磺化来瓦希尔骨架(MIL-101(Cr)-SO3H)/磺化酚酞侧基聚芳醚砜杂化质子交换膜的制备及性能

韩光鲁, 陈哲, 蔡立芳, 张永辉, 张学波, 马环环, 冯明煦

韩光鲁, 陈哲, 蔡立芳, 等. 磺化来瓦希尔骨架(MIL-101(Cr)-SO3H)/磺化酚酞侧基聚芳醚砜杂化质子交换膜的制备及性能[J]. 复合材料学报, 2020, 37(3): 504-511. DOI: 10.13801/j.cnki.fhclxb.20190505.001
引用本文: 韩光鲁, 陈哲, 蔡立芳, 等. 磺化来瓦希尔骨架(MIL-101(Cr)-SO3H)/磺化酚酞侧基聚芳醚砜杂化质子交换膜的制备及性能[J]. 复合材料学报, 2020, 37(3): 504-511. DOI: 10.13801/j.cnki.fhclxb.20190505.001
HAN Guanglu, CHEN Zhe, CAI Lifang, et al. Preparation and properties of sulfonated lavoisier framework(MIL-101(Cr)-SO3H)/sulfonated polyarylethersulfone with cardo hybrid proton exchange membranes[J]. Acta Materiae Compositae Sinica, 2020, 37(3): 504-511. DOI: 10.13801/j.cnki.fhclxb.20190505.001
Citation: HAN Guanglu, CHEN Zhe, CAI Lifang, et al. Preparation and properties of sulfonated lavoisier framework(MIL-101(Cr)-SO3H)/sulfonated polyarylethersulfone with cardo hybrid proton exchange membranes[J]. Acta Materiae Compositae Sinica, 2020, 37(3): 504-511. DOI: 10.13801/j.cnki.fhclxb.20190505.001

磺化来瓦希尔骨架(MIL-101(Cr)-SO3H)/磺化酚酞侧基聚芳醚砜杂化质子交换膜的制备及性能

基金项目: 国家自然科学基金青年基金(21606211);国家自然科学基金(21771166);河南省科技计划基础与前沿技术研究计划(152300410127);河南省高等学校大学生创新训练计划项目;郑州轻工业学院博士科研基金(2014BSJJ056)
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    通讯作者:

    韩光鲁,博士,讲师,硕士生导师,研究方向为功能膜材料的制备和应用,E-mail:2014115@zzuli.edu.cn

  • 中图分类号: TB332

Preparation and properties of sulfonated lavoisier framework(MIL-101(Cr)-SO3H)/sulfonated polyarylethersulfone with cardo hybrid proton exchange membranes

  • 摘要: 应用水热合成法制备了来瓦希尔骨架材料(MIL-101(Cr)),通过后磺化法将磺酸(SO3H)基团引入MIL-101(Cr)的笼状结构中,得到具有质子传导功能的MIL-101(Cr)-SO3H。FTIR结果表明,磺酸基团成功引入到MIL-101(Cr)中。SEM和XRD结果表明,磺化前后材料的粒径在纳米尺寸范围,且MIL-101(Cr)-SO3H颗粒的晶体结构无坍塌。元素分析结果表明,MIL-101(Cr)-SO3H的磺化度为0.36。然后将MIL-101(Cr)-SO3H掺杂到磺化酚酞侧基聚芳醚砜(SPES-C)中制备了MIL-101(Cr)-SO3H/SPES-C燃料电池用杂化质子交换膜。SEM结果说明,MIL-101(Cr)-SO3H/SPES-C杂化膜内MIL-101(Cr)-SO3H分散均匀,SPES-C与MIL-101(Cr)-SO3H两相相容性较好,膜内无缺陷。TGA分析结果表明,MIL-101(Cr)-SO3H/SPES-C杂化膜热稳定性优良。MIL-101(Cr)-SO3H的引入可以提高MIL-101(Cr)-SO3H/SPES-C杂化膜吸水率并降低甲醇渗透性。随填充物MIL-101(Cr)-SO3H的含量增加和测试温度升高,MIL-101(Cr)-SO3H/SPES-C杂化膜的质子传导率随之增大。当温度为80℃时,MIL-101(Cr)-SO3H填充量为5wt%的MIL-101(Cr)-SO3H/SPES-C杂化膜的质子传导率达到0.162 S·cm-1,比商用Nafion膜的质子传导率(0.134 S·cm-1)提高了20.1%。
    Abstract: The material of institute lavoisier framework (MIL-101(Cr)) was synthesized through hydrothermal synthesis. Then sulfonic groups (SO3H) were introduced into cages of MIL-101(Cr) by post sulfonation reaction to obtain MIL-101(Cr)-SO3H with proton conduction property. FTIR results confirm the successful introduction of sulfonic groups to MIL-101(Cr). SEM and XRD results indicate that the particle size of MIL-101(Cr) and MIL-101(Cr)-SO3H are in the range of nanometer scale, and no crystal structural collapse can be observed for as-prepared MIL-101(Cr)-SO3H. The elemental analysis shows that the sulfonation degree of MIL-101(Cr)-SO3H is 0.36. Then MIL-101(Cr)-SO3H is embedded into sulfonated polyarylethersulfone with cardo (SPES-C) to obtain a series of MIL-101(Cr)-SO3H/SPES-C hybrid proton exchange membranes for fuel cell application. SEM characterization demonstrates that MIL-101(Cr)-SO3H is uniformly dispersed in the MIL-101(Cr)-SO3H/SPES-C hybrid membrane. SPES-C and MIL-101(Cr)-SO3H show good compatibility and no interfacial defects appear in the MIL-101(Cr)-SO3H/SPES-C hybrid membranes. TGA analysis results show that the thermal stability of MIL-101(Cr)-SO3H/SPES-C hybrid membranes is excellent. The introduction of MIL-101(Cr)-SO3H enhances the water uptake of MIL-101(Cr)-SO3H/SPES-C hybrid membranes and reduces the methanol permeability. The proton conductivity of MIL-101(Cr)-SO3H/SPES-C hybrid membranes increases with increasing MIL-101(Cr)-SO3H mass fraction and testing temperature. When mass fraction of MIL-101(Cr)-SO3H is 5wt%, the proton conductivity of MIL-101(Cr)-SO3H/SPES-C hybrid membrane reaches to 0.162 S·cm-1 at 80℃, which is 20.1% higher than that of the commercial Nafion membrane (0.134 S·cm-1).
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出版历程
  • 收稿日期:  2019-03-05
  • 刊出日期:  2020-03-14

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