张素风,李楠,李金瑞.纳米纤维素/金属有机框架复合质子交换膜的制备及性能研究[J].中国造纸,2026,45(2):145-156 本文二维码信息
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纳米纤维素/金属有机框架复合质子交换膜的制备及性能研究
Preparation and Properties of Nanocellulose/Metal Organic Framework Composite Proton Exchange Membranes
收稿日期：2025-09-06  修订日期：2025-11-16
DOI：10.11980/j.issn.0254-508X.2026.02.016
关键词:  纤维素纳米晶体  金属有机框架  原位生长  质子交换膜
Key Words:cellulose nanocrystals  metal organic framework  in situ growth  proton exchange membranes
基金项目:国家自然科学基金（22378247、22078187）；陕西国际科技合作基地生物质化学与材料国际联合研究中心（2018GHJD-19）。
作者单位邮编
张素风* 陕西科技大学轻工科学与工程学院,陕西西安,710021 710021
李楠 陕西科技大学轻工科学与工程学院,陕西西安,710021 710021
李金瑞 陕西科技大学轻工科学与工程学院,陕西西安,710021 710021
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摘要:针对氢燃料电池质子交换膜（PEMs）在高温低湿条件下传导性能骤降，以及在高湿条件下尺寸稳定性不足的挑战，本研究提出一种纳米纤维素基PEMs的构筑策略。首先，通过硫酸水解和高压均质法制备带有磺酸基的纤维素纳米晶体（SCNCs），随后在碳纳米管（CNTs）表面原位生长磺化金属有机框架材料（UIO-66-SO3H），构建具有界面协同效应的杂化填料（S-UIO-66@CNT），最终通过真空抽滤实现SCNC@S-UIO-66@CNT复合膜的自组装。结果表明，该方法不仅有效抑制了S-UIO-66@CNT的团聚，还通过填料的均匀分布构建了连续质子传输通道，使其能够吸附并保留更多水分，显著提升质子传导性能。当S-UIO-66@CNT与SCNCs的质量比为10∶1时，复合膜的拉伸强度为163 MPa，吸水润胀率仅7.1%，质子传导率在80 ℃、100%相对湿度下达150.0 mS/cm，在低湿（33%）条件下仍可保持61.8 mS/cm。
Abstract:To overcome the performance degradation of proton exchange membranes under high-temperature and low-humidity conditions， as well as their inadequate dimensional stability under high humidity， a construction strategy for nanocellulose-based proton exchage membranes (PEMs) was proposed. Sulfonated cellulose nanocrystals were first prepared via sulfuric acid hydrolysis followed by high-pressure homogenization. Subsequently， sulfonated metal-organic frameworks (UiO-66-SO3H) were grown in situ on carbon nanotubes (CNTs) surface to form hybrid fillers (S-UiO-66@CNT) with enhanced interfacial synergy. The SCNC@S-UiO-66@CNT composite membranes were then assembled through vacuum-assisted filtration. The resulting architecture effectively suppressed the aggregation of S-UiO-66@CNT and promoted uniform dispersion of fillers within the SCNCs matrix， thereby constructing continuous proton transport pathways. This hierarchical structure enhanced water adsorption and retention abilities， significantly improving the proton conductivity. At an optimized mass ratio of 10∶1 (S-UiO-66@CNT to SCNCs)， the composite membrane exhibited an outstanding tensile strength of 163 MPa and a remarkably low water swelling ratio of 7.1%. Notably， the proton conductivity reached 150.0 mS/cm at 80 ℃ and 100% relative humidity， and remained as high as 61.8 mS/cm even at 33% relative humidity.
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