Araneose Ti3+ self-doping TiO2/SiO2 nanowires membrane for removal of aqueous MB under visible light irradiation

  • Zhao Gao
  • Hanpei YangEmail author
  • Jingtao Mao
  • Li Kang
  • Ruichen Zhang
  • Siqi Chai
  • Junming Wu
  • Wei LiEmail author
Research Article


Araneose Ti3+ self-doped TiO2/SiO2 nanowires (RTiO2/SiO2) were prepared and anchored onto a polyethersulfone (PES) membrane. Careful characterizations and measurements indicated a covalent grafting of SiO2 onto reduced TiO2 (RTiO2) through Ti–O–Si linkages, acquiring uniformed RTiO2/SiO2 nanowires of almost complete anatase and benign hydrophilicity. The RTiO2/SiO2-based PES membrane showed a significantly enhanced visible light–driven degradation rate of methylene blue (MB) (90.7%), compared with that on bare PES (11.1%) and PES-RTiO2 (59.6%) membranes. The residual MB in filtered water was less than 5% after reusing three times. The normalized permeate flux of the modified membrane was 0.83, and the transmembrane pressure only increased by 0.4 MPa under irradiation of visible light. The improved performance of the PES-RTiO2/SiO2 was attributed to efficient intercept of MB molecular, light harvesting of visible light, and separation of charge carriers on araneose RTiO2/SiO2 nanowires.


Reduced TiO2 SiO2 Araneose nanowires Membrane Anti-fouling Decontamination 


Funding information

This project was financially supported by the Foundation of National Key Scientific Instrument and Equipment Development Project of China (No.2014YQ060773), the Priority Academic Program Development of Jiangsu Higher Education Institutions, and the Fundamental Research Funds for the Central Universities (2019B63114).


