Growth of Extra-Large Chromophore Supramolecular Polymers for Enhanced Hydrogen Production
Abstract
The control of morphology in bioinspired chromophore assemblies is key to the rational design of functional materials for light harvesting. We investigate here morphological changes in perylene monoimide chromophore assemblies during thermal annealing in aqueous environments of high ionic strength to screen electrostatic repulsion. We found that annealing under these conditions leads to the growth of extra-large ribbon-shaped crystalline supramolecular polymers of widths from about 100 nm to several micrometers and lengths from 1 to 10 μm while still maintaining a unimolecular thickness. This growth process was monitored by variable-temperature absorbance spectroscopy, synchrotron X-ray scattering, and confocal microscopy. Furthermore, the extra-large single-crystal-like supramolecular polymers are highly porogenic, thus creating loosely packed hydrogel scaffolds that showed greatly enhanced photocatalytic hydrogen production with turnover numbers as high as 13 500 over ~110 h compared to 7500 when smaller polymers are used. Our results indicate great functional opportunities in thermally and pathway-controlled supramolecular polymerization.
- Authors:
-
[1];
[1];
[1];
[1];
[1];
[3];
[3]
- Northwestern Univ., Evanston, IL (United States)
- Northwestern Univ., Argonne, IL (United States)
- Northwestern Univ., Evanston, IL (United States); Northwestern Univ., Chicago, IL (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1823109
- Alternate Identifier(s):
- OSTI ID: 1846600
- Grant/Contract Number:
- FG02-99ER14999; SC0000989; SC0020884; SC0018093; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nano Letters
- Additional Journal Information:
- Journal Volume: 21; Journal Issue: 9; Journal ID: ISSN 1530-6984
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 99 GENERAL AND MISCELLANEOUS; supramolecular polymerization; chromophore amphiphiles; two-dimensional crystals; solar energy harvesting; supramolecular structures and assemblies; crystallization; x-ray scattering; hydrogels; polymers; 36 MATERIALS SCIENCE
Citation Formats
Dannenhoffer, Adam J., Sai, Hiroaki, Harutyunyan, Boris, Narayanan, Ashwin, Powers-Riggs, Natalia E., Edelbrock, Alexandra N., Passarelli, James V., Weigand, Steven J., Wasielewski, Michael R., Bedzyk, Michael J., Palmer, Liam C., and Stupp, Samuel I. Growth of Extra-Large Chromophore Supramolecular Polymers for Enhanced Hydrogen Production. United States: N. p., 2021.
Web. doi:10.1021/acs.nanolett.0c05024.
Dannenhoffer, Adam J., Sai, Hiroaki, Harutyunyan, Boris, Narayanan, Ashwin, Powers-Riggs, Natalia E., Edelbrock, Alexandra N., Passarelli, James V., Weigand, Steven J., Wasielewski, Michael R., Bedzyk, Michael J., Palmer, Liam C., & Stupp, Samuel I. Growth of Extra-Large Chromophore Supramolecular Polymers for Enhanced Hydrogen Production. United States. https://doi.org/10.1021/acs.nanolett.0c05024
Dannenhoffer, Adam J., Sai, Hiroaki, Harutyunyan, Boris, Narayanan, Ashwin, Powers-Riggs, Natalia E., Edelbrock, Alexandra N., Passarelli, James V., Weigand, Steven J., Wasielewski, Michael R., Bedzyk, Michael J., Palmer, Liam C., and Stupp, Samuel I. Tue .
"Growth of Extra-Large Chromophore Supramolecular Polymers for Enhanced Hydrogen Production". United States. https://doi.org/10.1021/acs.nanolett.0c05024. https://www.osti.gov/servlets/purl/1823109.
@article{osti_1823109,
title = {Growth of Extra-Large Chromophore Supramolecular Polymers for Enhanced Hydrogen Production},
author = {Dannenhoffer, Adam J. and Sai, Hiroaki and Harutyunyan, Boris and Narayanan, Ashwin and Powers-Riggs, Natalia E. and Edelbrock, Alexandra N. and Passarelli, James V. and Weigand, Steven J. and Wasielewski, Michael R. and Bedzyk, Michael J. and Palmer, Liam C. and Stupp, Samuel I.},
abstractNote = {The control of morphology in bioinspired chromophore assemblies is key to the rational design of functional materials for light harvesting. We investigate here morphological changes in perylene monoimide chromophore assemblies during thermal annealing in aqueous environments of high ionic strength to screen electrostatic repulsion. We found that annealing under these conditions leads to the growth of extra-large ribbon-shaped crystalline supramolecular polymers of widths from about 100 nm to several micrometers and lengths from 1 to 10 μm while still maintaining a unimolecular thickness. This growth process was monitored by variable-temperature absorbance spectroscopy, synchrotron X-ray scattering, and confocal microscopy. Furthermore, the extra-large single-crystal-like supramolecular polymers are highly porogenic, thus creating loosely packed hydrogel scaffolds that showed greatly enhanced photocatalytic hydrogen production with turnover numbers as high as 13 500 over ~110 h compared to 7500 when smaller polymers are used. Our results indicate great functional opportunities in thermally and pathway-controlled supramolecular polymerization.},
doi = {10.1021/acs.nanolett.0c05024},
journal = {Nano Letters},
number = 9,
volume = 21,
place = {United States},
year = {Tue Apr 20 00:00:00 EDT 2021},
month = {Tue Apr 20 00:00:00 EDT 2021}
}
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