Synthesis of zeolite NaY supported Mn-doped ZnS quantum dots and investigation of their photodegradation ability towards organic dyes

  • Zahra Ahmadi
  • Hamed Ramezani
  • Seyed Naser AziziEmail author
  • Mohammad Javad Chaichi
Research Article


In this work, Mn-doped ZnS quantum dots capped by L-cysteine (Mn@ZnS/L-cyst) and polyethylene glycol (Mn@ZnS/PEG) and also Mn-doped ZnS on zeolite NaY (Mn@ZnS/Y) were synthesized. These compounds were characterized by Fourier transform infrared (FT-IR), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and ultraviolet-visible and fluorescence spectroscopy. Then, the photodegradation ability of these three photocatalysts was investigated for degradation of 4′,5′-dibromofluorescein dye under ultraviolet irradiation. In the next stage, the different effective parameters on degradation performance, such as pH, catalyst dosage, and initial dye concentration, were studied. Results demonstrated that the optimum initial concentration was 40 mg L−1 for all three catalysts. The optimum catalyst dosage for both Mn-doped ZnS quantum dots capped by L-cysteine and Mn-doped ZnS on zeolite NaY was 0.017 g L−1 and for Mn-doped ZnS quantum dots capped by polyethylene glycol was 0.033 g L−1. The degradation efficiency of 97% for all three photocatalysts was achieved; therefore, by considering the higher production yield of quantum dots onto zeolite and also the more convenient recovery of the Mn-doped ZnS on zeolite NaY from the solution, it seems synthesis of quantum dots onto the zeolites is a reasonable strategy.


Zeolite NaY L-Cysteine Mn-ZnS quantum dot Polyethylene glycol Photocatalyst Organic dye 



The authors thank the University of Mazandaran for the financial support.

Supplementary material

11356_2019_7192_MOESM1_ESM.docx (443 kb)
ESM 1 (DOCX 442 kb)


