Liu Jing, Li Heguo, Yan Bin, Zhong Chao, Zhao Yue, Guo Xuan, Zhong Jinyi
State Key Laboratory of NBC Protection for Civilian, Institute of Chemical Defense, Beijing100191, China.
National Engineering Laboratory for Clean Technology of Leather Manufacture, College of Biomass Science and Engineering, Sichuan University, Chengdu610065, China.
ACS Appl Mater Interfaces. 2022 Nov 30;14(47):53421-53432. doi: 10.1021/acsami.2c16711. Epub 2022 Nov 16.
Developing high-performance protective materials is important for soldiers and civilians who are exposed to the atmosphere of highly toxic chemical warfare agents (CWAs). Polyelectrolyte membranes are promising candidates with excellent chemical resistance and moisture permeability, but they cannot efficiently degrade CWAs. Here, we design and prepare a hybrid membrane through growth of catalytically active zirconium-based metal-organic frameworks (Zr-MOFs) on a polyelectrolyte membrane mediated by biofilm-inspired curli nanofibers (CNFs). Superior to the bare polyelectrolyte membrane, the prepared MOF-808@CNF-PQ hybrid membrane exhibits improved rejection of the nerve agent simulant dimethyl methyl phosphonate (DMMP) vapor and permeation of the water vapor by 113 and 45%, respectively. The water/DMMP selectivity of the hybrid membrane reaches 498.6, approximately 13 times that of the commercial polyelectrolyte membrane Nafion 117. In addition, the hybrid membrane possesses appreciable catalytic activity for the hydrolysis of the nerve agent simulant dimethyl 4-nitrophenyl phosphate (DMNP) with a half-life of ∼38 min. Nanomechanical characterization results based on atomic force microscopy (AFM) techniques demonstrate the critical role of CNFs in mediating Zr-MOF nucleation and the dominant effect of electrostatic interactions on self-assembly of CNFs on polyelectrolyte base. It is also confirmed that the Zr-MOF toppings serve as the key components in physically adsorbing and chemically degrading the DMNP molecules through multiple strong intermolecular interactions. Our work offers a rational strategy to develop advanced membranes toward efficient chemical protection, moisture permeation, and catalytic detoxification against CWAs.
开发高性能防护材料对于暴露于剧毒化学战剂（CWA）环境中的士兵和平民来说至关重要。聚电解质膜是具有优异耐化学性和透湿性的有前途的候选材料，但它们不能有效地降解CWA。在此，我们通过在受生物膜启发的卷曲纳米纤维（CNF）介导的聚电解质膜上生长具有催化活性的锆基金属有机框架（Zr-MOF）来设计和制备一种混合膜。与裸露的聚电解质膜相比，制备的MOF-808@CNF-PQ混合膜对神经毒剂模拟物甲基膦酸二甲酯（DMMP）蒸汽的截留率提高，水蒸气渗透率分别提高了113%和45%。混合膜的水/DMMP选择性达到498.6，约为商业聚电解质膜Nafion 117的13倍。此外，该混合膜对神经毒剂模拟物对硝基苯基磷酸二甲酯（DMNP）的水解具有可观的催化活性，半衰期约为38分钟。基于原子力显微镜（AFM）技术的纳米力学表征结果表明，CNF在介导Zr-MOF成核中起关键作用，静电相互作用对CNF在聚电解质基底上的自组装起主导作用。还证实，Zr-MOF涂层通过多种强分子间相互作用作为物理吸附和化学降解DMNP分子的关键成分。我们的工作为开发针对CWA的高效化学防护、透湿和催化解毒的先进膜提供了一种合理的策略。
