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Efficient and recyclable photocatalytic degradation of methylene blue dye in aqueous solutions using nanostructured Cd1 − xCoxS films of different doping levels

  • Original Paper: Functional coatings, thin films and membranes (including deposition techniques)
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Abstract

This study outlines the impact of Co doping on the structures, morphologies, optical, and photochemical activities of nanoporous CdS films for efficient solar energy conversion. A sequence of nanotextured films of cadmium cobalt sulfide (Cd1 − xCoxS; where x = 0, 0.02, 0.04, 0.06, and 0.08) were grown on glass substrates using spray pyrolysis method followed by annealing at 300 °C for 2 h. The grown Cd1  xCoxS films are of single wurtzite phase and polycrystalline nature. The preferential crystallographic growth of Cd1 − xCoxS nanocrystallites along the (002) is changed to (101) direction for x ≥ 0.06. The crystallite size and lattice parameters are decreased for x ≤ 0.04. Also, the absorption is increased and the optical bandgap is decreased to 2.40 eV at 6% Co-doping. The morphological study reveals the growth of agglomerated pure CdS nanorods. The incorporation of Co increases the density of nanorods, which self-assembled to form nanoporous surface at 2 and 4%. A random distribution of irregular nanorods accompanied by patterned spherical clusters is observed at 6%, which is assembled to a nanoporous pattern at 8%. The photocatalytic performances and reaction kinetics of the films are investigated for methylene blue dye decomposition under sunlight and artificial light illumination. The 6% Co-doped film reached the complete removal after 240 min under sunlight irradiation. This film showed higher stability than pure CdS film for 7 runs. Therefore, the combination of spray pyrolysis and adjustable doping level is a viable way for producing large-scale and reusable photocatalytic films for eco-friendly removal of dyes from industrial wastewater.

Highlights

  • Cd1 − xCoxS nanofilms of different doping levels (0 ≤ x ≤ 8%) have been designed.

  • Morphological, structural, and optical properties of Cd1 − xCoxS films were studied.

  • The photocatalytic performance and stability of Cd1 − xCoxS films were investigated

  • Cd0.94Co0.06S film is the most suitable film for MB dye degradation under sunlight.

  • Reaction kinetics and reusability are studied under sunlight and artificial light.

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References

  1. Selopal GS, Zhao H, Wang ZM, Rosei F (2020) Core/shell quantum dots solar cells. Adv Funct Mater 30(13):1908762

    CAS  Google Scholar 

  2. Bhambhani P, Alvi PA (2016) A systematic study of the optical properties of Co-, and Ni-doped colloidal cadmium sulphide nanoparticles. J Optoelectron Eng 4(1):11–16

    Google Scholar 

  3. Mintcheva N, Gicheva G, Panayotova M, Wunderlich W, Kuchmizhak AA, Kulinich SA (2019) Preparation and photocatalytic properties of CdS and ZnS nanomaterials derived from metal xanthate. Materials 12(20):313

  4. Edvinsson T (2018) Optical quantum confinement and photocatalytic properties in two-, one- and zero-dimensional nanostructures. R Soc Open Sci 5:180387

    CAS  Google Scholar 

  5. Yilmaz S, Töreli SB, Polat I, Olgar MA, Tomakin M, Bacaks E (2017) Enhancement in the optical and electrical properties of CdS thin films through Ga and K co-doping. Mater Sci Semicond Process 60:45–52

    CAS  Google Scholar 

  6. Gunjal SD, Khollam YB, Arote SA, Jadkar SR, Shelke PN, Mohite KC (2015) Structural, optical and electrical properties of spray pyrolysis deposited CdS films. Macromol Symp 347(1):9–15

    CAS  Google Scholar 

  7. Demir R, Kaya İ (2019) Comparison of electrical characteristics of zinc oxide and cadmium sulfide films covered with 8-hydroxyquinoline for diode applications. J Mater Sci: Mater Electron 30:7103–7109

    CAS  Google Scholar 

  8. Sivaraman T, Balu AR, Nagarethinam VS (2014) Effect of magnesium incorporation on the structural, morphological, optical and electrical properties of CdS thin films. Mater Sci Semicond Process 27:915–923

    CAS  Google Scholar 

  9. Aksay S, Polat M, Özer T, Köse S, Gürbüz G (2011) Investigations on structural, vibrational, morphological and optical properties of CdS and CdS/Co films by ultrasonic spray pyrolysis. Appl Surf Sci 257(23):10072–10077

    CAS  Google Scholar 

  10. Saravanakumar S, Premarani R, Chandramohan R, Devadasan JJ, Balamurali S (2016) Structural and magnetic properties of co doped cds thin films by cbd method. J Phys Chem Nanotechnol 1(1):32–36

