Frontiers of Materials Science

, Volume 12, Issue 3, pp 292–303 | Cite as

Mesocrystalline TiO2/sepiolite composites for the effective degradation of methyl orange and methylene blue

  • Ruirui LiuEmail author
  • Zhijiang JiEmail author
  • Jing Wang
  • Jinjun Zhang
Research Article


Mesocrystalline TiO2/sepiolite (TiS) composites with the function of adsorption and degradation of liquid organic pollutants were successfully fabricated via a facile and low-cost solvothermal reaction. The prepared TiS composites were characterized by FESEM, HRTEM, XRD, XPS, N2 adsorption-desorption, UV–vis DRS, and EPR. Results revealed the homogeneous dispersion of highly reactive TiO2 mesocrystals on the sepiolite nanofibers. Thereinto each single–crystal–like TiO2 mesocrystal comprised many [001]-oriented anatase nanoparticles about 10–20 nm in diameter. The photocatalytic activity was further evaluated by the degradation of anionic dye (methyl orange) and cationic dye (methylene blue) under the UV-vis light (350≤λ≤780 nm) irradiation. By selecting appropriate experimental conditions, we can easily manipulate the photocatalytic performance of TiS composites. The optimal TiS catalyst (the sepiolite content of 28.5 wt.%, and the reaction time of 24 h) could efficiently degrade methyl orange to 90.7% after 70 min, or methylene blue to 97.8% after 50 min, under UV-vis light irradiation. These results can be attributed to their synergistic effect of high crystallinity, large specific surface area, abundant hydroxyl radicals, and effective photogenerated charge separation.


TiO2/sepiolite mesocrystal solvothermal composites photocatalysis 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.



This work was supported by the Key Science and Technology Projects Program of China (Grant No. 2016YFC0700902).


