Pollution

Pollution

Facile Control of Anatase-Rutile Phase Ratio in TiO2 Nanoparticles for Highly Efficient Photocatalytic Degradation of Methylene Blue

Document Type : Original Research Paper

Authors
1 Faculty of Applied Science, University of Transport Technology, Trieu Khuc, Thanh Liet, Hanoi 100000, Vietnam
2 Faculty of Information Technology, University of Transport Technology, 54 Trieu Khuc, Hanoi 100000, Vietnam
3 Vinh Phuc College of Engineering and Technology, Phu Tho, Vietnam
4 Hanoi Pedagogical University 2, Phu Tho, Vietnam
10.22059/poll.2026.414221.3330
Abstract
Spherical TiO₂ nanoparticles with tunable phase compositions were successfully synthesized via a one-step hydrothermal method by modulating HNO₃ dosage. The results reveal that acidity plays a decisive role in governing nucleation kinetics, particle size, and phase evolution from pure rutile to anatase–rutile mixed structures. XRD analysis confirms a transition from 100% rutile (1 mL HNO₃) to the most effective mixed-phase composition (62.8% anatase/37.2% rutile at 3 mL and 73.7% anatase/26.3% rutile at 5 mL). This structural evolution is accompanied by particle size refinement from 14.1 nm to 12 nm and enhanced surface hydroxylation. Optical studies show that the 3-HNO₃ sample exhibits the lowest photoluminescence intensity and a reduced bandgap (3.05 eV), indicating efficient charge separation. As a result, this sample delivers superior photocatalytic performance, achieving 99% Methylene Blue removal within 150 min under UV irradiation, with a high apparent rate constant of 0.028 min⁻¹. The enhanced activity is attributed to the synergistic effect of optimized anatase-rutile heterojunctions and nanoscale size control, which promote interfacial charge transfer and suppress electron-hole recombination. This work provides a simple yet effective strategy for phase engineering of TiO₂ toward high-performance photocatalytic applications.
Keywords

