journal article·2022-02-03Open access

Synthesis and Characterization of Anatase TiO2 Nanorods: Insights from Nanorods’ Formation and Self-Assembly

Seyed Naveed Hosseini, Xiaodan Chen, Patrick J. Baesjou, Arnout Imhof, Alfons van Blaaderen

Applied Sciences· Volume 12· Issue 3

Abstract

Highly crystalline, organic-solvent-dispersible titanium dioxide (TiO2) nanorods (NRs) present promising chemicophysical properties in many diverse applications. In this paper, based on a modified procedure from literature, TiO2 NRs were synthesized via a ligand-assisted nonhydrolytic sol-gel route using oleic acid as the solvent, reagent, and ligand and titanium (IV) isopropoxide as the titanium precursor. This procedure produced monodisperse TiO2 NRs, as well as some semi-spherical titania nanocrystals (NCs) that could be removed by size-selective precipitation. X-ray diffraction and selected area electron diffraction results showed that the nanorods were anatase, while the semipheres also contained the TiO2(B) phase. By taking samples during the particle growth, it was found that the average length of the initially grown NRs decreased during the synthesis. Possible reasons for this unusual growth path, partially based on high-resolution transmission electron microscopy (HRTEM) observations during the growth, were discussed. The dispersion of anatase TiO2 nanorods was capable of spontaneous formation of lyotropic liquid crystals on the TEM grid and in bulk. Considering high colloidal stability together with the large optical birefringence displayed by these high refractive index liquid crystalline domains, we believe these TiO2 NRs dispersions are promising candidates for application in transparent and switchable optics.
Source: crossref · Quality: baseline

Research context

OpenAlex topics: TiO2 Photocatalysis and Solar Cells · Quantum Dots Synthesis And Properties · Advanced Photocatalysis Techniques

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University, Princetonplein 1, 3584 CC Utrecht, The Netherlands

Funding

NWO-TTW · European Research Council for their support via the ERC Consolidator Grant NANO-INSITU

References (94)

