Nucleation and Growth of Covalent Organic Frameworks from Solution: The Example of COF-5

Handle URI:
http://hdl.handle.net/10754/625973
Title:
Nucleation and Growth of Covalent Organic Frameworks from Solution: The Example of COF-5
Authors:
Li, Haoyuan ( 0000-0002-2469-5842 ) ; Chavez, Anton D.; Li, Huifang; Li, Hong; Dichtel, William R.; Bredas, Jean-Luc ( 0000-0001-7278-4471 )
Abstract:
The preparation of two-dimensional covalent organic frameworks (2D COFs) with large crystalline domains and controlled morphology is necessary for realizing the full potential of their atomically precise structures and uniform, tailorable porosity. Currently 2D COF syntheses are developed empirically, and most materials are isolated as insoluble and unprocessable powders with typical crystalline domain sizes smaller than 50 nm. Little is known about their nucleation and growth processes, which involve a combination of covalent bond formation, degenerate exchange, and non-covalent stacking processes. A deeper understanding of the chemical processes that lead to COF polymerization and crystallization is key to achieving improved materials quality and control. Here, we report a kinetic Monte Carlo (KMC) model that describes the formation of a prototypical boronate-ester linked 2D COF known as COF-5 from its 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylene bis(boronic acid) monomers in solution. The key rate parameters for the KMC model were derived from experimental measurements when possible and complemented with reaction pathway analyses, molecular dynamics simulations, and binding free-energy calculations. The essential features of experimentally measured COF-5 growth kinetics are reproduced well by the KMC simulations. In particular, the simulations successfully captured a nucleation process followed by a subsequent growth process. The nucleating species are found to be multi-layer structures that form through multiple pathways. During the growth of COF-5, extensions in the lateral (in-plane) and vertical (stacking) directions are both seen to be linear with respect to time and are dominated by monomer addition and oligomer association, respectively. Finally, we show that the experimental observations of increased average crystallite size with the addition of water are modeled accurately by the simulations. These results will inform the rational development of 2D COF polymerizations to control the rate of nucleation, thereby increasing their materials quality.
KAUST Department:
Laboratory for Computational and Theoretical Chemistry of Advanced Materials; Physical Sciences and Engineering (PSE) Division
Citation:
Li H, Chavez AD, Li H, Li H, Dichtel WR, et al. (2017) Nucleation and Growth of Covalent Organic Frameworks from Solution: The Example of COF-5. Journal of the American Chemical Society. Available: http://dx.doi.org/10.1021/jacs.7b09169.
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
24-Oct-2017
DOI:
10.1021/jacs.7b09169
Type:
Article
ISSN:
0002-7863; 1520-5126
Sponsors:
We would like to thank Dr. Brian J. Smith (Cornell) and Dr. Zhen Cao (KAUST) for helpful discussions. The work at KAUST was supported by internal funding from King Abdullah University of Science and Technology; we are grateful to the KAUST IT Research Computing Team and Supercomputing Laboratory for providing outstanding assistance as well as computational and storage resources. A.D.C. was supported by a National Defense Science and Engineering Graduate Fellowship. This work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), the State of Illinois, and International Institute for Nanotechnology (IIN). The collaborative work at Northwestern and Georgia Tech was supported by the Army Research Office under the MURI Center for Advanced Two-dimensional Organic Networks, CATON, under Award No. W911NF-15-1-0447, and under Award No. W911NF-17-1-0339 to Georgia Tech.