  1. [1]
    Trandafilovic L V, Jovanovic D J, Zhang X, et al. Enhanced photocatalytic degradation of methylene blue and methylorange by ZnO:Eu nanoparticles. Applied Catalysis B: Environmental, 2017, 203: 740–752CrossRefGoogle Scholar
  2. [2]
    Stathatos E, Papoulis D, Aggelopoulos C A, et al. TiO2/palygorskite composite nanocrystalline films prepared by surfactant templating route: synergistic effect to the photocatalytic degradation of an azo-dye in water. Journal of Hazardous Materials, 2012, 211–212: 68–76CrossRefGoogle Scholar
  3. [3]
    Kibanova D, Sleiman M, Cervini-Silva J, et al Adsorption and photocatalytic oxidation of formaldehyde on a clay-TiO2 composite. Journal of Hazardous Materials, 2012, 211–212: 233–239CrossRefGoogle Scholar
  4. [4]
    Zhang Y L, Wang D J, Zhang G K. Photocatalytic degradation of organic contaminants by TiO2/sepiolite composites prepared at low temperature. Chemical Engineering Journal, 2011, 173(1): 1–10CrossRefGoogle Scholar
  5. [5]
    Lei X F, Xue X X, Yang H. Preparation and characterization of Ag-doped TiO2 nanomaterials and their photocatalytic reduction of Cr(VI) under visible light. Applied Surface Science, 2014, 321: 396–403CrossRefGoogle Scholar
  6. [6]
    Akkari M, Aranda P, Mayoral A, et al. Sepiolite nanoplatform for the simultaneous assembly of magnetite and zinc oxide nanoparticles as photocatalyst for improving removal of organic pollutants. Journal of Hazardous Materials, 2017, 340: 281–290CrossRefGoogle Scholar
  7. [7]
    Chen X, Mao S S. Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications. Chemical Reviews, 2007, 107(7): 2891–2959CrossRefGoogle Scholar
  8. [8]
    Fu X X, Ren Z M, Fan C Y, et al. Designed fabrication of anatase mesocrystals constructed from crystallographically oriented nanocrystals for improved photocatalytic activity. RSC Advances, 2015, 5(51): 41218–41223CrossRefGoogle Scholar
  9. [9]
    Dai H, Xu G, Zhang S, et al. A ratiometric biosensor for metallothionein based on a dual heterogeneous electro-chemiluminescent response from a TiO2 mesocrystalline interface. Chemical Communications, 2015, 51(36): 7697–7700CrossRefGoogle Scholar
  10. [10]
    Ye J, Liu W, Cai J, et al. Nanoporous anatase TiO2 mesocrystals: additive-free synthesis, remarkable crystalline-phase stability, and improved lithium insertion behavior. Journal of the American Chemical Society, 2011, 133(4): 933–940CrossRefGoogle Scholar
  11. [11]
    Zhang P, Tachikawa T, Fujitsuka M, et al. Efficient charge separation on 3D architectures of TiO2 mesocrystals packed with a chemically exfoliated MoS2 shell in synergetic hydrogen evolution. Chemical Communications, 2015, 51(33): 7187–7190CrossRefGoogle Scholar
  12. [12]
    Li F F, Dai Y Z, Gong M, et al. Synthesis, characterization of magnetic-sepiolite supported with TiO2, and the photocatalytic performance over Cr(VI) and 2,4-dichlorophenol co-existed wastewater. Journal of Alloys and Compounds, 2015, 638: 435–442CrossRefGoogle Scholar
  13. [13]
    Okte A N, Sayinsoz E. Characterization and photocatalytic activity of TiO2 supported sepiolite catalysts. Separation and Purification Technology, 2008, 62(3): 535–543CrossRefGoogle Scholar
  14. [14]
    Zhang G K, Xiong Q, Xu W, et al. Synthesis of bicrystalline TiO2 supported sepiolite fibers and their photocatalytic activity for degradation of gaseous formaldehyde. Applied Clay Science, 2014, 102: 231–237CrossRefGoogle Scholar
  15. [15]
    Portela R, Jansson I, Suárez S, et al. Natural silicate-TiO2 hybrids for photocatalytic oxidation of formaldehyde in gas phase. Chemical Engineering Journal, 2017, 310: 560–570CrossRefGoogle Scholar
  16. [16]
    Ugurlu M, Karaoglu M H. TiO2 supported on sepiolite: preparation, structural and thermal characterization and catalytic behaviour in photocatalytic treatment of phenol and lignin from olive mill wastewater. Chemical Engineering Journal, 2011, 166 (3): 859–867CrossRefGoogle Scholar
  17. [17]
