Dipole polarization modulating of vinylene-linked covalent organic frameworks for efficient photocatalytic hydrogen evolution

IF 15.7 1区 化学 Q1 CHEMISTRY, APPLIED Chinese Journal of Catalysis Pub Date : 2024-10-01 DOI:10.1016/S1872-2067(24)60113-0
Ming Wang , Yaling Li , Dengxin Yan , Hui Hu , Yujie Song , Xiaofang Su , Jiamin Sun , Songtao Xiao , Yanan Gao
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Abstract

Photocatalytic hydrogen (H2) evolution using covalent organic frameworks (COFs) is an attractive and promising avenue for exploration, but one of its big challenges is low photo-induced charge separation. In this study, we present a straightforward and facile dipole polarization engineering strategy to enhance charge separation efficiency, achieved through atomic modulation (O, S, and Se) of the COF monomer. Our findings demonstrate that incorporating atoms with varying electronegativities into the COF matrix significantly influences the local dipole moment, thereby affecting charge separation efficiency and photostability, which in turn affects the rates of photocatalytic H2 evolution. As a result, the newly developed TMT-BO-COF, which contains highly electronegative O atoms, exhibits the lowest exciton binding energy, the highest efficiency in charge separation and transportation, and the longest lifetime of the active charges. This leads to an impressive average H2 production rate of 23.7 mmol g−1 h−1, which is 2.5 and 24.5 times higher than that of TMT-BS-COF (containing S atoms) and TMT-BSe-COF (containing Se atoms), respectively. A novel photocatalytic hydrogen evolution mechanism based on proton-coupled electron transfer on N in the structure of triazine rings in vinylene-linked COFs is proposed by theoretical calculations. Our findings provide new insights into the design of highly photoactive organic framework materials for H2 evolution and beyond.
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调节乙烯基连接共价有机框架的偶极极化以实现高效光催化氢进化
利用共价有机框架(COFs)进行光催化氢(H2)进化是一条极具吸引力和前景的探索之路,但其面临的一大挑战是光诱导电荷分离率低。在本研究中,我们提出了一种简单易行的偶极子极化工程策略,通过对 COF 单体进行原子调制(O、S 和 Se)来提高电荷分离效率。我们的研究结果表明,在 COF 基体中加入电负性不同的原子会显著影响局部偶极矩,从而影响电荷分离效率和光稳定性,进而影响光催化 H2 演化的速率。因此,新开发的含有高电负性 O 原子的 TMT-BO-COF 具有最低的激子结合能、最高的电荷分离和传输效率以及最长的活性电荷寿命。这使得平均产氢率达到惊人的 23.7 mmol g-1 h-1,分别是 TMT-BS-COF(含 S 原子)和 TMT-BSe-COF(含 Se 原子)的 2.5 倍和 24.5 倍。通过理论计算,我们提出了一种新型光催化氢进化机制,该机制基于乙烯基连接的 COF 中三嗪环结构中 N 上的质子耦合电子转移。我们的研究结果为设计用于氢气进化及其他用途的高光活性有机框架材料提供了新的见解。
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来源期刊
Chinese Journal of Catalysis
Chinese Journal of Catalysis 工程技术-工程:化工
CiteScore
25.80
自引率
10.30%
发文量
235
审稿时长
1.2 months
期刊介绍: The journal covers a broad scope, encompassing new trends in catalysis for applications in energy production, environmental protection, and the preparation of materials, petroleum chemicals, and fine chemicals. It explores the scientific foundation for preparing and activating catalysts of commercial interest, emphasizing representative models.The focus includes spectroscopic methods for structural characterization, especially in situ techniques, as well as new theoretical methods with practical impact in catalysis and catalytic reactions.The journal delves into the relationship between homogeneous and heterogeneous catalysis and includes theoretical studies on the structure and reactivity of catalysts.Additionally, contributions on photocatalysis, biocatalysis, surface science, and catalysis-related chemical kinetics are welcomed.
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