Yang Shoukun, Zhong Zicheng, Hu Jiarui, Wang Xiaoyan, Tan Bien
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, Wuhan, 430074, China.
Adv Mater. 2024 May;36(19):e2307579. doi: 10.1002/adma.202307579. Epub 2024 Feb 13.
Hyper-cross-linked polymers (HCPs) with ultra-high porosity, superior physicochemical stability, and excellent cost-effectiveness are attractive candidates for methane storage. However, the construction of HCPs with BET surface areas exceeding 3000 m g remains extremely challenging. In this work, a newly developed DBM-knitting method with a slow-knitting rate is employed to increase the cross-linking degree, in which dichloromethane (DCM) is replaced by dibromomethane (DBM) as both solvent and electrophilic cross-linker, resulting in highly porous and physicochemically stable HCPs. The BET surface areas of DBM-knitted SHCPs-Br are 44%-120% higher than that of DCM-knitted SHCPs-Cl using the same building blocks. Remarkably, SHCP-3-Br exhibits an unprecedentedly high porosity (S = 3120 m g) among reported HCPs, and shows a competitive volumetric 5-100 bar working methane capacity of 191 cm (STP) cm at 273 K calculated by using real packing density, which outperforms sate-of-art metal-organic framework (MOFs) at comparable conditions. This facile and versatile low-knitting-rate strategy enables effective improvement in the porosity of HCPs for porosity-desired applications.
具有超高孔隙率、卓越物理化学稳定性和出色性价比的超交联聚合物（HCPs）是极具吸引力的甲烷储存候选材料。然而，构建比表面积超过3000 m²/g的HCPs仍然极具挑战性。在这项工作中，采用了一种新开发的编织速率缓慢的DBM编织方法来提高交联度，其中二氯甲烷（DCM）被二溴甲烷（DBM）取代，作为溶剂和亲电交联剂，从而得到具有高孔隙率和物理化学稳定性的HCPs。使用相同的结构单元，DBM编织的SHCPs-Br的比表面积比DCM编织的SHCPs-Cl高44%-120%。值得注意的是，在已报道的HCPs中，SHCP-3-Br展现出前所未有的高孔隙率（S = 3120 m²/g），并且在273 K下，使用实际堆积密度计算得出，其在5-100 bar工作压力下的甲烷体积储存容量为191 cm³(STP)/cm³，在可比条件下优于目前最先进的金属有机框架（MOF）材料。这种简便且通用的低编织速率策略能够有效提高HCPs的孔隙率，以满足对孔隙率有要求的应用。
