Facile synthesis of novel microporous CdSe/SiO2 nanocomposites selective for removal of methylene blue dye by tandem adsorption and photocatalytic process

  • M. A. AhmedEmail author
  • M. F. Abdel-Messih
  • Eman H. Ismail


CdSe is considered a promising photocatalyst that exhibits a lower band gap energy (1.7 eV). However, the high cost of its metal precursors, low surface area and the rapid electron–hole recombination are the main problems that limit its industrialization. In this research work, incorporation of various proportions of CdSe (0–10 wt%) on the surface of microporous silica (432 m2/g) were carried out through ultrasonic route to enhance the chemical interaction between the synthesized nanoparticles and the support. X-ray diffraction (XRD), N2-adsorption–desorption isotherm, diffuse reflectance spectra, photoluminescence, field emission scanning electron microscope and high resolution transmission electron microscope (HRTEM) were carried out to investigate the physicochemical properties of the novel nanocomposites. HRTEM and XRD analysis indicate the homogeneous dispersion of CdSe nanoparticles of crystallite size (8–19) nm on silica surface. The influence of varying the concentration of CdSe on its degree of dispersion on silica via the hydroxyl group that dispersed on silica negatively charged surface was monitored. The experimental results have pointed out that the nominal value required for spreading CdSe as monolayer on silica surface is 3.25 molecules of CdSe per 100 Å2 of silica that is considered the most reactive photocatalyst in removal of MB dye. Below this nominal value, the amount of CdSe dispersed on silica is not enough to produce the required number of reactive radicals responsible for dye degradation. However, above the nominal value, the aggregation of CdSe layers on silica surface prevent the light penetration and induce electron–hole centers that reduce the lifetime of the photocatalyst. The removal of methylene blue dye via tandem adsorption and photocatalytic route increases with increasing CdSe concentration up to 10 wt% that is responsible for removal 90% of MB dye followed by reducing the reactivity for the sample containing 15 wt% CdSe. A direct relationship between adsorption and the photocatalytic reactivity is purposed assuming that the photocatalytic process require adsorption on high surface area nanoparticles as prime key step in increasing the contact probability between the photocatalyst and the organic dye that facilitate the production of large number of reactive radicals available for dye mineralization. TOC and COD analysis confirmed the complete mineralization of MB dye. The scavenger results indicate that both positive hole and hydroxyl radicals are the predominant reactive species for degradation of MB dye over CdSe and CdSe10. The achievement of controlling the dispersion of metal selenide on a support using ultrasonic route would certainly open a new approach for catalysis preparation.



  1. 1.
    C. Li, T. Lou, X. Yan, Y. Ze Long, G. Cui, X. Wang, Fabrication of pure chitosan nanofibrous membranes as effective absorbent for dye removal. Int. J. Biol. Macromol. 106(2018), 768–774 (2018)CrossRefGoogle Scholar
  2. 2.
    T. Robinson, G. McMullan, R. Marchant, P. Nigam, Remediation of dyes in textile effluent: a critical review on current treatment technologies with a proposed alternative. Biores. Technol. 77, 247–255 (2001)CrossRefGoogle Scholar
  3. 3.
    C.J. Ogugbue, T. Sawidis, Bioremediation and detoxification of synthetic wastewater containing triarylmethane dyes by Aeromonas hydrophila isolated from industrial effluent. Biotechnol. Res. Int. 168, 925–967 (2011)Google Scholar
  4. 4.
    W. Przystaś, E.Z. Godlewska, E.G. Sota, Biological removal of azo and triphenylmethane dyes and toxicity of process by-products. Water Air Soil Pollut. 223, 1581–1592 (2012)CrossRefGoogle Scholar
  5. 5.
    R. Couto, Dye removal by immobilized fungi. Biotechnol. Adv. 27, 227–235 (2009)CrossRefGoogle Scholar
  6. 6.
