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 journalArticle

33 Citations (Scopus)

Abstract

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
Volume5
Issue number18
DOIs
StatePublished - Sep 18 2014

Fingerprint

Photocathodes
brushes
photocathodes
Brushes
Hydrogen
Polymers
catalysts
Catalysts
polymers
hydrogen
Semiconductor materials
Electrodes
difluorides
Hydrogen production
Cobalt
Catalyst supports
electrodes
Boron
hydrogen production
Hydrolysis

Keywords

  • Energy and charge transport
  • Energy conversion and storage

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Using molecular design to control the performance of hydrogen-producing polymer-brush-modified photocathodes. / Cedeno, Diana; Krawicz, Alexandra; Doak, Peter; Yu, Min; Neaton, Jeffrey B.; Moore, Gary.

In: Journal of Physical Chemistry Letters, Vol. 5, No. 18, 18.09.2014, p. 3222-3226.

Research output: Contribution to journalArticle

Cedeno, Diana ; Krawicz, Alexandra ; Doak, Peter ; Yu, Min ; Neaton, Jeffrey B. ; Moore, Gary. / Using molecular design to control the performance of hydrogen-producing polymer-brush-modified photocathodes. In: Journal of Physical Chemistry Letters. 2014 ; Vol. 5, No. 18. pp. 3222-3226.
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