Inexpensive synthesis of a high-performance Fe₃O₄-SiO₂-TiO₂ photocatalyst: Magnetic recovery and reuse

Abstract

A sol-gel technique has been developed for the synthesis of a magnetite-silica-titania (Fe₃O₄-SiO₂-TiO₂) tertiary nanocomposite with improved photocatalytic properties based on the use of inexpensive titania and silica precursors. The exceptional photocatalytic activity of the resulting materials was demonstrated by using them to photocatalyze the degradation of methylene blue solution. The best formulation achieved 98% methylene blue degradation. An interesting feature of the present work was the ability to magnetically separate and reuse the catalyst. The efficiency of the catalyst remained high during two reuses. The synthesized nanomaterials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, ultra-violet-visible spectroscopy, diffuse reflectance spectroscopy, and thermogravimetric analysis. XRD analysis revealed the formation of multicrystalline systems of cubic magnetite and anatase titania crystals. SEM and TEM characterization revealed well-developed and homogeneously dispersed particles of size less than 15 nm. FTIR spectra confirmed the chemical interaction of titania and silica. It was further noticed that the optical properties of the prepared materials were dependent on the relative contents of their constituent metal oxides.

Graphical abstract

Keywords

sol-gel / photocatalysis / magnetic recovery / TiO₂ / Fe₃O₄ / SiO₂

References

[1] Wang P, Shi Q, Shi Y, Clark K K, Stucky G D, Keller A A. Magnetic permanently confined micelle arrays for treating hydrophobic organic compound contamination. Journal of the American Chemical Society, 2008, 131(1): 182–188

[2] Yu K, Yang S, Liu C, Chen H, Li H, Sun C, Boyd S A. Degradation of organic dyes via bismuth silver oxide initiated direct oxidation coupled with sodium bismuthate based visible light photocatalysis. Environmental Science & Technology, 2012, 46(13): 7318–7326

[3] Ali I. New generation adsorbents for water treatment. Chemical Reviews, 2012, 112(10): 5073–5091

[4] Ahmed M A, El-Katori E E, Gharni Z H. Photocatalytic degradation of methylene blue dye using Fe₂O₃/TiO₂ nanoparticles prepared by sol-gel method. Journal of Alloys and Compounds, 2013, 553: 19–29

[5] Tiwari J N, Mahesh K, Le N H, Kemp K C, Timilsina R, Tiwari R N, Kim K S. Reduced graphene oxide-based hydrogels for the efficient capture of dye pollutants from aqueous solutions. Carbon, 2013, 56: 173–182

[6] Panizza M, Cerisola G. Direct and mediated anodic oxidation of organic pollutants. Chemical Reviews, 2009, 109(12): 6541–6569

[7] Ni M, Leung M K H, Leung D Y C, Sumathy K. A review and recent developments in photocatalytic water-splitting using TiO₂ for hydrogen production. Renewable & Sustainable Energy Reviews, 2007, 11(3): 401–425

[8] Chen X, Mao S S. Titanium dioxide nanomaterials: Synthesis, properties, modifications, and applications. Chemical Reviews, 2007, 107(7): 2891–2959

[9] Roy P, Berger S, Schmuki P. TiO₂ nanotubes: Synthesis and applications. Angewandte Chemie International Edition, 2011, 50(13): 2904–2939

[10] Tobaldi D M, Pullar R C, Gualtieri F, Seabra M P, Labrincha J A. Sol-gel synthesis, characterisation and photocatalytic activity of pure, W-, Ag- and W/Ag co-doped TiO₂ nanopowders. Chemical Engineering Journal, 2013, 214: 364–375

[11] Ding Z, Lu G Q, Greenfield P F. Role of the crystallite phase of TiO₂ in heterogeneous photocatalysis for phenol oxidation in water. Journal of Physical Chemistry B, 2000, 104(19): 4815–4820

[12] Wu M, Liu J, Jin J, Wang C, Huang S, Deng Z, Li Y, Su B L. Probing significant light absorption enhancement of titania inverse opal films for highly exalted photocatalytic degradation of dye pollutants. Applied Catalysis B: Environmental, 2014, 150-151: 411–420

