<br>具有可调双钴协同位点的 1D 共价有机框架，用于高效的 CO2 光还原,Macromolecular Rapid Communications

当前位置： X-MOL 学术 › Macromol. Rapid Commun. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

具有可调双钴协同位点的 1D 共价有机框架，用于高效的 CO2 光还原
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2024-12-27 , DOI: 10.1002/marc.202400780
Shu-Kun Xia ₁ , Yong Liu ₁ , Ruo-Meng Zhu ₁ , Jing-Dong Feng ₁ , Wang-Kang Han ₁ , Zhi-Guo Gu ₁

Affiliation

双原子催化剂通过协同效应增强光催化 CO₂ 还原。然而，精确调节两个催化中心之间的距离以实现协同催化带来了重大挑战。在这项研究中，设计了一系列具有可调节微孔的一维（1D）共价有机框架（COF），以促进高效的 CO₂ 光还原。CO₂ 分子锚定在微孔内的双钴中心之间，从而有效地降低其活化能并启动光催化过程。此外，*COOH 中间体的形成受到双钴位点周围配位微环境的显著影响。值得注意的是，COF-Co-N₄ 表现出显著的 CO₂ 光还原活性，CO 析出速率为 110.3 μmol·^g-1·^h-1，超过了大多数以前报道的单原子位点光催化剂。综合表征和密度泛函理论（DFT）计算表明，具有双钴位点的 1D COF 具有锚定 CO₂ 分子的能力，从而增强协同催化的功效。同时，具有四重氮配位的 COF-Co-N₄ 显著降低了关键的 *COOH 中间体的能垒，促进了高效的光催化 CO₂ 还原。这项研究精心调制了双钴协同位点周围的配位微环境，为高性能光催化剂的设计提供了新的见解。

"点击查看英文标题和摘要"

1D Covalent Organic Frameworks with Tunable Dual-Cobalt Synergistic Sites for Efficient CO2 Photoreduction

Diatomic catalysts enhance photocatalytic CO₂ reduction through synergistic effects. However, precisely regulating the distance between two catalytic centers to achieve synergistic catalysis poses significant challenges. In this study, a series of one-dimensional (1D) covalent organic frameworks (COFs) are designed with adjustable micropores to facilitate efficient CO₂ photoreduction. CO₂ molecules are anchored between dual-cobalt centers within micropores, thus effectively reducing their activation energy and initiating the photocatalytic process. Additionally, the formation of *COOH intermediates is significantly influenced by the coordination microenvironment around dual-cobalt sites. Notably, COF-Co-N₄ exhibited remarkable CO₂ photoreduction activity with a CO evolution rate of 110.3 µmol·g⁻¹·h⁻¹, which surpasses most of previously reported single-atom-site photocatalysts. Comprehensive characterization and density functional theory (DFT) calculations revealed that 1D COFs with dual-cobalt sites possess the ability to anchor CO₂ molecules, thereby enhancing the efficacy of synergistic catalysis. Simultaneously, COF-Co-N₄ with quadruple nitrogen coordination significantly reduced the energy barrier of crucial *COOH intermediate, facilitating efficient photocatalytic CO₂ reduction. This study meticulously modulated the coordination microenvironment surrounding dual-cobalt synergistic sites, providing new insight into the design of high-performance photocatalysts.

更新日期：2024-12-27

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南