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Award Detail

Awardee:CORNELL UNIVERSITY
Doing Business As Name:Cornell University
PD/PI:
  • William R Dichtel
  • (607) 254-2356
  • wdichtel@cornell.edu
Award Date:01/06/2011
Estimated Total Award Amount: $ 650,000
Funds Obligated to Date: $ 650,000
  • FY 2013=$240,000
  • FY 2011=$290,000
  • FY 2012=$120,000
Start Date:02/01/2011
End Date:01/31/2016
Transaction Type:Grant
Agency:NSF
Awarding Agency Code:4900
Funding Agency Code:4900
CFDA Number:47.049
Primary Program Source:040100 NSF RESEARCH & RELATED ACTIVIT
Award Title or Description:CAREER: Synthesis of Covalent Organic Frameworks with Novel Optoelectronic Properties
Federal Award ID Number:1056657
DUNS ID:872612445
Parent DUNS ID:002254837
Program:Macromolec/Supramolec/Nano
Program Officer:
  • Suk-Wah Tam-Chang
  • (703) 292-8684
  • stamchan@nsf.gov

Awardee Location

Street:373 Pine Tree Road
City:Ithaca
State:NY
ZIP:14850-2820
County:Ithaca
Country:US
Awardee Cong. District:23

Primary Place of Performance

Organization Name:Cornell University
Street:373 Pine Tree Road
City:Ithaca
State:NY
ZIP:14850-2820
County:Ithaca
Country:US
Cong. District:23

Abstract at Time of Award

In this project funded by the Macromolecular, Supramolecular and Nanochemistry Program of the Chemistry Division, William Dichtel of Cornell University will study covalent organic frameworks (COFs) that exhibit efficient charge transport as a consequence of their long-range order. Despite their great promise, the limited syntheses of COFs have remained a significant roadblock to increasing their complexity. The research objectives include developing new methods for COF formation, preparing COF-based materials with morphologies long thought to be ideal for organic photovoltaic performance, and studying their charge separation and transport properties. The project integrates several educational initiatives with these research efforts, including science workshops on solar energy for middle school students, professional support for high school science teachers, and developing engaging content that will enhance public awareness of organic chemistry. This work offers a new strategy for improving the performance of organic electronic devices, whose economic importance is expected to grow significantly over the next decade. New synthetic methods for COFs will enable and inspire many other applications for these exciting materials. The project will also contribute to a deeper understanding of charge separation and transport in organic materials, key processes for increasing the efficiency of organic photovoltaic devices. New photovoltaic technologies are critical to sustainable energy generation and the future of the United States economy.

Publications Produced as a Result of this Research

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DeBlase, C. R.; Silberstein, K. E.; Truong, T.; Abrun?a, H. D.; Dichtel, W. R. "?-Ketoenamine-linked covalent organic frameworks capable of pseudocapacitive energy storage." J. Am. Chem. Soc., v.135, 2013, p.16821.

Colson, J. W. and Dichtel, W. R. "Rationally synthesized two-dimensional polymers" Nature Chemistry, v.5, 2013, p.453-465.

Koo, Brian T.; Dichtel, W. R.; Clancy, P. "A classification scheme for the stacking of two-dimensional covalent organic frameworks" Chem. Mater., v.22, 2012, p.17460-69.

John W. Colson, Jason A. Mann, Catherine R. DeBlase, and William R. Dichtel "Patterned Growth of Oriented 2D Covalent Organic Framework Thin Films on Single Layer Graphene" J. Polym. Sci., Part A: Polym. Chem., v.53, 2015, p.378. doi:10.1002/pola.27399 

Bunck, David N.; Dichtel, William R. "Postsynthetic functionalization of 3D covalent organic frameworks" CHEMICAL COMMUNICATIONS, v.49, 2013, p.2457-2459.

Spitler, EL; Koo, BT; Novotney, JL; Colson, JW; Uribe-Romo, FJ; Gutierrez, GD; Clancy, P; Dichtel, WR "A 2D Covalent Organic Framework with 4.7-nm Pores and Insight into Its Interlayer Stacking" JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.133, 2011, p.19416. doi:10.1021/ja206242  View record at Web of Science

Smith, B. J.; Overholts, A. C.; Hwang, G.; Dichtel, W. R. "Insight into the crystallization of amorphous imine-linked polymer networks to 2D covalent organic frameworks" Chem. Commun., v.52, 2016, p.3690. doi:10.1039/C5CC10221A 

Smith, B. J.; Dichtel, W. R. "Mechanistic Studies of Two-Dimensional Covalent Organic Frameworks Rapidly Polymerized from Initially Homogenous Conditions" J. Am. Chem. Soc., v.136, 2014, p.8783. doi:10.1021/ja5037868 

Bunck, D. N.; Dichtel, W. R. "Bulk synthesis of exfoliated 2D polymers using hydrazone-linked covalent organic frameworks" J. Am. Chem. Soc., v.135, 2013, p.14952.

Spitler, EL; Colson, JW; Uribe-Romo, FJ; Woll, AR; Giovino, MR; Saldivar, A; Dichtel, WR "Lattice Expansion of Highly Oriented 2D Phthalocyanine Covalent Organic Framework Films" ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, v.51, 2012, p.2623. doi:10.1002/anie.20110707  View record at Web of Science

Spitler, EL; Giovino, MR; White, SL; Dichtel, WR "A mechanistic study of Lewis acid-catalyzed covalent organic framework formation" CHEMICAL SCIENCE, v.2, 2011, p.1588. doi:10.1039/c1sc00260  View record at Web of Science

Bunck, David N.; Dichtel, William R. "Mixed Linker Strategies for Organic Framework Functionalization" CHEMISTRY-A EUROPEAN JOURNAL, v.19, 2013, p.818-827.

