Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Luoyu Road No. 1037, Wuhan 430074, Hubei, China.
State Key Laboratory of Digital Manufacturing Equipment and Technology, School of Mechanical Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China.
Sci Adv. 2017 Mar 31;3(3):e1602610. doi: 10.1126/sciadv.1602610. eCollection 2017 Mar.
Two-dimensional (2D) nanomaterials, especially 2D organic nanomaterials with unprecedentedly diverse and controlled structure, have attracted decent scientific interest. Among the preparation strategies, the top-down approach is one of the considered low-cost and scalable strategies to obtain 2D organic nanomaterials. However, some factors of their layered counterparts limited the development and potential applications of 2D organic nanomaterials, such as type, stability, and strict synthetic conditions of layered counterparts. We report a class of layered solvent knitting hyper-cross-linked microporous polymers (SHCPs) prepared by improving Friedel-Crafts reaction and using dichloroalkane as an economical solvent, stable electrophilic reagent, and external cross-linker at low temperature, which could be used as layered counterparts to obtain previously unknown 2D SHCP nanosheets by method of ultrasonic-assisted solvent exfoliation. This efficient and low-cost strategy can produce previously unreported microporous organic polymers with layered structure and high surface area and gas storage capacity. The pore structure and surface area of these polymers can be controlled by tuning the chain length of the solvent, the molar ratio of AlCl, and the size of monomers. Furthermore, we successfully obtain an unprecedentedly high-surface area HCP material (3002 m g), which shows decent gas storage capacity (4.82 mmol g at 273 K and 1.00 bar for CO; 12.40 mmol g at 77.3 K and 1.13 bar for H). This finding provides an opportunity for breaking the constraint of former knitting methods and opening up avenues for the design and synthesis of previously unknown layered HCP materials.
二维（2D）纳米材料，特别是具有前所未有的多样化和可控结构的 2D 有机纳米材料，引起了相当大的科学兴趣。在制备策略中，自上而下的方法是获得 2D 有机纳米材料的一种低成本和可扩展的策略。然而，其层状对应物的一些因素限制了 2D 有机纳米材料的发展和潜在应用，例如层状对应物的类型、稳定性和严格的合成条件。我们报告了一类通过改进 Friedel-Crafts 反应并使用二氯代烷作为经济溶剂、稳定的亲电试剂和低温下的外部交联剂制备的层状溶剂针织超交联微孔聚合物（SHCPs），可以用作层状对应物通过超声辅助溶剂剥离法获得以前未知的 2D SHCP 纳米片。这种高效且低成本的策略可以生产具有层状结构和高表面积和气体存储能力的以前未报道的微孔有机聚合物。通过调节溶剂的链长、AlCl 的摩尔比和单体的大小，可以控制这些聚合物的孔结构和表面积。此外，我们成功地获得了一种前所未有的高表面积 HCP 材料（3002 m g），其气体存储能力表现出色（在 273 K 和 1.00 bar 下 CO 的存储量为 4.82 mmol g；在 77.3 K 和 1.13 bar 下 H 的存储量为 12.40 mmol g）。这一发现为打破以前的编织方法的限制提供了机会，并为设计和合成以前未知的层状 HCP 材料开辟了途径。
