Phase Transformations among TiO2 Polymorphs

Song, Miao; Lu, Zexi; Li, Dongsheng

doi:10.1039/D0NR06226J

Phase Transformations among TiO2 Polymorphs

Journal Article · Sun Dec 06 23:00:00 EST 2020 · Nanoscale

DOI:https://doi.org/10.1039/D0NR06226J· OSTI ID:1734517

Song, Miao ^[1]; Lu, Zexi ^[1]; ^[1]

BATTELLE (PACIFIC NW LAB)

Polymorphs widely exist in nature and synthetic systems and are well known to determine material properties. Understanding phase transformation mechanisms among polymorphs enables the design of structures and tuning of phases to tailor material properties. However, current understanding is limited due to the lack of direct observations that track the processes and the structural evolution is not known at atomic scale. Here, integrating (semi) in situ transmission electron microscopy and density functional theory, we report atomic structural evolutions of phase transformation from anatase (A) to rutile (R), brookite (B), R-phase, and TiO. Besides the consistent paths with previous reports, we discover several unreported paths, including a [001] direction and (020) plane of anatase to [100]A and (011)R of rutile, respectively, ( , ) and , . Density functional theory analysis elucidates atomic structural evolution during the processes and over 16% of Ti-O bonds break and reform during the processes with energy barriers of ~0.7-1.0 eV per TiO2 formula unit. Under electron-beam irradiation, anatase particles transform into TiO2-R phase or TiO at high or room temperature, respectively. We also reveal the anisotropic nature of electron-beam effect, which is seldom discussed: dependence of crystallographic orientation with respect to electron-beam irradiation direction. Understanding the atomic structural evolution sheds light on interpreting and controlling TiO2 polymorphs and interface structures for various applications. The revealed electron-beam effects in our work provide guidance for in situ transmission electron microscopy studies.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1734517

Report Number(s):: PNNL-SA-155296

Journal Information:: Nanoscale, Journal Name: Nanoscale Journal Issue: 45 Vol. 12

Country of Publication:: United States

Language:: English

References (46)

