Abstract
Covalent organic frameworks (COFs) consist of monomers arranged in predictable structures with emergent properties. However, improved crystallinity, porosity, and solution processability remain major challenges. To this end, colloidal COF nanoparticles are useful for mechanistic studies of nucleation and growth and enable advanced spectroscopy and solution processing of thin films. Here we present a general approach to synthesize imine-linked 2D COF nanoparticles and control their size by favoring imine polymerization while preventing the nucleation of new particles. The method yields uniform, crystalline, and high-surface-area particles and is applicable to several imine-linked COFs. In situ X-ray scattering experiments reveal the nucleation of amorphous polymers, which crystallize via imine exchange processes during and after particle growth, consistent with previous mechanistic studies of imine-linked COF powders. The separation of particle formation and growth processes offers control of particle size and may enable further improvements in crystallinity in the future.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 3796-3801 |
| Number of pages | 6 |
| Journal | Chemical Science |
| Volume | 10 |
| Issue number | 13 |
| DOIs | |
| State | Published - 2019 |
Funding
We acknowledge the Army Research Office for a Multidisciplinary University Research Initiatives (MURI) award under grant number W911NF-15-1-0447. Parts of this work were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and the Dow Chemical Company. This research used resources of the Advanced Photon Source and Center for Nanoscale Materials, both U.S. Department of Energy (DOE) Office of Science User Facilities operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC0206CH11357. A. M. E. is supported by the National Science Foundation Graduate Research Fellowship under Grant No. (DGE-1324585), the Ryan Fellowship and the Northwestern University International Institute for Nanotechnology. This work has also made use of the IMSERC, EPIC, and Keck II facility of NUANCE Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the Keck Foundation, the State of Illinois and International Institute for Nanotechnology (IIN). N. C. F. and L. X. C. are partially supported by Basic Energy Science, CBG Division, US Department of Energy through Argonne National Laboratory under Contract No. DE-AC02-06CH11357. I. C. is partially supported by the Army Research Office under grant W911NF-18-1-0359 and by the National Science Foundation under Grant No. (DMR-1720139). Author contributions R. L. L., N. C. F., A. M. E., W. J., and W. R. D. performed and interpreted the colloid growth and characterizations. R. L. L., N. C. F., A. M. E., L. X. C., and W. R. D. performed and interpreted the in situ X-ray diffraction experiments. I. C. and N. C. G. performed and interpreted TEM experiments. All authors wrote and revised the manuscript. We acknowledge the Army Research Office for a Multidisciplinary University Research Initiatives (MURI) award under grant number W911NF-15-1-0447. Parts of this work were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and the Dow Chemical Company. This research used resources of the Advanced Photon Source and Center for Nanoscale Materials, both U.S. Department of Energy (DOE) Office of Science User Facilities operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC0206CH11357. A. M. E. is supported by the National Science Foundation Graduate Research Fellowship under Grant No. (DGE-1324585), the Ryan Fellowship and the Northwestern University International Institute for Nanotechnology. This work has also made use of the IMSERC, EPIC, and Keck II facility of NUANCE Center at Northwestern University, which has received support from the So and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the Keck Foundation, the State of Illinois and International Institute for Nanotechnology (IIN). N. C. F. and L. X. C. are partially supported by Basic Energy Science, CBG Division, US Department of Energy through Argonne National Laboratory under Contract No. DE-AC02-06CH11357. I. C. is partially supported by the Army Research Office under grant W911NF-18-1-0359 and by the National Science Foundation under Grant No. (DMR-1720139). Author contributions R. L. L., N. C. F., A. M. E., W. J., and W. R. D. performed and interpreted the colloid growth and characterizations. R. L. L., N. C. F., A. M. E., L. X. C., and W. R. D. performed and interpreted the in situ X-ray diffraction experiments. I. C. and N. C. G. performed and interpreted TEM experiments. All authors wrote and revised the manuscript.
ASJC Scopus subject areas
- General Chemistry