Direct sunlight-driven degradation of 2-chlorophenol catalyzed by kaolinite-supported ZnO

  • A. H. ZyoudEmail author
  • T. Zorba
  • M. Helal
  • S. Zyoud
  • N. Qamhiya
  • A-R. Hajamohideen
  • Sh. Zyoud
  • H. S. Hilal
Original Paper


Commercial and laboratory-prepared ZnO nanoparticles are assessed here as a photocatalyst in photodegradation of aqueous 2-chlorophenol under direct sunlight. Kaolinite is used as a support for ZnO to enable its recovery after reuse. The composite ZnO/kaolinite is prepared by growing ZnO nanoparticles directly on kaolinite surface and is characterized by a number of methods such as electronic absorption spectra, photoluminescence spectra, X-ray diffraction and scanning electron microscopy. All ZnO systems (commercial, synthetic and supported) exhibit the wurtzite phase. The composite ZnO/kaolinite shows higher photocatalysis efficiency in 2-chlorophenol degradation over both commercial and synthetic ZnO powders. The composite ZnO/kaolinite is also easier to recover and reuse, showing no observable loss in its catalyst efficiency even after five cycles. These features highlight the merit of using composite ZnO/kaolinite as photocatalyst in water purification with direct sunlight for the first time. All catalyst systems are more efficient in basic media (pH ~ 8.5) than in neutral and acidic media, as rationalized by the point of zero charge concepts here. Moreover, the composite ZnO/kaolinite shows enhanced catalytic efficiency in 2-chlorophenol photodegradation in a wider pH range, compared to other counterparts, which shows another added value.


Photodegradation ZnO photocatalyst Kaolinite support 2-Chlorophenol Surface charge 



The authors wish to thank An-Najah N. University for financial support. Assistance from technical staff of the Department of Chemistry is acknowledged. The authors also wish to acknowledge help from United Arab Emirates University for SEM and XRD measurements.

Author’s contributions

The results shown here are partly based on T. Zorba thesis (supervised by H. S. Hilal and A. H. Zyoud). A. H. Zyoud performed extra needed experiments. S. Zyoud, N. Qamhiya and A-R. Hajamohideen performed SEM, EDX and additional XRD measurements. Sh. Zyoud helped in TOC analysis. M. Helal helped in reviewing the literature and formulating the study. A. H. Zyoud and H. S. Hilal wrote up the manuscript. All authors read and approved the manuscript.

Compliance with Ethical Standards

Conflicts of interest

The authors declare that there are no conflicts of interest regarding the publication of this paper.

Supplementary material

13762_2019_2272_MOESM1_ESM.docx (3.1 mb)
Supplementary material 1 (DOCX 3175 kb)