    Liu R R, Wang J, Zhang J J, et al. Honeycomb-like micromesoporous structure TiO2/sepiolite composite for combined chemisorption and photocatalytic elimination of formaldehyde. Microporous and Mesoporous Materials, 2017, 248: 234–245CrossRefGoogle Scholar
  18. [18]
    Aranda P, Kun R, Martín-Luengo M A, et al. Titania–sepiolite nanocomposites prepared by a surfactant templating colloidal route. Chemistry of Materials, 2008, 20(1): 84–91CrossRefGoogle Scholar
  19. [19]
    Bautista F M, Campelo J M, Luna D, et al. Vanadium oxides supported on TiO2–sepiolite and sepiolite: preparation, structural and acid characterization and catalytic behaviour in selective oxidation of toluene. Applied Catalysis A: General, 2007, 325(2): 336–344CrossRefGoogle Scholar
  20. [20]
    Knapp C, Gil-Llambías F J, Gulppi-Cabra M, et al. Phase distribution in titania–sepiolite catalyst supports prepared by different methods. Journal of Materials Chemistry, 1997, 7(8): 1641–1645CrossRefGoogle Scholar
  21. [21]
    Liu Y Q, Zhang Y, Wang J. Mesocrystals as a class of multifunctional materials. CrystEngComm, 2014, 16(27): 5948–5967CrossRefGoogle Scholar
  22. [22]
    Cölfen H, Antonietti M. Mesocrystals: inorganic superstructures made by highly parallel crystallization and controlled alignment. Angewandte Chemie International Edition, 2005, 44(35): 5576–5591CrossRefGoogle Scholar
  23. [23]
    Zhou L, O’Brien P. Mesocrystals: a new class of solid materials. Small, 2008, 4(10): 1566–1574CrossRefGoogle Scholar
  24. [24]
    Ma Y, Wu X Y, Zhang G K. Core–shell Ag@Pt nanoparticles supported on sepiolite nanofibers for the catalytic reduction of nitrophenols in water: Enhanced catalytic performance and DFT study. Applied Catalysis B: Environmental, 2017, 205: 262–270CrossRefGoogle Scholar
  25. [25]
    Krekeler M P S, Guggenheim S. Defects in microstructure in palygorskite–sepiolite minerals: A transmission electron microscopy (TEM) study. Applied Clay Science, 2008, 39(1–2): 98–105CrossRefGoogle Scholar
  26. [26]
    Wei S H, Ni S, Xu X X. A new approach to inducing Ti3+ in anatase TiO2 for efficient photocatalytic hydrogen production. Chinese Journal of Catalysis, 2018, 39(3): 510–516CrossRefGoogle Scholar
  27. [27]
    Laskova B, Moehl T, Kavan L, et al. Electron kinetics in dye sensitized solar cells employing anatase with (101) and (001) facets. Electrochimica Acta, 2015, 160: 296–305CrossRefGoogle Scholar
  28. [28]
    Pei Z X, Zhu M S, Huang Y, et al. Dramatically improved energy conversion and storage efficiencies by simultaneously enhancing charge transfer and creating active sites in MnOx/TiO2 nanotube composite electrodes. Nano Energy, 2016, 20: 254–263CrossRefGoogle Scholar
  29. [29]
    Rasalingam S, Kibombo H S, Wu C M, et al. Influence of Ti–O–Si hetero-linkages in the photocatalytic degradation of Rhodamine B. Catalysis Communications, 2013, 31: 66–70CrossRefGoogle Scholar
  30. [30]
    Hu X L, Sun Z M, Song J Y, et al. Facile synthesis of nano-TiO2/stellerite composite with efficient photocatalytic degradation of phenol. Advanced Powder Technology, 2018, 29(7): 1644–1654CrossRefGoogle Scholar
  31. [31]
    Liu R R, Ji Z J, Wang J, et al. Solvothermal fabrication of TiO2/sepiolite composite gel with exposed {001} and {101} facets and its enhanced photocatalytic activity. Applied Surface Science, 2018, 441: 29–39CrossRefGoogle Scholar
  32. [32]
    Zhang G K, Qin X. Efficient photocatalytic degradation of gaseous formaldehyde by the TiO2/tourmaline composites. Materials Research Bulletin, 2013, 48(10): 3743–3749CrossRefGoogle Scholar
  33. [33]
    Zhang Y Y, Gu D, Zhu L Y, et al. Highly ordered Fe3+/TiO2 nanotube arrays for efficient photocataltyic degradation of nitrobenzene. Applied Surface Science, 2017, 420: 896–904CrossRefGoogle Scholar
  34. [34]
    Jimenez-Relinque E, Llorente I, Castellote M. TiO2 cement-based materials: Understanding optical properties and electronic band structure of complex matrices. Catalysis Today, 2017, 287: 203–209CrossRefGoogle Scholar
  35. [35]
    Chen S F, Zhao W, Liu W, et al. Preparation, characterization and activity evaluation of p-n junction photocatalyst p-CaFe2O4/n-ZnO. Chemical Engineering Journal, 2009, 155(1–2): 466–473Google Scholar
