Systematic Tuning and Multifunctionalization of Covalent Organic Polymers for Enhanced Carbon Capture

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• 作者：Zhonghua Xiang ; Rocio Mercado ; Johanna M. Huck ; Hui Wang ; Zhanhu Guo ; Wenchuan Wang ; Dapeng Cao ; Maciej Haranczyk ; Berend Smit
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：October 21, 2015
• 年：2015
• 卷：137
• 期：41
• 页码：13301-13307
• 全文大小：507K
• ISSN：1520-5126

文摘

Porous covalent polymers are attracting increasing interest in the fields of gas adsorption, gas separation, and catalysis due to their fertile synthetic polymer chemistry, large internal surface areas, and ultrahigh hydrothermal stabilities. While precisely manipulating the porosities of porous organic materials for targeted applications remains challenging, we show how a large degree of diversity can be achieved in covalent organic polymers by incorporating multiple functionalities into a single framework, as is done for crystalline porous materials. Here, we synthesized 17 novel porous covalent organic polymers (COPs) with finely tuned porosities, a wide range of Brunauer鈥揈mmett鈥揟eller (BET) specific surface areas of 430鈥?624 m² g^鈥?, and a broad range of pore volumes of 0.24鈥?.50 cm³ g^鈥?, all achieved by tailoring the length and geometry of building blocks. Furthermore, we are the first to successfully incorporate more than three distinct functional groups into one phase for porous organic materials, which has been previously demonstrated in crystalline metal鈥搊rganic frameworks (MOFs). COPs decorated with multiple functional groups in one phase can lead to enhanced properties that are not simply linear combinations of the pure component properties. For instance, in the dibromobenzene-lined frameworks, the bi- and multifunctionalized COPs exhibit selectivities for carbon dioxide over nitrogen twice as large as any of the singly functionalized COPs. These multifunctionalized frameworks also exhibit a lower parasitic energy cost for carbon capture at typical flue gas conditions than any of the singly functionalized frameworks. Despite the significant improvement, these frameworks do not yet outperform the current state-of-art technology for carbon capture. Nonetheless, the tuning strategy presented here opens up avenues for the design of novel catalysts, the synthesis of functional sensors from these materials, and the improvement in the performance of existing covalent organic polymers by multifunctionalization.