  1. Aarthi T, Narahari P, Madras G (2007) Photocatalytic degradation of Azure and Sudan dyes using nano TiO2. J Hazard Mater 149:725–734CrossRefGoogle Scholar
  2. Ahadi M, Saber Tehrani M, Aberoomand Azar P, Waqif Husain S (2016) Novel preparation of sensitized ZnS nanoparticles and its use in photocatalytic degradation of tetracycline. Int J Environ Sci Technol 13:2797–2804CrossRefGoogle Scholar
  3. Andreozzi R, Caprio V, Insola A et al (1999) Advanced oxidation processes (AOP) for water purification and recovery. Catal Today 53:51–59CrossRefGoogle Scholar
  4. Azizi SN, Chaichi MJ, Shakeri P, Bekhradnia A (2013) Determination of atropine using Mn-doped ZnS quantum dots as novel luminescent sensitizers. J Lumin 144:34–40CrossRefGoogle Scholar
  5. Beaulac R, Archer PI, Gamelin DR (2008a) Luminescence in colloidal Mn2+-doped semiconductor nanocrystals. J Solid State Chem 181:1582–1589CrossRefGoogle Scholar
  6. Beaulac R, Archer PI, Liu X, Lee S, Salley GM, Dobrowolska M, Furdyna JK, Gamelin DR (2008b) Spin-polarizable excitonic luminescence in colloidal Mn2+-doped CdSe quantum dots. Nano Lett 8:1197–1201CrossRefGoogle Scholar
  7. Chaguetmi S, Mammeri F, Nowak S, Decorse P, Lecoq H, Gaceur M, Naceur JB, Achour S, Chtourou R, Ammar S (2013) Photocatalytic activity of TiO2 nanofibers sensitized with ZnS quantum dots. RSC Adv 3:2572–2580CrossRefGoogle Scholar
  8. Chantada-Vázquez MP, Sánchez-González J, Peña-Vázquez E, Tabernero MJ, Bermejo AM, Bermejo-Barrera P, Moreda-Piñeiro A (2016) Synthesis and characterization of novel molecularly imprinted polymer - coated Mn-doped ZnS quantum dots for specific fluorescent recognition of cocaine. Biosens Bioelectron 75:213–221CrossRefGoogle Scholar
  9. Chauhan R, Kumar A, Chaudhary RP (2013) Structural, optical and photocatalytic studies of Fe doped ZnS nanoparticles. J Sol-Gel Sci Technol 67:376–383CrossRefGoogle Scholar
  10. Chen J, Zhu Y, Zhang Y (2016) Glutathione-capped Mn-doped ZnS quantum dots as a room-temperature phosphorescence sensor for the detection of Pb2+ ions Spectrochim. Acta Part A 164:98–102CrossRefGoogle Scholar
  11. Ding SL, Wang XK, Jiang WQ, Meng X, Zhao RS, Wang C, Wang X (2013) Photodegradation of the antimicrobial triclocarban in aqueous systems under ultraviolet radiation. Environ Sci Pollut Res 20:3195–3201CrossRefGoogle Scholar
  12. Esmaili-Hafshejani J, Nezamzadeh-Ejhieh A (2016) Increased photocatalytic activity of Zn(II)/Cu(II) oxides and sulfides by coupling and supporting them onto clinoptilolite nanoparticles in the degradation of benzophenone aqueous solution. J Hazard Mater 316:194–203CrossRefGoogle Scholar
  13. Garcia-Cortes M, Sotelo González E, Fernández-Argüelles MT, Encinar JR, Costa-Fernández JM, Sanz-Medel A (2017) Capping of Mn-doped ZnS quantum dots with DHLA for their stabilization in aqueous media: determination of the nanoparticle number concentration and surface ligand density. Langmuir 33:6333–6341CrossRefGoogle Scholar
  14. Ghaedi M, Heidarpour S, Nasiri Kokhdan S, Sahraie R, Daneshfar A, Brazesh B (2012) Comparison of silver and palladium nanoparticles loaded on activated carbon for efficient removal of methylene blue: kinetic and isotherm study of removal process. Powder Technol 228:18–25CrossRefGoogle Scholar
  15. Ghasemi F, Hormozi-Nezhad MR, Mahmoudi M (2017) Time-resolved visual chiral discrimination of cysteine using unmodified CdTe quantum dots. Sci Rep 890:1–7Google Scholar
  16. Ghobadi N (2013) Band gap determination using absorption spectrum fitting procedure. International Nano Letters 3:1–4CrossRefGoogle Scholar
  17. Ginter D (2001) In: Robson H (ed) Verified syntheses of zeolitic materials, 2nd edn. Elsevier Science B.V, Amsterdam, pp 156–157Google Scholar