Anatase TiO ₂ with Dominant High-Energy {001} Facets: Synthesis, Properties, and Applications Liu, Shengwei; Yu, Jiaguo; Jaroniec, Mietek Chemistry of Materials, Vol. 23, Issue 18 https://doi.org/10.1021/cm200597m	journal	September 2011
Why is anatase a better photocatalyst than rutile? - Model studies on epitaxial TiO2 films Luttrell, Tim; Halpegamage, Sandamali; Tao, Junguang Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep04043	journal	February 2014
Surface-stress-induced phase transformation in metal nanowires Diao, Jiankuai; Gall, Ken; Dunn, Martin L. Nature Materials, Vol. 2, Issue 10 https://doi.org/10.1038/nmat977	journal	September 2003
Nanosized Anatase TiO2 Single Crystals with Tunable Exposed (001) Facets for Enhanced Energy Conversion Efficiency of Dye-Sensitized Solar Cells Wu, Xia; Chen, Zhigang; Lu, Gao Qing Max Advanced Functional Materials, Vol. 21, Issue 21 https://doi.org/10.1002/adfm.201100828	journal	August 2011
Growth Mechanism of Highly Branched Titanium Dioxide Nanowires via Oriented Attachment Li, Dongsheng; Soberanis, Frank; Fu, Jia Crystal Growth & Design, Vol. 13, Issue 2 https://doi.org/10.1021/cg301388e	journal	January 2013
Particle size effects on transformation kinetics and phase stability in nanocrystalline TiO ₂ Gribb, Amy A.; Banfield, Jillian F. American Mineralogist, Vol. 82, Issue 7-8 https://doi.org/10.2138/am-1997-7-809	journal	August 1997
α to β Phase Transformation and Microestructural Changes of PVDF Films Induced by Uniaxial Stretch Sencadas, V.; Gregorio, R.; Lanceros-Méndez, S. Journal of Macromolecular Science, Part B, Vol. 48, Issue 3 https://doi.org/10.1080/00222340902837527	journal	May 2009
Explaining the Enhanced Photocatalytic Activity of Degussa P25 Mixed-Phase TiO ₂ Using EPR Hurum, Deanna C.; Agrios, Alexander G.; Gray, Kimberly A. The Journal of Physical Chemistry B, Vol. 107, Issue 19 https://doi.org/10.1021/jp0273934	journal	May 2003
Atomic structure and formation mechanism of (101) rutile twins from Diamantina (Brazil) Daneu, N.; Re nik, A.; Mader, W. American Mineralogist, Vol. 99, Issue 4 https://doi.org/10.2138/am.2014.4672	journal	April 2014
Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals Chen, X.; Liu, L.; Yu, P. Y. Science, Vol. 331, Issue 6018 https://doi.org/10.1126/science.1200448	journal	January 2011
Oriented attachment and growth, twinning, polytypism, and formation of metastable phases; insights from nanocrystalline TiO ₂ Penn, R. Lee; Banfield, Jillian F. American Mineralogist, Vol. 83, Issue 9-10 https://doi.org/10.2138/am-1998-9-1016	journal	October 1998
Size Dependence of the Kinetic Rate Constant for Phase Transformation in TiO ₂ Nanoparticles Zhang, Hengzhong; Banfield, Jillian F. Chemistry of Materials, Vol. 17, Issue 13 https://doi.org/10.1021/cm0508423	journal	June 2005
Material’s Design beyond Lateral Attachment: Twin-Controlled Spatial Branching of Rutile TiO ₂ Jordan, Vanja; Dasireddy, Venkata D. B. C.; Likozar, Blaž Crystal Growth & Design, Vol. 18, Issue 8 https://doi.org/10.1021/acs.cgd.8b00479	journal	June 2018
A universal cooperative assembly-directed method for coating of mesoporous TiO ₂ nanoshells with enhanced lithium storage properties Guan, Bu Yuan; Yu, Le; Li, Ju Science Advances, Vol. 2, Issue 3 https://doi.org/10.1126/sciadv.1501554	journal	March 2016
Crystal shape engineering of anatase TiO ₂ and its biomedical applications Yang, Shuang; Huang, Nian; Jin, Yong Mei CrystEngComm, Vol. 17, Issue 35 https://doi.org/10.1039/C5CE00804B	journal	January 2015
Transformation induced crack deflection in a metastable titanium alloy and implications on transformation toughening Song, M.; He, S. Y.; Du, K. Acta Materialia, Vol. 118 https://doi.org/10.1016/j.actamat.2016.07.041	journal	October 2016