    Google Scholar 

  11. Yadav AA, Barote MA, Masumdar EU (2010) Studies on nanocrystalline cadmium sulphide (CdS) thin films deposited by spray pyrolysis. Solid State Sci 12(7):1173–1177

    CAS  Google Scholar 

  12. Memarian N, Rozati SM, Concina I, Vomiero A (2017) Deposition of nanostructured CdS thin films by thermal evaporation method: effect of substrate temperature. Materials 10(7):773

    Google Scholar 

  13. Dhawankar SH, Suryavanshi BM (2016) Characterization of cadmium sulphide (CdS) thin film deposited by spray pyrolysis technique. 4(2):58–61

  14. Manthrammel MA, Shkir M, Anis M, Shaikh SS, Ali HE, AlFaify S (2020) Facile spray pyrolysis fabrication of Al:CdS thin films and their key linear and third order nonlinear optical analysis for optoelectronic applications. Optical Mater 100:109696

    CAS  Google Scholar 

  15. Shao QP, Zhang H, Men CL, Tian Z, An ZH (2013) The effect of substrate temperatures on CdS film prepared by thermal evaporation. Appl Mech Mater 291–294:33–37

    Google Scholar 

  16. Okafor Patricia C. EAJ (2015) Effect of manganese doping percentage on band gap energy of cadmium sulphide (CdS) nanofilms prepared by electrodeposition method. Int J Sci Res 4(12):2280–2284

    Google Scholar 

  17. Sivaraman T, Nagarethinam VS, Balu AR (2014) CdS thin films fabricated by a simplified spray technique from different substrate temperatures—structural, morphological, optical and electrical analysis. J Mater Sci 2(2):6–15

    CAS  Google Scholar 

  18. Aboud AA, Mukherjee A, Revaprasadu N, Mohamed AN (2019) The effect of Cu-doping on CdS thin films deposited by the spray pyrolysis technique. J Mater Res Technol 8(2):2021–2030

    CAS  Google Scholar 

  19. El Sayed AM, Shaban M (2015) Structural, optical and photocatalytic properties of Fe and (Co, Fe) co-doped copper oxide spin coated films. Spectrochim Acta Part A 149:638–646

    CAS  Google Scholar 

  20. Zayed M, Ahmed AM, Shaban M (2019) Synthesis and characterization of nanoporous ZnO and Pt/ZnO thin films for dye degradation and water splitting applications. Int J Hydrog Energy 44:17630–17648

    CAS  Google Scholar 

  21. Shaban M, Mustafa M, El Sayed AM (2016) Structural, optical, and photocatalytic properties of the spray deposited nanoporous CdS thin films; influence of copper doping, annealing, and deposition parameters. Mater Sci Semicond Process 56:329–343

    CAS  Google Scholar 

  22. Yang J, Liu R, Huang S, Shao Y, Huang Y, Yu Y (2014) Enhanced photocatalytic activity and stability of interstitial Ga-doped CdS: combination of experiment and calculation. Catal Today 224:104–113

    CAS  Google Scholar 

  23. Wu J, Li Z, Li F (2013) Synthesis and visible-light-driven photocatalytic activity of one-dimensional CdS/α-Fe2O3. Superlattice Microst 54:146–154

    CAS  Google Scholar 

  24. Luo M, Liu Y, Hu J, Liu H, Li J (2012) One-pot synthesis of CdS and Ni-doped CdS hollow spheres with enhanced photocatalytic activity and durability. ACS Appl Mater Interf 4:1813–1821

    CAS  Google Scholar 

  25. Chandramohan SSR, Jebaraj RPJ (2017) Studies on dilute magnetic semiconducting co-doped CdS thin films prepared by chemical bath deposition method. J Mater Sci Mater Electron 28:12092–12099

    Google Scholar 

  26. Devadoss I, Muthukumaran S (2016) Doping induced structural, band gap and photoluminescence properties of Cd0.9−2xZn0.1CoxS nanoparticles. J Mater Sci Mater Electron 2016(7):1–9

    Google Scholar 

  27. Olakog lu T, Bacaksiz E, Tomakinb M, Altunbas M, Parlak M (2008) Structural, optical and magnetic properties of Cd1−xCoxS thin films prepared by spray pyrolysis. Phys B J 403:3740–3745

    Google Scholar 

  28. Ahmed FirasHashem (2010) Investigation of structural properties of CdS thin films grown by chemical bath deposition technique. Educ Coll Al-Mustansirya 61:107–112

    Google Scholar 

  29. Chandramohan S, Kanjilal a, Sarangi SN, Majumder S, Sathyamoorthy R, Som T (2010) Effect of Fe-ion implantation doping on structural and optical properties of CdS thin films. Appl Phys A 99(4):837–842

