MnO2 Nanoparticles Supported on Porous Al2O3 Substrate for Wastewater Treatment: Synergy of Adsorption, Oxidation, and Photocatalysis

  • Sherif ElbasuneyEmail author
  • Mohamed A. Elsayed
  • Sherif F. Mostafa
  • Waleed F. Khalil


Even though photocatalyst nanoparticles can offer effective degradation of organic pollutants, this can stimulate another pollution problem related to contamination with nanoparticle themselves. Furthermore particle aggregation could cause reduction of interfacial surface area and photocatalytic efficiency. One effective approach for wastewater treatment is superimposing photocatalyst on a high surface area porous support. MnO2 has attracted attention as its electronic structure is semiconducting. The d–d electronic transitions can take place under illumination as the d-orbitals are not completely occupied. This study reports on a new approach of sustainable fabrication of mono-dispersed MnO2 particles (20 nm average particle size) with a constant product quality using hydrothermal synthesis procedures. TEM and SEM procedures were utilized to study the particle size and morphological structure of the prepared MnO2 particles. While the crystalline phase was measured using XRD. The synthesized colloidal MnO2 particles were supported onto porous aluminum oxide and physically attached to the support free surface via calcinations at 500 °C. MnO2-coated Al2O3 demonstrated an extensive surface area of 140 m2/g. The catalytic activity of MnO2-coated AL2O3 was evaluated by degrading organic contaminant. Catalytic process in presence of UV-irradiation and H2O2 removed 95% of contaminant within 10 min. The mechanism of dye-removal was reported to be a novel combinatorial synergistic effect of adsorption, oxidation, and photocatalysis. Coupling different semiconductor metal oxides together extended sample’s light response to visible region and enhance photo-generated e-h+ separation efficiency. This study shaded the light on novel high interfacial surface area photocatalyst; that can be easily isolated avoiding contamination with nanoparticles.


Nanoparticles Manganese oxide Adsorption Photocatalyst Catalyst support Water treatment 



  1. 1.
    H. Atout et al., Integration of adsorption and photocatalytic degradation of methylene blue using\hbox TiO2 supported on granular activated carbon. Arab. J. Sci. Eng. 42(4), 1475–1486 (2017)CrossRefGoogle Scholar
  2. 2.
    S. Liu et al., Synthesis and adsorption/photocatalysis performance of pyrite FeS2. Appl. Surf. Sci. 268, 213–217 (2013)CrossRefGoogle Scholar
  3. 3.
    T.-T. Lim et al., TiO2/AC composites for synergistic adsorption-photocatalysis processes: present challenges and further developments for water treatment and reclamation. Crit. Rev. Environ. Sci. Technol. 41(13), 1173–1230 (2011)CrossRefGoogle Scholar
  4. 4.
    Y. Wang et al., Visible light driven type II heterostructures and their enhanced photocatalysis properties: a review. Nanoscale 5(18), 8326–8339 (2013)CrossRefGoogle Scholar
  5. 5.
    A. Šutka et al., Photocatalytic activity of anatase–nickel ferrite heterostructures. physica status solidi (a). 212(4), 796–803 (2015)Google Scholar
  6. 6.
    R. Solomon et al., Enhanced photocatalytic degradation of azo dyes using nano Fe3O4. J. Iran. Chem. Soc. 9(2), 101–109 (2012)CrossRefGoogle Scholar
  7. 7.
    A. Gutierrez-Mata et al., Recent overview of solar photocatalysis and solar photo-fenton processes for wastewater treatment. Int. J. Photoenergy (2017) Google Scholar
  8. 8.
    Y. Li et al., Photocatalytic degradation of methyl orange by TiO2-coated activated carbon and kinetic study. Water Res 40(6), 1119–1126 (2006)CrossRefGoogle Scholar
  9. 9.
    L. Zhang, D. He, P. Jiang, MnO2-doped anatase TiO2–an excellent photocatalyst for degradation of organic contaminants in aqueous solution. Catal. Commun. 10(10), 1414–1416 (2009)CrossRefGoogle Scholar
  10. 10.
    A. Iyer et al., Nanoscale manganese oxide octahedral molecular sieves (OMS-2) as efficient photocatalysts in 2-propanol oxidation. Appl. Catal. A 375(2), 295–302 (2010)CrossRefGoogle Scholar
  11. 11.
    V.B.R. Boppana et al., Nanostructured alkaline-cation-containing δ-MnO2 for photocatalytic water oxidation. Adv. Func. Mater. 23(7), 878–884 (2013)CrossRefGoogle Scholar
  12. 12.
