Preserving Porosity of Mesoporous Metal-Organic Frameworks through the Introduction of Polymer Guests

Li Peng, Shuliang Yang, Sudi Jawahery, Seyed Mohamad Moosavi, Aron J. Huckaba, Mehrdad Asgari, Emad Oveisi, Mohammad Khaja Nazeeruddin, Berend Smit, Wendy L. Queen

Research output: Contribution to journalArticlepeer-review

68 Scopus citations

Abstract

High internal surface areas, an asset that is highly sought after in material design, has brought metal-organic frameworks (MOFs) to the forefront of materials research. In fact, a major focus in the field is on creating innovative ways to maximize MOF surface areas. Despite this, large-pore MOFs, particularly those with mesopores, continue to face problems with pore collapse upon activation. Herein, we demonstrate an easy method to inhibit this problem via the introduction of small quantities of polymer. For several mesoporous, isostructural MOFs, known as M2(NDISA) (where M = Ni2+, Co2+, Mg2+, or Zn2+), the accessible surface areas are increased dramatically, from 5 to 50 times, as the polymer effectively pins the MOFs open. Postpolymerization, the high surface areas and crystallinity are now readily maintained after heating the materials to 150 °C under vacuum. These activation conditions, which could not previously be attained due to pore collapse, also provide accessibility to high densities of open metal coordination sites. Molecular simulations are used to provide insight into the origin of instability of the M2(NDISA) series and to propose a potential mechanism for how the polymers immobilize the linkers, improving framework stability. Last, we demonstrate that the resulting MOF-polymer composites, referred to as M2(NDISA)-PDA, offer a perfect platform for the appendage/immobilization of small nanocrystals inside rendering high-performance catalysts. After decorating one of the composites with Pd (average size: 2 nm) nanocrystals, the material shows outstanding catalytic activity for Suzuki-Miyaura cross-coupling reactions.

Original languageEnglish
Pages (from-to)12397-12405
Number of pages9
JournalJournal of the American Chemical Society
Volume141
Issue number31
DOIs
StatePublished - Aug 7 2019

Bibliographical note

Publisher Copyright:
© 2019 American Chemical Society.

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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