  1. Abdelraheem WHM, Patil MK, Nadagouda MN (2019) Hydrothermal synthesis of photoactive nitrogen- and boron- codoped TiO2nanoparticles for the treatment of bisphenol A in wastewater: synthesis, photocatalytic activity, degradation byproducts and reaction pathways. Appl Catal B Environ 241:598–611CrossRefGoogle Scholar
  2. Ahmad AL, Abdulkarim AA, Ooi BS, Ismaila S (2013) Recent development in additives modifications of polyethersulfone membrane for flux enhancement. Chem Eng J 223:246–267CrossRefGoogle Scholar
  3. Bai S, Zhang N, Gao C, Xiong YJ (2018) Defect engineering in photocatalytic materials. Nano Energy 53:296–336CrossRefGoogle Scholar
  4. Cao HB, Du PF, Song LX, Xiong J, Yang JJ, Xing TH, Liu X, Wu RR, Wang MC, Shao XL (2013) Co-electrospinning fabrication and photocatalytic performance of TiO2/SiO2 core/sheath nanofibers with tunable sheath thickness. Mater Res Bull 48:4673–4678CrossRefGoogle Scholar
  5. Cao Y, Xing ZP, Li ZZ, Wu XY, Hu MQ, Yan X, Zhu Q, Yang SL, Zhou W (2018) Mesoporous black TiO2-x/Ag nanospheres coupled with g-C3N4 nanosheets as 3D/2D ternary heterojunctions visible light photocatalysts. J Hazard Mater 343:181–190CrossRefGoogle Scholar
  6. Cappelletti G, Ardizzone S, Bianchi CL, Gialanella S, Naldoni A, Pirola C, Ragaini V (2009) Photodegradation of pollutants in air: enhanced properties of nano-TiO2 prepared by ultrasound. Nanoscale Res Lett 4:97–105CrossRefGoogle Scholar
  7. Celik E, Liu L, Choi H (2011) Protein fouling behavior of carbon nanotube/polyethersulfone composite membranes during water filtration. Water Res 45:5287–5294CrossRefGoogle Scholar
  8. Chen Y, Wu Q, Liu L, Wang J, Song YT (2019) The fabrication of self-floating Ti3+/N co-doped TiO2/diatomite granule catalyst with enhanced photocatalytic performance under visible light irradiation. Appl Surf Sci 467-468:514–525CrossRefGoogle Scholar
  9. Chu L, Wang S, Chen W (2005) Surface modification of ceramic-supported polyethersulfone membranes by interfacial polymerization for reduced membrane fouling. Macromol Chem Phys 206:1934–1940CrossRefGoogle Scholar
  10. Cui JY, Zhou ZP, Xie AT, Meng MJ, Cui YH, Liu SW, Zhou S, Yan YS, Dong HJ (2019) Bio-inspired fabrication of superhydrophilic nanocomposite membrane based on surface modification of SiO2 anchored by polydopamine towards effective oil-water emulsions separation. Sep Purif Technol 209:434–442CrossRefGoogle Scholar
  11. Deng YC, Tang L, Zeng GM, Zhu ZJ, Yan M, Zhou YY, Wang JJ, Liu YN, Wang JJ (2017) Insight into highly efficient simultaneous photocatalytic removal of Cr(VI) and 2,4-diclorophenol under visible light irradiation by phosphorus doped porous ultrathin g-C3N4 nanosheets from aqueous media: performance and reaction mechanism. Appl Catal B Environ 203:343–354CrossRefGoogle Scholar
  12. Dong XA, Dong XA, Zhang WD, Sun YJ, Li JY, Cen WL, Cui ZH, Huang HW, Dong F (2018) Visible-light-induced charge transfer pathway and photocatalysis mechanism on bi semimetal@defective BiOBr hierarchical microspheres. Catal. 357:41–50CrossRefGoogle Scholar
  13. Fang XF, Li JS, Ren BX, Huang Y, Wang DP, Liao ZP, Li Q, Wang LJ, Dionysiou DD (2019) Polymeric ultrafiltration membrane with in situ formed nano-silver within the inner pores for simultaneous separation and catalysis. J Membr Sci 579:190–198CrossRefGoogle Scholar
  14. Gao Z, Yang HP, Zhu HY (2018) Versatility of CoPcS in CoPcS/TiO2 for MB degradation: photosensitization, charge separation and oxygen activation. RSC Adv 8:36596–36603CrossRefGoogle Scholar
  15. Gao Z, Yang HP, Cao Y, Mao JT, Wu JM (2019) Complete mineralization of a humic acid by SO4 •- generated on CoMoO4/gC3N4 under visible-light irradiation. Nanotechnology 30:255704–255713CrossRefGoogle Scholar
  16. Gao P, Liu MH, Tai DD (2013) Multifunctional graphene oxide–TiO2 microsphere hierarchical membrane for clean water production. Appl Catal B Environ 138-139:17–25CrossRefGoogle Scholar
  17. Hou YD, Wang XC, Wu L, Chen XF, Ding ZX, Wang XX, Fu XZ (2008) N-doped SiO2/TiO2 mesoporous nanoparticles with enhanced photocatalytic activity under visible-light irradiation. Chemosphere. 72:414–421CrossRefGoogle Scholar
  18. Huang HT, Yu JY, Guo HX, Shen YB, Yang F, Wang H, Liu R, Liu Y (2018) Improved antifouling performance of ultrafiltration membrane via preparing novel zwitterionic polyimide. Appl Surf Sci 427:38–47CrossRefGoogle Scholar
