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Nano Research 2023, 16(5): 6251-6259 https://doi.org/10.1007/s12274-022-5332-0
Research Article | Issue | Published: 17 November 2022

In-situ polarization of covalent organic frameworks in seawater enables enhanced photocatalytic hydrogen evolution under visible-light irradiation

Show Author's Information Qihong Yue§,  Guoqing Li§,  Ping Fu,  Biao Meng,  Fangpei Ma,  Yu Zhou( ),  Jun Wang( )
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, China

§ Qihong Yue and Guoqing Li contributed equally to this work.

Keywords:
photocatalysis, hydrogen evolution reaction, covalent organic frameworks, seawater polarization
Topics:
Photocatalysis
Cite this article:
Yue Q, Li G, Fu P, et al. In-situ polarization of covalent organic frameworks in seawater enables enhanced photocatalytic hydrogen evolution under visible-light irradiation. Nano Research, 2023, 16(5): 6251-6259. https://doi.org/10.1007/s12274-022-5332-0
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Abstract Full text About this article

Photocatalytic hydrogen (H2) production from seawater over a photocatalyst is of great significance for the utilization of theearth’s abundant seawater resources and the storage of inexhaustible solar energy with low-energy density. However, the designation of efficient photocatalytic systems by using seawater usually suffers from activation decline when replacing pure water with seawater. Herein, we synthesized three β-ketoenamine-linked covalent organic frameworks (COFs), demonstrating their promotion in the photocatalytic decomposition of seawater relative to pure water under visible-light irradiation. The target COFs were synthesized via a microwave assisted solvothermal method by using 1,3,5-triformylphloroglucinol (Tp) as the aldehyde monomer to react with diamino units with different numbers of benzene rings. By surveying the building blocks, the constructed COF with a high density of β-ketoenamine units exhibited the so far highest photocatalytic H2 evolution rate (41.3 mmol·g−1·h−1) in seawater, about 1.66 times higher than that in pure water. The β-ketoenamine units allowed the in-situ polarization of the COF framework through the adsorption of metal salts when proceeding with the photocatalytic H2 production in seawater. This polarization effect significantly increases the dielectric constant of the organic semiconductor to lower exciton dissociation energy and thus enhances the charge separation and transfer to promote the H2 photoproduction in seawater.


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In-situ polarization of covalent organic frameworks in seawater enables enhanced photocatalytic hydrogen evolution under visible-light irradiation

Show Author's information Qihong Yue§, Guoqing Li§, Ping Fu, Biao Meng, Fangpei Ma, Yu Zhou( ), Jun Wang( )
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, China

§ Qihong Yue and Guoqing Li contributed equally to this work.

Abstract

Photocatalytic hydrogen (H2) production from seawater over a photocatalyst is of great significance for the utilization of theearth’s abundant seawater resources and the storage of inexhaustible solar energy with low-energy density. However, the designation of efficient photocatalytic systems by using seawater usually suffers from activation decline when replacing pure water with seawater. Herein, we synthesized three β-ketoenamine-linked covalent organic frameworks (COFs), demonstrating their promotion in the photocatalytic decomposition of seawater relative to pure water under visible-light irradiation. The target COFs were synthesized via a microwave assisted solvothermal method by using 1,3,5-triformylphloroglucinol (Tp) as the aldehyde monomer to react with diamino units with different numbers of benzene rings. By surveying the building blocks, the constructed COF with a high density of β-ketoenamine units exhibited the so far highest photocatalytic H2 evolution rate (41.3 mmol·g−1·h−1) in seawater, about 1.66 times higher than that in pure water. The β-ketoenamine units allowed the in-situ polarization of the COF framework through the adsorption of metal salts when proceeding with the photocatalytic H2 production in seawater. This polarization effect significantly increases the dielectric constant of the organic semiconductor to lower exciton dissociation energy and thus enhances the charge separation and transfer to promote the H2 photoproduction in seawater.

Keywords: photocatalysis, hydrogen evolution reaction, covalent organic frameworks, seawater polarization

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Publication history
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Acknowledgements

Publication history

Received: 26 August 2022
Revised: 01 November 2022
Accepted: 16 November 2022
Published: 17 November 2022
Issue date: May 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

The authors are thankful for funding from the National Natural Science Foundation of China (Nos. 22072065, 22178162, and 22222806), the Distinguished Youth Foundation of Jiangsu Province (No. BK20220053), and the Six Talent Peaks Project in Jiangsu Province (No. JNHB-035). The High-Performance Computing Center of Nanjing Tech University is grateful for its computational support.

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