  36. [36]
    Zhang Y, Tang Z R, Fu X, et al. TiO2–graphene nanocomposites for gas-phase photocatalytic degradation of volatile aromatic pollutant: is TiO2–graphene truly different from other TiO2–carbon composite materials? ACS Nano, 2010, 4(12): 7303–7314CrossRefGoogle Scholar
  37. [37]
    Zhu H J, Li Z K, Yang J H. A novel composite hydrogel for adsorption and photocatalytic degradation of bisphenol A by visible light irradiation. Chemical Engineering Journal, 2018, 334: 1679–1690CrossRefGoogle Scholar
  38. [38]
    Liu B K, Mu L L, Han B, et al. Fabrication of TiO2/Ag2O heterostructure with enhanced photocatalytic and antibacterial activities under visible light irradiation. Applied Surface Science, 2017, 396: 1596–1603CrossRefGoogle Scholar
  39. [39]
    Zhu Q W, Zhang Y H, Lv F Z, et al. Cuprous oxide created on sepiolite: Preparation, characterization, and photocatalytic activity in treatment of red water from 2,4,6-trinitrotoluene manufacturing. Journal of Hazardous Materials, 2012, 217–218: 11–18CrossRefGoogle Scholar
  40. [40]
    Tahir M. Photocatalytic carbon dioxide reduction to fuels in continuous flow monolith photoreactor using montmorillonite dispersed Fe/TiO2 nanocatalyst. Journal of Cleaner Production, 2018, 170: 242–250CrossRefGoogle Scholar
  41. [41]
    Wang L, Wu D P, Guo Z, et al. Ultra-thin TiO2 sheets with rich surface disorders for enhanced photocatalytic performance under simulated sunlight. Journal of Alloys and Compounds, 2018, 745: 26–32CrossRefGoogle Scholar
  42. [42]
    Gordon T R, Cargnello M, Paik T, et al. Nonaqueous synthesis of TiO2 nanocrystals using TiF4 to engineer morphology, oxygen vacancy concentration, and photocatalytic activity. Journal of the American Chemical Society, 2012, 134(15): 6751–6761CrossRefGoogle Scholar
  43. [43]
    Ye F, Wang F, Meng C C, et al. Crystalline phase engineering on cocatalysts: A promising approach to enhancement on photocatalytic conversion of carbon dioxide to fuels. Applied Catalysis B: Environmental, 2018, 230: 145–153CrossRefGoogle Scholar
  44. [44]
    Zhang G X, Song A K, Duan Y W, et al. Enhanced photocatalytic activity of TiO2/zeolite composite for abatement of pollutants. Microporous and Mesoporous Materials, 2018, 255: 61–68CrossRefGoogle Scholar
  45. [45]
    Yang J J, Chen D M, Zhu Y, et al. 3D-3D porous Bi2WO6/graphene hydrogel composite with excellentsynergistic effect of adsorption-enrichment and photocatalytic degradation. Applied Catalysis B: Environmental, 2017, 205: 228–237CrossRefGoogle Scholar
  46. [46]
    Chen Y, Liu K. Preparation and characterization of nitrogendoped TiO2/diatomite integrated photocatalytic pellet for the adsorption–degradation of tetracycline hydrochloride using visible light. Chemical Engineering Journal, 2016, 302: 682–696CrossRefGoogle Scholar
  47. [47]
    Cheng W H, Li C D, Ma X, et al. Effect of SiO2-doping on photogenerated cathodic protection of nano-TiO2 films on 304 stainless steel. Materials & Design, 2017, 126: 155–161CrossRefGoogle Scholar
  48. [48]
    Zhou C H, Li G L, Zhuang X Y, et al. Roles of texture and acidity of acid-activated sepiolite catalysts in gas-phase catalytic dehydration of glycerol to acrolein. Molecular Catalysis, 2017, 434: 219–231CrossRefGoogle Scholar
  49. [49]
    Kelly M T, Chun J K M, Bocarsly A B. General bronsted acid behavior of porous silicon: a mechanistic evaluation of protongated quenching of photoemission from oxide-coated porous silicon. Journal of Physical Chemistry, 1997, 101(14): 2702–2708CrossRefGoogle Scholar
  50. [50]
    Chen J, Guan M, Cai W, et al. The dominant {001} facetdependent enhanced visible-light photoactivity of ultrathin BiOBr nanosheets. Physical Chemistry Chemical Physics, 2014, 16(38): 20909–20914CrossRefGoogle Scholar

Copyright information

© Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.State Key Laboratory of Green Building MaterialsChina Building Materials AcademyBeijingChina

Personalised recommendations