Abstract For high-performance hybrid membranes, it is crucial to design multi-functional filler to rationally manipulate the structure-property relationship. In this study, a novel kind of hybrid membrane was fabricated by incorporating zinc ion loaded sulfonated pitch (SP-Zn2+) nanofillers into poly (ether-block-amide) (Pebax) matrix for CO2/CH4 separation. Sulfonated pitch (SP) with high sulfonate content was functionalized by zinc ion (Zn2+) via complexation reaction to synthesize SP-Zn2+ nanofillers with high Zn2+ loading. Mixed gas separation performances of membranes with different SP-Zn2+ loading were conducted. Meanwhile, the effect of operating pressure on separation performance and long-term operation stability were investigated. The hybrid membranes displayed significantly enhanced permeability and CO2/CH4 selectivity. First, the hydrophilic sulfonate group in SP had good compatibility with Pebax matrix and effectively suppressed interfacial defects. Second, zinc ions and sulfonate group could form zinc-sulfonate complex network. The sulfonated moiety afforded strong affinity toward CO2 due to multiple interactions whereas the Zn2+ moiety afforded a transport highway for CO2. Third, the incorporation of SP-Zn2+ nanofillers could disturb the Pebax chain packing and optimize the free volume characteristics. Particularly, Pebax/SP-Zn2+(2) membrane exhibited an increment of 104% and 70.2% in CO2 permeability and CO2/CH4 selectivity respectively, much higher than that of Pebax membrane.

中文翻译：

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在 Pebax-pitch 混合膜中通过锌离子和磺酸盐的协同作用显着增强了 CO 2 捕获性能

摘要 对于高性能杂化膜，设计多功能填料以合理操纵结构-性能关系至关重要。在这项研究中，通过将负载锌离子的磺化沥青 (SP-Zn2+) 纳米填料掺入聚（醚-嵌段-酰胺）（Pebax）基质中制备了一种新型混合膜，用于 CO2/CH4 分离。具有高磺酸盐含量的磺化沥青 (SP) 被锌离子 (Zn2+) 通过络合反应官能化，以合成具有高 Zn2+ 负载量的 SP-Zn2+ 纳米填料。进行了不同SP-Zn2+负载量膜的混合气体分离性能。同时，研究了操作压力对分离性能和长期运行稳定性的影响。混合膜显示出显着增强的渗透性和 CO2/CH4 选择性。第一的，SP中的亲水性磺酸盐基团与Pebax基体具有良好的相容性，有效抑制了界面缺陷。其次，锌离子和磺酸根可以形成锌-磺酸根络合物网络。由于多重相互作用，磺化部分对 CO2 具有很强的亲和力，而 Zn2+ 部分则为 CO2 提供了一条运输通道。第三，SP-Zn2+ 纳米填料的加入会干扰 Pebax 链堆积并优化自由体积特性。特别是Pebax/SP-Zn2+(2)膜的CO2渗透性和CO2/CH4选择性分别提高了104%和70.2%，远高于Pebax膜。锌离子与磺酸根可形成锌-磺酸根络合物网络。由于多重相互作用，磺化部分对 CO2 具有很强的亲和力，而 Zn2+ 部分则为 CO2 提供了一条运输通道。第三，SP-Zn2+ 纳米填料的加入会干扰 Pebax 链堆积并优化自由体积特性。特别是Pebax/SP-Zn2+(2)膜的CO2渗透性和CO2/CH4选择性分别提高了104%和70.2%，远高于Pebax膜。锌离子与磺酸根可形成锌-磺酸根络合物网络。由于多重相互作用，磺化部分对 CO2 具有很强的亲和力，而 Zn2+ 部分则为 CO2 提供了一条运输通道。第三，SP-Zn2+ 纳米填料的加入会干扰 Pebax 链堆积并优化自由体积特性。特别是Pebax/SP-Zn2+(2)膜的CO2渗透性和CO2/CH4选择性分别提高了104%和70.2%，远高于Pebax膜。