磺化来瓦希尔骨架(MIL-101(Cr)-SO<sub>3</sub>H)/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

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

1.
郑州轻工业学院材料与化学工程学院, 郑州 450001;
2.
河南省化工分离过程强化工程技术研究中心, 郑州 450001

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）

详细信息

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
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出版历程
- 收稿日期: 2019-03-05
- 刊出日期: 2020-03-14

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

1.
School of Materials and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450001, China;
2.
Henan Engineering Research Center of Chemical Engineering Separation Process Intensification, Zhengzhou 450001, China

摘要

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%。
- 合成 /
- 制备 /
- 杂化 /
- 燃料电池 /
- 质子交换膜
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).
- synthesis /
- preparation /
- hybrid /
- fuel cell /
- proton exchange membrane