Structural and Optical Interplay of Palladium-Modified TiO 2 Nanoheterostructure

Li, Jun; Sham, Tsun-Kong; Ye, Yifan; Zhu, Junfa; Guo, Jinghua

doi:10.1021/jp511080q

Structural and Optical Interplay of Palladium-Modified TiO ₂ Nanoheterostructure

Journal Article · Mon Jan 05 00:00:00 UTC 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/jp511080q· OSTI ID:1512161

Li, Jun ^[1]; Sham, Tsun-Kong ^[1]; Ye, Yifan ^[2]; Zhu, Junfa ^[3]; Guo, Jinghua ^[4]

Department of Chemistry, University of Western Ontario, 1151 Richmond Street, London, Ontario N6A5B7, Canada
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States; National Synchrotron Radiation Laboratory and Collaborative Innovation Center of Suzhou Nano Science and Technology, University of Science and Technology of China, Hefei, Anhui 230029, People’s Republic of China
National Synchrotron Radiation Laboratory and Collaborative Innovation Center of Suzhou Nano Science and Technology, University of Science and Technology of China, Hefei, Anhui 230029, People’s Republic of China
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States

The electronic structure and optical properties of Pd-modified TiO₂ nanotubes (NTs) with a vertically aligned nanotubular structure grown by a two-step electrochemical anodization method have been studied using X-ray spectroscopy. X-ray absorption near-edge structure (XANES) at the Ti L_3,2- and O K-edges was used to investigate the TiO₂ NTs before and after Pd modification. It was found that Pd nanoparticles (NPs) are uniformly coated on the NT surface. The Pd L₃-edge of the deposited Pd NPs shows a more intense whiteline and a blue shift for the Pd L₃-edge absorption threshold relative to Pd metal, indicating charge depletion from the Pd 4d orbital as a result NP formation. The lattice of Pd is slightly contracted upon NP formation, although it remains fcc as revealed by extended X-ray absorption fine structure (EXAFS) analysis at the Pd K-edge. X-ray-excited optical luminescence (XEOL) together with XANES with element and site specificity was used to study the optical luminescence from TiO₂ NTs. It was found that the defect-originated XEOL intensity dropped noticeably in the Pd NP-coated NTs, suggesting a Pd NP–TiO₂-interaction-mediated reduction in the radiative recombination of electrons and holes. Finally, further evidence is provided by Ti ₂p resonant inelastic X-ray scattering (RIXS), in which no low-energy loss features (d–d transitions) were observed. The implications of these results are discussed.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1512161

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 4 Vol. 119; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
X-ray absorption near edge structure
X-ray excited optical luminescence
electronic structure
extended X-ray absorption fine structure
resonant inelastic X-ray scattering