pp 1–16 | Cite as

Photocatalytic and magnetic porous cellulose macrospheres for water purification

  • Alexandra S. M. WittmarEmail author
  • Qian Fu
  • Mathias Ulbricht
Original Research


In this work, we report the preparation of photocatalytically active and easy to recycle porous cellulose-based spheres from polymer solutions in ionic liquid/dimethylsulfoxide mixtures by using the dropping cum phase separation technique. The factors affecting the sphere structure formation in relation to their efficiency as photocatalysts have been studied in detail. It was found that the increase of the nanoparticulate dopant fraction (TiO2 and/or Fe3O4) in the casting solution led to the formation of nanocomposites with a higher specific surface area as well as with enhanced photocatalytic activity. The embedment of the TiO2 nanoparticles in the polymeric matrix did not change the bandgap of the photocatalyst. Furthermore, the co-doping with Fe3O4 had no negative impact on the photocatalytic activity of the TiO2 doped porous cellulose spheres. The addition of a moderate amount of dimethylsulfoxide led to an improvement of the photocatalytic activity of the formed nanocomposites, due to an increase of the matrix porosity without an agglomeration of the active nanoparticles. However, higher fractions of dimethylsulfoxide led to the agglomeration of the photocatalytic nanoparticles and therefore a decrease of the photocatalytic activity of the hybrid materials. The obtained porous spheres could be successfully recycled and reused in at least five consecutive cycles for the photocatalytic degradation of the model organic pollutant Rhodamine B in aqueous solution. Additionally, the prepared porous spheres also exhibited good adsorber properties toward Cu2+ ions which were used in this study as model metal ion pollutant in water.

Graphical abstract


Supported photocatalysts Cellulose nanocomposites Ionic liquids Water purification Titania nanoparticles Magnetite nanoparticles 



The financial support through the Deutsche Forschungsgemeinschaft (DFG) project WI 4325/2-1 is kindly acknowledged. We gratefully acknowledge the collaboration with Mrs. Claudia Schenk (BET characterization) and Mr. Smail Boukercha (SEM characterization) at the University of Duisburg-Essen.

Supplementary material

10570_2019_2401_MOESM1_ESM.docx (4.7 mb)
Supplementary material 1 (DOCX 4812 kb)


