• International Journal of Technology (IJTech)
  • Vol 10, No 6 (2019)

Effect of NaCl Addition on Nano Rosette Tio2 Crystal Growth during Hydrothermal Deposition

Nofrijon Sofyan, Aga Ridhova, Akhmad Herman Yuwono, Marshall C. Sianturi

Corresponding email: nofrijon.sofyan@ui.ac.id

Cite this article as:
Sofyan, N., Ridhova, A., Yuwono, A.H., Sianturi, M.C., 2019. Effect of NaCl Addition on Nano Rosette Tio2 Crystal Growth during Hydrothermal Deposition. International Journal of Technology. Volume 10(6), pp. 1235-1242

Nofrijon Sofyan Department of Metallurgical and Materials Engineering, Faculty of Engineering, Universitas Indonesia, Kampus UI Depok, Depok 16424, Indonesia
Aga Ridhova Research Center for Metallurgy and Materials, Indonesian Institute of Sciences, Tangerang Selatan, Banten 15314, Indonesia
Akhmad Herman Yuwono Department of Metallurgical and Materials Engineering, Faculty of Engineering, Universitas Indonesia, Kampus UI Depok, Depok 16424, Indonesia
Marshall C. Sianturi Department of Metallurgical and Materials Engineering, Faculty of Engineering, Universitas Indonesia, Kampus UI Depok, Depok 16424, Indonesia
Email to Corresponding Author


The effect of NaCl on the crystal growth of nano rosette TiO2 hydrothermally grown on a glass substrate was examined. Nano rosette TiO2 was synthesized through deposition on a glass substrate via hydrothermal reaction at 170°C for 6 hours. The effect of NaCl on nano rosette TiO2 crystal growth during the hydrothermal process was observed through the addition of concentrations of 0, 2.5, 5, and 10% v/v NaCl to the mixture of the precursors. Formation and growth of the crystal were characterized using X-ray diffraction, whereas morphology was examined using a scanning electron microscope. X-ray diffractograms revealed that the crystal belonged to rutile P42/mnm with lattice parameters of a = 4.557(6) Å and c = 2.940(5) Å. Morphology of the reaction product showed that the addition of NaCl inhibited the crystal growth of nano rosette TiO2 with an average rosette petal cross-sectional size 80% smaller than that of the crystal grown with no NaCl addition.

Hydrothermal; Nano rosette; Nanoscale; Sodium chloride; Titanium dioxide


In current advanced materials development, nanomaterials are attracting the attention of many researchers due to inherent properties resulting from the physicochemical changes of a substance at nanoscale. Nanoscale building blocks, specifically in the forms of 3D architectures of hierarchical nanostructures such as nanowires (Zhu et al., 2018), nanorods (Govindaraj et al., 2017), nanosheets (Zhong et al., 2015) and nanoflowers (Ma et al., 2017), have become the focus, receiving closer attention due to their unique properties and promising applications in many areas (Banfield & Veblen, 1992).

For a long time, Titanium dioxide or TiO2 has been the subject of intensive research because of its unique properties with promising application in numerous areas. Titanium dioxide is also known for its polymorphic characteristic, in which it may have several crystal structures, including brookite, anatase, and rutile crystal structures (Khan et al., 2017). Due to these unique properties, not only has it been used tremendously in conventional applications such as white pigment in paint, food coloring, and personal care products (Bai & Zhou, 2014), but it has also been used as advanced materials for sensors (Nakata & Fujishima, 2012), photocatalysts (Xie et al., 2009; Liang et al.,  2017;  Longoni et al., 2017;  Rahman et al., 2018),  dye-sensitized solar cells  (Sofyan et al., 2017;  Sofyan et al., 2019),  perovskite  solar  cells (Dahl et al.,  2014),  and batteries (Saif et al., 2012).

The use of 3D nanostructures TiO2 in the form of hierarchical flower-like TiO2 nanostructures has recently increased due to their excellent optical, electrical, and electronic properties with promising use in many applications (Bu et al., 2015; Zhang et al., 2018). As a result, many investigators have put their efforts into improving methods in synthesizing 3D flower-like nanostructure TiO2. For example, TiO2 with 3D nano-flower hierarchical structures has been proven to enhance its photocatalytic property (Zhou et al., 2013; Bu et al., 2015). In separate work, Xiao et al. (2017) and Govindasamy et al. (2016) have reported that the use of a combination of TiO2 compact layers with the growth of TiO2 nanorods as an electron transporting layer has improved the performance of perovskite solar cells.

