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Titanium-Defected Undoped Anatase TiO2 with p-Type Conductivity, Room-Temperature Ferromagnetism, and Remarkable Photocatalytic Performance

Wang, Songbo, Pan, Lun, Song, Jia-Jia, Mi, Wenbo, Zou, Ji-Jun, Wang, Li, Zhang, Xiangwen·2015·Journal of the American Chemical Society

Abstract

Defects are critically important for metal oxides in chemical and physical applications. Compared with the often studied oxygen vacancies, engineering metal vacancies in n-type undoped metal oxides is still a great challenge, and the effect of metal vacancies on the physiochemical properties is seldom reported. Here, using anatase TiO2, the most important and widely studied semiconductor, we demonstrate that metal vacancies (VTi) can be introduced in undoped oxides easily, and the presence of VTi results in many novel physiochemical properties. Anatase Ti0.905O2 was synthesized using solvothermal treatment of tetrabutyl titanate in an ethanol-glycerol mixture and then thermal calcination. Experimental measurements and DFT calculations on cell lattice parameters show the unstoichiometry is caused by the presence of VTi rather than oxygen interstitials. The presence of VTi changes the charge density and valence band edge of TiO2, and an unreported strong EPR signal at g = 1.998 presents under room temperature. Contrary to normal n-type and nonferromagnetic TiO2, Ti-defected TiO2 shows inherent p-type conductivity with high charge mobility, and room-temperature ferromagnetism stronger than Co-doped TiO2 nanocrystalline. Moreover, Ti-defected TiO2 shows much better photocatalytic performance than normal TiO2 in H2 generation (4.4-fold) and organics degradation (7.0-fold for phenol), owing to the more efficient charge separation and transfer in bulk and at semiconductor/electrolyte interface. Metal-defected undoped oxides represent a unique material; this work demonstrates the possibility to fabricate such material in easy and reliable way and thus provides new opportunities for multifunctional materials in chemical and physical devices.

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Metadata

Authors
Wang, S., Pan, L., Song, J.-J., Mi, W., Zou, J.-J., Wang, L., & Zhang, X.
Venue
Journal of the American Chemical Society
Published
2015-02-18
Volume
137
Issue
8
Pages
2975-2983
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
OpenAlex
W2326810084
Cited by
718
References
50
FWCI
17.60
Type
journal article
Language
en
Open access
closed

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