用于光催化氢气进化的供体-分子-供体共价有机框架中质子化和共轭作用的双重增强

IF 7.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Huan He, Rongchen Shen, Yuhao Yan, Dejun Chen, Zhixiong Liu, Lei Hao, Xin Zhang, Peng Zhang and Xin Li
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引用次数: 0

摘要

共价有机框架(COF)已成为极具前景的光催化水分离平台。然而,探索不同 COF 系统中的结构-活性关系仍然具有挑战性。本研究精心挑选了三种相对纯净的供体-受体(D-I-D)COFs 作为模型材料,以研究质子化和共轭对光催化 H2 演化机理的影响。与广泛报道的供体-受体(D-A)COF 体系不同,这三种理想的 COF 具有较短的电子通道,并且缺乏化学键异构性和构件中的杂原子。这些方面有利于全面研究亚胺键活性位点的基本机制。计算和实验结果都表明,增加共轭强度可以提高激子解离效率和电荷转移速率。质子化还能显著提高 D-I-D COF 的光吸收能力和电子传输效率。质子化后,具有最佳共轭强度的 Py-hCOF 在可见光下的 H2 演化率高达 44.2 mmol g-1 h-1,是 Tpe-hCOF 的 88.4 倍。这一结果凸显了质子化和共轭同时增强在提高 COF 光催化氢气进化中的关键作用,为设计 COF 材料以实现光催化中的优异电子功能提供了宝贵的启示。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Double enhancement of protonation and conjugation in donor–imine–donor covalent organic frameworks for photocatalytic hydrogen evolution†

Double enhancement of protonation and conjugation in donor–imine–donor covalent organic frameworks for photocatalytic hydrogen evolution†

Double enhancement of protonation and conjugation in donor–imine–donor covalent organic frameworks for photocatalytic hydrogen evolution†

Covalent organic frameworks (COFs) have emerged as highly promising platforms for photocatalytic water splitting. However, exploring the structure–activity relationships in different COF systems remains challenging. In this study, three donor–imine–donor (D–I–D) COFs as relatively pure model materials were carefully selected to investigate the effect of protonation and conjugation on the mechanism of photocatalytic H2 evolution. Unlike widely reported donor–acceptor (D–A) COF systems, these three ideal COFs have short electronic channels and lack chemical bond isomerism and heteroatoms in building blocks. These aspects are beneficial for a comprehensive investigation of the underlying mechanisms at the active sites of the imine bond. Both the calculation and experimental results indicate that increasing the conjugation intensity can enhance the efficiency of exciton dissociation and charge transfer rates. Protonation can also dominantly enhance the light absorption capacity and electron transport efficiency of D–I–D COFs. After protonation, the Py-hCOF with optimal conjugation intensity exhibits a remarkable H2 evolution rate of 44.2 mmol g−1 h−1 under visible light, which is 88.4 times higher than that of Tpe-hCOF. This result highlights the crucial roles of simultaneous enhancement of the protonation and conjugation in improving photocatalytic hydrogen evolution of COFs, providing valuable insights for the design of COF materials to achieve the superior electronic functions in photocatalysis.

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来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
期刊介绍: Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.
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