Despite its promising use in many applications, there are still many problems in synthesizing flower-like structure TiO2, such as homogeneity and coverage area, in the case of the deposition process. There are also very few references that discuss the direct synthesis of rutile TiO2 with high homogeneity, especially in the form of rutile nano rosette TiO2. Another problem comes from the fact that, if the deposition can have a high coverage area and be homogeneous, the crystal might grow uncontrolled and thus result in quite large crystal size. Because of this, during the process, growth needs to be controlled.

In this work, 3D hierarchical nano rosette TiO2 has been grown via a hydrothermal process on a glass substrate with enhanced homogeneity and coverage area, whilst at the same time offering a controllable crystal growth during the synthesis, resulting in a controlled size of nano rosette TiO2. The characteristics of the nano rosette TiO2 from the reaction products in different controlled environments using sodium chloride (NaCl) at different concentrations on crystal formation and growth during the hydrothermal deposition are presented and discussed. 


The effect of hydrothermal reaction time and NaCl addition on the characteristics of nano rosette TiO2 crystal growth during hydrothermal reaction has been examined. With no addition of NaCl, the nano rosette forms at full growth indicated by high intensity of the crystal structure indexed to rutile P42/mnm with lattice parameters of a = 4.557(6) Å and c = 2.940(5) Å. The cross-sectional rosette petal grew up to 250 nm. On the contrary, with the addition of NaCl, the crystal growth during hydrothermal reaction could be controlled. In this work, with the addition of 2.5% v/v NaCl, the cross-sectional rosette size was only of about 50 nm, 80% smaller than that of the crystal grown with no NaCl addition. 


This work was funded by the Directorate of Research and Community Services (DRPM) Universitas Indonesia under Hibah PITTA No. 2504/UN2.R3.1/HKP.05.00/2018.

Supplementary Material
MME-3630-20191015134155.pdf Copyright form
MME-3630-20191015134222.pdf Response to reviewers
MME-3630-20191015134326.pdf Cover Letter

Bai, J., Zhou, B., 2014. Titanium Dioxide Nanomaterials for Sensor Applications. Chemical Review, Volume 114, pp. 10131–10176

Banfield, J.F., Veblen, D.R., 1992. Conversion of Perovskite to Anatase and TiO2 (B): A TEM Study and the Use of Fundamental Building Blocks for Understanding Relationships among the TiO2 Minerals. American Mineralogist, Volume 77, pp. 545–557

Bu, J., Fang, J., Leow, W.R., Zheng, K., Chen, X., 2015. Single-Crystalline Rutile TiO2 Nano-Flower Hierarchical Structures for Enhanced Photocatalytic Selective Oxidation from Amine to Imine. RSC Advances, Volume 5(126), pp. 103895–103900

Dahl, M., Liu, Y., Yin, Y., 2014. Composite Titanium Dioxide Nanomaterials. Chemical Review, Volume 114, pp. 9853–9889

Govindaraj, R., Santhosh, N., Pandian, M.S., Ramasamy, P., 2017. Synthesis of Nanocrystalline TiO2 Nanorods via Hydrothermal Method: An Efficient Photoanode Material for Dye Sensitized Solar Cells. Journal of Crystal Growth, Volume 468, pp. 125–128

Govindasamy, G., Murugasen, P., Sagadevan, S., 2016. Investigations on the Synthesis, Optical and Electrical Properties of TiO2 Thin Films by Chemical Bath Deposition (CBD) Method. Materials Research, Volume 19(2), pp. 413–419

Khan, J., Gu, J., Meng, Y., Chai, Z., He, S., Wu, Q., Tong, S., Ahmed, G., Mai, W., Wu, M., 2017. Anatase TiO2 Single Crystal Hollow Nanoparticles: Their Facile Synthesis and High-Performance in Dye-sensitized Solar Cells. CrystEngComm, Volume 19, pp. 325–334

Liang, C., Wu, Z., Li, P., Fan, J., Zhang, Y., Shao, G., 2017. Chemical Bath Deposited Rutile TiO2 Compact Layer Toward Efficient Planar Heterojunction Perovskite Solar Cells. Applied Surface Science, Volume 391(B), pp. 337–344

Liu, B., Aydil, E.S., 2009. Growth of Oriented Single-crystalline Rutile TiO2 Nanorods on Transparent Conducting Substrates for Dye-sensitized Solar Cells. Journal of American Chemical Society, Volume 131, pp. 3985–3990