  1. Akhtar MJ, Ahamed M, Kumar S, Khan MM, Ahmad J, Alrokayan SA (2012) Zinc oxide nanoparticles selectively induce apoptosis in human cancer cells through reactive oxygen species. Int J Nanomed 7:845Google Scholar
  2. Bazrafshan E, Mostafapour FK, Faridi H, Zazouli MA (2012) Application of Moringa peregrina seed extract as a natural coagulant for phenol removal from aqueous solutions. Afr J Biotech 11:16758–16766Google Scholar
  3. Behnajady M, Modirshahla N, Hamzavi R (2006) Kinetic study on photocatalytic degradation of CI acid yellow 23 by ZnO photocatalyst. J Hazard Mater 133:226–232CrossRefGoogle Scholar
  4. Bondarenko O, Juganson K, Ivask A, Kasemets K, Mortimer M, Kahru A (2013) Toxicity of Ag, CuO and ZnO nanoparticles to selected environmentally relevant test organisms and mammalian cells in vitro: a critical review. Arch Toxicol 87:1181–1200CrossRefGoogle Scholar
  5. Cardenas-Peña AM, Ibanez JG, Vasquez-Medrano R (2012) Determination of the point of zero charge for electrocoagulation precipitates from an iron anode. Int J Electrochem Sci 7:6142–6153Google Scholar
  6. Chen X, Wu Z, Liu D, Gao Z (2017) Preparation of ZnO photocatalyst for the efficient and rapid photocatalytic degradation of azo dyes. Nanoscale Res Lett 12:143CrossRefGoogle Scholar
  7. Collard X, El Hajj M, Su B-L, Aprile C (2014) Synthesis of novel mesoporous ZnO/SiO2 composites for the photodegradation of organic dyes. Microporous Mesoporous Mater 184:90–96CrossRefGoogle Scholar
  8. Diamond S, Kinter EB (1958) Surface areas of clay minerals as derived from measurements of glycerol retention. Clays Clay Miner 5:334–347CrossRefGoogle Scholar
  9. Ding L, Yifeng E, Fan L, Yang S (2013) Growing vertical ZnO nanorod arrays within graphite: efficient isolation of large size and high quality single-layer graphene. Chem Commun 49:6286–6288CrossRefGoogle Scholar
  10. Hilal HS, Al-Nour GY, Zyoud A, Helal MH, Saadeddin I (2010) Pristine and supported ZnO-based catalysts for phenazopyridine degradation with direct solar light. Solid State Sci 12:578–586CrossRefGoogle Scholar
  11. Huo C, Yang H (2010) Synthesis and characterization of ZnO/palygorskite. Appl Clay Sci 50:362–366CrossRefGoogle Scholar
  12. Kosmulski M (2009) Surface charging and points of zero charge. CRC Press, Boca RatonCrossRefGoogle Scholar
  13. Krupskaya VV, Zakusin SV, Tyupina EA, Dorzhieva OV, Zhukhlistov AP, Belousov PE, Timofeeva MN (2017) Experimental study of montmorillonite structure and transformation of its properties under treatment with inorganic acid solutions. Minerals 7:49CrossRefGoogle Scholar
  14. Kutláková KM, Tokarský J, Peikertová P (2015) Functional and eco-friendly nanocomposite kaolinite/ZnO with high photocatalytic activity. Appl Catal B 162:392–400CrossRefGoogle Scholar
  15. Michaleowicz J (2005) The occurrence of chlorophenols, chlorocatechols and chlorinated methoxyphenols in drinking water of the largest cities in Poland. Pol J Environ Stud 14:327–333Google Scholar
  16. Michałowicz J, Duda W (2007) Phenols-Sources and toxicity. Pol J Environ Stud 16:347Google Scholar
  17. Misra AJ, Das S, Rahman AH, Das B, Jayabalan R, Behera SK, Suar M, Tamhankar AJ, Mishra A, Lundborg CS (2018) Doped ZnO nanoparticles impregnated on Kaolinite (Clay): a reusable nanocomposite for photocatalytic disinfection of multidrug resistant Enterobacter sp. under visible light. J Colloid Interface Sci 530:610–623CrossRefGoogle Scholar
  18. Muthirulan P, Meenakshisundararam M, Kannan N (2013) Beneficial role of ZnO photocatalyst supported with porous activated carbon for the mineralization of alizarin cyanin green dye in aqueous solution. Journal of advanced research 4:479–484CrossRefGoogle Scholar
  19. Pang X-Y (2010) Adsorption capacity and mechanism of expanded graphite for polyethylene glycol and oils. J Chem 7:1258–1265Google Scholar
  20. Rajamanickam D, Shanthi M (2016) Photocatalytic degradation of an organic pollutant by zinc oxide–solar process. Arab J Chem 9:S1858–S1868CrossRefGoogle Scholar
  21. Rappoport Z (2004) The chemistry of phenols. Wiley, HobokenGoogle Scholar
  22. Yahaya S, Jikan SS, Badarulzaman NA, Adamu AD (2017) Chemical composition and particle size analysis of kaolin. Path Sci 3:1001CrossRefGoogle Scholar
  23. Zbik MS, Smart RSC, Morris GE (2008) Kaolinite flocculation structure. J Colloid Interface Sci 328:73–80CrossRefGoogle Scholar
  24. Zyoud AH, Hilal HS (2008) Silica-supported CdS-sensitized TiO2 particles in photo-driven water purification: assessment of efficiency, stability and recovery future perspectives, Chapter in a book, Water Purification, Novascience Pub, New York (in press, 2008)Google Scholar
  25. Zyoud A, Hilal H (2013) Curcumin-sensitized anatase TiO2 nanoparticles for photodegradation of methyl orange with solar radiation. In: 1st international conference and exhibition on the applications of information technology to renewable energy processes and systems (IT-DREPS). IEEE, pp 31–36Google Scholar
  26. Zyoud AH, Zaatar N, Saadeddin I, Ali C, Park D, Campet G, Hilal HS (2010) CdS-sensitized TiO2 in phenazopyridine photo-degradation: catalyst efficiency, stability and feasibility assessment. J Hazard Mater 173:318–325CrossRefGoogle Scholar
  27. Zyoud A, Zaatar N, Saadeddin I, Helal MH, Campet G, Hakim M, Park D, Hilal HS (2011) Alternative natural dyes in water purification: anthocyanin as TiO2-sensitizer in methyl orange photo-degradation. Solid State Sci 13:1268–1275CrossRefGoogle Scholar
  28. Zyoud A, Zu’bi A, Helal MH, Park D, Campet G, Hilal HS (2015) Optimizing photo-mineralization of aqueous methyl orange by nano-ZnO catalyst under simulated natural conditions. J Environ Health Sci Eng 13:46CrossRefGoogle Scholar
  29. Zyoud A, Dwikat M, Al-Shakhshir S, Ateeq S, Shteiwi J, Zu’bi A, Helal MH, Campet G, Park D, Kwon H (2016) Natural dye-sensitized ZnO nano-particles as photo-catalysts in complete degradation of E. coli bacteria and their organic content. J Photochem Photobiol A: Chem 328:207–216CrossRefGoogle Scholar
  30. Zyoud A, Jondi W, AlDaqqah N, Asaad S, Qamhieh N, Hajamohideen A, Helal MH, Kwon H, Hilal HS (2017) Self-sensitization of tetracycline degradation with simulated solar light catalyzed by ZnO@ montmorillonite. Solid State Sci 74:131–143CrossRefGoogle Scholar

Copyright information

© Islamic Azad University (IAU) 2019

Authors and Affiliations

  1. 1.SSERL, Department of ChemistryAn-Najah National UniversityNablusPalestine
  2. 2.Department of ChemistryAn-Najah National UniversityNablusPalestine
  3. 3.College of Pharmacy and NutritionUniversity of SaskatchewanSaskatoonCanada
  4. 4.Department of Mathematics and ScienceAjman UniversityAjmanUnited Arab Emirates
  5. 5.Department of PhysicsUnited Arab Emirates UniversityAl-AinUnited Arab Emirates
  6. 6.Department of Building EngineeringPalestine Technical University (Kadoorie)TulkarmPalestine

Personalised recommendations