Show source-provided references
1. Titanium dioxide nanomaterials for photovoltaic applications10.1021/cr400606n ↗
2. Titanium dioxide photocatalysis: Fundamentals and application on photoinactivation
3. Engineering titania nanostructure to tune and improve its photocatalytic activity10.1073/pnas.1524806113 ↗
4. Titanium dioxide (Anatase and Rutile): Surface chemistry, liquid-solid interface chemistry, and scientific synthesis of supported catalysts10.1021/cr300230q ↗
5. Nonaqueous synthesis of TiO2 nanocrystals using TiF4 to engineer morphology, oxygen vacancy concentration, and photocatalytic activity10.1021/ja300823a ↗
6. Casavola, M., Buonsanti, R., Caputo, G., and Cozzoli, P.D. (2008). Colloidal strategies for preparing oxide-based hybrid nanocrystals. Eur. J. Inorg. Chem., 837–854.10.1002/ejic.200701047 ↗
7. A review on the synthesis of the various types of anatase TiO2 facets and their applications for photocatalysis10.1016/j.cej.2019.123384 ↗
8. Structural characteristics and mechanical and thermodynamic properties of nanocrystalline TiO210.1021/cr500072j ↗
9. Titanium Dioxide-Based Nanomaterials for Photocatalytic Fuel Generations10.1021/cr500008u ↗
10. Titanium Dioxide Nanomaterials for Sensor Applications10.1021/cr400625j ↗
11. Electrolytic deposition of titania films as interference coatings on biomedical implants: Microstructure, chemistry and nano-mechanical properties10.1016/j.tsf.2005.09.068 ↗
12. Sungur, Ş. (2021). Titanium Dioxide Nanoparticles. Handbook of Nanomaterials and Nanocomposites for Energy and Environmental Applications, Springer.10.1007/978-3-030-36268-3_9 ↗
13. Thermodynamic analysis of phase stability of nanocrystalline titania10.1039/a802619j ↗
14. Energetics of nanocrystalline TiO210.1073/pnas.251534898 ↗
15. Understanding polymorphic phase transformation behavior during growth of nanocrystalline aggregates: Insights from TiO210.1021/jp000499j ↗
16. Interconnected nanofibrous titanium dioxide bronze: An emerging lithium ion anode material for high rate performance10.1039/c2ra22847e ↗
17. Peering into the mechanism of low-temperature synthesis of bronze-type TiO2 in ionic liquids10.1021/acs.cgd.7b01231 ↗
18. Smectic Liquid Crystalline Titanium Dioxide Nanorods: Reducing Attractions by Optimizing Ligand Density10.1002/adfm.202005491 ↗
19. Liquid Crystalline Order and Electric Switching of Upconversion Luminescence in Colloidal Nanorod Suspensions10.1002/adom.201900041 ↗
20. Low-Temperature Synthesis of Soluble and Low-Temperature Synthesis of Soluble and Processable10.1021/ja036505h ↗
21. One-dimensional titanium dioxide nanomaterials: Nanotubes10.1021/cr500061m ↗
22. Solution-Phase Synthesis of Titanium Dioxide Nanoparticles and Nanocrystals10.1021/cr500170p ↗
23. New trends in colloidal liquid crystals based on mineral moieties10.1002/(SICI)1521-4095(200001)12:1<9::AID-ADMA9>3.0.CO;2-6 ↗
24. Inorganic lyotropic liquid crystals10.1039/a802666a ↗
25. Synthesis of TiO2 nanocrystals by nonhydrolytic solution-based reactions10.1021/ja983361b ↗
26. Chemseddine, A., and Moritz, T. (1999). Nanostructuring titania: Control over nanocrystal structure, size, shape, and organization. Eur. J. Inorg. Chem., 235–245.10.1002/(SICI)1099-0682(19990202)1999:2<235::AID-EJIC235>3.0.CO;2-N ↗
27. Surfactant-Assisted Elimination of a High Energy Facet as a Means of Controlling the Shapes of TiO2 Nanocrystals10.1021/ja0369515 ↗
28. Benzyl alcohol and titanium tetrachloride - A versatile reaction system for the nonaqueous and low-temperature preparation of crystalline and luminescent titania nanoparticles10.1021/cm021203k ↗
29. A Solution Chemistry Study of Nonhydrolytic Sol - Gel Routes to Titania10.1021/cm960337t ↗
30. Nonhydrolytic processing of oxide-based materials: Simple routes to control homogeneity, morphology, and nanostructure10.1021/cm802348c ↗
31. Aminolysis route to monodisperse titania nanorods with tunable aspect ratio10.1002/anie.200500410 ↗