Longoni, G., Cabrera, R.L.P., Polizzi, S., D’Arienzo, M., Mari, C.M., Cui, Y., Ruffo, R., 2017. Shape-controlled TiO2 Nanocrystals for Na-ion Battery Electrodes: The Role of Different Exposed Crystal Facets on the Electrochemical Properties. Nano Letters, Volume 17, pp. 992–1000

Ma, J., Ren, W., Zhao, J., Yang, H., 2017. Growth of TiO2 Nanoflowers Photoanode for Dye-sensitized Solar Cells. Journal of Alloys and Compounds, Volume 692, pp. 1004–1009

Nakata, K., Fujishima, A., 2012. TiO2 Photocatalysis: Design and Applications. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, Volume 13(3), pp. 169–189

Patterson, A.L., 1939. The Scherrer Formula for X-Ray Particle Size Determination. Physical Review, Volume 56, pp. 978–982

Rahman, A., Nurjayadi, M., Wartilah, R., Kusrini, E., Prasetyanto, E.A., Degermenci, V., 2018. Enhanced Activity of TiO2/Natural Zeolite Composite for Degradation of Methyl Orange under Visible Light Irradiation. International Journal of Technology, Volume 9(6), pp. 1159–1167

Saif, M., Aboul-Fotouh, S.M.K., El-Molla, S.A., Ibrahim, M.M., Ismail, L.F.M., 2012. Improvement of the Structural, Morphology, and Optical Properties of TiO2 for Solar Treatment of Industrial Wastewater. Journal of Nanoparticle Research, Volume 14(1227), pp. 101–111

Sofyan, N., Ridhova, A., Yuwono, A.H., Udhiarto, A., 2017. Fabrication of Solar Cells with TiO2 Nanoparticles Sensitized using Natural Dye Extracted from Mangosteen Pericarps. International Journal of Technology, Volume 8(7), pp. 1229–1238

Sofyan, N., Ridhova, A., Yuwono, A.H., Udhiarto, A., Fergus, J.W., 2019. Synthesis of TiO2 Nanoparticles at Low Hydrothermal Temperature and Its Performance for DSSC Sensitized using Natural Dye Extracted from Melastoma Malabathricum L. Seeds. International Journal of Energy Research, Volume 43(11), pp. 5959–5968

Sofyan, N., Ridhova, A., Yuwono, A.H., Wu, J., 2018. Characteristics of Nano Rosette TiO2 Hydrothermally Grown on a Glass Substrate at Different Reaction Times and Acid Concentrations. International Journal of Technology, Volume 9(6), pp. 1196–1204

Xiao, G., Shi, C., Li, L., Zhang, Z., Ma, C., Lv, K., 2017. A 200-nm length TiO2 Nanorod Array with a Diameter of 13 nm and Areal Density of 1100 ?m -2 for Efficient Perovskite Solar cells. Ceramics International, Volume 43(15), pp. 12534–12539

Xie, J., Lü, X., Liu, J., Shu, H., 2009. Brookite Titania Photocatalytic Nanomaterials: Synthesis, Properties, and Applications. Pure and Applied Chemistry, Volume 81(12), pp. 2407–2415

Zhang, H., Chen, W.-G., Li, Y.-Q., Jin, L.-F., Cui, F., Song, Z.-H., 2018. 3D Flower-Like NiO Hierarchical Structures Assembled With Size-controllable 1D Blocking Units: Gas Sensing Performances Towards Acetylene. Frontiers in chemistry, Volume 6(472), pp. 1–6

Zhong, D., Jiang, Q., Huang, B., Zhang, W.-H., Li, C., 2015. Synthesis and Characterization of Anatase TiO2 Nanosheet Arrays on FTO Substrate. Journal of Energy Chemistry, Volume 24, pp. 626–631

Zhou, J., Tian, G., Chen, Y., Wang, J.-Q., Cao, X., Shi, Y., Pan, K., Fu, H., 2013. Synthesis of Hierarchical TiO2 Nanoflower with Anatase-rutile Heterojunction as Ag Support for Efficient Visible-light Photocatalytic Activity. Dalton Transactions, Volume 42(31), pp. 11242–11251

Zhu, Z., Lin, S.-J., Wu, C.-H., Wu, R.-J., 2018. Synthesis of TiO2 Nanowires for Rapid NO2 Detection. Sensors and Actuators A, Volume 272, pp. 288–294