School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory of Electrical Insulation and Thermal Ageing, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai200240, China.
Center for Advancing Electronics Dresden (CFAED) & Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Mommsenstrasse 4, Dresden01069, Germany.
J Am Chem Soc. 2022 Aug 31;144(34):15497-15508. doi: 10.1021/jacs.2c02881. Epub 2022 Aug 18.
Bicontinuous porous materials, which possess 3D interconnected pore channels facilitating a smooth mass transport, have attracted much interest in the fields of energy and catalysis. However, their synthesis remains very challenging. We report a general approach, using polymer cubosomes as the template, for the controllable synthesis of bicontinuous porous polymers with an ordered single primitive (SP) cubic structure, including polypyrrole (SP-PPy), poly--phenylenediamine (SP-PmPD), and polydopamine (SP-PDA). Specifically, the resultant SP-PPy had a unit cell parameter of 99 nm, pore diameter of 45 nm, and specific surface area of approximately 60 m·g. As a proof of concept, the I-adsorbed SP-PPy was employed as the cathode materials of newly emerged Na-I batteries, which delivered a record-high specific capacity (235 mA·h·g at 0.5 C), excellent rate capability, and cycling stability (with a low capacity decay of 0.12% per cycle within 400 cycles at 1 C). The advantageous contributions of the bicontinuous structure and I adsorption mechanism of SP-PPy were revealed by a combination of ion diffusion experiments and theoretical calculations. This study opens a new avenue for the synthesis of porous polymers with new topologies, broadens the spectrum of bicontinuous-structured materials, and also develops a novel potential application for porous polymers.
双连续多孔材料具有 3D 相互连接的孔道,有利于物质的顺利传输,因此在能源和催化领域引起了广泛的关注。然而,它们的合成仍然极具挑战性。我们报告了一种通用方法,使用聚合物立方相作为模板,可控合成具有有序单原胞(SP)立方结构的双连续多孔聚合物,包括聚吡咯(SP-PPy)、聚对苯二胺(SP-PmPD)和聚多巴胺(SP-PDA)。具体来说,所得的 SP-PPy 的单元晶胞参数为 99nm,孔径为 45nm,比表面积约为 60m·g。作为概念验证,吸附 I 的 SP-PPy 被用作新兴的 Na-I 电池的阴极材料,其比容量高达 235mA·h·g(在 0.5C 下),具有优异的倍率性能和循环稳定性(在 1C 下 400 次循环内的容量衰减率低至 0.12%)。通过离子扩散实验和理论计算的结合,揭示了 SP-PPy 的双连续结构和 I 吸附机制的优势贡献。这项研究为具有新拓扑结构的多孔聚合物的合成开辟了新途径,拓宽了双连续结构材料的范围,并为多孔聚合物开发了一种新的潜在应用。