    T. Gao, H. Fjellvåg, P. Norby, Structural and morphological evolution of β-MnO2 nanorods during hydrothermal synthesis. Nanotechnology 20(5), 055610 (2009)CrossRefGoogle Scholar
  13. 13.
    H. Cao, S.L. Suib, Highly efficient heterogeneous photooxidation of 2-propanol to acetone with amorphous manganese oxide catalysts. J. Am. Chem. Soc. 116(12), 5334–5342 (1994)CrossRefGoogle Scholar
  14. 14.
    J. Chen et al., Photoassisted catalytic oxidation of alcohols and halogenated hydrocarbons with amorphous manganese oxides. Catal. Today 33(1–3), 205–214 (1997)CrossRefGoogle Scholar
  15. 15.
    S.R. Segal et al., Photoassisted decomposition of dimethyl methylphosphonate over amorphous manganese oxide catalysts. Chem. Mater. 11(7), 1687–1695 (1999)CrossRefGoogle Scholar
  16. 16.
    M. Xue et al., The direct synthesis of mesoporous structured MnO2/TiO2 nanocomposite: a novel visible-light active photocatalyst with large pore size. Nanotechnology 19(18), 185604 (2008)CrossRefGoogle Scholar
  17. 17.
    J. Zhao et al., Visible-light-driven photocatalytic degradation of ciprofloxacin by a ternary Mn2O3/Mn3O4/MnO2 valence state heterojunction. Chem. Eng. J. 353, 805–813 (2018)CrossRefGoogle Scholar
  18. 18.
    Q. Zhang et al., Roles of manganese oxides in degradation of phenol under UV-Vis irradiation: adsorption, oxidation, and photocatalysis. J. Environ. Sci. 23(11), 1904–1910 (2011)CrossRefGoogle Scholar
  19. 19.
    S.K. Maji et al., Synthesis, characterization and photocatalytic activity of α-Fe2O3 nanoparticles. Polyhedron 33(1), 145–149 (2012)CrossRefGoogle Scholar
  20. 20.
    T.K. Tseng et al., A review of photocatalysts prepared by sol-gel method for VOCs removal. Int. J. Mol. Sci. 11(6), 2336–2361 (2010)CrossRefGoogle Scholar
  21. 21.
    T.O. Fufa, A.T.M.O.P. Yadav, Synthesis, characterization and photocatalytic activity of MnO2/Al2O3/Fe2O3 nanocomposite for phenol degradation. Synthesis 6(10) (2014)Google Scholar
  22. 22.
    S. Shukla et al., Synthesis and characterization of highly crystalline polyaniline film promising for humid sensor. Adv. Mater. Lett. 1, 129–134 (2010)CrossRefGoogle Scholar
  23. 23.
    G. Lövestam et al., Considerations on a definition of nanomaterial for regulatory purposes. Joint Research Centre (JRC) Reference Reports, 2010: pp. 80004–1Google Scholar
  24. 24.
    X. Wang et al., Recycling application of waste Li–MnO2 batteries as efficient catalysts based on electrochemical lithiation to improve catalytic activity. Green Chemistry 20, 4901 (2018)CrossRefGoogle Scholar
  25. 25.
    A. Eslami, M. Hashemi, F. Ghanbari, Degradation of 4-chlorophenol using catalyzed peroxymonosulfate with nano-MnO2/UV irradiation: toxicity assessment and evaluation for industrial wastewater treatment. J. Clean. Prod. 195, 1389–1397 (2018)CrossRefGoogle Scholar
  26. 26.
    S. Elbasuney, Dispersion characteristics of dry and colloidal nano-titania into epoxy resin. Powder Technol. 268, 158–164 (2014)CrossRefGoogle Scholar
  27. 27.
    K. Byrappa, S. Ohara, T. Adschiri, Nanoparticles synthesis using supercritical fluid technology—towards biomedical applications. Adv. Drug Deliv. Rev. 60(3), 299–327 (2008)CrossRefGoogle Scholar
  28. 28.
    S. Elbasuney, S.F. Mostafa, Continuous flow formulation and functionalization of magnesium di-hydroxide nanorods as a clean nano-fire extinguisher. Powder Technol. 278, 72–83 (2015)CrossRefGoogle Scholar
  29. 29.
    M.A. Elsayed, M. Gobara, S. Elbasuney, Instant synthesis of bespoke nanoscopic photocatalysts with enhanced surface area and photocatalytic activity for wastewater treatment. J. Photochem. Photobiol., A 344, 121–133 (2017)CrossRefGoogle Scholar
  30. 30.
