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

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

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
Pages (from-to)12199-12207
Number of pages9
JournalACS Nano
Volume8
Issue number12
DOIs
Publication statusPublished - Dec 23 2014

Fingerprint

Iron oxides
iron oxides
Photons
Oxidation
oxidation
Water
water
photons
Electrodes
Ultrathin films
Hematite
Photocatalysts
Valence bands
Quantum efficiency
Alloying
Reaction kinetics
water splitting
Energy gap
Substitution reactions
electrode materials

Keywords

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

ASJC Scopus subject areas

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

Cite this

Kim, D. W., Riha, S. C., Demarco, E. J., Martinson, A. B. F., Farha, O. K., & Hupp, J. T. (2014). Greenlighting photoelectrochemical oxidation of water by iron oxide. ACS Nano, 8(12), 12199-12207. https://doi.org/10.1021/nn503869n

Greenlighting photoelectrochemical oxidation of water by iron oxide. / Kim, Dong Wook; Riha, Shannon C.; Demarco, Erica J.; Martinson, Alex B F; Farha, Omar K.; Hupp, Joseph T.

In: ACS Nano, Vol. 8, No. 12, 23.12.2014, p. 12199-12207.

Research output: Contribution to journalArticle

Kim, DW, Riha, SC, Demarco, EJ, Martinson, ABF, Farha, OK & Hupp, JT 2014, 'Greenlighting photoelectrochemical oxidation of water by iron oxide', ACS Nano, vol. 8, no. 12, pp. 12199-12207. https://doi.org/10.1021/nn503869n
Kim DW, Riha SC, Demarco EJ, Martinson ABF, Farha OK, Hupp JT. Greenlighting photoelectrochemical oxidation of water by iron oxide. ACS Nano. 2014 Dec 23;8(12):12199-12207. https://doi.org/10.1021/nn503869n
Kim, Dong Wook ; Riha, Shannon C. ; Demarco, Erica J. ; Martinson, Alex B F ; Farha, Omar K. ; Hupp, Joseph T. / Greenlighting photoelectrochemical oxidation of water by iron oxide. In: ACS Nano. 2014 ; Vol. 8, No. 12. pp. 12199-12207.
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