    CAS  Google Scholar 

  30. Dhruvashi PKS (2016) Effect of cobalt doping on ZnO thin fi lms deposited by sol-gel method. Thin Solid Films 612:55–60

    CAS  Google Scholar 

  31. Rmili HEA, Ouachtari F, Bouaoud A, Louardi A, Chtouki T, Elidrissi B (2013) Structural, optical and electrical properties of Ni-doped CdS thin films prepared by spray pyrolysis. J Alloy Compd 557:53–59

    CAS  Google Scholar 

  32. Sathyamoorthy R, Sudhagar P, Balerna A, Balasubramanian C, Bellucci S (2010) Surfactant-assisted synthesis of Cd1−xCoxS nanocluster alloys and their structural, optical and magnetic properties. J Alloy Compd 493(1–2):240–245

    CAS  Google Scholar 

  33. Shah NA, Sagar RR, Mahmood W, Syed WAA (2012) Cu-doping effects on the physical properties of cadmium sulfide thin films. J Alloy Compd 512(1):185–189

    CAS  Google Scholar 

  34. Bacaksiz TCE, Tomakin M, Altunbas M, Parlak M (2008) Structural, optical and magnetic properties of Cd1−xCoxS thin films prepared by spray pyrolysis. Phys B 403:3740–3745

    CAS  Google Scholar 

  35. Anbarasi M, Nagarethinam VS, Baskaran R, Narasimman V (2016) Studies on the structural, morphological and optoelectrical properties of spray deposited CdS: Pb thin films. Pac Sci Rev A Nat Sci Eng 8(1):6–11

    Google Scholar 

  36. Sivaraman T, Balu AR, Nagarethinam VS (2014) Effect of magnesium incorporation on the structural, morphological, optical and electrical properties of CdS thin films. Mater Sci Semicond Process 27:915–923

    CAS  Google Scholar 

  37. Solanki RG, Rajaram P, Bajpai PK (2017) Growth, characterization and estimation of lattice strain and size in CdS nanoparticles: X-ray peak profile analysis. Indian J Phys 92:1–9

    Google Scholar 

  38. Dakhel AA (2012) Structural and optoelectronic properties of Zn-incorporated CdO films prepared by sol–gel method. J Alloy Compd 539:26–31

    CAS  Google Scholar 

  39. Ezekoye BA, Ighodalo KO, Ezekoye VA, Emeakaroha TM, Ezema JI (2015) Nanocrystalline cadmium sulfide (CdS) thin film synthesized at different dip times by chemical bath deposition technique. 10(13):403–412

  40. Aji IQSN, Hdayer IMANHK, Ohammed HAIM (2013) The effect of annealing temperature on the optical properties of CdS and CdS: Al thin films introduction: experimental procedure. Int J Appl or Innov Eng Manag 2(6):556–561

    Google Scholar 

  41. Elmas S, Ozcan S, Ozder S, Bilgin V (2012) Influence of annealing temperature on the electrical and optical properties of CdS thin films. Appl Phys Mater Sci 121(1):10–12

    Google Scholar 

  42. Sreenivas M, Harish GS, Reddy PS (2014) Synthesis and characterization of Mn, Ce Co-doped CDS nanoparticles synthesized via co-precipitation method. Int J Mod Eng Res 4:1–6

    Google Scholar 

  43. Chandramohan S, Kanjilal a, Tripathi JK, Sarangi SN, Sathyamoorthy R, Som T (2009) Structural and optical properties of Mn-doped CdS thin films prepared by ion implantation. J Appl Phys 105:123507

    Google Scholar 

  44. Sivaraman T, Narasimman V, Nagarethinam VS, Balu AR (2015) Effect of chlorine doping on the structural, morphological, optical and electrical properties of spray deposited CdS thin films. Prog Nat Sci Mater Int 25(5):392–398

    CAS  Google Scholar 

  45. Nath SK, Paul DP, Nandi SK, Gafur MdA (2013) Structural and optical characterization of cobalt-doped ZnO thin film deposited by spray pyrolysis method. Int J Emerg Technol Comput Appl Sci (IJETCAS) 4(2):125–134

    Google Scholar 

  46. Saha SK, Rahman MA, Sarkar MRH, Shahjahan M, Khan MKR (2015) Effect of Co doping on structural, optical, electrical and thermal properties of nanostructured ZnO thin films. J Semicond 36(3):033004

    Google Scholar 

  47. Muruganandam S, Anbalagan G, Murugadoss G (2015) Optical, electrochemical and thermal properties of Co 2 +-doped CdS nanoparticles using polyvinylpyrrolidone. Appl Nanoscience 5:245–253

    CAS  Google Scholar 

  48. Titova LV, Hoang TB, Jackson HE, Smith LM (2006) Low temperature photoluminescence imaging and time-resolved spectroscopy of single CdS nanowires. Appl Phys Lett 89:1–4

