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Core-Shell Nanostructured “Black” Rutile Titania as Excellent Catalyst for Hydrogen Production Enhanced by Sulfur Doping

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† CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, P. R. China
‡ Beijing National Laboratory for Molecular Sciences and State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China
§ Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115, United States
∥ High Pressure Science and Engineering Center (HiPSEC), University of Nevada, Las Vegas, Nevada 89154, United States
⊥ State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050, P. R. China
[email protected]
Cite this: J. Am. Chem. Soc. 2013, 135, 47, 17831–17838
Publication Date (Web):October 28, 2013
https://doi.org/10.1021/ja4076748
Copyright © 2013 American Chemical Society
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Abstract

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Modification of rutile titanium dioxide (TiO2) for hydrogen generation and water cleaning is a grand challenge due to the chemical inertness of rutile, while such inertness is a desired merit for its stability in photoelectrochemical applications. Herein, we report an innovative two-step method to prepare a core–shell nanostructured S-doped rutile TiO2 (R′-TiO2-S). This modified black rutile TiO2 sample exhibits remarkably enhanced absorption in visible and near-infrared regions and efficient charge separation and transport. As a result, the unique sulfide surface (TiO2–x:S) boosts the photocatalytic water cleaning and water splitting with a steady solar hydrogen production rate of 0.258 mmol h–1 g–1. The black titania is also an excellent photoelectrochemical electrode exhibiting a high solar-to-hydrogen conversion efficiency of 1.67%. The sulfided surface shell is proved to be an effective strategy for enhancing solar light absorption and photoelectric conversion.

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Detail sample characterizations, XRD, XPS, Raman, TEM, and cycling tests of photocatalytic. This material is available free of charge via the Internet at http://pubs.acs.org.

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