    E. Forgacs, T. Cserháti, G. Oros, Removal of synthetic dyes from wastewaters: a review. Environ. Int. 30, 953–971 (2004)CrossRefGoogle Scholar
  7. 7.
    H. She, H. Zhou, L. Li, L. Wang, J. Huang, Q. Wang, Nickel-doped excess oxygen defects titanium dioxide for efficient selective photocatalytic oxidation of benzyl alcohol under visible light irradiation. ACS Sustain. Chem. Eng. 6(9), 11939–11948 (2018)CrossRefGoogle Scholar
  8. 8.
    H. She, H. Zhou, L. Li, Z. Zhao, M. Jiang, J. Huang, L. Wang, Q. Wang, Construction of a two-dimensional composite derived from TiO2 and SnS2 for enhanced photocatalytic reduction of CO2 into CH4. ACS Sustain. Chem. Eng. 7, 650–659 (2019)CrossRefGoogle Scholar
  9. 9.
    L. Wang, P. Jin, S. Duan, H. She, J. Huang, Q. Wang, In-situ incorporation of copper(II) porphyrin functionalized zirconium MOF and TiO2 for efficient photocatalytic CO2 reduction. Sci. Bull. 64, 926–933 (2019)CrossRefGoogle Scholar
  10. 10.
    M.A. Ahmed, Synthesis and structural features of mesoporous NiO/TiO2 nanocomposites prepared by sol–gel method for photodegradation of methylene blue dye. J. Photochem. Photobiol. 238, 63–70 (2012)CrossRefGoogle Scholar
  11. 11.
    M.A. Ahmed, E.E. El-Katori, Z.H. Gharni, Photocatalytic degradation of methylene blue dye using Fe2O3/TiO2 nanoparticles prepared by sol–gel method. J. Alloys Compd. 553, 19–29 (2013)CrossRefGoogle Scholar
  12. 12.
    M.A. Ahmed, Z.M. Abou-Gamra, A.M. Salem, Photocatalytic degradation of methylene blue dye over novel spherical mesoporous Cr2O3/TiO2 nanoparticles prepared by sol-gel using octadecylamine template. J. Environ. Chem. Eng. 5, 4251–4261 (2017)CrossRefGoogle Scholar
  13. 13.
    M.F. Abdel-Messih, M.A. Ahmed, A.S. El-Sayed, Photocatalytic decolorization of Rhodamine B dye using novel mesoporous SnO2–TiO2 nano mixed oxides prepared by sol–gel method. J. Photochem. Photobiol. A 260, 1–8 (2013)CrossRefGoogle Scholar
  14. 14.
    M.F. Abdel-Messih, M.A. Ahmed, A. Soltan, S.S. Anis, Facile approach for homogeneous dispersion of metallic silver nanoparticles on the surface of mesoporous titania for photocatalytic degradation of methylene blue and indigo carmine dyes. J. Photochem. Photobiol. A 335, 40–51 (2017)CrossRefGoogle Scholar
  15. 15.
    P. Wang, D. Li, J. Chen, X. Zhang, J. Xian, X. Yang, X. Zheng, X. Li, Yu. Shao, A novel and green method to synthesize CdSe quantum dots-modifiedTiO2 and its enhanced visible light photocatalytic activity. Appl. Catal. B 160–161, 217–226 (2014)CrossRefGoogle Scholar
  16. 16.
    J. Jin, J. Yu, G. Liu, P.K. Wong, Single crystal CdS nanowires with high visible-light photocatalytic H2-production performance. J. Mater. Chem. A 1, 10927–10934 (2013)CrossRefGoogle Scholar
  17. 17.
    J. He, L. Chen, F. Wang, Y. Liu, P. Chen, C.T. Au, S.F. Yin, CdS nanowires decorated with ultrathin MoS2 nanosheets as an efficient photocatalyst for hydrogen evolution. ChemSusChem 9, 624–630 (2016)CrossRefGoogle Scholar
  18. 18.
