Mechanochemical Synthesis Of Anatase-Rutile Phases At Ball Milling In Different Conditions And Its Cause And Effect On A Photo-Oxidation Process / Síntese mecano-química de fases anatômicas na moagem de bolas em diferentes condições e sua causa e efeito em um processo de foto-oxidação

Jean César Marinozi Vicentini, Gimerson Weigert Subtil, Daiane Marques de Oliveira, Fernanda de Oliveira Tavares, Mara Heloisa Neves Olsen Scaliante, Marcos de Souza


This study aims to evaluate the effect of the grinding parameters applied to TiO2 comminution, which forms a heterojunction of anatase-rutile phases and reduces markedly the size particle. This material is a well-knowm photocatalyst in environmental issues such as degradation of synthetic dyes, mainly due to the large surface area and oxidative radicals generations ability. The influence of time, rotational speed and the solvent was investigated in the grinding process. Catalysts were prepared by a deposition method and were characterized by XRD, textural analysis (BET area), potential electrophoretic, photoacoustic and Mössbauer spectroscopy. The comminution procedure reduced the size of TiO2 crystallites from 87 nm to 22 nm as well as the surface area and pore diameter. The best photocatalytic activity was for TiO2 comminuted for 10 min and 300 rpm in a dry medium supported on ZSM-5. It was registered that the photoactivity of TiO2 decreased with the transition of anatase to rutile phase and also by the iron oxides insertion during the comminution process. This study has a great technologic contribution because it elucidates primary issues on the particle sizes reduction in the catalysts production, whose function is to have a better metal distribution on the support’s surface.


ZSM-5, photocatalysis, pseudobrookite, Mössbauer Spectroscopy, grinding.


Brites FF, Santana VS, Fernandes-Machado NRC. Effect of support on the photocatalytic degradation of textile effluents using Nb2O5 and ZnO: Photocatalytic degradation of textile dye. Top Catal 2011;54:264–9.

Körlü AE, Yapar S, Perinçek S, Yılmaz H, Bağıran C. Dye removal from textile waste water through the adsorption by pumice used in stone washing. Autex Res J 2015;15:158–63.

Vicentini JCM, Medeiros GB, Watanabe MCC, Piccoli KR, Camilo FC, Scaliante MHNO. Synergistic effect between oxides semiconductors and zeolites on photobleaching of RB250 textile dye. Acta Sci - Technol 2018;40:1–8.

Znad H, Abbas K, Hena S, Awual MR. Synthesis a novel multilamellar mesoporous TiO2/ZSM-5 for photo-catalytic degradation of methyl orange dye in aqueous media. J Environ Chem Eng 2018;6:218–27.

Subtil GW, Vicentini JCM, Cordeiro PHY, Scaliante MHNO. Fotodegradação De Corante Textil Azul Rb 250 E Produção Fotocatalítica De H2 Utilizando Tio2 Nano Suportado Em Zeolita Zsm-5 / Rb 250 Blue Dye Photodegradation and H2 Photocatalytic Production Using Tio2 Nano Supported on Zeolite Zsm-5. Brazilian J Dev 2020;6:67238–48.

Saggioro EM, Oliveira AS, Moreira JC. Heterogeneous Photocatalysis Remediation of Wastewater Polluted by Indigoid Dyes. Text Wastewater Treat 2016.

Goedecke C, Sojref R, Nguyen TY, Piechotta C. Immobilization of photocatalytically active TiO2 nanopowder by high shear granulation. Powder Technol 2017;318:465–70.

Suryanarayana C. Mechanical alloying and milling. Mech Alloy Milling 2004:1–472.

Anand K, Varghese S, Kurian T. Preparation of ultra-fine dispersions of zinc oxide by simple ball-milling: Optimization of process parameters. Powder Technol 2015;271:187–92.

Jung HJ, Sohn Y, Sung HG, Hyun HS, Shin WG. Physicochemical properties of ball milled boron particles: Dry vs. wet ball milling process. Powder Technol 2015;269:548–53.

Furlani E, Aneggi E, de Leitenburg C, Maschio S. High energy ball milling of titania and titania-ceria powder mixtures. Powder Technol 2014;254:591–6.

Dabhade V V., Rama Mohan TR, Ramakrishnan P. Nanocrystalline titanium powders by high energy attrition milling. Powder Technol 2007;171:177–83.

Miszczak S, Pietrzyk B. Anatase–rutile transformation of TiO2 sol–gel coatings deposited on different substrates. Ceram Int 2015;41:7461–5.

Rodríguez-Torres CE, Cabrera AF, Errico LA, Adn C, Requejo FG, Weissmann M, et al. Local structure and magnetic behaviour of Fe-doped TiO2 anatase nanoparticles: Experiments and calculations. J Phys Condens Matter 2008;20.

Hanaor DAH, Sorrell CC. Review of the anatase to rutile phase transformation. J Mater Sci 2011;46:855–74.

Kordouli E, Bourikas K, Lycourghiotis A, Kordulis C. The mechanism of azo-dyes adsorption on the titanium dioxide surface and their photocatalytic degradation over samples with various anatase/rutile ratios. Catal Today 2014.