[13] Yuan C, Wu H B, Xie Y, Lou X W. Mixed transition-metal oxides: Design, synthesis, and energy-related applications. Angewandte Chemie International Edition, 2014, 53(6): 1488–1504

[14] Khan M M, Lee J, Cho M H. Au@ TiO₂ nanocomposites for the catalytic degradation of methyl orange and methylene blue: An electron relay effect. Journal of Industrial and Engineering Chemistry, 2014, 20(4): 1584–1590

[15] Gaya U I, Abdullah A H. Heterogeneous photocatalytic degradation of organic contaminants over titanium dioxide: A review of fundamentals, progress and problems. Journal of Photochemistry and Photobiology A Chemistry, 2008, 9(1): 1–12

[16] Llano B, Hidalgo M C, Rios L A, Navio J A. Effect of the type of acid used in the synthesis of titania-silica mixed oxides on their photocatalytic properties. Applied Catalysis B: Environmental, 2014, 150-151: 389–395

[17] Gawande M B, Pandey R K, Jayaram R V. Role of mixed metal oxides in catalysis science—versatile applications in organic synthesis. Catalysis Science & Technology, 2012, 2(6): 1113–1125

[18] Yan X M, Mei P, Xiong L, Gao L, Yang Q, Gong L. Mesoporous titania-silica-polyoxometalate nanocomposite materials for catalytic oxidation desulfurization of fuel oil. Catalysis Science & Technology, 2013, 3(8): 1985–1992

[19] Guin A K, Nayak S K, Rout T K, Bandyopadhyay N, Sengupta D K. Corrosion behavior of nanohybrid titania-silica composite coating on phosphated steel sheet. Journal of Coatings Technology and Research, 2012, 9(1): 97–106

[20] Yu X, Liu S, Yu J. Superparamagnetic g-Fe₂O₃@SiO₂@TiO₂ composite microspheres with superior photocatalytic properties. Applied Catalysis B: Environmental, 2011, 104(1-2): 12–20

[21] Cheng J P, Ma R, Li M, Wu J S, Liu F, Zhang X B. Anatase nanocrystals coating on silica-coated magnetite: Role of polyacrylic acid treatment and its photocatalytic properties. Chemical Engineering Journal, 2012, 210: 80–86

[22] Abbas N, Shao G N, Haider M S, Imran S M, Park S S, Kim H T. Sol-gel synthesis of TiO₂-Fe₂O₃ systems: Effects of Fe₂O₃ content and their photocatalytic properties. Journal of Industrial and Engineering Chemistry, 2016,

[23] Kokate M, Garadkar K, Gole A. One pot synthesis of magnetite-silica nanocomposites: Applications as tags, entrapment matrix and in water purification. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2013, 1(6): 2022–2029

[24] Costa A L, Ballarin B, Spegni A, Casoli F, Gardini D. Synthesis of nanostructured magnetic photocatalyst by colloidal approach and spray-drying technique. Journal of Colloid and Interface Science, 2012, 388(1): 31–39

[25] Zhu J, Xie J, Chen M, Jiang D, Wu D. Low temperature synthesis of anatase rare earth doped titania-silica photocatalyst and its photocatalytic activity under solar-light. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2010, 355(1-3): 178–182

[26] Harraz F A, Abdel-Salam O E, Mostafa A A, Mohamed R M, Hanafy M. Rapid synthesis of titania-silica nanoparticles photocatalyst by a modified sol-gel method for cyanide degradation and heavy metals removal. Journal of Alloys and Compounds, 2013, 551: 1–7

[27] Cong Y, Li Z, Zhang Y, Wang Q, Xu Q. Synthesis of α-Fe₂O₃/TiO₂ nanotube arrays for photoelectro-Fenton degradation of phenol. Chemical Engineering Journal, 2012, 191: 356–363

[28] Patra A K, Dutta A, Bhaumik A. Highly ordered mesoporous TiO₂-Fe₂O₃ mixed oxide synthesized by sol-gel pathway: An efficient and reusable heterogeneous catalyst for dehalogenation reaction. ACS Applied Materials & Interfaces, 2012, 4(9): 5022–5028

