Imidazolium-Based Sulfonating Agent to Control the Degree of Sulfonation of Aromatic Polymers and Enable Plastics-to-Electronics Upgrading
| Author(s) | Lo, Chun-Yuan | |
| Author(s) | Koutsoukos, Kelsey P. | |
| Author(s) | Nguyen, Dan My | |
| Author(s) | Wu, Yuhang | |
| Author(s) | Angel Trujillo, David Alejandro | |
| Author(s) | Miller, Tabitha | |
| Author(s) | Shrestha, Tulaja | |
| Author(s) | Mackey, Ethan | |
| Author(s) | Damani, Vidhika S. | |
| Author(s) | Kanbur, Uddhav | |
| Author(s) | Opila, Robert | |
| Author(s) | Martin, David C. | |
| Author(s) | Kaphan, David | |
| Author(s) | Kayser, Laure V. | |
| Date Accessioned | 2024-07-26T18:34:02Z | |
| Date Available | 2024-07-26T18:34:02Z | |
| Publication Date | 2024-07-03 | |
| Description | This article was originally published in JACS Au. The version of record is available at: https://doi.org/10.1021/jacsau.4c00355. Copyright © 2024 The Authors. Published by American Chemical Society This research was featured in UDaily on 07/18/2024 at: https://www.udel.edu/udaily/2024/july/plastic-upcycling-kayser-laure-chemistry-polystyrene-pedotpss/ | |
| Abstract | The accumulation of plastic waste in the environment is a growing environmental, economic, and societal challenge. Plastic upgrading, the conversion of low-value polymers to high-value materials, could address this challenge. Among upgrading strategies, the sulfonation of aromatic polymers is a powerful approach to access high-value materials for a range of applications, such as ion-exchange resins and membranes, electronic materials, and pharmaceuticals. While many sulfonation methods have been reported, achieving high degrees of sulfonation while minimizing side reactions that lead to defects in the polymer chains remains challenging. Additionally, sulfonating agents are most often used in large excess, which prevents precise control over the degree of sulfonation of aromatic polymers and their functionality. Herein, we address these challenges using 1,3-disulfonic acid imidazolium chloride ([Dsim]Cl), a sulfonic acid-based ionic liquid, to sulfonate aromatic polymers and upgrade plastic waste to electronic materials. We show that stoichiometric [Dsim]Cl can effectively sulfonate model polystyrene up to 92% in high yields, with minimal defects and high regioselectivity for the para position. Owing to its high reactivity, the use of substoichiometric [Dsim]Cl uniquely allows for precise control over the degree of sulfonation of polystyrene. This approach is also applicable to a wide range of aromatic polymers, including waste plastic. To prove the utility of our approach, samples of poly(styrene sulfonate) (PSS), obtained from either partially sulfonated polystyrene or expanded polystyrene waste, are used as scaffolds for poly(3,4-ethylenedioxythiophene) (PEDOT) to form the ubiquitous conductive material PEDOT:PSS. PEDOT:PSS from plastic waste is subsequently integrated into organic electrochemical transistors (OECTs) or as a hole transport layer (HTL) in a hybrid solar cell and shows the same performance as commercial PEDOT:PSS. This imidazolium-mediated approach to precisely sulfonating aromatic polymers provides a pathway toward upgrading postconsumer plastic waste to high-value electronic materials. | |
| Sponsor | Research reported in this publication was supported by seed funding from the University of Delaware (UD) and Argonne National Laboratories (ANL) awarded to L.V.K. and D.K. It was subsequently supported by the American Chemical Society Petroleum Research Fund, Doctoral New Investigator award (#66259-DNI7) (synthesis and plastic upgrading) and CAREER award from the National Science Foundation (NSF) (grant No. DMR-2237888) (structure–property relationships of PEDOT:PSS) to L.V.K. Work at ANL was supported through Laboratory Directed Research and Development (LDRD) funding from Argonne National Laboratory, provided by the Director, Office of Science, of the U.S. Department of Energy under Contract DE-AC-02-06CH11357. The authors thank the Surface Analysis Facility at the University of Delaware and Dr. Xu Feng for XPS assistance, and the UD Nanofabrication Facility for the film thickness measurements. XPS analysis was performed with the instrument sponsored by the NSF under grant No. CHE-1428149. The J–V measurements were made at the Institute of Energy Conversion (IEC). We thank Prof. Epps and Prof. Messina for access to their organic SEC. We thank Chemours for donating Capstone FS-30 used in the fabrication of the solar cells, and the Solar Power Laboratory at Arizona State University for providing the silicon substrates for the solar cell fabrication. | |
| Citation | Lo, Chun-Yuan, Kelsey P. Koutsoukos, Dan My Nguyen, Yuhang Wu, David Alejandro Angel Trujillo, Tabitha Miller, Tulaja Shrestha, et al. “Imidazolium-Based Sulfonating Agent to Control the Degree of Sulfonation of Aromatic Polymers and Enable Plastics-to-Electronics Upgrading.” JACS Au 4, no. 7 (July 22, 2024): 2596–2605. https://doi.org/10.1021/jacsau.4c00355. | |
| ISSN | 2691-3704 | |
| URL | https://udspace.udel.edu/handle/19716/34611 | |
| Language | en_US | |
| Publisher | JACS Au | |
| dc.rights | Attribution 4.0 International | en |
| dc.rights.uri | http://creativecommons.org/licenses/by/4.0/ | |
| Keywords | sulfonation | |
| Keywords | plastic upgrading | |
| Keywords | polyelectrolytes | |
| Keywords | electrophilic aromatic substitution | |
| Keywords | PEDOT:PSS | |
| Keywords | organic electrochemical transistors | |
| Keywords | hybrid solar cells | |
| Title | Imidazolium-Based Sulfonating Agent to Control the Degree of Sulfonation of Aromatic Polymers and Enable Plastics-to-Electronics Upgrading | |
| Type | Article |
Files
Original bundle
1 - 1 of 1
Loading...
- Name:
- Imidazolium-Based Sulfonating Agent to Control the Degree of Sulfonation of Aromatic Polymers and Enable Plastics-to-Electronics Upgrading.pdf
- Size:
- 3.6 MB
- Format:
- Adobe Portable Document Format
- Description:
- Main article
License bundle
1 - 1 of 1
No Thumbnail Available
- Name:
- license.txt
- Size:
- 2.22 KB
- Format:
- Item-specific license agreed upon to submission
- Description: