Fabrication of Zn(II) and Cu(II) supported metal-organic frameworks for removal of some 3d metals from aqueous solutions

  • H. K. OkoroEmail author
  • S. O. Ayika
  • A. C. Tella
  • O. Ajibola
  • J. C. Ngila
  • C. Zvinowanda
Original Paper


Remediation of copper(II) and zinc(II) ions with the aid of metal-organic frameworks (MOFs) from its respective aqueous media was carried out. The MOFs were prepared by a solvothermal synthesis procedure of copper and zinc with benzene 1,4-dicarboxylic acid (BDC). Resultant metal-organic frameworks characterization was done with the aid of X-ray diffraction (XRD), Fourier transform infrared spectrophotometry (FT-IR), energy-dispersive X-ray (EDS) spectroscopy, scanning electron microscopy (SEM), transmission electron micrograph (TEM) and pH point of zero charge (PZC). The adsorptive procedure employed to test the kinetics, equilibrium characters and thermodynamics was the batch process. Data obtained from the process were attested with the help of Temkin, Langmuir and Freundlich isotherm models; Langmuir model best fitted the data. Pseudo-first-order and pseudo-second-order rate equations were considered for kinetics. Results reveal that for copper; the metal-organic frameworks have an adsorptive capacity of 157.316 mg/g and 134.643 mg/g for Cu-BDC and Zn-BDC while the MOFs have an adsorption capacity of 145.144 mg/g and 138.158 mg/g for Cu-BDC and Zn-BDC when tested with zinc. The experimental data of the synthesized MOFs clearly indicates that they have great potential in remediating the subject metals in aqueous medium.

Graphical abstract


Adsorption Copper Isotherm Kinetics Metal-organic frameworks Zinc 



The authors, Dr. H. K. Okoro and Prof. J.C. Ngila, thank UJ Global Excellence and Stature Scholarship for the running cost paid through the Water Research Commission (WRC) Project No. K5/2365. They are also grateful to the Royal Society of Chemistry for awarding the 2015 research fund to them to facilitate the study. Dr. Caliphs Zvinowanda thanks NRF—SA/Egypt collaboration Grants No. 108685. The authors also thank the University of Ilorin, Ilorin, Nigeria, and the University of Johannesburg, South Africa, for making available their respective library database and laboratory facilities. Their acknowledgement also goes to Mr. Ismaila Jimoh, Psychometrics Department, JAMB, Nigeria, for the editorial assistance.

Compliance with ethical standards

Conflict of interest

All authors declare that they have no conflict of interest.

Supplementary material

13762_2019_2459_MOESM1_ESM.docx (1.4 mb)
Supplementary material 1 (DOCX 1401 kb)


