Rapid Synthesis of High Surface Area Imine-Linked 2D Covalent Organic Frameworks by Avoiding Pore Collapse During Isolation

Cameron H. Feriante, Samik Jhulki, Austin M. Evans, Raghunath R. Dasari, Kaitlin Slicker, William R. Dichtel*, Seth R. Marder

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

13 Scopus citations

Abstract

Imine-linked 2D covalent organic frameworks (COFs) form more rapidly than previously reported under Brønsted acid-catalyzed conditions, showing signs of crystallinity within a few minutes, and maximum crystallinity within hours. These observations contrast with the multiday reaction times typically employed under these conditions. In addition, vacuum activation, which is often used to isolate COF materials significantly erodes the crystallinity and surface area of the several isolated materials, as measured by N2 sorption and X-ray diffraction. This loss of material quality during isolation for many networks has historically obscured otherwise effective polymerization conditions. The influence of the activation procedure is characterized in detail for three COFs, with the commonly used 1,3,5-tris(4-aminophenyl)benzene-terephthaldehyde network (TAPB-PDA COF), the most prone to pore collapse. When the networks are activated carefully, rapid COF formation is general for all five of the imine-linked 2D COFs studied, with all exhibiting excellent crystallinity and surface areas, including the highest surface areas reported to date for three materials. Furthermore, to simplify the workup of COF materials, a simple nitrogen flow method provides high-quality materials without the need for specialized equipment. These insights have important implications for studying and understanding how 2D COFs form.

Original languageEnglish (US)
Article number1905776
JournalAdvanced Materials
Volume32
Issue number2
DOIs
StatePublished - Jan 1 2020

Keywords

  • activation procedures
  • covalent organic frameworks
  • critical point drying
  • imine

ASJC Scopus subject areas

  • Materials Science(all)
  • Mechanics of Materials
  • Mechanical Engineering

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