Petkowicz DI, Pergher SBC, da Silva CDS, da Rocha ZN, dos Santos JHZ. Catalytic photodegradation of dyes by in situ zeolite-supported titania. Chem Eng J 2010;158:505–12.

Opalka SM, Zhu T. Influence of the Si/Al ratio and Al distribution on the H-ZSM-5 lattice and Brønsted acid site characteristics. Microporous Mesoporous Mater 2016;222:256–70.

Jenkins R, Snyder R. Introduction to X-Ray Powder Diffractometry. Wiley & Sons Ltd; 1996.

Chen W, Liu M, Wang Y, Gao L, Dang H, Mao L. Non-noble metal Co as active sites on TiO 2 nanorod for promoting photocatalytic H 2 production. Mater Res Bull 2019;116:16–21.

Nguyen NT, Ozkan S, Hejazi S, Denisov N, Tomanec O, Zboril R, et al. Providing significantly enhanced photocatalytic H2 generation using porous PtPdAg alloy nanoparticles on spaced TiO2 nanotubes. Int J Hydrogen Energy 2019;44:22962–71.

Deshmane VG, Owen SL, Abrokwah RY, Kuila D. Mesoporous nanocrystalline TiO2 supported metal (Cu, Co, Ni, Pd, Zn, and Sn) catalysts: Effect of metal-support interactions on steam reforming of methanol. J Mol Catal A Chem 2015;408:202–13.

Ghosh P, Chelli VR, Giri AS, Golder AK. Steroid glycosides as potential analytes for Cu-doping on TiO 2 for photocatalytic water treatment. Environ Prog Sustain Energy 2018;37:1973–81.

Arul AR, Manjulavalli TE, Venckatesh R. Visible light proven Si doped TiO2 nanocatalyst for the photodegradation of Organic dye. Mater Today Proc 2019;18:1760–9.

Ali MHH, Al-Afify AD, Goher ME. Preparation and characterization of graphene – TiO2 nanocomposite for enhanced photodegradation of Rhodamine-B dye. Egypt J Aquat Res 2018;44:263–70.

Tauc J, Grigorovici R, Vancu A. Optical Properties and Electronic Structure of Amorphous Germanium. Phys Status Solidi 1966;15:627–37.

Arzenšek D, Podgornik R, Kuzman D. Dynamic light scattering and application to proteins in solutions. Seminar 2010:1–18.

Nejat T, Jalalinezhad P, Hormozi F, Bahrami Z. Hydrogen production from steam reforming of ethanol over Ni-Co bimetallic catalysts and MCM-41 as support. J Taiwan Inst Chem Eng 2019;97:216–26.

Brites-Nóbrega FF, Lacerda IA, Santos S V., Amorim CC, Santana VS, Fernandes-Machado NRC, et al. Synthesis and characterization of new NaX zeolite-supported Nb, Zn, and Fe photocatalysts activated by visible radiation for application in wastewater treatment. Environ Sci Technol 1995;29:240.

Kosmulski M. pH-dependent surface charging and points of zero charge. IV. Update and new approach. J Colloid Interface Sci 2009;337:439–48.

Kosmulski M. The pH-dependent surface charging and points of zero charge. V. Update. J Colloid Interface Sci 2011;353:1–15.

Xu N, Shi Z, Fan Y, Dong J, Shi J, Hu MZC. Effects of particle size of TiO2 on photocatalytic degradation of methylene blue in aqueous suspensions. Ind Eng Chem Res 1999;38:373–9.

Jang HD, Kim SK, Kim SJ. Effect of particle size and phase composition of titanium dioxide nanoparticles on the photocatalytic properties. J Nanoparticle Res 2001;3:141–7.

Fox MA, Dulay MT. Heterogeneous Photocatalysis. Chem Rev 1992:135–70.

Li X, Zhu K, Pang J, Tian M, Liu J, Rykov AI, et al. Unique role of MÖssbauer spectroscopy in assessing structural features of heterogeneous catalysts. Appl Catal B Environ 2018;224:518–32.

Rodríguez-Torres CE, Cabrera AF, Van Raap MBF, Sánchez FH. Mössbauer study of mechanical alloyed Fe-doped TiO2 compounds. Phys B Condens Matter 2004;354:67–70.

Pal B, Sharon M, Nogami G. Preparation and characterization of TiO2/Fe2O3 binary mixed oxides and its photocatalytic properties. Mater Chem Phys 1999;59:254–61.

Lemine OM, Sajieddine M, Bououdina M, Msalam R, Mufti S, Alyamani A. Rietveld analysis and Mössbauer spectroscopy studies of nanocrystalline hematite α-Fe2O3. J Alloys Compd 2010;502:279–82.

Kalska-Szostko B, Satuła D, Olszewski W. Mössbauer spectroscopy studies of the magnetic properties of ferrite nanoparticles. Curr Appl Phys 2015;15:226–31.

Cristóbal AA, Ramos CP, Botta P, Aglietti EF, Saragovi C, Porto JM. Characterization of a mechanochemically activated titanium-hematite mixture: Mössbauer spectroscopy study. Phys B Condens Matter 2009;404:2751–3.



  • There are currently no refbacks.