Supramolecular Packing Controls H 2 Photocatalysis in Chromophore Amphiphile Hydrogels

Weingarten, Adam S.; Kazantsev, Roman V.; Palmer, Liam C.; Fairfield, Daniel J.; Koltonow, Andrew R.; Stupp, Samuel I.

doi:10.1021/jacs.5b10027

Title: Supramolecular Packing Controls H ₂ Photocatalysis in Chromophore Amphiphile Hydrogels

Journal Article · Sat Nov 21 00:00:00 EST 2015 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5b10027· OSTI ID:1387519

Weingarten, Adam S. ^[1]; Kazantsev, Roman V. ^[1]; Palmer, Liam C. ^[2]; Fairfield, Daniel J. ^[3]; Koltonow, Andrew R. ^[3]; Stupp, Samuel I. ^[4]

Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States; Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208, United States
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States; Simpson Querrey Institute for BioNanotechnology, Northwestern University, Chicago, Illinois 60611, United States
Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, United States
Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States; Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208, United States; Simpson Querrey Institute for BioNanotechnology, Northwestern University, Chicago, Illinois 60611, United States; Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, United States; Department of Medicine, Northwestern University, Chicago, Illinois 60611, United States

Light harvesting supramolecular assemblies are potentially useful structures as components of solar-to-fuel conversion materials. The development of these functional constructs requires an understanding of optimal packing modes for chromophores. We investigated here assembly in water and the photocatalytic function of perylene monoimide chromophore amphiphiles with different alkyl linker lengths separating their hydrophobic core and the hydrophilic carboxylate headgroup. We found that these chromophore amphiphiles (CAs) self-assemble into charged nanostructures of increasing aspect ratio as the linker length is increased. The addition of salt to screen the charged nanostructures induced the formation of hydrogels and led to internal crystallization within some of the nanostructures. For linker lengths up to seven methylenes, the CAs were found to pack into 2D crystalline unit cells within ribbon-shaped nanostructures, whereas the nine methylene CAs assembled into long nanofibers without crystalline molecular packing. At the same time, the different molecular packing arrangements after charge screening led to different absorbance spectra, despite the identical electronic properties of all PMI amphiphiles. While the crystalline CAs formed electronically coupled H-aggregates, only CAs with intermediate linker lengths showed evidence of high intermolecular orbital overlap. Photocatalytic hydrogen production using a nickel-based catalyst was observed in all hydrogels, with the highest turnovers observed for CA gels having intermediate linker lengths. We conclude that the improved photocatalytic performance of the hydrogels formed by supramolecular assemblies of the intermediate linker CA molecules likely arises from improved exciton splitting efficiencies due to their higher orbital overlap.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: SC0001059

OSTI ID:: 1387519

Journal Information:: Journal of the American Chemical Society, Vol. 137, Issue 48; Related Information: ANSER partners with Northwestern University (lead); Argonne National Laboratory; University of Chicago; University of Illinois, Urbana-Champaign; Yale University; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis (homogeneous)
catalysis (heterogeneous)
solar (photovoltaic)
solar (fuels)
photosynthesis (natural and artificial)
bio-inspired
hydrogen and fuel cells
electrodes - solar
defects
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materials and chemistry by design
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synthesis (novel materials)
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Title: Supramolecular Packing Controls H 2 Photocatalysis in Chromophore Amphiphile Hydrogels

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Title: Supramolecular Packing Controls H ₂ Photocatalysis in Chromophore Amphiphile Hydrogels