Two-Dimensional Benzobisthiazole-Vinylene-Linked Covalent Organic Frameworks Outperform One-Dimensional Counterparts in Photocatalysis

Li S, Ma R, Xu S, Zheng T, Wang H, Fu G, Yang H, Hou Y, Liao Z, Wu B, Feng X, Wu LZ, Li XB, Zhang T (2023)

Publication Type: Journal article

Publication year: 2023

Journal

ACS Catalysis American Chemical Society

Book Volume: 13

Pages Range: 1089-1096

Journal Issue: 2

DOI: 10.1021/acscatal.2c05023

Abstract

Vinylene/olefin-linked two-dimensional covalent organic frameworks (v-2D-COFs), featured with vinylene-linked in-plane conjugations, high chemical stabilities, and designable chemical structures, are promising for optoelectronic/photocatalytic applications. Developing v-2D-COFs with superior π-conjugation and optoelectronic properties is meaningful but remains challenging. In this work, we present the crystalline benzobisthiazole-bridged unsubstituted v-2D-COF (v-2D-COF-NS1 and v-2D-COF-NS2) synthesized via a benzothiazole-mediated aldol-type polycondensation. Interestingly, the resultant v-2D-COF exhibits a high chemical stability under both strong acidic (12 M HCl) and basic conditions (saturated KOH) due to the robust vinylene-linked skeletons. Moreover, the electron-deficient thiazole units and 2D π-conjugations endow v-2D-COFs (i.e., v-2D-COF-NS1) a narrow band gap of ∼1.85 eV with a conduction band of −3.65 eV vs vacuum, which are desirable for photocatalytic hydrogen evolution. As such, the v-2D-COF-NS1-based photoelectrode gives a photocurrent up to ∼47 μA cm-2 at 0.3 V vs reversible hydrogen electrode (RHE), which is much higher than the value of the corresponding linear polymer (LP-NS1) and outstanding among the reported COF photoelectrodes. Under a continuous visible light irradiation, v-2D-COF-NS1 generates hydrogen gas with an excellent rate of ∼4.4 mmol h-1 g-1 over 12 h. This work demonstrates the synthesis of unsubstituted v-2D-COFs that intrinsically contain benzobisthiazole-based building blocks and shows great potential in photocatalytic reactions.

Involved external institutions

Zhejiang University of Technology (ZJUT) / 浙江工业大学 CN China (CN) Chinese Academy of Sciences (CAS) / 中国科学院 CN China (CN) Technische Universität Dresden DE Germany (DE) Zhejiang University CN China (CN) Fraunhofer-Institut für Keramische Technologien und Systeme (IKTS) DE Germany (DE)

How to cite

APA:

Li, S., Ma, R., Xu, S., Zheng, T., Wang, H., Fu, G.,... Zhang, T. (2023). Two-Dimensional Benzobisthiazole-Vinylene-Linked Covalent Organic Frameworks Outperform One-Dimensional Counterparts in Photocatalysis. ACS Catalysis, 13(2), 1089-1096. https://doi.org/10.1021/acscatal.2c05023

MLA:

Li, Shengxu, et al. "Two-Dimensional Benzobisthiazole-Vinylene-Linked Covalent Organic Frameworks Outperform One-Dimensional Counterparts in Photocatalysis." ACS Catalysis 13.2 (2023): 1089-1096.

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