    S. Elbasuney, H.E. Mostafa, Synthesis and surface modification of nanophosphorous-based flame retardant agent by continuous flow hydrothermal synthesis. Particuology 22, 82–88 (2015)CrossRefGoogle Scholar
  31. 31.
    S. Elbasuney et al., Stabilized super-thermite colloids: a new generation of advanced highly energetic materials. Appl. Surf. Sci. 419, 328–336 (2017)CrossRefGoogle Scholar
  32. 32.
    J. Li, Engineering Nanoparticles in Near-critical and Supercritical Water (Nottingham, University of Nottingham, 2008)Google Scholar
  33. 33.
    J.A. Darr, M. Poliakoff, New directions in inorganic and metal-organic coordination chemistry in supercritical fluids. Chem. Rev. 99(2), 495–541 (1999)CrossRefGoogle Scholar
  34. 34.
    T. Adschiri, Y. Hakuta, K. Arai, Hydrothermal synthesis of metal oxide fine particles at supercritical conditions. Ind. Eng. Chem. Res. 39(12), 4901–4907 (2000)CrossRefGoogle Scholar
  35. 35.
    T. Adschiri, K. Kanazawa, K. Arai, Rapid and continuous hydrothermal synthesis of boehmite particles in subcritical and supercritical water. Am. Ceram. Soc. 75(9), 2615–2618 (1992)CrossRefGoogle Scholar
  36. 36.
    S. Elbasuney, Surface engineering of layered double hydroxide (LDH) nanoparticles for polymer flame retardancy. Powder Technol. 277, 63–73 (2015)CrossRefGoogle Scholar
  37. 37.
    S. Elbasuney, Novel colloidal nanothermite particles (MnO2/Al) for advanced highly energetic systems. J. Inorg. Organomet. Polym. Mater. 28(5), 1793–1800 (2018)CrossRefGoogle Scholar
  38. 38.
    M. Elsayed, P. Hall, M. Heslop, Preparation and structure characterization of carbons prepared from resorcinol-formaldehyde resin by CO2 activation. Adsorption 13(3–4), 299–306 (2007)CrossRefGoogle Scholar
  39. 39.
    S. Elbasuney, Sustainable steric stabilization of colloidal titania nanoparticles. Appl. Surf. Sci. 409, 438–447 (2017)CrossRefGoogle Scholar
  40. 40.
    S. Jana et al., Synthesis of superparamagnetic β-MnO2 organosol: a photocatalyst for the oxidative phenol coupling reaction. Inorg. Chem. 47(13), 5558–5560 (2008)CrossRefGoogle Scholar
  41. 41.
    K. Kai et al., Room-temperature synthesis of manganese oxide monosheets. J. Am. Chem. Soc. 130(47), 15938–15943 (2008)CrossRefGoogle Scholar
  42. 42.
    T. Dang et al., Bio-silica coated with amorphous manganese oxide as an efficient catalyst for rapid degradation of organic pollutant. Colloids Surf. B 106, 151–157 (2013)CrossRefGoogle Scholar
  43. 43.
    J. Fei et al., Controlled preparation of MnO2 hierarchical hollow nanostructures and their application in water treatment. Adv. Mater. 20(3), 452–456 (2008)CrossRefGoogle Scholar
  44. 44.
    H. Chen, J. He, Facile synthesis of monodisperse manganese oxide nanostructures and their application in water treatment. J. Phys. Chem. C 112(45), 17540–17545 (2008)CrossRefGoogle Scholar
  45. 45.
    J. Rouquerol et al., Adsorption by Powders and Porous Solids: Principles, Methodology and Applications (Academic Press, Oxford, 2013)Google Scholar
  46. 46.
    V. Vimonses et al., An adsorption–photocatalysis hybrid process using multi-functional-nanoporous materials for wastewater reclamation. Water Res. 44(18), 5385–5397 (2010)CrossRefGoogle Scholar
  47. 47.
    N. Kumara et al., Equilibrium isotherm studies of adsorption of pigments extracted from Kuduk-kuduk (Melastoma malabathricum L.) pulp onto TiO2 nanoparticles. J. Chem. (2014). Google Scholar
  48. 48.
    P.K. Malik, Use of activated carbons prepared from sawdust and rice-husk for adsorption of acid dyes: a case study of acid yellow 36. Dyes Pigm. 56(3), 239–249 (2003)CrossRefGoogle Scholar
  49. 49.
    S.-H. Kim et al., Adsorption and photocatalysis kinetics of herbicide onto titanium oxide and powdered activated carbon. Sep. Purif. Technol. 58(3), 335–342 (2008)CrossRefGoogle Scholar
  50. 50.
