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Self-assembling hydrogel scaffolds for photocatalytic hydrogen production

Nature Chemistry volume 6, pages 964–970 (2014)Cite this article

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Abstract

Integration into a soft material of all the molecular components necessary to generate storable fuels is an interesting target in supramolecular chemistry. The concept is inspired by the internal structure of photosynthetic organelles, such as plant chloroplasts, which colocalize molecules involved in light absorption, charge transport and catalysis to create chemical bonds using light energy. We report here on the light-driven production of hydrogen inside a hydrogel scaffold built by the supramolecular self-assembly of a perylene monoimide amphiphile. The charged ribbons formed can electrostatically attract a nickel-based catalyst, and electrolyte screening promotes gelation. We found the emergent phenomenon that screening by the catalyst or the electrolytes led to two-dimensional crystallization of the chromophore assemblies and enhanced the electronic coupling among the molecules. Photocatalytic production of hydrogen is observed in the three-dimensional environment of the hydrogel scaffold and the material is easily placed on surfaces or in the pores of solid supports.

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Figure 1: Self-assembly of PMI CAs into supramolecular ribbons.
Figure 2: Gelation of CA ribbons with salts.
Figure 3: Charge screening induces crystallization within supramolecular polymers.
Figure 4: Optical properties of CA solutions and crystalline gels.
Figure 5: Photocatalytic H2 production.

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Acknowledgements

This work was supported as part of the Argonne-Northwestern Solar Energy Research (ANSER) Center, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE-SC0001059. Use of the Advanced Photon Source (APS) was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. SAXS experiments were performed at the DuPont–Northwestern–Dow Collaborative Access Team (DND-CAT) located at Sector 5 of APS. DND-CAT is supported by E.I. DuPont de Nemours & Co., The Dow Chemical Company and Northwestern University. WAXS experiments were conducted at BioCARS Sector 14 at the APS supported by grants from the National Center for Research Resources (5P41RR007707) and the National Institute of General Medical Sciences (8P41GM103543) from the National Institutes of Health. GIXS data were collected at Sector 12 of the APS. We thank the Biological Imaging Facility at Northwestern for the use of TEM equipment, and the Electron Probe Instrumentation Center facilities of the Northwestern University Atomic and Nanoscale Characterization Experimental Center for the use of SEM equipment. NMR and MS equipment at the Integrated Molecular Structure Education and Research Center was supported by the National Science Foundation under CHE-9871268. The authors acknowledge J. Lehrman and Y. Velichko of the Stupp laboratory and K. Lefler, W. Salamant, M. Vagnini, B. Veldkamp and D. Gardner of the Wasielewski laboratory for helpful discussions.

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Author notes

  1. Adam S. Weingarten and Roman V. Kazantsev: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Chemistry, Northwestern University, 2220 Campus Drive, Evanston, 60208, Illinois, USA

    Adam S. Weingarten, Roman V. Kazantsev, Liam C. Palmer, Amanda P. S. Samuel, Derek J. Kiebala, Michael R. Wasielewski & Samuel I. Stupp

  2. Argonne–Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, 60208, Illinois, USA

    Adam S. Weingarten, Roman V. Kazantsev, Liam C. Palmer, Amanda P. S. Samuel, Michael R. Wasielewski & Samuel I. Stupp

  3. Simpson Querrey Institute for BioNanotechnology, Northwestern University, Chicago, 60611, Illinois, USA

    Liam C. Palmer & Samuel I. Stupp

  4. Department of Chemical and Biological Engineering, 2220 Campus Drive, Evanston, 60208, Illinois, USA

    Mark McClendon

  5. Department of Materials Science and Engineering, 2220 Campus Drive, Evanston, 60208, Illinois, USA

    Andrew R. Koltonow & Samuel I. Stupp

  6. Department of Medicine, Northwestern University, 2220 Campus Drive, Evanston, 60208, Illinois, USA

    Samuel I. Stupp

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Contributions

A.S.W., R.V.K., L.C.P., M.R.W. and S.I.S designed the experiments. A.S.W., R.V.K., M.M., A.R.K., A.P.S.S. and D.J.K. performed the experimental work. A.S.W., R.V.K., L.C.P., M.R.W. and S.I.S. analysed the data and wrote the paper.

Corresponding authors

Correspondence to Michael R. Wasielewski or Samuel I. Stupp.

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The authors declare no competing financial interests.

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Weingarten, A., Kazantsev, R., Palmer, L. et al. Self-assembling hydrogel scaffolds for photocatalytic hydrogen production. Nature Chem 6, 964–970 (2014). https://doi.org/10.1038/nchem.2075

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