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
{"title":"Dipole polarization modulating of vinylene-linked covalent organic frameworks for efficient photocatalytic hydrogen evolution","authors":"","doi":"10.1016/S1872-2067(24)60113-0","DOIUrl":null,"url":null,"abstract":"<div><div>Photocatalytic hydrogen (H<sub>2</sub>) 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 H<sub>2</sub> 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 H<sub>2</sub> production rate of 23.7 mmol g<sup>−1</sup> h<sup>−1</sup>, 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 H<sub>2</sub> evolution and beyond.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":null,"pages":null},"PeriodicalIF":15.7000,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chinese Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1872206724601130","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
引用次数: 0

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.
查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
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。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 去求助
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.
期刊最新文献
Mechanism study on the influence of surface properties on the synthesis of dimethyl carbonate from CO2 and methanol over ceria catalysts Efficient electrocatalytic urea synthesis from CO2 and nitrate over the scale-up produced FeNi alloy-decorated nanoporous carbon Unraveling the roles of atomically-dispersed Au in boosting photocatalytic CO2 reduction and aryl alcohol oxidation Interfacial coordination bonds accelerate charge separation for unprecedented hydrogen evolution over S-scheme heterojunction Activating d10 electronic configuration to regulate p-band centers as efficient active sites for solar energy conversion into H2 by surface atomic arrangement
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1