ∼18 μA/cm2under AM 1.5G irradiation at -0.3 V vs reversible hydrogen electrode (RHE), which is twice the value of v-2D-COF-NO2 (∼9.1 μA/cm2). With Pt as a cocatalyst, v-2D-COF-NO1 demonstrates a photocatalytic hydrogen evolution rate of ∼1.97 mmol h-1g-1, also in clear contrast to that of v-2D-COF-NO2 (∼0.86 mmol h-1g-1) under identical conditions. This work demonstrates the synthesis of v-2D-COFs via benzobisoxazole-mediated aldol polycondensation with isomeric structures and distinct photocatalytic properties.

Details

Original languageEnglish
Pages (from-to)13953-13960
Number of pages8
JournalJournal of the American Chemical Society
Volume144
Issue number30
Publication statusPublished - 3 Aug 2022
Peer-reviewedYes

External IDs

PubMed 35877552

Keywords