  18. Green M (2010) The nature of quantum dot capping ligands. J Mater Chem 20:5797–5809CrossRefGoogle Scholar
  19. He Y, Wang HF, Yan XP (2008) Exploring Mn-doped ZnS quantum dots for the room-temperature phosphorescence detection of enoxacin in biological fluids. Anal Chem 80:3832–3837CrossRefGoogle Scholar
  20. Houas A, Lachheb H, Ksibi M, Elaloui E, Guillard C, Herrmann JM (2001) Photocatalytic degradation pathway of methylene blue in water. Appl Catal B 31:145–157CrossRefGoogle Scholar
  21. Humayun M, Zheng Z, Fu Q, Luo W (2019) Photodegradation of 2,4-dichlorophenol and rhodamine B over n-type ZnO /p -type BiFeO3 heterojunctions:detailed reaction pathway and mechanism. Environ Sci Pollut Res 26:17696–17706CrossRefGoogle Scholar
  22. Karge HG (2001) In: Robson H (ed) Verified syntheses of zeolitic materials, 2nd edn. Elsevier Science B.V, Amsterdam, pp 69–71Google Scholar
  23. Kaur S, Sharma S, Kansal SK (2016) Synthesis of ZnS/CQDs nanocomposite and its application as a photocatalyst for the degradation of an anionic dye, ARS. Superlattice Microst 98:86–95CrossRefGoogle Scholar
  24. Kaur S, Sharma S, Umar A, Singh S, Mehta SK, Kansal SK (2017) Solar light driven enhanced photocatalytic degradation of brilliant green dye based on ZnS quantum dots. Superlattice Microst 103:365–375CrossRefGoogle Scholar
  25. Kim HS, Yoon KB (2014) Preparation and characterization of CdS and PbS quantum dots in zeolite Y and their applications for nonlinear optical materials and solar cell. Coord Chem Rev 263-264:239–256CrossRefGoogle Scholar
  26. Kiran S, Adeel S, Nosheen S et al (2017) Recent trends in textile effluent treatments: a review. In: Islam S (ed) advanced materials for wastewater treatment, 1st edn. Wiley, Beverly, pp 29–50CrossRefGoogle Scholar
  27. Li L, Shen Q, Li J, Hao Z, Xu ZP, Lu GQM (2008) Iron-exchanged FAU zeolites: preparation, characterization and catalytic properties for N2O decomposition. Appl Catal A 344:31–41CrossRefGoogle Scholar
  28. Mansur AAP, Mansur HS, Ramanery FP, Oliveira LC, Souza PP (2014) Green colloidal ZnS quantum dots/chitosan nano-photocatalysts for advanced oxidation processes:study of the photodegradation of organic dye pollutants. Appl Catal, B 158-159:269–279CrossRefGoogle Scholar
  29. Martínez-Castañón GA, MG S-L, JR M-M, Ruiz F (2005) Synthesis of CdS nanoparticles: a simple method in aqueous media. Adv Technol Mater Mater Process J(ATM) 7:171–174Google Scholar
  30. Nezamzadeh Ejhieh A, Khorsandi M (2010) Photodecolorization of Eriochrome Black T using NiS–P zeolite as a heterogeneous catalyst. J Hazard Mater 176:629–637CrossRefGoogle Scholar
  31. Pirillo S, Einschlag FSG, Ferreira ML, Rueda EH (2010) Eriochrome Blue Black R and fluorescein degradation by hydrogen peroxide oxidation with horseradish peroxidase and hematin as biocatalysts. J Mol Catal B Enzym 66:63–71CrossRefGoogle Scholar
  32. Pouretedal HR, Norozi A, Keshavarz MH, Semnani A (2009) Nanoparticles of zinc sulfide doped with manganese, nickel and copper as nanophotocatalyst in the degradation of organic dyes. J Hazard Mater 162:674–681CrossRefGoogle Scholar
  33. Pradhan N, Goorskey D, Thessing J, Peng X (2005) An alternative of CdSe nanocrystal emitters : pure and tunable impurity emissions in ZnSe nanocrystals. J Am Chem Soc 127:17586–17587CrossRefGoogle Scholar
  34. Rajabi HR, Farsi M (2015) Effect of transition metal ion doping on the photocatalytic activity of ZnS quantum dots:synthesis, characterization, and application for dye decolorization. J Mol Catal A Chem 399:53–61CrossRefGoogle Scholar