32. Nonhydrolytic synthesis of high-quality anisotropically shaped brookite TiO2 nanocrystals10.1021/ja803559b ↗
33. Hyperbranched Anatase TiO2 Nanocrystals: Nonaqueous Synthesis, Growth Mechanism, and Exploitation in Dye-Sensitized Solar Cells10.1021/ja208418z ↗
34. Joo, J., Kwon, S.G., Yu, T., Cho, M., Lee, J., and Yoon, J. (2005). Large-Scale Synthesis of TiO2 Nanorods via Nonhydrolytic Sol - Gel Ester Elimination Reaction and Their Application to Photocatalytic Inactivation of E. coli. J. Phys. Chem. B, 15297–15302.10.1021/jp052458z ↗
35. Simultaneous phase- and size-controlled synthesis of TiO2 nanorods via non-hydrolytic sol-gel reaction of syringe pump delivered precursors10.1021/jp065372u ↗
36. Levy, D., and Marcos, Z. (2015). The Sol-Gel Handbook, Wiley-VCH.10.1002/9783527670819 ↗
37. Epoxy-based hybrids using TiO2 nanoparticles prepared via a non-hydrolytic sol-gel route10.1002/aoc.3027 ↗
38. Revealing the Effects of the Non-solvent on the Ligand Shell of Nanoparticles and Their Crystallization10.1021/jacs.9b06010 ↗
39. Phase behavior of colloidal silica rods10.1039/c2fd20084h ↗
40. Niederberger, M., and Pinna, N. (2009). Metal Oxide Nanoparticles in Organic Solvents: Synthesis, Formation, Assembly and Application, Springer.10.1007/978-1-84882-671-7 ↗
41. Synthesis And Characterization Of Monodisperse Nanocrystals And Close-Packed Nanocrystal Assemblies10.1146/annurev.matsci.30.1.545 ↗
42. Israelachvili, J.N. (2011). Intermolecular and Surface Forces, Elsevier. [3rd ed.].
43. Morphology development and crystal growth in nanocrystalline aggregates under hydrothermal conditions: Insights from titania10.1016/S0016-7037(99)00037-X ↗
44. Non-aqueous routes to crystalline metal oxide nanoparticles: Formation mechanisms and applications10.1016/j.progsolidstchem.2005.11.032 ↗
45. Nonaqueous Sol – Gel Routes to Metal Oxide Nanoparticles10.1021/ar600035e ↗
46. Deshmukh, R., and Niederberger, M. (2015). Nonhydrolytic Sol – Gel Methods. The Sol–Gel Handbook: Synthesis, Characterization, and Applications, Wiley-VCH.10.1002/9783527670819.ch02 ↗
47. Detachment induced by rayleigh-instability in metal oxide nanorods: Insights from TiO210.1021/cg300473u ↗
48. Benzyl alcohol and transition metal chlorides as a versatile reaction system for the nonaqueous and low-temperature synthesis of crystalline nano-objects with controlled dimensionality10.1021/ja027115i ↗
49. Near monodisperse TiO2 nanoparticles and nanorods10.1002/chem.200500893 ↗
50. Jiang, D., Xu, Y., Hou, B., Wu, D., and Sun, Y. (2008). A simple non-aqueous route to anatase TiO2. Eur. J. Inorg. Chem., 1236–1240.10.1002/ejic.200700650 ↗
51. Preparation of high photocatalytic activity TiO2 with a bicrystalline phase containing anatase and TiO2 (B)10.1016/j.matlet.2005.05.072 ↗
52. Control of Metal Nanocrystal Size Role for Ceria Catalysts
53. Topologically controlled growth of magnetic-metal-functionalized semiconductor oxide nanorods10.1021/nl070550w ↗
54. Prediction of TiO2 nanoparticle phase and shape transitions controlled by surface chemistry10.1021/nl050355m ↗
55. Synthesis of recrystallized anatase TiO2 mesocrystals with Wulff shape assisted by oriented attachment10.1039/c0nr01016b ↗
56. Impact of the colloidal state on the oriented attachment growth mechanism10.1039/c0nr00338g ↗
57. Progress of nanocrystalline growth kinetics based on oriented attachment10.1039/B9NR00047J ↗
58. Nichols, F.A., and Mullins, W.W. (1965). Contributions to Morphological Changes Driven by Capillarity. Trans. Met. Soc. AIME, 233.
59. Influence of crystallinity on the Rayleigh instability of gold nanowires10.1088/0022-3727/40/12/031 ↗
60. Rayleigh-instability-induced metal nanoparticle chains encapsulated in nanotubes produced by atomic layer deposition10.1021/nl0721766 ↗
61. General assembly method for linear metal nanoparticle chains embedded in nanotubes10.1021/nl801548h ↗