  1. Ali I (2012) New generation adsorbents for water treatment. Chem Rev 112:5073–5091. Google Scholar
  2. Andreozzi R, Caprio V, Insola A, Marotta R (1999) Advanced oxidation processes (AOP) for water purification and recovery. Catal Today 53:51–59. Google Scholar
  3. Bashar MM, Khan MA (2013) An overview on surface modification of cotton fiber for apparel use. J Polym Environ 21:181–190. Google Scholar
  4. Brandes R, Trindade ECA, Vanin DF, Vargas VMM, Carminatti CA, Al-Qureshi HA, Recouvreux DOS (2018) Spherical bacterial cellulose/TiO2 nanocomposite with potential application in contaminants removal from wastewater by photocatalysis. Fibers Polym 19(9):1861–1868. Google Scholar
  5. Carpenter AW, de Lannoy CF, Wiesner MR (2015) Cellulose nanomaterials in water treatment technologies. Environ Sci Technol 49:5277–5284. Google Scholar
  6. Chong MN, Jin B, Chow CWK, Saint C (2010) Recent developments in photocatalytic water treatment technology: a review. Water Res 44:2997–3027. Google Scholar
  7. Czaja W, Krystynowicz A, Bielecki S, Brown RM Jr (2006) Microbial cellulose—the natural power to heal wounds. Biomaterials 27:145–151. Google Scholar
  8. De Gisi S, Lofrano G, Grassi M, Notarnicola M (2016) Characteristics and adsorption capacities of low-cost sorbents for wastewater treatment: a review. Sustain Mat Technol 9:10–40. Google Scholar
  9. Duan J, He X, Zhang L (2015) Magnetic cellulose-TiO2 nanocomposite microspheres for highly selective enrichment of phosphopeptides. Chem Commun 51:338–341. Google Scholar
  10. Fane AG, Wang R, Hu MX (2015) Synthetic membranes for water purification: status and future. Angew Chem Int Ed 54:3368–3386. Google Scholar
  11. Geise MG, Lee HS, Miller DJ, Freeman BD, McGrath JE, Paul DR (2010) Water purification by membranes: the role of the polymer science. J Polym Sci Part B Polym Phys 48(15):1685–1718. Google Scholar
  12. Ghasemi M, Tsianou M, Alexandridis P (2017) Assessment of solvents for cellulose dissolution. Biores Technol 228:330–338. Google Scholar
  13. Jo S, Oh Y, Park S, Kan E, Lee SH (2017) Cellulose/carrageenan/TiO2 nanocomposite for adsorption and photodegradation of cationic dye. Biotechnol Bioproc Eng 22:734–738. Google Scholar
  14. Kim MS, Hong KM, Chung JG (2003) Removal of Cu (II) from aqueous solutions by adsorption process with anatase-type titanium dioxide. Water Res 37:3524–3529. Google Scholar
  15. Klemm D, Heublein B, Fink HP, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44:3358–3393. Google Scholar
  16. Le KA, Rudaz C, Budtova T (2014) Phase diagram, solubility limit and hydrodynamic properties of cellulose in binary solvents with ionic liquid. Carbohyd Polym 105:237–343. Google Scholar
  17. Lee SY, Park SJ (2013) TiO2 photocatalyst for water treatment applications. J Ind Eng Chem 19:1761–1769. Google Scholar
  18. Lee KY, Aitomäki Y, Berglund LA, Oksman K, Bismarck A (2014) On the use of nanocellulose as reinforcement in polymer matrix composites. Comp Sci Technol 105:15–27. Google Scholar
  19. Lee A, Elam JW, Darling SB (2016) Membrane materials for water purification: design, development and application. Environ Sci Water Res Technol 2:17–42. Google Scholar
  20. Li N, Bai R (2005) Copper adsorption on chitosan–cellulose hydrogel beads: behaviors and mechanisms. Sep Purif Technol 42:237–247. Google Scholar
  21. Liebert T (2010) Cellulose solvents—remarkable history, bright future. ACS Symp Ser 1033:3–54. Google Scholar
  22. Linsebigler AL, Lu G, Yates JT Jr (1995) Photocatalysis on TiO2 surfaces: principles, mechanisms and selected results. Chem Rev 95:735–758. Google Scholar
  23. Luo X, Zeng J, Liu S, Zhang L (2015) An effective and recyclable adsorbent for the removal of heavy metal ions from aqueous system: magnetic chitosan/cellulose microspheres. Biores Technol 194:403–406. Google Scholar
  24. Luo X, Lei X, Cai N, Xie X, Xue Y, Yu F (2016a) Removal of heavy metal ions from water by magnetic cellulose-based beads with embedded chemically modified magnetite nanoparticles and activated carbon. ACS Sustain Chem Eng 4:3960–3969. Google Scholar
  25. Luo X, Lei X, Xie X, Yu B, Cai N, Yu F (2016b) Adsorptive removal of Lead from water by the effective and reusable magnetic cellulose nanocomposite beads entrapping activated bentonite. Carbohyd Polym 151:640–648. Google Scholar
  26. Maaloul N, Oulego P, Rendueles M, Ghorbal A, Diaz M (2019) Synthesis and characterization of eco-freiendly cellulose beads for cooper (II) removal from aqueous solutions. Environ Sci Pollut Res.
  27. Moon RJ, Martini A, Narin J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994. Google Scholar
  28. Morawski AW, Kusiak-Nejman E, Przepiorski J, Kordala R, Pernak J (2013) Cellulose—TiO2 nanocomposite with enhanced UV–Vis light absorption. Cellulose 20:1293–1300. Google Scholar