  1. Afkhami A, Saber-Tehrani M, Bagheri H (2010) Simultaneous removal of heavy-metal ions in wastewater samples using nano-alumina modified with 2,4-dinitrophenylhydrazine. J Hazard Mater 181:836–844CrossRefGoogle Scholar
  2. Ajmal M, Rao RA, Ahmed K, Ahmed R (2000) Adsorption studies on Citrus reticulate (fruit peel of orange): removal and recovery of Ni(II) from electroplating wastewater. J Hazard Mater 79:117–131CrossRefGoogle Scholar
  3. Alejandro Aguayo-Villarreal I, Bonilla-Petriciolet A, Hernández-Montoya V, Montes-Moránc MA, Reynel-Avila HE (2011) Batch and column studies of Zn2+ removal from aqueous solution using chicken feathers as sorbents. Chem Eng J 167(2011):67–76CrossRefGoogle Scholar
  4. Alshikh A (2011) Analysis of heavy metals and organic pollutants of ground water samples of South Saudi. Life Sci J 8(4):438–441Google Scholar
  5. Aman T, Kazi AA, Sabri MU, Bano Q (2008) Potato peels as solid waste for the removal of heavy metal copper(II) from waste water/industrial effluent. Colloids Surf B Biol Interfaces 63:116–121CrossRefGoogle Scholar
  6. Barka N, Ouzaouit K, Abdennouri M, El Ma-khfouk M (2013) Dried prickly pear cactus (Opuntia ficus indica) cladodes as a low-cost and eco-friendly biosorbent for dyes removal from aqueous solutions. J Taiwan Inst Chem Eng 44(1):52–60. CrossRefGoogle Scholar
  7. Chowdhury IH, Chowdhury AH, Bose P, Mandal S, Naskar MK (2016) Effect of anion type on the synthesis of mesoporous nanostructured MgO, and its excellent adsorption capacity for the removal of toxic heavy metal ions from water. RSC Adv 2016(6):6038–6047CrossRefGoogle Scholar
  8. Demirbas E, Kobya M, Konukman AES (2008) Error analysis of equilibrium studies for the almond shell activated carbon adsorption of Cr(VI) from aqueous solutions. J Hazard Mater 154:787–794CrossRefGoogle Scholar
  9. Dey SS, Kind J, Pagie L, de Vries SS, Nahidiazar L, Bienko M, Zhan Y (2015) Genome-wide maps of nuclear lamina interactions in single human cells. Cell 163(1):134–147CrossRefGoogle Scholar
  10. Dias EM, Petit C (2015) Towards the use of metal-organic frameworks for water reuse: a review of the recent advances in the field of organic pollutants removal and degradation and the next steps in the field. J Mat Chem A 4(9):3565CrossRefGoogle Scholar
  11. Ezekiel D, Dikio A, Mohamed F (2013) Synthesis, characterization and comparative study of copper and zinc metal organic frameworks. Chem Sci Trans 2(4):1386–1394. ISSN/E-ISSN: 2278-3458/2278-3318
  12. Gielar A, Rybicka EH, Moller S, Einax JW (2012) Multivariate analysis of sediment data from the upper and middle Odra River (Poland). Appl Geochem 27:1540–1545CrossRefGoogle Scholar
  13. Giwa AA, Olajire AA, Oladipo MA, Bello MO, Bello IA (2013) Adsorption of ternary metal system onto the sawdust of locust bean tree (Parkia biglobosa): equilibrium, kinetics and thermodynamics studies. Int J Sci Eng Res 4(6):1275–1296Google Scholar
  14. Jhung SH, Yoon JW, Hwang J-S, Cheetham AK, Chang J-S (2005) Facile synthesis of nanoporous nickel phosphates with organic templates under microwave irradiation. Chem Mater 17(17):4455–4460. CrossRefGoogle Scholar
  15. Jimoh TO, Buoro AT, Muriana M (2012) Utilization of Bilighia sapida (Akee apple) pod in the removal of lead, cadmium and cobalt ions from aqueous solution. J Environ Chem Ecotoxicol 4(10):178–187CrossRefGoogle Scholar
  16. Kermani M, Pourmoghaddas H, Bina B, Khazaei Z (2006) Removal of phenol from aqueous solutions by rice husk and activated carbon. Pak J Biol Sci 9(10):1905–1910CrossRefGoogle Scholar
  17. Khan NA, Hasan Z, Jhung SH (2013) Adsorptive removal of hazardous materials using metal-organic frame works (MOFS): a review. J Hazard Mater 244–245(15):444–456. CrossRefGoogle Scholar
  18. Khormaei M, Nasernejad B, Edrisi M, Eslamzadeh T (2007) Copper biosorption from aqueous solutions by sour orange residue. J Haz Mat 149(2):269–274. CrossRefGoogle Scholar
  19. Li J, Wu Y, Li Z, Zu M, Li F (2014) Characteristics of arsenate removal from water by metal–organic frameworks (MOFs). Water Sci Technol 70(8):1391–1397. CrossRefGoogle Scholar
  20. Mahata P, Ramya KV, Natarajan S (2007) Synthesis, structure and optical properties of rare-earth benzene carboxylates. Dalton Trans 36:4017–4026CrossRefGoogle Scholar
  21. Okoli JU, Ezuma I (2014). Adsorption studies of heavy metals by low-cost adsorbents. J Appl Sci Environ Manag 18 (3):443–448. ISSN 1119-8362Google Scholar
  22. Okoro HK, Adeniyi A, Omollo EJ, Bhekumusa JX (2012) Physico-chemical analysis of selected groundwater samples of Ilorin town in Kwara State, Nigeria. Sci Res Essays 7(23):2063–2069Google Scholar
  23. Okoro HK, Fatoki OS, Adekola FA, Ximba BJ, Snyman RG (2014) Geochemical assessment of sediment in Cape Town Harbour, South Africa. Bull Chem Soc Ethiopia 28(1):17–28CrossRefGoogle Scholar
  24. Okoro HK, Alao ST, Adebayo GB, Basheer KA (2015) Evaluation of heavy and trace metals in fingernails of young school children and adults in Ilorin, Kwara State, Nigeria. J Appl Sci Environ Manag 19(2):319–324Google Scholar
  25. Okoro HK, Ige JO, Iyiola OA, Ngila JC (2017) Fractionation profile, mobility patterns and correlations of heavy metals in estuary sediments from Olonkoro River, in Tede catchment of western region, Nigeria. Environ Nanotechnol Monitor Manag 8:53–62. CrossRefGoogle Scholar
  26. Okoro HK, Ayika SO, Ngila JC, Tella AC (2018) Rising profile on the use of metal-organic frameworks (MOFs) for the removal of heavy metals from the environment: an overview. Appl Water Sci. 8:169. CrossRefGoogle Scholar
  27. Okoro HK, Ayika SO, Tella AC, Ngila JC (2019) Metal–organic frameworks (MOFs) derived from carboxylate ligand as potential materials for remediation of Cd(II) and Pb(II) from aqueous solution. J Turk Chem Soc (JOTCSA) 6(2):165–176. CrossRefGoogle Scholar
  28. Ortega LM, Lebrun R, Blais JF, Hauslerd R, Drogui P (2008) Effectiveness of soil washing, nanofiltration and electrochemical treatment for the recovery of metal ions coming from a contaminated soil. Water Res 42:1943–1952CrossRefGoogle Scholar
  29. Paknikar KM, Pethkar AV, Puranik PR (2003) Bioremediation of metalliferous wastes and products using inactivated microbial biomass. Indian J Biotechnol 2:426–443Google Scholar
  30. Pally NK (2013) Synthesis and structures of new three-dimensional copper metal-organic frameworks. Masters Theses & Specialist Projects. Paper 1295.
  31. Pehlivan E, Altun T, Parlayici S (2012) Modified barley straw as a potential biosorbent for removal of copper ions from aqueous solution. Food Chem 135(4):2229–2234. CrossRefGoogle Scholar
  32. Ruyra A, Yazdi A, Espín J (2015) Synthesis, culture medium stability, and in vitro and in Vivo zebrafish embryo toxicity of metal-organic framework nanoparticles. Chemistry 21:2508–2518. CrossRefGoogle Scholar
  33. Sagar TP, Shah P (2014) Adsorptive removal of hazardous waste materials using metal-organic frameworks. In: international conference on multidisciplinary research and practice, vol I, no VIII IJRSI ISSN 2321-2705Google Scholar
  34. Sajid M (2016) Toxicity of nanoscale metal organic frameworks: a perspective. Env Sci Poll Res 23(15):14805–14807. CrossRefGoogle Scholar
  35. Shooto ND, Dikio ED, Wankasi D, Sikhwivhilu L (2015) Synthesis, morphology and lead ion adsorption properties of metal organic frameworks of copper and cobalt. Chem Sci J. 6:113. Google Scholar
  36. Suparna R, Anantharaman P (2017) Heavy metals accumulation of different parts of Turbinaria spp. along the Olaikuda Coast, Rameshwaram, Tamilnadu. Int Adv Res J Sci Eng Technol 4(3):99–102CrossRefGoogle Scholar
  37. Tahmasebi E, Mosoomi MY, Yamini Y, Morsali A (2015) Application of mechano-synthesized azine-decorated zinc(II) metal-organic frameworks for highly efficient removal and extraction of some heavy-metal ions from aqueous samples: a comparative study. Inorg Chem 54(2):425–433. CrossRefGoogle Scholar
  38. Tan JC, Ryder MR (2014) Nanoporous metal organic framework materials for smart applications. Mater Sci Technol 30(13a):1598–1612Google Scholar
  39. Tella AC, Olawale MD, Neuburger M, Obaleye JA (2017a) Synthesis and crystal structure of Cd-based metal-organic framework for removal of methyl-orange from aqueous solution. J Solid State Chem 255:157–166CrossRefGoogle Scholar
  40. Tella AC, Oladipo AC, Adeyemi OG, Oluwafemi OS, Oguntoye SO, Alimi LO, Ajayi JT, Degni SK (2017b) Solid state synthesis, spectroscopic and X-ray studies of metal complexes of 2-picolinic acid and vapochromic behavior of [Co(Pic)2(H2O)2]·2H2O. Solid State Sci 68:1–9CrossRefGoogle Scholar
  41. Tella AC, Owalude SO, Olatunji SJ, Adimula VO, Elaigwu SE, Alimi LO, Ajibade PA, Oluwafemi OS (2018) Synthesis of zinc-carboxylate metal–organic frameworks for the removal of emerging drug contaminant (amodiaquine) from aqueous solution. J Environ Sci 64:264–275CrossRefGoogle Scholar
  42. Veli S, Alyüz B (2007) Adsorption of copper and zinc from aqueous solutions by using natural clay. J Harz Mat 149(1):226–233. CrossRefGoogle Scholar
  43. Venkatesham V, Madhu GM, Satyanarayana SV, Preetham HS (2013) Adsorption of lead on gel combustion derived nano ZnO. Proc Eng 51:308–313CrossRefGoogle Scholar
  44. Verma P, Navlani-García M, Kuwahara Y., Mori K, Yamashita H (2017) Mesoporous silica supported Pd/Ag bimetallic nanoparticles as a plasmonic catalyst for chemoselective hydrogenation of p-nitrostyrene under visible light irradiation. J Chem Sci 129:1661–1669. CrossRefGoogle Scholar
  45. Wu YN, Zhang B, Li F, Zhu W, Xu D, Hannam P, Li G (2012) Electrospun fibrous mats as a skeleton for fabricating hierarchically structured materials as sorbents for Cu2+. J Mater Chem 22:5089–5097CrossRefGoogle Scholar
  46. Yang H, Rose NL (2003) Distribution of Hg in the lake sediments across the UK. Sci Total Environ 304:391–404CrossRefGoogle Scholar
  47. Zamani MR, Rostami M, Aghajanzadeh M, Manjili HK, Rostamizadeh K, Danafar H (2017) Mesoporous titanium dioxide@zinc oxide-graphene oxide nanocarries for colon-specific drug delivery. J Mater Sci. Google Scholar
  48. Zhou H-C, Kuppler RJ, Timmons DJ, Fang Q-R, Li J-R, Makal TA, Young MD, Yuan D, Zhao D, Zhuang W (2009) Potential applications of metal-organic frameworks. Coord Chem Rev 253:3042–3066CrossRefGoogle Scholar

Copyright information

© Islamic Azad University (IAU) 2019

Authors and Affiliations

  • H. K. Okoro
    • 1
    Email author
  • S. O. Ayika
    • 1
  • A. C. Tella
    • 2
  • O. Ajibola
    • 1
  • J. C. Ngila
    • 3
  • C. Zvinowanda
    • 3
  1. 1.Analytical-Environmental and Material Science Research Group, Department of Industrial Chemistry, Faculty of Physical SciencesUniversity of IlorinIlorinNigeria
  2. 2.Laboratory of Synthetic Inorganic and Materials Chemistry, Department of Chemistry, Faculty of Physical SciencesUniversity of IlorinIlorinNigeria
  3. 3.Analytical-Environmental and Membrane Nanotechnology Research Group, Department of Chemical Sciences, Faculty of Science, Doornfontein CampusUniversity of JohannesburgDoornfontein, JohannesburgRepublic of South Africa

Personalised recommendations