Unraveling the nanostructures and self-assembly behavior of perfluorosulfonic acid in water/ethanol solvent: Effect of EW and side-chain chemistry

Jingnan Song; Suyan Wang; Wutong Zhao; Bonan Hao; Ming Zhang; Yecheng Zou; Gang Wei; Jia Liu; Guangying Chen; Huan Ren; Xuefei Wu; Xuesong Jiang; Yongfeng Zhou; Feng Liu; Yongming Zhang

Giant (Dec 2024)

Unraveling the nanostructures and self-assembly behavior of perfluorosulfonic acid in water/ethanol solvent: Effect of EW and side-chain chemistry

Jingnan Song,
Suyan Wang,
Wutong Zhao,
Bonan Hao,
Ming Zhang,
Yecheng Zou,
Gang Wei,
Jia Liu,
Guangying Chen,
Huan Ren,
Xuefei Wu,
Xuesong Jiang,
Yongfeng Zhou,
Feng Liu,
Yongming Zhang

Affiliations

Jingnan Song: School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Center of Hydrogen Science, Shanghai Jiao Tong University, Shanghai, 200240, PR China; Corresponding authors.
Suyan Wang: School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Center of Hydrogen Science, Shanghai Jiao Tong University, Shanghai, 200240, PR China
Wutong Zhao: School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Center of Hydrogen Science, Shanghai Jiao Tong University, Shanghai, 200240, PR China
Bonan Hao: School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Center of Hydrogen Science, Shanghai Jiao Tong University, Shanghai, 200240, PR China
Ming Zhang: School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Center of Hydrogen Science, Shanghai Jiao Tong University, Shanghai, 200240, PR China
Yecheng Zou: State Key Laboratory of Fluorinated Functional Membrane Materials and Dongyue Future Hydrogen Energy Materials Company, Zibo, Shandong, 256401, PR China
Gang Wei: State Key Laboratory of Fluorinated Functional Membrane Materials and Dongyue Future Hydrogen Energy Materials Company, Zibo, Shandong, 256401, PR China
Jia Liu: Shanghai Hydrogen Propulsion Technology Co. Ltd., Shanghai, 201800, PR China
Guangying Chen: Shanghai Hydrogen Propulsion Technology Co. Ltd., Shanghai, 201800, PR China
Huan Ren: Shanghai Hydrogen Propulsion Technology Co. Ltd., Shanghai, 201800, PR China
Xuefei Wu: Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA
Xuesong Jiang: School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Center of Hydrogen Science, Shanghai Jiao Tong University, Shanghai, 200240, PR China
Yongfeng Zhou: School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Center of Hydrogen Science, Shanghai Jiao Tong University, Shanghai, 200240, PR China
Feng Liu: School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Center of Hydrogen Science, Shanghai Jiao Tong University, Shanghai, 200240, PR China; State Key Laboratory of Fluorinated Functional Membrane Materials and Dongyue Future Hydrogen Energy Materials Company, Zibo, Shandong, 256401, PR China; Corresponding authors.
Yongming Zhang: School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Center of Hydrogen Science, Shanghai Jiao Tong University, Shanghai, 200240, PR China; State Key Laboratory of Fluorinated Functional Membrane Materials and Dongyue Future Hydrogen Energy Materials Company, Zibo, Shandong, 256401, PR China; Corresponding authors.

Journal volume & issue: Vol. 20
p. 100332

Abstract

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The perfluorosulfonic acid (PFSA) ionomers are key materials for proton exchange membranes (PEMs) and catalyst layers (CLs). Their morphology is profoundly influenced by the chain assembly behavior of PFSA in dispersions. Hence, we combine the characterization techniques of dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and cryo-transmission electron microscopy (Cryo-TEM) to study the nanostructures of PFSA dispersions, and provide a structure model for diverse PFSA ionomers in water/ethanol solvent. It is seen that PFSA ionomers self-assembly into a rod-like particle in dilute dispersion. As the concentration increases, the primary rod aggregates gradually assemble into a swollen- or Gaussian-network structure. Beyond this feature, we see that different PFSA ionomers show different nanostructures in dispersion. For the long-side-chain (LSC) PFSA ionomers, the 800-LSC PFSA tends to form monodisperse rod-like aggregates that is in a highly ordered arrangement with a rod diameter of 3.16 nm and a length of 28.72 nm. As the equivalent weight (EW) increases to 960, the poor solubility of the main chains in water/ethanol solvents leads to the “end-to-end” assemblies of the primary rod particles and dendritic secondary aggregates. The short-side-chain (SSC) PFSA ionomer that shares the same backbone with 960-LSC PFSA exhibit remarkable mono-dispersity and ordered arrangement of rod-like aggregates in water/ethanol solvents due to the strong electrostatic repulsion.

Published in Giant

ISSN: 2666-5425 (Online)
Publisher: Elsevier
Country of publisher: United Kingdom
LCC subjects: Science: Science (General)
Website: https://www.journals.elsevier.com/giant

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