Using molecular design to control the performance of hydrogen-producing polymer-brush-modified photocathodes

Diana Cedeno, Alexandra Krawicz, Peter Doak, Min Yu, Jeffrey B. Neaton, Gary Moore

Research output: Contribution to journalArticlepeer-review

50 Scopus citations


Attachment of difluoroborylcobaloxime catalysts to a polymer-brush-modified GaP semiconductor allows improved hydrogen production levels and photoelectrochemical performance under aqueous acidic conditions (pH = 4.5) as compared to the performance of electrodes without catalyst treatment. The catalytic assembly used in this work incorporates a boron difluoride (BF2) capping group on the glyoximate ligand of the catalyst, a synthetic modification previously used to enhance the stability of nonsurface-attached complexes toward acid hydrolysis and to shift the cobalt reduction potentials of the complex to less negative, and thus technologically more relevant, values. The pH-dependent photoresponses of the cobaloxime- and difluoroborylcobaloxime-modified semiconductors are shown to be consistent with those from analogous studies using non-surface-attached cobaloxime catalysts as well as catalysts supported on conductive electrodes. Thus, this work illustrates the potential to control and optimize the properties of visible-light-absorbing semiconductors using polymeric overcoating techniques coupled with the principles of synthetic molecular design.

Original languageEnglish (US)
Pages (from-to)3222-3226
Number of pages5
JournalJournal of Physical Chemistry Letters
Issue number18
StatePublished - Sep 18 2014


  • Energy and charge transport
  • Energy conversion and storage

ASJC Scopus subject areas

  • General Materials Science


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