@article{d3c3345b4e5e4b95886d97b393905f92,
title = "Photodriven hydrogen evolution by molecular catalysts using Al2O3-protected perylene-3,4-dicarboximide on NiO electrodes",
abstract = "The design of efficient hydrogen-evolving photocathodes for dye-sensitized photoelectrochemical cells (DSPECs) requires the incorporation of molecular light absorbing chromophores that are capable of delivering reducing equivalents to molecular proton reduction catalysts at rates exceeding those of charge recombination events. Here, we report the functionalization and kinetic analysis of a nanostructured NiO electrode with a modified perylene-3,4-dicarboximide chromophore (PMI) that is stabilized against degradation by atomic layer deposition (ALD) of thick insulating Al2O3 layers. Following photoinduced charge injection into NiO in high yield, films with Al2O3 layers demonstrate longer charge separated lifetimes as characterized via femtosecond transient absorption spectroscopy and photoelectrochemical techniques. The photoelectrochemical behavior of the electrodes in the presence of Co(ii) and Ni(ii) molecular proton reduction catalysts is examined, revealing reduction of both catalysts. Under prolonged irradiation, evolved H2 is directly observed by gas chromatography supporting the applicability of PMI embedded in Al2O3 as a photocathode architecture in DSPECs.",
author = "Kamire, {Rebecca J.} and Majewski, {Marek B.} and Hoffeditz, {William L.} and Phelan, {Brian T.} and Farha, {Omar K.} and Hupp, {Joseph T.} and Wasielewski, {Michael R.}",
note = "Funding Information: This work was supported by the Argonne-Northwestern Solar Energy Research (ANSER) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, under award number DE-SC0001059. Profilometry and ellipsometry measurements were performed in the Keck-II facility of the NUANCE Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. UV-Vis absorption measurements with the integrating sphere were performed in the Keck Biophysics Facility at Northwestern University, which is supported in part by grant NCI CCSG P30 CA060553 awarded to the Robert H Lurie Comprehensive Cancer Center. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry",
year = "2016",
doi = "10.1039/c6sc02477g",
language = "English (US)",
volume = "8",
pages = "541--549",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",
number = "1",
}