Epitaxial growth of TiO2 thin films on SrTiO3, LaAlO3 and yttria-stabilized zirconia substrates by electron beam evaporation Lotnyk, A.; Senz, S.; Hesse, D. Thin Solid Films, Vol. 515, Issue 7-8 https://doi.org/10.1016/j.tsf.2006.10.106	journal	February 2007
A new polymorph of Na2MnP2O7 as a 3.6 V cathode material for sodium-ion batteries Barpanda, Prabeer; Ye, Tian; Avdeev, Maxim Journal of Materials Chemistry A, Vol. 1, Issue 13 https://doi.org/10.1039/c3ta10210f	journal	January 2013
Formation of rutile nuclei at anatase (112) twin interfaces and the phase transformation mechanism in nanocrystalline titania Penn, R. Lee; Banfield, Jillian F. American Mineralogist, Vol. 84, Issue 5-6 https://doi.org/10.2138/am-1999-5-621	journal	June 1999
Understanding Polymorphic Phase Transformation Behavior during Growth of Nanocrystalline Aggregates: Insights from TiO ₂ Zhang, Hengzhong; Banfield, Jillian F. The Journal of Physical Chemistry B, Vol. 104, Issue 15 https://doi.org/10.1021/jp000499j	journal	April 2000
Deformation twinning Christian, J. W.; Mahajan, S. Progress in Materials Science, Vol. 39, Issue 1-2 https://doi.org/10.1016/0079-6425(94)00007-7	journal	January 1995
Hierarchical rutile TiO2 mesocrystals assembled by nanocrystals-oriented attachment mechanism Wang, Hai; Liu, Yong; Liu, Zhong CrystEngComm, Vol. 14, Issue 6 https://doi.org/10.1039/c2ce06314j	journal	January 2012
Mesoporous TiO2 single crystals delivering enhanced mobility and optoelectronic device performance Crossland, Edward J. W.; Noel, Nakita; Sivaram, Varun Nature, Vol. 495, Issue 7440 https://doi.org/10.1038/nature11936	journal	March 2013
Atomic structure of conducting nanofilaments in TiO2 resistive switching memory Kwon, Deok-Hwang; Kim, Kyung Min; Jang, Jae Hyuck Nature Nanotechnology, Vol. 5, Issue 2 https://doi.org/10.1038/nnano.2009.456	journal	January 2010
Synthesis, properties, and applications of magnetic iron oxide nanoparticles Teja, Amyn S.; Koh, Pei-Yoong Progress in Crystal Growth and Characterization of Materials, Vol. 55, Issue 1-2 https://doi.org/10.1016/j.pcrysgrow.2008.08.003	journal	March 2009
Thermodynamic analysis of phase stability of nanocrystalline titania Zhang, Hengzhong; Banfield, Jillian F. Journal of Materials Chemistry, Vol. 8, Issue 9 https://doi.org/10.1039/a802619j	journal	January 1998
Self-assembly of multilevel branched rutile-type TiO2 structures via oriented lateral and twin attachment Jordan, Vanja; Javornik, Uroš; Plavec, Janez Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep24216	journal	April 2016
Constructing Hierarchical Spheres from Large Ultrathin Anatase TiO ₂ Nanosheets with Nearly 100% Exposed (001) Facets for Fast Reversible Lithium Storage Chen, Jun Song; Tan, Yi Ling; Li, Chang Ming Journal of the American Chemical Society, Vol. 132, Issue 17 https://doi.org/10.1021/ja100102y	journal	May 2010
Controllable and Repeatable Synthesis of Thermally Stable Anatase Nanocrystal−Silica Composites with Highly Ordered Hexagonal Mesostructures Dong, Weiyang; Sun, Yaojun; Lee, Chul Wee Journal of the American Chemical Society, Vol. 129, Issue 45 https://doi.org/10.1021/ja073804o	journal	November 2007
Oriented attachment induces fivefold twins by forming and decomposing high-energy grain boundaries Song, Miao; Zhou, Gang; Lu, Ning Science, Vol. 367, Issue 6473 https://doi.org/10.1126/science.aax6511	journal	November 2019
Calcium Phosphate Phase Transformation Produced by the Interaction of the Portland Cement Component of White Mineral Trioxide Aggregate with a Phosphate-containing Fluid Tay, Franklin R.; Pashley, David H.; Rueggeberg, Frederick A. Journal of Endodontics, Vol. 33, Issue 11 https://doi.org/10.1016/j.joen.2007.07.008	journal	November 2007
