“Black” TiO2 Nanotubes Formed by High-Energy Proton Implantation Show Noble-Metal-co-Catalyst Free Photocatalytic H2-Evolution

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Department of Materials Science WW-4, LKO, University of Erlangen-Nuremberg, Martensstrasse 7, 91058 Erlangen, Germany
Fraunhofer Institute for Integrated Systems and Device Technology IISB, Schttkystrasse 10, 91058 Erlangen, Germany
§ ECRC - Erlangen Catalysis Resource Center, University of Erlangen-Nuremberg, Egerlandstrasse 3, 91058 Erlangen, Germany
Institute of Micro- and Nanostructure Research (WW9) & Center for Nanoanalysis and Electron Microscopy (CENEM), University of Erlangen-Nuremberg, Cauerstrasse 6, 91058 Erlangen, Germany
National Institute of Advanced Industrial Science and Technology, Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
# Department of Materials Sciences 6, iMEET, University of Erlangen-Nuremberg, Martensstrasse 7, 91058 Erlangen, Germany
*E-mail: [email protected]. Tel.: +49 91318517575. Fax: +49 9131 852 7582.
Cite this: Nano Lett. 2015, 15, 10, 6815–6820
Publication Date (Web):September 4, 2015
Copyright © 2015 American Chemical Society
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We apply high-energy proton ion-implantation to modify TiO2 nanotubes selectively at their tops. In the proton-implanted region, we observe the creation of intrinsic cocatalytic centers for photocatalytic H2-evolution. We find proton implantation to induce specific defects and a characteristic modification of the electronic properties not only in nanotubes but also on anatase single crystal (001) surfaces. Nevertheless, for TiO2 nanotubes a strong synergetic effect between implanted region (catalyst) and implant-free tube segment (absorber) can be obtained.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.nanolett.5b02663.

  • Experimental details on the fabrication. Additional TRIM calculation depth distribution of proton implantation in TiO2 single crystal (Figure S1). Additional TEM and corresponding electron diffraction patterns (Figures S2–S4) Raman spectra for (001) anatase single crystal and TiO2 nanotubes before and after H-implantation (Figures S5 and S6). Calculation models and reference papers for the Eg Raman line shift and fwhm as a function of TiO2 feature size (Figures S7 and S8). Calculation details for Rietveld analysis. (PDF)

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