Delft University of Technology , Department of Chemical Engineering , Van der Maasweg 9 , 2629 HZ Delft , The Netherlands.
Wetsus-European centre of excellence for sustainable water technology , Oostergoweg 9 , 8932 PG Leeuwarden , The Netherlands.
Environ Sci Technol. 2019 Mar 5;53(5):2396-2404. doi: 10.1021/acs.est.8b05558. Epub 2018 Dec 21.
In this study, the preparation of a new, functional anion-exchange membrane (AEM), containing guanidinium groups as the anion-exchanging sites (Gu-100), is described as well as the membrane characterization by XPS, water uptake, permselectivities, and electrical resistances. The functional membrane was also employed in pH-dependent electrodialysis experiments using model dairy wastewater streams. The properties of the new membrane are compared to those of a commercially available anion-exchange membrane bearing conventional quaternary ammonium groups (Gu-0). Guanidinium was chosen for its specific binding properties toward oxyanions: e.g., phosphate. This functional moiety was covalently coupled to an acrylate monomer via a facile two-step synthesis to yield bulk-modified membranes upon polymerization. Significant differences were observed in the electrodialysis experiments for Gu-0 and Gu-100 at pH 7, showing an enhanced phosphate and citrate transport for Gu-100 in comparison to Gu-0. At pH 10 the difference is much more pronounced: for Gu-0 membranes almost no phosphate and citrate transport could be detected, while the Gu-100 membranes transported both ions significantly. We conclude that having guanidinium groups as anion-exchange sites improves the selectivity of AEMs. As the presented monomer synthesis strategy is modular, we consider the implementation of functional groups into a polymer-based membrane via the synthesis of tailor-made monomers as an important step toward selective ion transport, which is relevant for various fields, including water treatment processes and fuel cells.
在这项研究中,描述了一种新的、功能化的阴离子交换膜(AEM)的制备,其中含有胍基团作为阴离子交换位点(Gu-100),并通过 XPS、吸水率、选择渗透性和电阻进行了膜表征。该功能膜还用于 pH 依赖性电渗析实验,使用模型乳制品废水。将新膜的性能与具有传统季铵基团的商业可用阴离子交换膜(Gu-0)进行了比较。胍因其对氧阴离子(如磷酸盐)的特殊结合特性而被选中。该官能团通过简便的两步合成与丙烯酰胺单体共价偶联,聚合后得到本体改性膜。在 pH 7 时,Gu-0 和 Gu-100 的电渗析实验中观察到显著差异,与 Gu-0 相比,Gu-100 对磷酸盐和柠檬酸盐的传输能力增强。在 pH 10 时,差异更为明显:对于 Gu-0 膜,几乎检测不到磷酸盐和柠檬酸盐的传输,而 Gu-100 膜则能显著传输这两种离子。我们得出结论,胍基团作为阴离子交换位点可提高 AEM 的选择性。由于所提出的单体合成策略具有模块化,我们认为通过合成定制单体将官能团引入聚合物基膜是实现选择性离子传输的重要步骤,这对于包括水处理过程和燃料电池在内的各个领域都具有重要意义。