Probing the Nature of Bandgap States in Hydrogen-Treated TiO2 Nanowires

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Department of Chemistry and Biochemistry, University of California, Santa Cruz, 1156 High Street, Santa Cruz, California 95064, United States
Department of Chemistry, University of California, Riverside, 501 Big Springs Road, Riverside, California 92521 United States
§ NanoBio Interface Group, Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, United States
*E-mail [email protected], Ph (831)-459-1952 (Y.L.).
*E-mail [email protected], Ph (831) 459-3776 (Z.Z.).
Cite this: J. Phys. Chem. C 2013, 117, 50, 26821–26830
Publication Date (Web):December 2, 2013
https://doi.org/10.1021/jp409857j
Copyright © 2013 American Chemical Society
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Abstract

Hydrogen treatment of TiO2 has been demonstrated to significantly alter its optical properties, including substantially enhanced visible light absorption that has important implications for various applications. The chemical nature of the bandgap states responsible for the increased visible absorption is not yet well understood. This work reports a detailed study of the structural, optical, electronic, and ultrafast properties of hydrogen-treated TiO2 (H:TiO2) nanowires (NWs) using a combination of experimental techniques including high-resolution transmission electron microscopy (HRTEM), electron spin resonance spectroscopy (ESR), time-resolved fluorescence (TRF), and femtosecond transient absorption (TA) spectroscopy in order to explain the origin of the strong visible absorption. The combined TEM, ESR, TRF, and TA data suggest that the presence of a localized mid-bandgap oxygen vacancy (VO) occupied by a lone electron in an antibonding orbital situated at a surface site is likely responsible for the visible absorption of the material. The data further indicate that while untreated TiO2 NWs are fluorescent, the hydrogen treatment leads to quenching of the fluorescence and highly efficient charge carrier recombination from the VO state following excitation with visible light. With UV excitation, however, the charge carrier recombination of the H:TiO2 NWs exhibits a larger component of a slow decay compared to that of untreated TiO2, which is correlated with enhanced photoelectrochemical performance. Both the treated and untreated samples exhibit a fast decay that dominates the TA signals, which is likely caused by a high density of surface trap states. A simple model is proposed to explain all the key optical and dynamic features observed. The results have provided deeper insight into the chemical nature and photophysical properties of bandgap states in chemically modified TiO2 nanomaterials.

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