SPES-C/MIL-53(Al)-SO3H杂化质子交换膜的制备和性能

用水热合成法制备MIL-53(Al)，然后用后磺化法在其笼状结构中引入磺酸基团得到MIL-53(Al)-SO₃H纳米级金属有机框架(MOF)多孔晶体材料，最后将MIL-53(Al)-SO₃H掺杂到磺化酚酞侧基聚芳醚砜(SPES-C)高分子相中制备出一系列SPES-C/MIL-53(Al)-SO₃H燃料电池用杂化质子交换膜(PEM)。扫描电镜观测结果表明，杂化质子交换膜内没有缺陷，MIL-53(Al)-SO₃H在膜内分散均匀且两相的相容性好。热重分析结果证实，杂化膜具有优良的热稳定性。MIL-53(Al)-SO₃H的加入，提高了杂化膜的吸水率、尺寸稳定性和质子传导率。在温度为80℃时填充量为5%（质量分数）的杂化膜其M-5的质子传导率达到0.15 S·cm^-1，比纯SPES-C膜提高了32.5%且优于商用Nafion膜的质子传导率(0.134 S·cm^-1)。

Preparation and Properties of Hybrid Proton Exchange Membranes of SPES-C/MIL-53(Al)-SO3H

MIL-53(Al) was synthesized through hydrothermal synthesis, then sulfonic groups were introduced into MIL-53(Al) cages by sulfonation reaction to obtain MIL-53(Al)-SO₃H with proton conduction property. The post-synthetic MIL-53(Al)-SO₃H was incorporated into sulfonated polyarylethersulfone with cardo (SPES-C) polymer matrix to form hybrid PEMs. SEM results show that MIL-53(Al)-SO₃H dispersed uniformly in SPES-C phase and no obvious interfacial defects in membranes could be observed. The TGA analysis confirmed that the membranes of PEMs have excellent thermal stability. The water uptake was enhanced with embedding MIL-53(Al)-SO₃H and it presented positive correlation with composition. The incorporation of MIL-53(Al)-SO₃H also inhibited the swelling ratio, indicating the excellent dimensional stability of the as-prepared hybrid PEMs. The hybrid PEMs also showed encouraging proton conductivity. The proton conductivity of the hybrid PEMs with incorporation amount of 5% (in mass fraction) MIL-53(Al)-SO₃H reached to 0.15 S·cm^-1, which was 32.5% higher than that of the pristine SPES-C membrane, and exceeded that of the ordinary commercial Nafion membrane (0.134 S·cm^-1).