TY - JOUR
T1 - Growth of Extra-Large Chromophore Supramolecular Polymers for Enhanced Hydrogen Production
AU - Dannenhoffer, Adam J.
AU - Sai, Hiroaki
AU - Harutyunyan, Boris
AU - Narayanan, Ashwin
AU - Powers-Riggs, Natalia E.
AU - Edelbrock, Alexandra N.
AU - Passarelli, James V.
AU - Weigand, Steven J.
AU - Wasielewski, Michael R.
AU - Bedzyk, Michael J.
AU - Palmer, Liam C.
AU - Stupp, Samuel I.
N1 - Publisher Copyright:
© 2021 American Chemical Society.
PY - 2021/5/12
Y1 - 2021/5/12
N2 - 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. 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.
AB - 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. 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.
KW - chromophore amphiphiles
KW - solar energy harvesting
KW - supramolecular polymerization
KW - two-dimensional crystals
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U2 - 10.1021/acs.nanolett.0c05024
DO - 10.1021/acs.nanolett.0c05024
M3 - Article
C2 - 33877843
AN - SCOPUS:85105904267
SN - 1530-6984
VL - 21
SP - 3745
EP - 3752
JO - Nano letters
JF - Nano letters
IS - 9
ER -
