Chromophore amphiphile–polyelectrolyte hybrid hydrogels for photocatalytic hydrogen production
Abstract
Hybrid systems based on covalent polymers and supramolecular assemblies offer unique opportunities for functional materials based on the pathway-dependent dynamic structures of supramolecular assemblies and the mechanical stability of covalent polymers. We report here on the synthesis of functional hybrid hydrogels containing self-assembling chromophore amphiphiles and polyelectrolytes. Chromophore amphiphiles were introduced into non-aqueous solvent swollen polymer matrices and self-assembly of the chromophore amphiphiles into crystalline nanostructures was triggered in the confined environment of the covalent network upon solvent exchange for water. Opposite charges in the covalent polyelectrolyte and the chromophore amphiphiles and sterics entrap the supramolecular assemblies within the mechanically stable network. However, molecular components necessary for catalysis, byproducts from photocatalysis, and the hydrogen produced are able to diffuse in or out of the covalent network to create a reusable robust host for photocatalysis. By varying the monomer and crosslinker composition in the feed, we can tune the porosity of the network as well as the chemical environment in which supramolecular crystallization of the chromophore amphiphiles takes place. Furthermore, this allows optimization of the hydrogel mechanical properties, retention of the chromophore amphiphile assemblies, and the photocatalytic reaction efficiency. Coarse-grained molecular dynamics simulations revealed that the chromophore amphiphile assembly is guidedmore »
- Authors:
-
[1];
[2];
[6];
[7];
[8]
- Northwestern Univ., Chicago, IL (United States); Dept. of Materials Science and Engineering, Evanston, IL (United States)
- Dept. of Materials Science and Engineering, Evanston, IL (United States); Bilkent Univ., Ankara (Turkey)
- Dept. of Materials Science and Engineering, Evanston, IL (United States)
- Northwestern Univ., Evanston, IL (United States)
- Dept. of Materials Science and Engineering, Evanston, IL (United States); Univ. of Michigan, Ann Arbor, MI (United States)
- Northwestern Univ., Chicago, IL (United States); Northwestern Univ., Evanston, IL (United States)
- Dept. of Materials Science and Engineering, Evanston, IL (United States); Northwestern Univ., Evanston, IL (United States)
- Northwestern Univ., Chicago, IL (United States); Dept. of Materials Science and Engineering, Evanston, IL (United States); Northwestern Univ., Evanston, 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:
- 1822444
- Alternate Identifier(s):
- OSTI ID: 1577206; OSTI ID: 1846648
- Grant/Contract Number:
- SC0000989; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Chemistry. A
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2050-7488
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 99 GENERAL AND MISCELLANEOUS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Sai, Hiroaki, Erbas, Aykut, Dannenhoffer, Adam, Huang, Dongxu, Weingarten, Adam, Siismets, Erica, Jang, Kyujin, Qu, Karen, Palmer, Liam C., Olvera de la Cruz, Monica, and Stupp, Samuel I. Chromophore amphiphile–polyelectrolyte hybrid hydrogels for photocatalytic hydrogen production. United States: N. p., 2019.
Web. doi:10.1039/c9ta08974h.
Sai, Hiroaki, Erbas, Aykut, Dannenhoffer, Adam, Huang, Dongxu, Weingarten, Adam, Siismets, Erica, Jang, Kyujin, Qu, Karen, Palmer, Liam C., Olvera de la Cruz, Monica, & Stupp, Samuel I. Chromophore amphiphile–polyelectrolyte hybrid hydrogels for photocatalytic hydrogen production. United States. https://doi.org/10.1039/c9ta08974h
Sai, Hiroaki, Erbas, Aykut, Dannenhoffer, Adam, Huang, Dongxu, Weingarten, Adam, Siismets, Erica, Jang, Kyujin, Qu, Karen, Palmer, Liam C., Olvera de la Cruz, Monica, and Stupp, Samuel I. Thu .
"Chromophore amphiphile–polyelectrolyte hybrid hydrogels for photocatalytic hydrogen production". United States. https://doi.org/10.1039/c9ta08974h. https://www.osti.gov/servlets/purl/1822444.
@article{osti_1822444,
title = {Chromophore amphiphile–polyelectrolyte hybrid hydrogels for photocatalytic hydrogen production},
author = {Sai, Hiroaki and Erbas, Aykut and Dannenhoffer, Adam and Huang, Dongxu and Weingarten, Adam and Siismets, Erica and Jang, Kyujin and Qu, Karen and Palmer, Liam C. and Olvera de la Cruz, Monica and Stupp, Samuel I.},
abstractNote = {Hybrid systems based on covalent polymers and supramolecular assemblies offer unique opportunities for functional materials based on the pathway-dependent dynamic structures of supramolecular assemblies and the mechanical stability of covalent polymers. We report here on the synthesis of functional hybrid hydrogels containing self-assembling chromophore amphiphiles and polyelectrolytes. Chromophore amphiphiles were introduced into non-aqueous solvent swollen polymer matrices and self-assembly of the chromophore amphiphiles into crystalline nanostructures was triggered in the confined environment of the covalent network upon solvent exchange for water. Opposite charges in the covalent polyelectrolyte and the chromophore amphiphiles and sterics entrap the supramolecular assemblies within the mechanically stable network. However, molecular components necessary for catalysis, byproducts from photocatalysis, and the hydrogen produced are able to diffuse in or out of the covalent network to create a reusable robust host for photocatalysis. By varying the monomer and crosslinker composition in the feed, we can tune the porosity of the network as well as the chemical environment in which supramolecular crystallization of the chromophore amphiphiles takes place. Furthermore, this allows optimization of the hydrogel mechanical properties, retention of the chromophore amphiphile assemblies, and the photocatalytic reaction efficiency. Coarse-grained molecular dynamics simulations revealed that the chromophore amphiphile assembly is guided by the polyelectrolyte network via ionic interactions. We also demonstrate successful photocatalytic hydrogen production from catalyst-laden hybrid hydrogels with the turnover frequency approaching that of the supramolecular hydrogel system, and also show that the hybrid hydrogels can be reused over multiple cycles as photosensitizers.},
doi = {10.1039/c9ta08974h},
journal = {Journal of Materials Chemistry. A},
number = 1,
volume = 8,
place = {United States},
year = {Thu Dec 05 00:00:00 EST 2019},
month = {Thu Dec 05 00:00:00 EST 2019}
}
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