Anucha, C. B., Altin, I., Bacaksiz, E., & Stathopoulos, V. N. (2022). Titanium dioxide (TiO₂)-based photocatalyst materials activity enhancement for contaminants of emerging concern (CECs) degradation: In the light of modification strategies. Chem. Eng. J. Adv., 10; 100262.
Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K., & Taga, Y. (2001). Visible-light photocatalysis in nitrogen-doped titanium oxides. Science, 293(5528); 269–271.
Banfield, J. (1998). Thermodynamic analysis of phase stability of nanocrystalline titania. J. Mater. Chem., 8(9); 2073–2076.
Brinker, C. J., & Scherer, G. W. (1990). Sol-gel science: the physics and chemistry of sol-gel processing. Gulf Prof. Publ.
Byrappa, K., & Adschiri, T. (2007). Hydrothermal technology for nanotechnology. Prog. Cryst. Growth Charact. Mater., 53(2); 117–166.
Cargnello, M., Gordon, T. R., & Murray, C. B. (2014). Solution-phase synthesis of titanium dioxide nanoparticles and nanocrystals. Chem. Rev., 114(19); 9319–9345.
Chekir, N., Benhabiles, O., Tassalit, D., Laoufi, N. A., & Bentahar, F. (2016). Photocatalytic degradation of methylene blue in aqueous suspensions using TiO2 and ZnO. Desalin. Water Treat., 57(13), 6141-6147.
Chen, D., Cheng, Y., Zhou, N., Chen, P., Wang, Y., Li, K., Huo, S., Cheng, P., Peng, P., & Zhang, R. (2020). Photocatalytic degradation of organic pollutants using TiO2-based photocatalysts: A review. J. Clean. Prod., 268; 121725.
Cushing, B. L., Kolesnichenko, V. L., & O’connor, C. J. (2004). Recent advances in the liquid-phase syntheses of inorganic nanoparticles. Che. Rev., 104(9); 3893–3946.
Fan, Z., Meng, F., Zhang, M., Wu, Z., Sun, Z., & Li, A. (2016). Solvothermal synthesis of hierarchical TiO2 nanostructures with tunable morphology and enhanced photocatalytic activity. Appl. Surf. Sci., 360; 298–305.
Gribb, A. A., & Banfield, J. F. (1997). Particle size effects on transformation kinetics and phase stability in nanocrystalline TiO2. Am. Mineral., 82(7–8); 717–728.
Hanaor, D. A. H., & Sorrell, C. C. (2011). Review of the anatase to rutile phase transformation. J. Mater. Sci., 46(4); 855-874.
Henderson, M. A. (2011). A surface science perspective on TiO2 photocatalysis. Surf. Sci. Rep., 66(6–7); 185-297.
Ho, Y.-S., & McKay, G. (1999). Pseudo-second order model for sorption processes. Process Biochem., 34(5); 451-465.
Houas, A., Lachheb, H., Ksibi, M., Elaloui, E., Guillard, C., & Herrmann, J.-M. (2001). Photocatalytic degradation pathway of methylene blue in water. Appl. Catal. B: Environ., 31(2); 145–157.
Hsu, C.-Y., Mahmoud, Z. H., Abdullaev, S., Ali, F. K., Naeem, Y. A., Mizher, R. M., Karim, M. M., Abdulwahid, A. S., Ahmadi, Z., & Habibzadeh, S. (2024). Nano titanium oxide (nano-TiO2): A review of synthesis methods, properties, and applications. Case Stud. Chem. Environ. Eng., 9; 100626.
Hurum, D. C., Agrios, A. G., Gray, K. A., Rajh, T., & Thurnauer, M. C. (2003). Explaining the enhanced photocatalytic activity of Degussa P25 mixed-phase TiO2 using EPR. J. Phys. Chem. B, 107(19); 4545–4549.
Khan, H., & Shah, M. U. H. (2023). Modification strategies of TiO2 based photocatalysts for enhanced visible light activity and energy storage ability: A review. J. Environ. Chem. Eng., 11(6); 111532.
Khan, M. M., Ansari, S. A., Pradhan, D., Ansari, M. O., Han, D. H., Lee, J., & Cho, M. H. (2014). Band gap engineered TiO 2 nanoparticles for visible light induced photoelectrochemical and photocatalytic studies. J. Mater. Chem. A 2(3); 637–644.
Laghrib, S., Gherdaoui, C. E., Belgherbi, O., Benaskeur, N., Boudissa, M., Kanagaraj, A., & Aouffa, N. (2025). Photocatalytic degradation of methylene blue using TiO2 nanoparticles synthesized via the sol–gel method in acidic and neutral media. React. Kinet. Mech. Catal., 138(3); 1725–1745.
Lellis, B., Fávaro-Polonio, C. Z., Pamphile, J. A., & Polonio, J. C. (2019). Effects of textile dyes on health and the environment and bioremediation potential of living organisms. Biotechnol. Res. Innov., 3(2); 275–290.
Linsebigler, A. L., Lu, G., & Yates, J. T. (1995). Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results. Chem. Rev., 95(3); 735-758.
Low, J., Yu, J., Jaroniec, M., Wageh, S., & Al‐Ghamdi, A. A. (2017). Heterojunction photocatalysts. Adv. Mater., 29(20); 1601694.
Luttrell, T., Halpegamage, S., Tao, J., Kramer, A., Sutter, E., & Batzill, M. (2014). Why is anatase a better photocatalyst than rutile?-Model studies on epitaxial TiO2 films. Sci. Rep., 4(1); 4043.
Ohno, T., Tokieda, K., Higashida, S., & Matsumura, M. (2003). Synergism between rutile and anatase TiO2 particles in photocatalytic oxidation of naphthalene. Appl. Catal. A Gen., 244(2); 383–391.
Rafatullah, M., Sulaiman, O., Hashim, R., & Ahmad, A. (2010). Adsorption of methylene blue on low-cost adsorbents: a review. J. Hazard. Mater., 177(1–3); 70–80.
Reyes-Coronado, D., Rodríguez-Gattorno, G., Espinosa-Pesqueira, M. E., Cab, C., de Coss, R., & Oskam, G. (2008). Phase-pure TiO2 nanoparticles: anatase, brookite and rutile. Nanotechnology, 19(14); 145605.
Scanlon, D. O., Dunnill, C. W., Buckeridge, J., Shevlin, S. A., Logsdail, A. J., Woodley, S. M., Catlow, C. R. A., Powell, M. J., Palgrave, R. G., & Parkin, I. P. (2013). Band alignment of rutile and anatase TiO2. Nat. Mater., 12(9); 798–801.
Schneider, J., Matsuoka, M., Takeuchi, M., Zhang, J., Horiuchi, Y., Anpo, M., & Bahnemann, D. W. (2014). Understanding TiO2 photocatalysis: mechanisms and materials. Chem. Rev., 114(19); 9919–9986.
Sugimoto, T. (1987). Preparation of monodispersed colloidal particles. Adv. Colloid Interface Sci., 28; 65–108.
Sugimoto, T., Zhou, X., & Muramatsu, A. (2003). Synthesis of uniform anatase TiO2 nanoparticles by gel–sol method: 3. Formation process and size control. J. Colloid Interface Sci., 259(1), 43–52.
Victor K, B., LaMer, R. H., & Dinegar, T. (1950). Production and mechanism of formation of monodispersed hydrosols. J. Am. Chem. Soc, 72.
Whitehead, C. B., Özkar, S., & Finke, R. G. (2021). LaMer’s 1950 model of particle formation: a review and critical analysis of its classical nucleation and fluctuation theory basis, of competing models and mechanisms for phase-changes and particle formation, and then of its application to silver halide, semiconductor, metal, and metal-oxide nanoparticles. Mater. Adv., 2(1); 186–235.
Zhang, H., & Banfield, J. F. (2000a). Phase transformation of nanocrystalline anatase-to-rutile via combined interface and surface nucleation. J. Mater. Res., 15(2); 437–448.
Zhang, H., & Banfield, J. F. (2000b). Understanding polymorphic phase transformation behavior during growth of nanocrystalline aggregates: insights from TiO2. J. Phys. Chem. B, 104(15); 3481–3487.
Zhang, J., Zhou, P., Liu, J., & Yu, J. (2014). New understanding of the difference of photocatalytic activity among anatase, rutile and brookite TiO 2. Phys. Chem. Chem. Phys., 16(38); 20382–20386.