Bradforth, S. E.; Miller, E. R.; Dichtel, W. R.; Leibovich, A. K.; Feig, A. L.; Martin, J. D.; Bjorkman, K. S.; Schultz, Z. D.; Smith, T. L. "Improve Undergraduate Science Education" Nature, v.523, 2015, p.283. doi:10.1038/523282a 

Gopalakrishnan, D.; Dichtel, W. R. "Direct Detection of RDX Vapor Using a Conjugated Polymer Network" J. Am. Chem. Soc., v.2013, 2013, p.8357-8362.

Smith, B. J.; Hwang, N.; Chavez, A.; Novotney, J. L.; Dichtel, W. R. "Growth rates and water stability of 2D boronate ester covalent organic frameworks" Chemical Communications, v.51, 2015, p.7532. doi:10.1039/C5CC00379B 

Brucks, S. D.; Bunck, D. N.; Dichtel, W. R. "Functionalization of 3D covalent organic frameworks using monofunctional boronic acids." Polymer, v.55, 2014, p.330.

Bunck, DN; Dichtel, WR "Internal Functionalization of Three-Dimensional Covalent Organic Frameworks" ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, v.51, 2012, p.1885. doi:10.1002/anie.20110846  View record at Web of Science

Gopalakrishnan, D.; Dichtel, W. R. "Real-time detection of RDX vapors using thin films of a conjugated polymer network." Chem. Mater., v.27, 2015, p.3813. doi:10.1021/acs.chemmater.5b00857 


Project Outcomes Report

Disclaimer

This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.

This project resulted in major contributions to the chemistry of covalent organic frameworks (COFs), which are an emerging class of polymers with precise and designable two-dimensional and three-dimensional structures. COFs represent a new frontier in materials chemistry that had been discovered only shortly before this project was funded, and this CAREER award supported efforts to study the electronic processes and synthesis of COFs. Both of these efforts were highly successful and contributed to a dramatic increase in research activity surrounding COFs over the course of the funding period.

This project made the following important intellectual contributions to the chemistry of COFs:

1) At the outset of the project, COFs had been isolated only as insoluble powders that could not be easily interfaced to electrodes or built into electronic devices. We synthesized the first COF thin films directly on electrode surfaces, which has opened up a broad range of new applications, including solar cells, batteries, sensors, and many others (see image).

2) We reported the first COF that can accept and release electrons reversibly, and demonstrated that the unique features of the COF are desirable for storing electricity (see image "Redox-active COF").

3) We discovered new materials capable of detecting the explosive RDX from the vapor phase. Detecting RDX in this way has been a longstanding challenge that is extremely important for safeguarding our military personnel and for homeland security (see image "Detecting Explosives with Polymer Films").

4) At the outset of the project, COFs were synthesized by trial-and-error, with almost no understanding of how their building blocks react to form their unique ordered structures. We performed the first studies of the mechanisms of COF formation. This understanding is critical to improving the properties of COFs and allowing them to fulfill their full potential in future years.

The Broader Impacts of this project were:

1) Knowledge gained and reported from the research greatly heavily influenced the field of polymer chemistry and inspired great interest in the chemistry and applications of COFs. More than 200 COFs are now known, and papers describing key breakthroughs of the project have been heavily cited as the field has expanded. COFs are now being investigated for a wide range of applications that will benefit humankind, including batteries, fuel cell membranes, water purification, sensors, catalysts for making important chemical products efficiently, and many others.

2) Five graduate students earned their PhDs during this project, all of whom were awarded merit-based fellowships (4 NSF graduate fellowships; 1 external graduate fellowship) and awards during their graduate careers. Two students had international research experiences, including one representing the United States at an international meeting of Nobel Prize winners in 2012 in Lindau, Germany. Another student won a national competition held by the American Chemical Society for communicating science to the public. After earning her PhD, she became the director of public outreach at a major science museum (see image "Reactions_Jennifer Novotney"). Postdoctoral researchers supported by this project earned competitive positions in the chemical industry and academia. Therefore, this project led to the training of several future leaders in the scientific enterprise.

3) The PI and his research team contributed to a wide variety of efforts to broaden the participation of underrepresented groups in science. These projects included active-learning activities tailored for central New York high school teachers, female middle school students, and elementary school students from the City of Ithaca's after school programs. Members of our team also held internships at Ithaca's Sciencenter museum, coordinated NanoDays at Cornell, and co-organized an "American Chemical Society on Campus" day at Cornell.

4) The PI contributed to a redesign of Cornell's chemistry major to improve the overall experience for undergraduates and the retention of underrepresented groups in science, technology, engineering, and math (STEM) disciplines. He also co-organized a national workshop on evaluating teaching and learning in universities. A report describing its findings was published jointly by the Association of American Universities and the Research Corporation for Science Advancement. A highlight of the report, "Improve Undergraduate Science Education," was also published in the prominant scientific journal, Nature.

5) The purpose of the CAREER program is to provide an opportunity for developing the research and outreach efforts of PIs in the early stages of their academic careers. As a result of NSF support, the PI (Dichtel) was recognized as both an outstanding researcher and teacher by several national awards, most notably in the form of a MacArthur Fellowship, which supports highly creative individuals across many fields and professions.


Last Modified: 09/02/2016
Modified by: William R Dichtel

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