Additional Links:
http://pubs.acs.org/doi/10.1021/jacs.7b09169
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorLi, Haoyuanen
dc.contributor.authorChavez, Anton D.en
dc.contributor.authorLi, Huifangen
dc.contributor.authorLi, Hongen
dc.contributor.authorDichtel, William R.en
dc.contributor.authorBredas, Jean-Lucen
dc.date.accessioned2017-10-30T07:55:30Z-
dc.date.available2017-10-30T07:55:30Z-
dc.date.issued2017-10-24en
dc.identifier.citationLi H, Chavez AD, Li H, Li H, Dichtel WR, et al. (2017) Nucleation and Growth of Covalent Organic Frameworks from Solution: The Example of COF-5. Journal of the American Chemical Society. Available: http://dx.doi.org/10.1021/jacs.7b09169.en
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.doi10.1021/jacs.7b09169en
dc.identifier.urihttp://hdl.handle.net/10754/625973-
dc.description.abstractThe preparation of two-dimensional covalent organic frameworks (2D COFs) with large crystalline domains and controlled morphology is necessary for realizing the full potential of their atomically precise structures and uniform, tailorable porosity. Currently 2D COF syntheses are developed empirically, and most materials are isolated as insoluble and unprocessable powders with typical crystalline domain sizes smaller than 50 nm. Little is known about their nucleation and growth processes, which involve a combination of covalent bond formation, degenerate exchange, and non-covalent stacking processes. A deeper understanding of the chemical processes that lead to COF polymerization and crystallization is key to achieving improved materials quality and control. Here, we report a kinetic Monte Carlo (KMC) model that describes the formation of a prototypical boronate-ester linked 2D COF known as COF-5 from its 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylene bis(boronic acid) monomers in solution. The key rate parameters for the KMC model were derived from experimental measurements when possible and complemented with reaction pathway analyses, molecular dynamics simulations, and binding free-energy calculations. The essential features of experimentally measured COF-5 growth kinetics are reproduced well by the KMC simulations. In particular, the simulations successfully captured a nucleation process followed by a subsequent growth process. The nucleating species are found to be multi-layer structures that form through multiple pathways. During the growth of COF-5, extensions in the lateral (in-plane) and vertical (stacking) directions are both seen to be linear with respect to time and are dominated by monomer addition and oligomer association, respectively. Finally, we show that the experimental observations of increased average crystallite size with the addition of water are modeled accurately by the simulations. These results will inform the rational development of 2D COF polymerizations to control the rate of nucleation, thereby increasing their materials quality.en
dc.description.sponsorshipWe would like to thank Dr. Brian J. Smith (Cornell) and Dr. Zhen Cao (KAUST) for helpful discussions. The work at KAUST was supported by internal funding from King Abdullah University of Science and Technology; we are grateful to the KAUST IT Research Computing Team and Supercomputing Laboratory for providing outstanding assistance as well as computational and storage resources. A.D.C. was supported by a National Defense Science and Engineering Graduate Fellowship. This work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), the State of Illinois, and International Institute for Nanotechnology (IIN). The collaborative work at Northwestern and Georgia Tech was supported by the Army Research Office under the MURI Center for Advanced Two-dimensional Organic Networks, CATON, under Award No. W911NF-15-1-0447, and under Award No. W911NF-17-1-0339 to Georgia Tech.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/10.1021/jacs.7b09169en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/10.1021/jacs.7b09169.en
dc.subjectcovalent organic frameworks (COFs)en
dc.subjectnonclassical crystallizationen
dc.subjectcrystallization by particle attachmenten
dc.subjectkinetic Monte Carlo simulationen
dc.titleNucleation and Growth of Covalent Organic Frameworks from Solution: The Example of COF-5en
dc.typeArticleen
dc.contributor.departmentLaboratory for Computational and Theoretical Chemistry of Advanced Materialsen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalJournal of the American Chemical Societyen
dc.eprint.versionPost-printen
dc.contributor.institutionSchool of Chemistry and Biochemistry, Center for Organic Photonics and Electronics (COPE), Georgia Institute of Technology, Atlanta, Georgia 30332-0400, United States.en
dc.contributor.institutionDepartment of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, United Statesen
dc.contributor.institutionDepartment of Chemistry, Northwestern University, Evanston, Illinois 60208, United Statesen
kaust.authorLi, Haoyuanen
kaust.authorLi, Huifangen
kaust.authorLi, Hongen
kaust.authorBredas, Jean-Lucen
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