  29. Nevstrueva D, Pihlajamäki A, Mänttäri M (2015) Effect of a TiO2 additive on the morphology and permeability of cellulose ultrafiltration membranes prepared via immersion precipitation with ionic liquid as solvent. Cellulose 22(6):3865–3876. Google Scholar
  30. Okubayashi S, Griesser UJ, Bechtold T (2004) A kinetic study of moisture sorption and desorption on lyocell fibers. Carbohyd Polym 58:293–299. Google Scholar
  31. Peng S, Meng H, Ouyang Y, Chang J (2014) Nanoporous magnetic cellulose—chitosan composite microspheres: preparation, characterization and application for Cu(II) adsorption. Ind Eng Chem Res 53:2106–2113. Google Scholar
  32. Raval NP, Shah PU, Shah NK (2016) Adsorptive removal of nickel (II) ions from aqueous environment: a review. J Environ Manage 179:1–20. Google Scholar
  33. Singh NB, Nagpal G, Agrawal SR (2018) Water purification by using adsorbents: a review. Environ Technol Innov 11:187–240. Google Scholar
  34. Swatloski RP, Spear SK, Holbrey JD, Rogers RD (2002) Dissolution of cellulose with ionic liquids. J Am Chem Soc 124:4974–4975. Google Scholar
  35. Tokuda H, Hayamizu K, Ishii K, Susan MABH M, Watanabe M (2005) Physicochemical properties and structures of room temperature ionic liquids. 2. Variation of alkyl chain length in imidazolium cation. J Phys Chem B 109(3):6103–6110. Google Scholar
  36. Tran CD, Duri S, Delneri A, Franko M (2013) Cellulose-chitosan composite materials: preparation, characterization and application for removal of microcystin. J Haz Mater 252–253:355–366. Google Scholar
  37. Ueno K, Watanabe M (2011) From colloidal stability in ionic liquids to advanced soft materials using unique media. Langmuir 27(15):9105–9115. Google Scholar
  38. Ummartyotin S, Mamspiya H (2015) A critical review on cellulose: from fundamental to an approach on sensor technology. Renew Sustain Energy Rev 41:402–4012. Google Scholar
  39. Verma AK, Dash RR, Bhunia P (2012) A review on chemical coagulation/flocculation technologies for removal of colour from textile wastewaters. J Environ Manag 93:154–168. Google Scholar
  40. Vincente AT, Araujo A, Mendes MJ, Nunes D, Oliveira MJ, Sanchez-Sobrado O, Ferreira MP, Aquas H, Fortunado E, Martins R (2018) Multifunctional cellulose-paper for light harvesting and smart sensing applications. J Mater Chem C 6:3143–3181. Google Scholar
  41. Virkutyte J, Jegatheesan V, Varma RS (2012) Visible light activated TiO2/microcrystalline cellulose crystals to destroy organic contaminants in water. Biores Technol 113:288–293. Google Scholar
  42. Wang X, Yao C, Wang F, Li Z (2017) Cellulose-based nanomaterials for energy applications. Small 13:1702240–1702259. Google Scholar
  43. Wittmar ASM, Ulbricht M (2017) Ionic liquid-based route for the preparation of catalytically active cellulose—TiO2 porous films und spheres. Ind Eng Chem Res 56:2967–2975. Google Scholar
  44. Wittmar A, Thierfeld H, Köcher S, Ulbricht M (2015) Routes towards catalytically active TiO2 doped porous cellulose. RSC Adv 5:35866–35873. Google Scholar
  45. Wittmar ASM, Fu Q, Ulbricht M (2017) Photocatalytic and magnetic porous cellulose-based nanocomposite films prepared by a green method. ACS Sustain Chem Eng 5:9858–9868. Google Scholar
  46. Yang J, Li J (2018) Self-assembled cellulose materials for biomedicine: a review. Carbohyd Polym 181:264–274. Google Scholar
  47. Ying Y, Ying W, Li Q, Meng D, Ren G, Yan R, Peng X (2017) Recent advantages of nanomaterial-based membranes for water purification. Appl Mat Today 7:144–158. Google Scholar
  48. Zeng J, Liu S, Cai J, Zhang L (2010) TiO2 immobilized in cellulose matrix for photocatalytic degradation of phenol under weak UV light irradiation. J Phys Chem C 114(17):7806–7811. Google Scholar
  49. Zhang H, Wu J, Zhang J, He J (2005) 1-Allyl-3-methylimidazolium chloride room temperature ionic liquid: a new powerful nonderivatizing solvent for cellulose. Macromolec 38:8272–8277. Google Scholar
  50. Zhang J, Wu J, Yu J, Zhang X, He J, Zhang J (2017) Application of ionic liquids for dissolving cellulose and fabricating cellulose-based materials: state of the art and future trends. Mater Chem Front 1:1273–1290. Google Scholar
  51. Zhang L, Lu H, Yu J, Fan Y, Yang Y, Ma J, Wang Z (2018) Synthesis of lignocellulose-based composite hydrogel as a novel biosorbent for Cu2+ removal. Cellulose 25:7315–7328. Google Scholar
  52. Zhao Y, Liu X, Wang J, Zhang S (2013) Insight into the cosolvent effect of cellulose dissolution in imidazolium-based ionic liquids systems. J Phys Chem B 117:9042–9049. Google Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Lehrstuhl für Technische Chemie IIUniversität Duisburg-EssenEssenGermany
  2. 2.CENIDE – Center for Nanointegration Duisburg-Essen, NETZ – Nano Energie Technik ZentrumDuisburgGermany

Personalised recommendations