[29] Abbas M, Rao B P, Reddy V, Kim C. Fe₃O₄/TiO₂ core/shell nanocubes: Single-batch surfactantless synthesis, characterization and efficient catalysts for methylene blue degradation. Ceramics International, 2014, 40(7): 11177–11186

[30] Wu W, Xiao X, Zhang S, Ren F, Jiang C. Facile method to synthesize magnetic iron oxides/TiO₂ hybrid nanoparticles and their photodegradation application of methylene blue. Nanoscale Research Letters, 2011, 6(1): 533

[31] Wang C, Yin L, Zhang L, Kang L, Wang X, Gao R. Magnetic (g-Fe₂O₃@SiO₂)_n@TiO₂ functional hybrid nanoparticles with actived photocatalytic ability. Journal of Physical Chemistry C, 2009, 113(10): 4008–4011

[32] Paušová Š, Krýsa J, Jirkovský J, Prevot V, Mailhot G. Preparation of TiO₂-SiO₂ composite photocatalysts for environmental applications. Journal of Chemical Technology and Biotechnology (Oxford, Oxfordshire), 2014, 89(8): 1129–1135

[33] Tanemura S, Miao L, Jin P, Kaneko K, Terai A, Nabatova-Gabain N. Optical properties of polycrystalline and epitaxial anatase and rutile TiO₂ thin films by rf magnetron sputtering. Applied Surface Science, 2003, 212-213: 654–660

[34] Marfunin A S. Physics of Minerals and Inorganic Materials: An Introduction. Berlin: Springer-Verlag, 1979

[35] Yazdani F, Edrissi M. Effect of pressure on the size of magnetite nanoparticles in the coprecipitation synthesis. Materials Science and Engineering B, 2010, 171(1-3): 86–89

[36] Bickley R I, Gonzalez-Carreno T, Palmisano L. A study of the interaction between iron(III) oxide and titanium(IV) oxide at elevated temperatures. Materials Chemistry and Physics, 1991, 29(1-4): 475–487

[37] Karthikeyan K, Kalpana D, Amaresh S, Lee Y S. Microwave synthesis of graphene/magnetite composite electrode material for symmetric supercapacitor with superior rate performance. RSC Advances, 2012, 2(32): 12322–12328

[38] Ye Y, Kuai L, Geng B. A template-free route to a Fe₃O₄-Co₃O₄ yolk-shell nanostructure as a noble-metal free electrocatalyst for ORR in alkaline media. Journal of Materials Chemistry, 2012, 22(36): 19132–19138

[39] Tian Y, Yu B, Li X, Li K. Facile solvothermal synthesis of monodisperse Fe₃O₄ nanocrystals with precise size control of one nanometre as potential MRI contrast agents. Journal of Materials Chemistry, 2011, 21(8): 2476–2481

[40] Khataee A, Taseidifar M, Khorram S, Sheydaei M, Joo S W. Preparation of nanostructured magnetite with plasma for degradation of a cationic textile dye by the heterogeneous Fenton process. Journal of the Taiwan Institute of Chemical Engineers, 2015, 53: 132–139

[41] Yang H, Lu R, Wang L. Study of preparation and properties on solid superacid sulfated titania-silica nanomaterials. Materials Letters, 2003, 57(5-6): 1190–1196

[42] Nilchi A, Janitabar-Darzi S, Mahjoub A R, Rasouli-Garmarodi S. New TiO₂/SiO₂ nanocomposites—phase transformations and photocatalytic studies. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 2010, 361(1-3): 25–30

[43] Choi W, Termin A, Hoffmann M R. The role of metal ion dopants in quantum-sized TiO₂: Correlation between photoreactivity and charge carrier recombination dynamics. Journal of Physical Chemistry, 1994, 98(51): 13669–13679

[44] Feng Y, Ji X, Duan J, Zhu J, Jiang J, Ding H, Meng G, Ding R, Liu J, Hu A, Huang X. Synthesis of ZnO@TiO₂ core-shell long nanowire arrays and their application on dye-sensitized solar cells. Journal of Solid State Chemistry, 2012, 190(0): 303–308

[45] Tauc J, Grigorovici R, Vancu A. Optical properties and electronic structure of amorphous germanium. Physica Status Solidi. B, Basic Research, 1966, 15(2): 627–637

