Greenlighting photoelectrochemical oxidation of water by iron oxide

Dong Wook Kim, Shannon C. Riha, Erica J. Demarco, Alex B.F. Martinson, Omar K. Farha, Joseph T. Hupp*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

56 Scopus citations


Hematite (α-Fe2O3) is one of just a few candidate electrode materials that possess all of the following photocatalyst-essential properties for scalable application to water oxidation: excellent stability, earth-Abundance, suitability positive valence-band-edge energy, and significant visible light absorptivity. Despite these merits, hematites modest oxygen evolution reaction kinetics and its poor efficiency in delivering photogenerated holes, especially holes generated by green photons, to the electrode/solution interface, render it ineffective as a practical water-splitting catalyst. Here we show that hole delivery and catalytic utilization can be substantially improved through Ti alloying, provided that the alloyed material is present in ultrathin-thin-film form. Notably, the effects are most pronounced for charges photogenerated by photons with energy comparable to the band gap for excitation of Fe(3d) → Fe(3d) transitions (i.e., green photons). Additionally, at the optimum Ti substitution level the lifetimes of surface-localized holes, competent for water oxidation, are extended. Together these changes explain an overall improvement in photoelectrochemical performance, especially enhanced internal quantum efficiencies, observed upon Ti(IV) incorporation.

Original languageEnglish (US)
Pages (from-to)12199-12207
Number of pages9
JournalACS nano
Issue number12
StatePublished - Dec 23 2014


  • absorbed photon-to-current conversion efficiency (APCE)
  • green light
  • iron oxide
  • titanium incorporation
  • transient photocurrent
  • ultrathin film

ASJC Scopus subject areas

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)


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