State Key Laboratory of Molecular Engineering of Polymer, Department of Macromolecular Science and Laboratory of Advanced Materials, Fudan University , Shanghai 200433, People's Republic of China.
ACS Appl Mater Interfaces. 2013 Dec 26;5(24):13042-9. doi: 10.1021/am403946z. Epub 2013 Dec 5.
Proton conductivity and methanol permeability are the most important transport properties of proton exchange membranes (PEMs). The ratio of proton conductivity to methanol permeability is usually called selectivity. Herein, a novel strategy of in situ growth of MoS2 is employed to prepare MoS2/Nafion composite membranes for highly selective PEM. The strong interactions between the Mo precursor ((NH4)2MoS4) and Nafion's sulfonic groups in a suitable solvent environment (DMF) probably lead to a selective growth of MoS2 flakes mainly around the ionic clusters of the resultant MoS2/Nafion composite membrane. Therefore, it would significantly promote the aggregation and hence lead to a better connectivity of these ionic clusters, which favors the increase in proton conductivity. Meanwhile, the existence of MoS2 in the ionic channels effectively prevents methanol transporting through the PEM, contributing to the dramatic decrease in the methanol permeability. Consequently, the MoS2/Nafion composite membranes exhibit greatly increased selectivity. Under some severe conditions, such as 50 °C with 80 v/v% of methanol concentration, an increase in the membrane selectivity by nearly 2 orders of magnitude compared with that of the recast Nafion membrane could be achieved here, proving our method as a very promising way to prepare high-performance PEMs. All these conclusions are confirmed by various characterizations, such as (FE-) SEM, TEM, AFM, IR, Raman, TGA, XRD, etc.
质子传导率和甲醇渗透率是质子交换膜(PEM)最重要的传输性质。质子传导率与甲醇渗透率的比值通常称为选择性。在此,采用原位生长 MoS2 的新策略来制备具有高选择性的 PEM 的 MoS2/Nafion 复合膜。在合适的溶剂环境(DMF)中,Mo 前驱体((NH4)2MoS4)与 Nafion 的磺酸基团之间的强相互作用可能导致 MoS2 薄片主要在所得 MoS2/Nafion 复合膜的离子簇周围选择性生长。因此,这将显著促进这些离子簇的聚集,从而导致更好的连通性,有利于质子传导率的提高。同时,MoS2 存在于离子通道中,有效地阻止了甲醇通过 PEM 的传输,导致甲醇渗透率的急剧下降。因此,MoS2/Nafion 复合膜表现出大大提高的选择性。在一些苛刻的条件下,例如 50°C 时甲醇浓度为 80v/v%,与再铸 Nafion 膜相比,复合膜的选择性增加了近 2 个数量级,证明了我们的方法是制备高性能 PEM 的一种很有前途的方法。所有这些结论都通过各种特性分析得到证实,例如(FE-)SEM、TEM、AFM、IR、Raman、TGA、XRD 等。