title: Self-assembling hydrogel scaffolds for photocatalytic hydrogen production.
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.
authors.affiliation: 1] Department of Chemistry, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, USA [2] Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208, USA.
authors.forename: Adam S
authors.initials: AS
authors.lastname: Weingarten
authors.affiliation: 1] Department of Chemistry, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, USA [2] Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208, USA.
authors.forename: Roman V
authors.initials: RV
authors.lastname: Kazantsev
authors.affiliation: 1] Department of Chemistry, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, USA [2] Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208, USA [3] Simpson Querrey Institute for BioNanotechnology, Northwestern University, Chicago, Illinois 60611, USA.
authors.forename: Liam C
authors.initials: LC
authors.lastname: Palmer
authors.affiliation: Department of Chemical and Biological Engineering, 2220 Campus Drive, Evanston, Illinois 60208, USA.
authors.forename: Mark
authors.initials: M
authors.lastname: McClendon
authors.affiliation: Department of Materials Science and Engineering, 2220 Campus Drive, Evanston, Illinois 60208, USA.
authors.forename: Andrew R
authors.initials: AR
authors.lastname: Koltonow
authors.affiliation: 1] Department of Chemistry, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, USA [2] Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208, USA.
authors.forename: Amanda P S
authors.initials: AP
authors.lastname: Samuel
authors.affiliation: Department of Chemistry, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, USA.
authors.forename: Derek J
authors.initials: DJ
authors.lastname: Kiebala
authors.affiliation: 1] Department of Chemistry, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, USA [2] Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208, USA.
authors.forename: Michael R
authors.initials: MR
authors.lastname: Wasielewski
authors.affiliation: 1] Department of Chemistry, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, USA [2] Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University, Evanston, Illinois 60208, USA [3] Simpson Querrey Institute for BioNanotechnology, Northwestern University, Chicago, Illinois 60611, USA [4] Department of Materials Science and Engineering, 2220 Campus Drive, Evanston, Illinois 60208, USA [5] Department of Medicine, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, USA.
authors.forename: Samuel I
authors.initials: SI
authors.lastname: Stupp
mesh_terms: D002384:Catalysis; D003460:Crystallization; D004566:Electrodes; D004573:Electrolytes / Q000737:chemistry; D020136:Hydrogel, Polyethylene Glycol Dimethacrylate / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry / Q000378:metabolism*; D007094:Imides / Q000138:chemical synthesis / Q000737:chemistry; D008027:Light; D009532:Nickel / Q000737:chemistry; D010569:Perylene / Q000031:analogs & derivatives / Q000138:chemical synthesis / Q000737:chemistry; D011108:Polymers / Q000737:chemistry; D012492:Salts / Q000737:chemistry
chemical_list: D004573:Electrolytes; D007094:Imides; D011108:Polymers; D012492:Salts; C532868:perylenemonoimide; D020136:Hydrogel, Polyethylene Glycol Dimethacrylate; D010569:Perylene; D009532:Nickel; D006859:Hydrogen