    Z.D. Meng, L. Zhu, W.C. Oh, Preparation and high visible-light-induced photocatalytic activity of CdSe and CdSe-C60 nanoparticles. J. Ind. Eng. Chem. 18, 2004–2009 (2012)CrossRefGoogle Scholar
  19. 19.
    J. Wen, C. Ma, P. Huo, X. Liu, M. Wei, Y. Liu, X. Yao, Z. Ma, Y. Yan, Construction of vesicle CdSe nano-semiconductors photocatalysts with improved photocatalytic activity: enhanced photo induced carriers separation efficiency and mechanism insight. J. Environ. Sci. 60, 98–107 (2017)CrossRefGoogle Scholar
  20. 20.
    O. Amiri, M. Salavati-Niasari, S.M. Mashkani, A. Rafiei, S. Bagheri, Cadmium selenide@sulfide nanoparticle composites: facile precipitation preparation, characterization, and investigation of their photocatalyst activity. Mater. Sci. Semicond. Process. 27, 261–266 (2014)CrossRefGoogle Scholar
  21. 21.
    G.R. Bhand, N.B. Chaure, Synthesis of CdTe, CdSe and CdTe/CdSe core/shell QDs from wet chemical colloidal method. Mater. Sci. Semicond. Process. 68, 279–287 (2017)CrossRefGoogle Scholar
  22. 22.
    Z. Fang, L. Zhang, T. Yang, L. Sub, K.C. Chou, X. Hou, Cadmium sulfide with tunable morphologies: preparation and visible-light driven photocatalytic performance. Physica E 93, 116–123 (2017)CrossRefGoogle Scholar
  23. 23.
    J. Wang, X. Wang, Z. Tang, S. Gao, D. He, Y. Ke, S.Han Zheng, Facile synthesis and properties of CdSe quantum dots in a novel two-phase liquid/liquid system. Opt. Mater. 72, 737–742 (2017)CrossRefGoogle Scholar
  24. 24.
    M. Zhou, D. Han, X. Liu, C. Ma, H. Wang, Y. Tang, P. Huo, W. Shi, Y. Yan, J. Yang, Enhanced visible light photocatalytic activity of alkaline earth metal ions-doped CdSe/rGO photocatalysts synthesized by hydrothermal method. Appl. Catal. B 172–173, 174–184 (2015)CrossRefGoogle Scholar
  25. 25.
    P. Wang, D. Li, J. Chen, X. Zhang, J. Xian, X. Yang, X. Zheng, X. Li, Yu. Shao, A novel and green method to synthesize CdSe quantum dots-modified TiO2 and its enhanced visible light photocatalytic activity. Appl. Catal. B 160–161, 217–226 (2014)CrossRefGoogle Scholar
  26. 26.
    P. Wang, X. Li, J. Fang, D. Li, J. Chen, X. Zhang, Y. Shao, Y. He, A facile synthesis of CdSe quantum dots-decorated anatase TiO2 with exposed 001 facets and its superior photocatalytic activity. Appl. Catal. B 181, 838–847 (2016)CrossRefGoogle Scholar
  27. 27.
    P. Xie, S. Xue, Y. Wang, Z. Gao, H. Feng, L. Li, R. Zou, Morphology-controlled synthesis of CdSe microspheres on graphene oxide sheets and their photocatalytic properties. Ceram. Int. 42, 18264–18270 (2016)CrossRefGoogle Scholar
  28. 28.
    C. Ma, D. Wu, X. Yao, X. Liu, M. Wei, Y. Liu, Z. Ma, P. Huo, Y. Yan, Enhanced visible-light photocatalytic decomposition of organic dye over CdSe/Al2TiO5 heterojunction photocatalysts. J. Alloys Compd. 712, 486–493 (2017)CrossRefGoogle Scholar
  29. 29.