  35. Rajabi HR, Farsi M (2016) Study of capping agent effect on the structural, optical and photocatalytic properties of zinc sulfide quantum dots. Mater Sci Semicond Process 48:14–22CrossRefGoogle Scholar
  36. Rajabi HR, Khani O, Shamsipur M, Vatanpour V (2013) High-performance pure and Fe3+ -ion doped ZnS quantum dots as green nanophotocatalysts for the removal of malachite green under UV-light irradiation. J Hazard Mater 250-251:370–378CrossRefGoogle Scholar
  37. Ramezani H, Azizi SN, Hosseini SR (2017) NaY zeolite as a platform for preparation of Ag nanoparticles arrays in order to construction of H2O2. Sensors Actuators B Chem 248:571–579CrossRefGoogle Scholar
  38. Ramezani H, Azizi SN, Cravotto G (2019) Improved removal of methylene blue on modified hierarchical zeolite Y: achieved by a “destructive-constructive” method. Green Process Synth 8:730–741CrossRefGoogle Scholar
  39. Ramli NAS, Amin NAS (2015) Fe/HY zeolite as an effective catalyst for levulinic acid production from glucose: characterization and catalytic performance. Appl Catal B 163:487–498CrossRefGoogle Scholar
  40. Saeed M, Adeel S, Azhar Shahzad M et al (2015a) Pt/Al2O3 catalyzed decolorization of Rhodamine B dye in aqueous medium. Chiang Mai J Sci 42:730–744Google Scholar
  41. Saeed M, Adeel S, Ilyas M et al (2015b) Oxidative degradation of methyl orange catalyzed by lab prepared nickel hydroxide in aqueous medium. Desalin Water treat CrossRefGoogle Scholar
  42. Saeed M, Adeel S, Abdur-raoof H et al (2017) ZnO catalyzed degradation of methyl Orange in aqueous medium. Chiang Mai J Sci 44:1646–1653Google Scholar
  43. Samadi-Maybodi A, Sadeghi-Maleki MR (2018) Preparation of mesoporous SBA-15 supported CdS quantum dots and its application for photocatalytic degradation of organic pollutants in aqueous media. J Inorg Organomet Polym Mater 6:2620–2632CrossRefGoogle Scholar
  44. Shahryari Z, Soltani Goharrizi A, Azadi M (2010) Experimental study of methylene blue adsorption from aqueous solutions onto carbon nano tubes. Int J Water Res Environ Eng 2:16–28Google Scholar
  45. Shamsipur M, Rajabi HR (2014) Study of photocatalytic activity of ZnS quantum dots as efficient nanoparticles for removal of methyl violet:effect of ferric ion doping. Spectrochim Acta, Part A 122:260–267CrossRefGoogle Scholar
  46. Sooklal K, Cullum BS, Angel M S, Murphy CJ (1996) Photophysical properties of ZnS nanoclusters with spatially localized Mn2+. J Phys Chem100:4551–4555CrossRefGoogle Scholar
  47. Tauc J, Grigorovici R, Vancu A (1966) Optical properties and electronic structure of amorphous germanium. Phys Status Solidi B15:627–637CrossRefGoogle Scholar
  48. Wang Y, Liang X, Ma X, Hu Y, Hu X, Li X, Fan J (2014) Simple and greener synthesis of highly photoluminescence Mn2+-doped ZnS quantum dots and its surface passivation mechanism. Appl Surf Sci 316:54–61CrossRefGoogle Scholar
  49. Wang L, Wang P, Huang B, Ma X, Wang G, Dai Y, Zhang X, Qin X (2017) Synthesis of Mn-doped ZnS microspheres with enhanced visible light photocatalytic activity. Appl Surf Sci 391:557–564CrossRefGoogle Scholar
  50. Yang RT (2003) Adsorbents: fundamentals and applications. Wiley interscience, Hoboken, New JerseyCrossRefGoogle Scholar
  51. Zhao X, Li F, Zhang Q, Li Z, Zhou Y, Yang J, Dong C, Wang J, Shuang S (2015) Mn-doped ZnS quantum dots with a 3-mercaptopropionic acid assembly as a ratiometric fluorescence probe for the determination of curcumin. RSC Adv 5:21504–21510CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  • Zahra Ahmadi
    • 1
  • Hamed Ramezani
    • 1
  • Seyed Naser Azizi
    • 1
    Email author
  • Mohammad Javad Chaichi
    • 1
  1. 1.Analytical Division, Faculty of ChemistryUniversity of MazandaranBabolsarIran

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