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Phenyl/Perfluorophenyl Stacking Interactions Enhance Structural Order in Two-Dimensional Covalent Organic Frameworks

Journal Article · · Crystal Growth and Design
 [1];  [1];  [2];  [1];  [3];  [1];  [4];  [4];  [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Colorado School of Mines, Golden, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
  4. Colorado School of Mines, Golden, CO (United States)
+ Show Author Affiliations

A two-dimensional imine-based covalent organic framework (COF) was designed and synthesized such that phenyl and perfluorophenyl structural units can seamlessly alternate between layers of the framework. X-ray diffraction of the COF powders reveals a striking increase in crystallinity for the COF with self-complementary phenyl/perfluorophenyl interactions (FASt-COF). Whereas measured values of the Brunauer-Emmet-Teller (BET) surface areas for the nonfluorinated Base-COF and the COF employing hydrogen bonding were ~37% and 59%, respectively, of their theoretical Connolly surface areas, the BET value for FASt-COF achieves >90% of its theoretical value (~1700 m2/g). Transmission electron microscopy images also revealed unique micron-sized rodlike features in FASt-COF that were not present in the other materials. The results highlight a promising approach for improving surface areas and long-range order in two-dimensional COFs.

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Program (EE-3F)
Grant/Contract Number:
AC36-08GO28308
OSTI ID:
1457122
Alternate ID(s):
OSTI ID: 1502015
Report Number(s):
NREL/JA--5900-70871
Journal Information:
Crystal Growth and Design, Journal Name: Crystal Growth and Design Journal Issue: 7 Vol. 18; ISSN 1528-7483
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

Figures / Tables (6)

Scheme 1(p. 2)figure Scheme 1
Table 1(p. 3)table Table 1
Figure 1(p. 4)figure Figure 1
Figure 2(p. 4)figure Figure 2
Figure 3(p. 5)figure Figure 3
Figure 4(p. 5)figure Figure 4

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Related Subjects

36 MATERIALS SCIENCE
crystal
fluorination
frameworks
gas storage