62. Shape-Controlled Synthesis of Highly Crystalline Titania Nanocrystals10.1021/nn900940p ↗
63. Formation of rutile nuclei at anatase (112) twin interfaces and the phase transformation mechanism in nanocrystalline titania10.2138/am-1999-5-621 ↗
64. Bandgap studies on anatase titanium dioxide nanoparticles10.1016/S0254-0584(02)00343-7 ↗
65. The Scherrer equation versus the “Debye-Scherrer equation”10.1038/nnano.2011.145 ↗
66. Ligand-mediated shape control in the solvothermal synthesis of titanium dioxide nanospheres, nanorods and nanowires10.1039/c1nr10540j ↗
67. Tailored titanium dioxide nanomaterials: Anatase nanoparticles and brookite nanorods as highly active photocatalysts10.1021/cm903472p ↗
68. Anatase, brookite, and rutile nanocrystals via redox reactions under mild hydrothermal conditions: Phase-selective synthesis and physicochemical properties10.1021/jp0673258 ↗
69. The shape of TiO2-B nanoparticles10.1021/ja412387c ↗
70. Tracing the phase boundaries of hard spherocylinders10.1063/1.473404 ↗
71. The Effects of Shape on the Interaction of Colloidal Particles10.1111/j.1749-6632.1949.tb27296.x ↗
72. Isotropic-Nematic Phase Separation of Dispersion of Organophilic Boehmite Rods D/L10.1021/j100146a027 ↗
73. Polydispersity and Ordered Phases in Solutions of Rodlike Macromolecules10.1103/PhysRevLett.76.1396 ↗
74. Morphology and kinetics of the isotropic-nematic phase transition in dispersions of hard rods10.1021/ma981196e ↗
75. Smectic liquid-crystalline order in suspensions of highly polydisperse goethite nanorods10.1002/adma.200601112 ↗
76. Isotropic – nematic phase behavior of length- polydisperse hard rods10.1063/1.1599277 ↗
77. Sedimentation and multiphase equilibria in suspensions of colloidal hard rods10.1103/PhysRevE.70.051401 ↗
78. Savenko, S.V., and Dijkstra, M. (2006). Phase behavior of a suspension of colloidal hard rods and nonadsorbing polymer. J. Chem. Phys., 124.10.1063/1.2202853 ↗
79. Semiconductor nanorod self-assembly at the liquid/air interface studied by in situ GISAXS and ex situ TEM10.1021/nl302360u ↗
80. Self-Assembled Superlattices from Colloidal TiO2 Nanorods10.2174/157341310791171126 ↗
81. Two-step self-assembly and lyotropic liquid crystal behavior of TiO2 nanorods10.1155/2012/180989 ↗
82. Large-scale superlattices from colloidal TiO2nanorods: A facile self-assembly approach10.1016/j.apsusc.2016.01.218 ↗
83. Electric-field-assisted assembly of perpendicularly oriented nanorod superlattices10.1021/nl060866o ↗
84. Semiconductor nanorod liquid crystals and their assembly on a substrate10.1002/adma.200390093 ↗
85. Synthesis, characterization, and self-assembly of pencil-shaped CoO nanorods10.1021/ja0608702 ↗
86. Langmuir-Blodgett nanorod assembly10.1021/ja0059138 ↗
87. Smectic nanorod superlattices assembled on liquid subphases: Structure, orientation, defects, and optical polarization10.1021/acs.chemmater.5b00355 ↗
88. Vortical superlattices in a gold nanorods’ self-assembled monolayer10.1039/C3NR05992H ↗
89. Millimeter-scale assembly of CdSe nanorods into smectic superstructures by solvent drying kinetics10.1002/adma.200800125 ↗
90. Condensation and dissolution of nematic droplets in dispersions of colloidal rods with thermo-sensitive depletants10.1038/srep18432 ↗
91. Shape and director-field transformation of tactoids10.1103/PhysRevE.68.021701 ↗
92. Liquid crystalline tactoids: Ordered structure, defective coalescence and evolution in confined geometries10.1098/rsta.2017.0042 ↗
93. Experimental realization of crossover in shape and director field of nematic tactoids10.1103/PhysRevE.91.042507 ↗
94. Green, M.J., Parra-Vasquez, A.N.G., Behabtu, N., and Pasquali, M. (2009). Modeling the phase behavior of polydisperse rigid rods with attractive interactions with applications to single-walled carbon nanotubes in superacids. J. Chem. Phys., 131.10.1063/1.3204024 ↗