Photodriven hydrogen evolution by molecular catalysts using Al2O3-protected perylene-3,4-dicarboximide on NiO electrodes

Rebecca J. Kamire, Marek B. Majewski, William L. Hoffeditz, Brian T. Phelan, Omar K. Farha, Joseph T. Hupp, Michael R. Wasielewski*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

61 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)541-549
Number of pages9
JournalChemical Science
Issue number1
StatePublished - 2016

ASJC Scopus subject areas

  • Chemistry(all)


Dive into the research topics of 'Photodriven hydrogen evolution by molecular catalysts using Al<sub>2</sub>O<sub>3</sub>-protected perylene-3,4-dicarboximide on NiO electrodes'. Together they form a unique fingerprint.

Cite this