Mechanism of current hysteresis in reduced rutile TiO2 crystals for resistive memory Dong, R.; Lee, D. S.; Pyun, M. B. Applied Physics A, Vol. 93, Issue 2 https://doi.org/10.1007/s00339-008-4782-x	journal	November 2008
Enhanced Photocatalytic Hydrogen Production with Synergistic Two-Phase Anatase/Brookite TiO ₂ Nanostructures Tay, Qiuling; Liu, Xinfeng; Tang, Yuxin The Journal of Physical Chemistry C, Vol. 117, Issue 29 https://doi.org/10.1021/jp4040979	journal	July 2013
Radiation damage in the TEM and SEM Egerton, R. F.; Li, P.; Malac, M. Micron, Vol. 35, Issue 6 https://doi.org/10.1016/j.micron.2004.02.003	journal	August 2004
Deformation mechanisms in titanium dioxide single crystals Takeuchi, S.; Hashimoto, T. Journal of Materials Science, Vol. 25, Issue 1 https://doi.org/10.1007/BF00714049	journal	January 1990
Multifunctional nature of UV-irradiated nanocrystalline anatase thin films for biomedical applications Rupp, F.; Haupt, M.; Klostermann, H. Acta Biomaterialia, Vol. 6, Issue 12 https://doi.org/10.1016/j.actbio.2010.06.021	journal	December 2010
Polymorph Impact on the Bioavailability and Stability of Poorly Soluble Drugs Censi, Roberta; Di Martino, Piera Molecules, Vol. 20, Issue 10 https://doi.org/10.3390/molecules201018759	journal	October 2015
Review of the anatase to rutile phase transformation Hanaor, Dorian A. H.; Sorrell, Charles C. Journal of Materials Science, Vol. 46, Issue 4 https://doi.org/10.1007/s10853-010-5113-0	journal	December 2010
Prediction of TiO ₂ Nanoparticle Phase and Shape Transitions Controlled by Surface Chemistry Barnard, A. S.; Curtiss, L. A. Nano Letters, Vol. 5, Issue 7 https://doi.org/10.1021/nl050355m	journal	July 2005
Reaction of O2 with Subsurface Oxygen Vacancies on TiO2 Anatase (101) Setvin, M.; Aschauer, U.; Scheiber, P. Science, Vol. 341, Issue 6149 https://doi.org/10.1126/science.1239879	journal	August 2013
Topotaxial reactions during the genesis of oriented rutile/hematite intergrowths from Mwinilunga (Zambia) Rečnik, Aleksander; Stanković, Nadežda; Daneu, Nina Contributions to Mineralogy and Petrology, Vol. 169, Issue 2 https://doi.org/10.1007/s00410-015-1107-x	journal	February 2015
Light-induced amphiphilic surfaces Wang, Rong; Hashimoto, Kazuhito; Fujishima, Akira Nature, Vol. 388, Issue 6641 https://doi.org/10.1038/41233	journal	July 1997
Deformation twinning in bulk nanocrystalline metals: Experimental observations Zhu, Y. T.; Liao, X. Z.; Wu, X. L. JOM, Vol. 60, Issue 9 https://doi.org/10.1007/s11837-008-0120-1	journal	September 2008
What is Degussa (Evonik) P25? Crystalline composition analysis, reconstruction from isolated pure particles and photocatalytic activity test Ohtani, B.; Prieto-Mahaney, O. O.; Li, D. Journal of Photochemistry and Photobiology A: Chemistry, Vol. 216, Issue 2-3 https://doi.org/10.1016/j.jphotochem.2010.07.024	journal	December 2010
TiO ₂ Phase Transformation Mechanisms at Atomic Scale under Heating and Electron Beam Irradiation Song, Miao; Li, Dongsheng Microscopy and Microanalysis, Vol. 25, Issue S2 https://doi.org/10.1017/S1431927619010079	journal	August 2019
Anatase-to-Rutile Transformation in Titania Powders Gouma, Pelagia I.; Mills, Michael J. Journal of the American Ceramic Society, Vol. 84, Issue 3 https://doi.org/10.1111/j.1151-2916.2001.tb00709.x	journal	March 2001

Similar Records

Transitional Structures with Continuous Variations in Atomic Positions from Anatase to Rutile Improve Photocatalytic Activity

Journal Article · Thu May 11 00:00:00 EDT 2023 · Advanced Materials Interfaces · OSTI ID:1973286

Phase Transformations among TiO2 Polymorphs

Citation Formats

References (46)

Similar Records

Related Subjects