[46] Gutiérrez O Y, Fuentes G A, Salcedo C, Klimova T. SBA-15 supports modified by Ti and Zr grafting for NiMo hydrodesulfurization catalysts. Catalysis Today, 2006, 116(4): 485–497

[47] Zeng Y, Hao R, Xing B, Hou Y, Xu Z. One-pot synthesis of Fe₃O₄ nanoprisms with controlled electrochemical properties. Chemical Communications, 2010, 46(22): 3920–3922

[48] Peng L, Xie T, Lu Y, Fan H, Wang D. Synthesis, photoelectric properties and photocatalytic activity of the Fe₂O₃/TiO₂ heterogeneous photocatalysts. Physical Chemistry Chemical Physics, 2010, 12(28): 8033–8041

[49] Shao G N, Hilonga A, Kim Y N, Kim J K, Elineema G, Quang D V, Jeon S J, Kim H T. Peptization technique in the synthesis of titania-silica composites and their photocatalytic properties. Chemical Engineering Journal, 2012, 198: 122–129

[50] Shao G N, Hilonga A, Jeon S J, Lee J E, Elineema G, Quang D V, Kim J K, Kim H T. Influence of titania content on the mesostructure of titania-silica composites and their photocatalytic activity. Powder Technology, 2013, 233: 123–130

[51] Shao G N, Imran S M, Jeon S J, Engole M, Abbas N, Haider M S, Kang S J, Kim H T. Sol-gel synthesis of photoactive zirconia–titania from metal salts and investigation of their photocatalytic properties in the photodegradation of methylene blue. Powder Technology, 2014, 258: 99–109

[52] Kuo W S, Ho P H. Solar photocatalytic decolorization of methylene blue in water. Chemosphere, 2001, 45(1): 77–83

[53] Zhang Y, Gan H, Zhang G. A novel mixed-phase TiO₂/kaolinite composites and their photocatalytic activity for degradation of organic contaminants. Chemical Engineering Journal, 2011, 172(2): 936–943

[54] López A, Acosta D, Martínez A I, Santiago J. Nanostructured low crystallized titanium dioxide thin films with good photocatalytic activity. Powder Technology, 2010, 202(1): 111–117

[55] Yang J, Zhang X, Li B, Liu H, Sun P, Wang C, Wang L, Liu Y. Photocatalytic activities of heterostructured TiO₂-graphene porous microspheres prepared by ultrasonic spray pyrolysis. Journal of Alloys and Compounds, 2014, 584(0): 180–184

[56] Shao G N, Engole M, Imran S M, Jeon S J, Kim H T. Sol-gel synthesis of photoactive kaolinite-titania: Effect of the preparation method and their photocatalytic properties. Applied Surface Science, 2015, 331: 98–107

[57] Jumeri F A, Lim H N, Ariffin S N, Huang N M, Teo P S, Fatin S O, Chia C H, Harrison I. Microwave synthesis of magnetically separable ZnFe₂O₄-reduced graphene oxide for wastewater treatment. Ceramics International, 2014, 40(5): 7057–7065

[58] Anandan S, Sivasankar T, Lana-Villarreal T. Synthesis of TiO₂/WO₃ nanoparticles via sonochemical approach for the photocatalytic degradation of methylene blue under visible light illumination. Ultrasonics Sonochemistry, 2014, 21(6): 1964–1968

[59] Chauhan R, Kumar A, Pal Chaudhary R. Photocatalytic degradation of methylene blue with Cu doped ZnS nanoparticles. Journal of Luminescence, 2014, 145: 6–12

[60] Seftel E M, Niarchos M, Mitropoulos C, Mertens M, Vansant E F, Cool P. Photocatalytic removal of phenol and methylene-blue in aqueous media using TiO₂@LDH clay nanocomposites. Catalysis Today, 2015, 252: 120–127

Acknowledgements

This work was supported by the Human Resources Development Program (No. 20154030200680) of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea Government Ministry of Trade, Industry and Energy. Authors are also thankful to HEC (Higher education Commission) of Pakistan for providing financial aids.

Funding

RIGHTS & PERMISSIONS

2016 Higher Education Press and Springer-Verlag Berlin Heidelberg