    P. Huo, J. Guan, M. Zhou, C. Ma, X. Liu, Y. Yana, S. Yuan, Carbon quantum dots modified CdSe loaded reduced graphene oxide for enhancing photocatalytic activity. J. Ind. Eng. Chem. 50, 147–154 (2017)CrossRefGoogle Scholar
  30. 30.
    H. Liu, X. Wang, D. Wu, Tailoring of bi-functional microencapsulated phase change materials with CdS/SiO2 double-layered shell for solar photocatalysis and solar thermal energy storage. Appl. Therm. Eng. 134, 603–614 (2018)CrossRefGoogle Scholar
  31. 31.
    N. Gupta, B. Pal, Core–shell structure of metal loaded CdS–SiO2 hybrid nanocomposites for complete photomineralization of methyl orange by visible light. J. Mol. Catal. A 391, 158–167 (2014)CrossRefGoogle Scholar
  32. 32.
    D.C.T. Nguyen, L. Zhu, Q. Zhang, K.Y. Choc, W.C. Oh, A new synergetic mesoporous silica combined to CdSe-graphene nanocomposite for dye degradation and hydrogen evolution in visible light. Mater. Res. Bull. 107, 14–27 (2018)CrossRefGoogle Scholar
  33. 33.
    Z. Bao, L. Liu, X. Yang, P. Tang, K. Yang, H. Lu, S. He, J. Liu, X. Liu, B. Li, Synthesis and characterization of novel oxygenated CdSe window layer for CdTe thin film solar cells. Maters. Sci. Semicond. Process. 63, 12–17 (2017)CrossRefGoogle Scholar
  34. 34.
    S. Mahmood, Hussain; Preparation of highly pure CdSe hollow structures: their PL and hydrogen absorption properties. Mater. Lett. 92, 263–266 (2013)CrossRefGoogle Scholar
  35. 35.
    S.Z. Ajabshir, S.M. Derazkola, M.S. Niasari, Simple sonochemical synthesis of Ho2O3-SiO2 nanocomposites as an effective photocatalyst for degradation and removal of organic contaminant. Ultrason. Sonochem. 39, 452–460 (2017)CrossRefGoogle Scholar
  36. 36.
    M. Khodadadi, M.H. Ehrampoush, M.T. Ghaneian, A. Allahresani, A.H. Mahvi, Synthesis and characterizations of FeNi3@SiO2@TiO2 nanocomposite and its application in photo- catalytic degradation of tetracycline in simulated wastewater. J. Mol. Liq. 255, 224–232 (2018)CrossRefGoogle Scholar
  37. 37.
    Q.Y. Li, K.R. Ma, Z.J. Ma, Q. Wei, J.G. Liu, S.P. Cui, Z.R. Nie, Preparation and enhanced photocatalytic performance of a novel photocatalyst: Hollow network Fe3O4/mesoporous SiO2/TiO2 (FST) composite microspheres. Microporous Mesoporous Mater. 265, 18–25 (2018)CrossRefGoogle Scholar
  38. 38.
    T. Cetinkaya, L. Neuwirthova, K.M. Kutlakova, V. Tomasek, H. Akbulut, Synthesis of nanostructured TiO2/SiO2 as an effective photocatalyst for degradation of acid orange. Appl. Surf. Sci. 279, 384–390 (2013)CrossRefGoogle Scholar
  39. 39.
    S. Yaparatne, C.P. Tripp, A. Amirbahman, Photodegradation of taste and odor compounds in water in the presence of immobilized TiO2-SiO2 photocatalysts. J. Hazard. Mater. 346, 208–217 (2018)CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  • M. A. Ahmed
    • 1
    Email author
  • M. F. Abdel-Messih
    • 1
  • Eman H. Ismail
    • 1
  1. 1.Chemistry Department, Faculty of ScienceAin Shams UniversityCairoEgypt

Personalised recommendations