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 - Funding Information:
Synthesis and characterization were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under award no. DE-SC0020884. The photocatalysis experiment was supported by the Center for Bio-Inspired Energy Science (CBES), an Energy Frontier Research Center funded by the U.S. Department of Energy Office of Science, Basic Energy Sciences, under award no. DE-SC0000989. Data analysis on the X-ray scattering experiments was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under award no. DE-SC0018093. Transient absorption spectroscopy was supported by the Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-FG02-99ER14999 (M.R.W.). Solution X-ray scattering experiments and grazing incidence X-ray scattering experiments were performed at Sector 5 and Sector 8 of the Advanced Photon Source (APS), respectively. Use of the Advanced Photon Source (APS) was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under contract no. DE-AC02-06CH11357. The DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT), located at Sector 5 of APS, is supported by Northwestern University, the Dow Chemical Company, and DuPont de Nemours, Inc. This work made use of the BioCryo and Keck-II facilities at Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experiment (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1121262 and DMR-1720139) at the Materials Research Center at Northwestern University; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois. Nitrogen physisorption experiments were performed at the REACT Facility of the Northwestern University Center for Catalysis and Surface Science, which is supported by a grant from the U.S. Department of Energy (DE-SC0001329). Additional experiments were performed in the Keck Biophysics Core at Northwestern University, supported in part by NCI CCSG P30 CA06053 grant awarded to the Robert H. Lurie Comprehensive Cancer Center. A.N.E. received graduate research fellowships through the National Science Foundation (DGE-1842165). The authors gratefully acknowledge Luka D̵ord̵ević (Northwestern University) for providing additional materials. A.J.D. and H.S. contributed equally.
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 -