  19. Kandiel TA, Robben L, Alkaim A, Bahnemann D (2013) Brookite versus anatase TiO2 photocatalysts: phase transformations and photocatalytic activities. Photochem Photobiol Sci 12:602–607CrossRefGoogle Scholar
  20. Kong LN, Jiang ZQ, Wang CH, Wan FX, Li YY, Wu LZ, Zhi JF, Zhang XT, Chen SJ, Liu YC (2015) Simple ethanol impregnation treatment can enhance photocatalytic activity of TiO2 nanoparticles under visible-light irradiation. ACS Appl Mater Interfaces 7:7752–7758CrossRefGoogle Scholar
  21. Kong JJ, Yang T, Rui ZB, Ji HB (2019) Perovskite-based photocatalysts for organic contaminants removal: current status and future perspectives. Catal Today 327:47–63CrossRefGoogle Scholar
  22. Li ZJ, Hou B, Xu Y, Wu D, Sun YH (2005) Hydrothermal synthesis, characterization, and photocatalytic performance of silica-modified titanium dioxide nanoparticles. J Colloid Interface Sci 288:149–154CrossRefGoogle Scholar
  23. Li MZ, Li JH, Shao XS, Miao J, Wang JB, Zhang QQ, Xu XP (2012) Grafting zwitterionic brush on the surface of PVDF membrane using physisorbed free radical grafting technique. J Membr Sci 1:141–148CrossRefGoogle Scholar
  24. Li K, Gao SM, Wang QY, Xu H, Wang ZY, Huang BB, Dai Y, Lu J (2015) In-situ-reduced synthesis of Ti3+ self-doped TiO2/g-C3N4 heterojunctions with high photocatalytic performance under LED light irradiation. ACS Appl Mater Interfaces 7:9023–9030CrossRefGoogle Scholar
  25. Li N, Tian Y, Zhang J, Sun Z, Zhao J, Zhang J, Zuo W (2017) Precisely-controlled modification of PVDF membranes with 3D TiO2/ZnO nanolayer: enhanced anti-fouling performance by changing hydrophilicity and photocatalysis under visible light irradiation. J Membr Sci 528:359–368CrossRefGoogle Scholar
  26. Liao YL, Que WX, Jia QY (2012) Controllable synthesis of brookite/anatase/rutile TiO2 nanocomposites and single-crystalline rutile nanorods array. J Mater Chem 22:7937–7944CrossRefGoogle Scholar
  27. Liu YW, Wei R, Lin OK, Zhang WS, Du YZ, Wang C, Zhang CH (2017) Enhanced hydrophilic and antipollution properties of PES membrane by anchoring SiO2/HPAN nanomaterial. ACS Sustain Chem Eng 5:7812–7823CrossRefGoogle Scholar
  28. Mansourpanah Y, Madaeni SS, Rahimpour A, Farhadian A, Taheri AH (2009) Formation of appropriate sites on nanofiltration membrane surface for binding TiO2 photo-catalyst: performance, characterization and fouling-resistant capability. J Membr Sci 330:297–306CrossRefGoogle Scholar
  29. Muhamad MS, Salim MR, Lau WJ (2015) Surface modification of SiO2 nanoparticles and its impact on the properties of PES-based hollow fiber membrane. RSC Adv 5:58644–58654CrossRefGoogle Scholar
  30. Pan JQ, Dong ZJ (2019) The enhancement of photocatalytic hydrogen production via Ti3+ selfdoping black TiO2/g-C3N4 hollow core-shell nano-heterojunction. Appl. Catal. B-Environ. 242:92–99CrossRefGoogle Scholar
  31. Rahimpour A (2011) UV photo-grafting of hydrophilic monomers onto the surface of nano-porous PES membranes for improving surface properties. Desalination 265:93–101CrossRefGoogle Scholar
  32. Rahimpour A, Madaeni SS (2010) Improvement of performance and surface properties of nano-porous polyethersulfone (PES) membrane using hydrophilic monomers as additives in the casting solution. J Membr Sci 360:371–379CrossRefGoogle Scholar
  33. Rezakazem M, Dashti A, Harami HR, Hajilari N (2018) Inamuddin fouling-resistant membranes for water reuse. Environ Chem Lett 16:715–763CrossRefGoogle Scholar
  34. Robinson S, Abdullah SZ, Berube P, Le-Clech P (2016) Ageing of membranes for water treatment: linking changes to performance. J Membr Sci 503:177–187CrossRefGoogle Scholar
  35. Romero AI, Parentis ML, Habert AC, Gonzo EE (2011) Synthesis of polyetherimide/silica hybrid membranes by the sol-gel process: influence of the reaction conditions on the membrane properties. J Mater Sci 46:4701–4709CrossRefGoogle Scholar
  36. Sajjad U, Neto F, Pasa AA (2015) Enhanced photocatalytic properties of core@shell SiO2@TiO2 nanoparticles. Appl. Catal. B-Environ. 179:333–343CrossRefGoogle Scholar
  37. Shang QQ, Huang X, Tan X, Yu T (2017) High activity Ti3+-modified brookite TiO2/graphene nanocomposites with specific facets exposed for water splitting. Ind Eng Chem Res 56:9098–9106CrossRefGoogle Scholar
