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Enhanced Electron Transport in Nb-Doped TiO2 Nanoparticles via Pressure-Induced Phase Transitions

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† High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154, United States
‡ High Pressure Synergetic Consortium, Geophysical Laboratory, Carnegie Institution of Washington, Argonne, Illinois 60439, United States
§ Center for High Pressure Science and Technology Advanced Research, Pudong, Shanghai 201203, People’s Republic of China
∥ Earth and Environmental Sciences Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States
⊥ CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, People’s Republic of China
*[email protected]; [email protected]; [email protected]
Cite this: J. Am. Chem. Soc. 2014, 136, 1, 419–426
Publication Date (Web):December 9, 2013
https://doi.org/10.1021/ja410810w
Copyright © 2013 American Chemical Society
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Abstract

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Anatase TiO2 is one of the most important energy materials but suffers from poor electrical conductivity. Nb doping has been considered as an effective way to improve its performance in the applications of photocatalysis, solar cells, Li batteries, and transparent conducting oxide films. Here, we report the further enhancement of electron transport in Nb-doped TiO2 nanoparticles via pressure-induced phase transitions. The phase transition behavior and influence of Nb doping in anatase Nb-TiO2 have been systematically investigated by in situ synchrotron X-ray diffraction and Raman spectroscopy. The bulk moduli are determined to be 179.5, 163.3, 148.3, and 139.0 GPa for 0, 2.5, 5.0, and 10.0 mol % Nb-doped TiO2, respectively. The Nb-concentration-dependent stiffness variation has been demonstrated: samples with higher Nb concentrations have lower stiffness. In situ resistance measurements reveal an increase of 40% in conductivity of quenched Nb-TiO2 in comparison to the pristine anatase phase. The pressure-induced conductivity evolution is discussed in detail in terms of the packing factor model, which provides direct evidence for the rationality of the correlation of packing factors with electron transport in semiconductors. Pressure-treated Nb-doped TiO2 with unique properties surpassing those in the anatase phase holds great promise for energy-related applications.

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Text and figures giving details of four-probe resistance measurements in DAC, crystal structures of various TiO2 phases, TEM images, synchrotron XRD and Raman spectra of 2.5 and 10.0 mol % Nb-doped TiO2 samples, R–P curve of undoped TiO2, Raman spectra during various compression and decompression cycles, and microphotographs of the samples and ruby balls in DAC. This material is available free of charge via the Internet at http://pubs.acs.org.

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