Photofunctional construct that interfaces molecular cobalt-based catalysts for H2 production to a visible-light-absorbing semiconductor

Alexandra Krawicz, Jinhui Yang, Eitan Anzenberg, Junko Yano, Ian D. Sharp, Gary F. Moore

Research output: Contribution to journalArticlepeer-review

113 Scopus citations


Molecular cobalt-containing hydrogen production catalysts are grafted to a visible-light-absorbing semiconductor. The attachment procedure exploits the UV-induced immobilization chemistry of vinylpyridine to p-type (100) gallium phosphide (GaP). Single step surface-initiated photopolymerization yields a covalently attached polymer with pendent pyridyl groups that provide attachment points for assembling cobaloxime catalysts. Successful attachment is characterized by grazing angle attenuated total reflection Fourier transform infrared spectroscopy (GATR-FTIR), which shows distinct vibrational modes associated with the catalyst, as well as X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure spectroscopy (XANES) that confirm the presence of intact CoIII complex on the surface. The Co-functionalized photocathode shows significantly enhanced photoelectrochemical (PEC) performance in aqueous conditions at neutral pH, compared to results obtained on GaP without attached cobalt complex. PEC measurements, at 100 mW cm-2 illumination, yield a 2.4 mA cm-2 current density at a 310 mV underpotential.

Original languageEnglish (US)
Pages (from-to)11861-11868
Number of pages8
JournalJournal of the American Chemical Society
Issue number32
StatePublished - Aug 14 2013
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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