  38. Shen JN, Ruan HM, Wu LG, Gao CJ (2011) Preparation and characterization of PES-SiO2 organic-inorganic composite ultrafiltration membrane for raw water pretreatment. Chem Eng J 168:1272–1278CrossRefGoogle Scholar
  39. Shi H, He Y, Pan Y, Di HH, Zeng GY, Zhang L, Zhang CL (2016) A modified mussel-inspired method to fabricate TiO2 decorated superhydrophilic PVDF membrane for oil/water separation. J Membr Sci 506:60–70CrossRefGoogle Scholar
  40. Shockravi A, Vatanpour V, Najjar Z, Bahadori S, Javadi A (2017) A new high performance polyamide as an effective additive for modification of antifouling properties and morphology of asymmetric PES blend ultrafiltration membranes. Microporous Mesoporous Mater 246:24–36CrossRefGoogle Scholar
  41. Sitter KD, Dotremont C, Genné I, Stoops L (2014) The use of nanoparticles as alternative pore former for the production of more sustainable polyethersulfone ultrafiltration membranes. J Membr Sci 471:168–178CrossRefGoogle Scholar
  42. Tan HQ, Zhao Z, Niu M, Mao CY, Cao DP, Cheng DJ, Feng PY, Sun ZC (2014) A facile and versatile method for preparation of colored TiO2 with enhanced solar-driven photocatalytic activity. Nanoscale. 6:10216–10223CrossRefGoogle Scholar
  43. Tian ZL, Cui HL, Zhu GL, Zhao WL, Xu JJ, Shao F, He JQ, Huang FQ (2016) Hydrogen plasma reduced black TiO2-B nanowires for enhanced photoelectrochemical water-splitting. J Power Sources 325:697–705CrossRefGoogle Scholar
  44. Vatsha B, Ngila JC, Moutloali RM (2014) Preparation of antifouling poly-vinylpyrrolidone (PVP 40K) modified polyethersulfone (PES) ultrafiltration (UF) membrane for water purification. Phys Chem Earth (Parts A/B/C) 67-69:125–131CrossRefGoogle Scholar
  45. Vitiello G, Clarizia L, Abdelraheem W (2019) Near UV-irradiation of CuOx-impregnated TiO2 providing active species for H2 production through methanol photoreforming. ChemCatChem 11:4314–4326CrossRefGoogle Scholar
  46. Wang L, Zhang CB, Gao F, Mailhot G, Pan G (2017) Algae decorated TiO2/Ag hybrid nanofiber membrane with enhanced photocatalytic activity for Cr(VI) removal under visible light. Chem Eng J 314:622–630CrossRefGoogle Scholar
  47. Wei GP, Qi JW, Lin P, Pan SL, Sun XY, Shen JU, Han WQ, Wang WL, Li JS (2018) Polyethersulfone enwrapped hydrous zirconium oxide nanoparticles for efficient removal of Pb (II) from aqueous solution. Chem Eng J 349:500–508CrossRefGoogle Scholar
  48. Xu YF, Zhang C, Zhang LX, Zhang XH, Yao HL, Shi JL (2016) Pd-catalyzed instant hydrogenation of TiO2 with enhanced photocatalytic performance. Energy Environ Sci 9:2410–2417CrossRefGoogle Scholar
  49. Xu H, Ding MM, Chen W, Li Y, Wang K (2018) Nitrogen–doped GO/TiO2 nanocomposite ultrafiltration membranes for improved photocatalytic performance. Sep Purif Technol 195:70–82CrossRefGoogle Scholar
  50. Yu HX, Zhang YT, Sun XB, Liu JD, Zhang HQ, (2014) Improving the antifouling property of polyethersulfone ultrafiltration membrane by incorporation of dextran grafted halloysite nanotubes. Chem Eng J 237:322–328CrossRefGoogle Scholar
  51. Zhang XW, Du AJ, Lee PF, Sun DD, Leckie JO (2009) TiO2 nanowire membrane for concurrent filtration and photocatalytic oxidation of humic acid in water. J Membr Sci 313:44–51CrossRefGoogle Scholar
  52. Zhang HM, Liu XL, Li YB, Sun QF, Wang Y, Wood BJ, Liu PR, Yang DJ, Zhao HJ (2012) Vertically aligned nanorod-like rutile TiO2 single crystal nanowire bundles with superior electron transport and photoelectrocatalytic properties. J Mater Chem 22:2465–2472CrossRefGoogle Scholar
  53. Zhao CS, Xue JM, Ran F, Sun SD (2013) Modification of polyethersulfone membranes–a review of methods. Prog Mater Sci 58:76–150CrossRefGoogle Scholar
  54. Zhu J, Zhang DQ, Bian ZF, Li GS, Huo YN, Lu YF, Li HX (2009) Aerosol-spraying synthesis of SiO2/TiO2 nanocomposites and conversion to porous TiO2 and single-crystalline TiOF2. Chem Commun 36:5394–5396CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2020

Authors and Affiliations

  1. 1.Key Laboratory of Integrated Regulation and Resource Development on Shallow Lakes, Ministry of Education, College of EnvironmentHohai UniversityNanjingChina
  2. 2.College of Environment and EcologyChongqing UniversityChongqingChina

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