Magnéli-Phases in Anatase Strongly Promote Cocatalyst-Free Photocatalytic Hydrogen Evolution

  • Maximilian Domaschke
    Maximilian Domaschke
    Institute of Particle Technology, University of Erlangen-Nuremberg, Cauerstr. 4, 91058 Erlangen, Germany
  • Xuemei Zhou
    Xuemei Zhou
    Department of Materials Science WW-4 LKO, University of Erlangen-Nuremberg, Martensstr. 7, 91058 Erlangen, Germany
    More by Xuemei Zhou
  • Lukas Wergen
    Lukas Wergen
    Institute of Particle Technology, University of Erlangen-Nuremberg, Cauerstr. 4, 91058 Erlangen, Germany
    More by Lukas Wergen
  • Stefan Romeis
    Stefan Romeis
    Institute of Particle Technology, University of Erlangen-Nuremberg, Cauerstr. 4, 91058 Erlangen, Germany
  • Matthias E. Miehlich
    Matthias E. Miehlich
    Department of Chemistry and Pharmacy, Inorganic & General Chemistry, University of Erlangen-Nuremberg, Egerlandstrasse 1, 91058 Erlangen, Germany
  • Karsten Meyer
    Karsten Meyer
    Department of Chemistry and Pharmacy, Inorganic & General Chemistry, University of Erlangen-Nuremberg, Egerlandstrasse 1, 91058 Erlangen, Germany
  • Wolfgang Peukert*
    Wolfgang Peukert
    Institute of Particle Technology, University of Erlangen-Nuremberg, Cauerstr. 4, 91058 Erlangen, Germany
    *E-mail: [email protected]
  • , and 
  • Patrik Schmuki*
    Patrik Schmuki
    Department of Materials Science WW-4 LKO, University of Erlangen-Nuremberg, Martensstr. 7, 91058 Erlangen, Germany
    *E-mail: [email protected]
Cite this: ACS Catal. 2019, 9, 4, 3627–3632
Publication Date (Web):March 22, 2019
https://doi.org/10.1021/acscatal.9b00578
Copyright © 2019 American Chemical Society
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Abstract

Magnéli phases of titanium dioxide (such as Ti4O7, Ti5O9, etc.) provide electronic properties, namely, a stable metallic behavior at room temperature. In this manuscript, we demonstrate that nanoscopic Magnéli phases, formed intrinsically in anatase during a thermal aerosol synthesis, can enable significant photocatalytic H2 generation—this without the use of any extrinsic cocatalyst in anatase. Under optimized conditions, mixed-phase particles of 30% anatase, 25% Ti4O7, and 20% Ti5O9 are obtained that can provide, under solar light, direct photocatalytic H2 evolution at a rate of 145 μmol h–1 g–1. These anatase particles contain 5–10 nm size intergrown phases of Ti4O7 and Ti5O9. Key is the metallic band of Ti4O7 that induces a particle internal charge separation and transfer cascade with suitable energetics and favorable dimensions that are highly effective for H2 generation.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.9b00578.

  • Experimental section, SEM images of particles, stability tests of photocatalytic activity, Raman spectra, TEM images, XPS peaks, and EPR of commercial Magnéli powder (PDF)

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