    S. Wang et al., Fabrication of a novel bifunctional material of BiOI/Ag 3 VO 4 with high adsorption–photocatalysis for efficient treatment of dye wastewater. Appl. Catal. B 168, 448–457 (2015)CrossRefGoogle Scholar
  51. 51.
    H. Gulyas et al., Combining activated carbon adsorption with heterogeneous photocatalytic oxidation: lack of synergy for biologically treated greywater and tetraethylene glycol dimethyl ether. Environ. Technol. 34(11), 1393–1403 (2013)CrossRefGoogle Scholar
  52. 52.
    V.K. Garg et al., Basic dye (methylene blue) removal from simulated wastewater by adsorption using Indian Rosewood sawdust: a timber industry waste. Dyes Pigm. 63(3), 243–250 (2004)CrossRefGoogle Scholar
  53. 53.
    Y. Bulut, H. Aydın, A kinetics and thermodynamics study of methylene blue adsorption on wheat shells. Desalination 194(1–3), 259–267 (2006)CrossRefGoogle Scholar
  54. 54.
    J. Wei et al., MnO2 spontaneously coated on carbon nanotubes for enhanced water oxidation. Chem. Commun. 50(80), 11938–11941 (2014)CrossRefGoogle Scholar
  55. 55.
    S. Li et al., Influence of MnO2 on the photocatalytic activity of P-25 TiO2 in the degradation of methyl orange. Sci. China Ser. B 51(2), 179–185 (2008)CrossRefGoogle Scholar
  56. 56.
    A.R. Sorge et al., Decomposition of hydrogen peroxide on MnO2/TiO2 catalysts. J. Propul. Power 20(6), 1069–1075 (2004)CrossRefGoogle Scholar
  57. 57.
    R. Ullah, J. Dutta, Photocatalytic degradation of organic dyes with manganese-doped ZnO nanoparticles. J. Hazard. Mater. 156(1), 194–200 (2008)CrossRefGoogle Scholar
  58. 58.
    Y.L. Chan et al. Photocatalytic degradation of rhodamine B using MnO2 and ZnO nanoparticles. in Materials Science Forum, vol 756 (Trans Tech Publications, 2013), pp. 167–174Google Scholar
  59. 59.
    K. Barrett, M. McBride, Oxidative degradation of glyphosate and aminomethylphosphonate by manganese oxide. Environ. Sci. Technol. 39(23), 9223–9228 (2005)CrossRefGoogle Scholar
  60. 60.
    G. Li et al., 2,4,5-Trichlorophenol degradation using a novel TiO2-coated biofilm carrier: roles of adsorption, photocatalysis, and biodegradation. Environ. Sci. Technol. 45(19), 8359–8367 (2011)CrossRefGoogle Scholar
  61. 61.
    S. Lan et al., Hierarchical hollow structure ZnO: synthesis, characterization, and highly efficient adsorption/photocatalysis toward Congo red. Ind. Eng. Chem. Res. 53(8), 3131–3139 (2014)CrossRefGoogle Scholar
  62. 62.
    L. Zhang et al., Synthesis of a thin-layer MnO2 nanosheet-coated Fe3O4 nanocomposite as a magnetically separable photocatalyst. Langmuir 30(23), 7006–7013 (2014)CrossRefGoogle Scholar
  63. 63.
    R. Jothiramalingam, M. Wang, Synthesis, characterization and photocatalytic activity of porous manganese oxide doped titania for toluene decomposition. J. Hazard. Mater. 147(1), 562–569 (2007)CrossRefGoogle Scholar
  64. 64.
    V.B.R. Boppana, F. Jiao, Nanostructured MnO2: an efficient and robust water oxidation catalyst. Chem. Commun. 47(31), 8973–8975 (2011)CrossRefGoogle Scholar
  65. 65.
    Y. He et al., Synthesis of MnO2 nanosheets on montmorillonite for oxidative degradation and adsorption of methylene blue. J. Colloid Interface Sci. 510, 207–220 (2018)CrossRefGoogle Scholar
  66. 66.
    B. Xing et al., Preparation of TiO2/activated carbon composites for photocatalytic degradation of RhB under UV light irradiation. J. Nanomater. 2016, 3 (2016)CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Sherif Elbasuney
    • 1
    Email author
  • Mohamed A. Elsayed
    • 2
  • Sherif F. Mostafa
    • 2
  • Waleed F. Khalil
    • 2
  1. 1.Head of Nanotechnology Research CentreMilitary Technical CollegeCairoEgypt
  2. 2.School of Chemical EngineeringMilitary Technical CollegeCairoEgypt

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