β-Ketoenamine-Linked Covalent Organic Frameworks Capable of Pseudocapacitive Energy Storage
β-Ketoenamine-Linked Covalent Organic Frameworks Capable of Pseudocapacitive Energy Storage
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DOI：
10.1021/ja409421d
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发表时间：
2013-11-13
影响因子：
15
通讯作者：
Dichtel, William R.
中科院分区：
文献类型：
--
作者：
DeBlase, Catherine R.;Silberstein, Katharine E.;Dichtel, William R.
二维共价有机框架（2D COFs）是电荷存储设备的候选材料，因为它们具有微孔或介孔结构、高比表面积以及可预测地组织氧化还原活性基团的能力。已有的COF连接键（如硼氧环和硼酸酯）化学稳定性和氧化稳定性有限，这阻碍了这些应用，并且没有二维COF表现出可逆的氧化还原行为。在此，我们描述了一种β - 酮烯胺连接的二维COF，其蒽醌亚单元表现出可逆的电化学过程，对强酸性电解质具有优异的化学稳定性，并且是亚胺或烯胺连接的二维COF中比表面积最高的材料之一。用具有氧化还原活性的COF修饰的电极比用类似的无氧化还原活性的COF修饰的电极显示出更高的电容，即使在5000次充放电循环之后也是如此。这些发现证明了将二维COFs用于电容存储的前景。
Two-dimensional covalent organic frameworks (2D COFs) are candidate materials for charge storage devices because of their micro- or mesoporosity, high surface area, and ability to predictably organize redox-active groups. The limited chemical and oxidative stability of established COF linkages, such as boroxines and boronate esters, precludes these applications, and no 2D COF has demonstrated reversible redox behavior. Here we describe a beta-ketoenamine-linked 2D COF that exhibits reversible electrochemical processes of its anthraquinone subunits, excellent chemical stability to a strongly acidic electrolyte, and one of the highest surface areas of the imine- or enamine-linked 2D COFs. Electrodes modified with the redox-active COF show higher capacitance than those modified with a similar non-redox-active COF, even after 5000 charge discharge cycles. These findings demonstrate the promise of using 2D COFs for capacitive storage.