<br>定制 COF：通过聚吡咯层间编织将非导电 2D 分层 COF 转变为导电准 3D 架构,Journal of the American Chemical Society

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定制 COF：通过聚吡咯层间编织将非导电 2D 分层 COF 转变为导电准 3D 架构
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-12-29 , DOI: 10.1021/jacs.3c09937
Chitvan Jain , Rinku Kushwaha , Deepak Rase , Pragalbh Shekhar , Ankita Shelke ₁ , Disha Sonwani , Thalasseril G Ajithkumar ₁ , Chathakudath Prabhakaran Vinod ₂ , Ramanathan Vaidhyanathan

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提高共价有机框架（COF）的电子传导性和结构稳健性至关重要。在这里，我们将 2D COF 与聚吡咯 (Ppy) 链共价交联，形成准 3D COF。 3D COF 在 SAED 图案中显示出明确的反射，明显索引到其建模的晶体结构。这种具有共轭聚吡咯单元的 2D COF 层的编织将电子电导率从 10 ^–9提高到 10 ^–2 S m ^–1 。 3D COF 中费米能级附近的态密度的存在证实了这种电导率的提高，并且相对于母体 2D 吡咯功能化 COF，这将 COF 的价带最大值提高了 0.52 eV，这与光电非常吻合。电带隙。 HOMO 升高的程度表明主要存在极化子态（自由基阳离子），从而产生强烈的 EPR 信号，很可能源自交联聚吡咯链。用 COF20-Ppy 设计的超级电容器记录了 377.6 mF cm ^–2的高面积电容，高于负载非共价连接的聚吡咯链的 COF 的面积电容。因此，聚吡咯充当跨层的“共轭桥”，降低带隙并提供极化子和额外的传导路径。这标志着将许多 2D COF 转换为高度有序且导电的 3D COF 的一种影响深远的方法。

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Tailoring COFs: Transforming Nonconducting 2D Layered COF into a Conducting Quasi-3D Architecture via Interlayer Knitting with Polypyrrole

Improving the electronic conductivity and the structural robustness of covalent organic frameworks (COFs) is paramount. Here, we covalently cross-link a 2D COF with polypyrrole (Ppy) chains to form a quasi-3D COF. The 3D COF shows well-defined reflections in the SAED patterns distinctly indexed to its modeled crystal structure. This knitting of 2D COF layers with conjugated polypyrrole units improves electronic conductivity from 10^–9 to 10^–2 S m^–1. This conductivity boost is affirmed by the presence of density of states near the Fermi level in the 3D COF, and this elevates the COF’s valence band maximum by 0.52 eV with respect to the parent 2D pyrrole-functionalized COF, which agrees well with the opto–electro band gaps. The extent of HOMO elevation suggests the predominant existence of a polaron state (radical cation), giving rise to a strong EPR signal, most likely sourced from the cross-linking polypyrrole chains. A supercapacitor devised with COF20-Ppy records a high areal capacitance of 377.6 mF cm^–2, higher than that of the COF loaded with noncovalently linked polypyrrole chains. Thus, the polypyrrole acts as a “conjugation bridge” across the layers, lowering the band gap and providing polarons and additional conduction pathways. This marks a far-reaching approach to converting many 2D COFs into highly ordered and conducting 3D ones.

更新日期：2023-12-29

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