  49. Yilmaz S (2015) The investigation of spray pyrolysis grown CdS thin films doped with flourine atoms. Appl Surf Sci 357:873–879

    CAS  Google Scholar 

  50. Al-Jumaili HS, N. mahmood T. (2014) Structural and optical properties of CdS: in nanoparticle thin films prepared by CBD technique Int J Thin Film Sci Tec 2(10):60–64

    Google Scholar 

  51. Verma U, Thakur V, Rajaram P, Shrivastava AK (2015) Structural, morphological and optical properties of sprayed nanocrystalline thin films of Cd1−xZnxS solid solution. Electron Mater Lett 11(1):46–54

    CAS  Google Scholar 

  52. Shaban M, Sayed AMEl (2015) Influences of lead and magnesium co-doping on the nanostructural, optical properties and wettability of spin coated zinc oxide films. Mater Sci Semicond Process 39:136–147

    CAS  Google Scholar 

  53. Shaban M, Zayed M, Hamdy H (2017) Nanostructured ZnO thin films for self-cleaning applications. RSC Adv 7(2):617–631

    CAS  Google Scholar 

  54. Al-Zahrani JH, El-Hagary M, El-Taher A (2015) Gamma irradiation induced effects on optical properties and single oscillator parameters of Fe-doped CdS diluted magnetic semiconductors thin films. Mater Sci Semicond Process 39:74–78

    CAS  Google Scholar 

  55. Lu Y, Lin Y, Wang D, Wang L, Xie T, Jiang T (2011) A high performance cobalt-doped ZnO visible light photocatalyst and its photogenerated charge transfer properties. Nano Res 4(11):1144–1152

    CAS  Google Scholar 

  56. Xiao Q, Zhang J, Xiao C, Tan X (2007) Photocatalytic decolorization of methylene blue over Zn1-xCoxO under visible light irradiation. Mater Sci Eng B Solid-State Mater Adv Technol 142(2–3):121–125

    CAS  Google Scholar 

  57. Kuriakose S, Satpati B, Mohapatra S (2014) Enhanced photocatalytic activity of Co doped ZnO nanodisks and nanorods prepared by a facile wet chemical method. Phys Chem Chem Phys 16(25):12741–12749

    CAS  Google Scholar 

  58. Firtina Ertis I, Boz I (2017) Synthesis and Characterization of Metal-Doped (Ni, Co, Ce, Sb) CdS Catalysts and their use in methylene blue degradation under visible light irradiation. Mod Res Catal 6:1–14

    Google Scholar 

  59. Zheng Y, Zheng L, Zhan Y, Lin X, Zheng Q, Wei K (2007) Ag/ZnO heterostructure nanocrystals. Synth Charact Photocatal 46(17):6980–6986

    CAS  Google Scholar 

  60. Barick KC, Singh S, Aslam M, Bahadur D (2010) Microporous and mesoporous materials porosity and photocatalytic studies of transition metal doped ZnO nanoclusters. Microporous Mesoporous Mater 134(1–3):195–202

    CAS  Google Scholar 

  61. Ekambaram S, Iikubo Y, Kudo A (2007) Combustion synthesis and photocatalytic properties of transition metal-incorporated ZnO. 433(3):237–240

  62. Karunakaran C, Rajeswari V, Gomathisankar P (2011) Enhanced photocatalytic and antibacterial activities of sol–gel synthesized ZnO and Ag–ZnO. Mater Sci Semicond Process 14(2):133–138

    CAS  Google Scholar 

  63. Xu J, Ao Y, Fu D, Yuan C (2008) Low-temperature preparation of F-doped TiO2 film and its photocatalytic activity under solar light. Appl Surf Sci 254(10):3033–3038

    CAS  Google Scholar 

  64. Rupa AV, Manikandan D, Divakar D, Sivakumar T (2007) Effect of deposition of Ag on TiO2 nanoparticles on the photodegradation of Reactive Yellow-17. J Hazard Mater 147(3):906–913

    CAS  Google Scholar 

  65. Moore J, Louder R, Thompson C (2014) Photocatalytic activity and stability of porous polycrystalline ZnO thin-films grown via a two-step thermal oxidation process. Coatings 4(3):651–669

    Google Scholar 

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Shaban, M., Elwahab, F.A., Ghitas, A.E. et al. Efficient and recyclable photocatalytic degradation of methylene blue dye in aqueous solutions using nanostructured Cd1 − xCoxS films of different doping levels. J Sol-Gel Sci Technol 95, 276–288 (2020). https://doi.org/10.1007/s10971-020-05331-x

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  • DOI: https://doi.org/10.1007/s10971-020-05331-x

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