4.6 Article

Selective Formation of Polyaniline Confined in the Nanopores of a Metal-Organic Framework for Supercapacitors

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 27, Issue 10, Pages 3560-3567

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202004516

Keywords

conducting polymer; nanocomposite; pore confinement; pseudocapacitive material; zirconium-based MOF

Funding

  1. Ministry of Science and Technology (MOST) of Taiwan [MOST 107-2218-E-006-054-MY3]
  2. Yushan Young Scholar Program, under Ministry of Education (MOE), Taiwan
  3. Higher Education Sprout Project, MOE, Taiwan

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In this study, a new strategy was developed to confine polyaniline within the nanopores of a metal-organic framework without forming bulk PANI. The resulting PANI/UiO-66-NH2 composite material showed superior electrochemical activity and charge-storage capacities, making it a promising electrode material for supercapacitors.
In this study, a strategy that can result in the polyaniline (PANI) solely confined within the nanopores of a metal-organic framework (MOF) without forming obvious bulk PANI between MOF crystals is developed. A waterstable zirconium-based MOF, UiO-66-NH2, is selected as the MOF material. The polymerization of aniline is initiated in the acidic suspension of UiO-66-NH2 nanocrystals in the presence of excess poly(sodium 4-styrenesulfonate) (PSS). Since the pore size of UiO-66-NH2 is too small to enable the insertion of the bulky PSS, the quick formation of pore-confined solid PANI and the slower formation of well dispersed PANI:PSS occur within the MOF crystals and in the bulk solution, respectively. By taking advantage of the resulting homogeneous PANI:PSS polymer solution, the bulk PANI:PSS can be removed from the PANI/UiO-66-NH2 solid by successive washing the sample with fresh acidic solutions through centrifugation. As this is the first time reporting the PANI solely confined in the pores of a MOF, as a demonstration, the obtained PANI/UiO-66-NH2 composite material is applied as the electrode material for supercapacitors. The PANI/UiO-66-NH2 thin films exhibit a pseudocapacitive electrochemical characteristic, and their resulting electrochemical activity and charge-storage capacities are remarkably higher than those of the bulk PANI thin films.

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