Adsorptive removal of Cr(VI) onto UiO-66-NH2 and its determination by radioanalytical techniques

  • Suraj Prakash Tripathy
  • Satyabrata Subudhi
  • Rashmi AcharyaEmail author
  • Raghunath Acharya
  • Mira Das
  • Kulamani ParidaEmail author


UiO-66-NH2 (UNH), a Zr-based metal organic framework was synthesised by solvothermal technique. The formation of UNH was confirmed by XRD and SEM–EDX results. The adsorptive behaviour of UNH towards Cr(VI) was investigated with respect to pH, temperature, contact time and adsorbent dose. Radioanalytical techniques such as PIXE and INAA were employed for determination of adsorbed Cr(VI), which was well validated from Diphenylcarbazide method. Adsorption process was endothermic and followed pseudo second order kinetics. The maximum adsorption capacity was found to be 25.9 mg g−1 at pH 2.0 and adsorbent dose of 1 g L−1 in 3 h.


UNH Solvothermal Cr(VI) Adsorption capacity Radioanalytical NAA 



Authors are thankful to BRNS, DAE, Govt. of India, for the project and financial support under the project number 37(2)/14/02/2018/37002. The management of S‘O’A (Deemed to be university), Bhubaneswar are thankfully acknowledged for their encouragement and constant support in this work. Authors thank Dr. P.K. Pujari, Associate Director, RC&I Group and Head, RCD, BARC for his support and encouragements. Authors thank operation staff of PCF of Dhruva research reactor, BARC as well as scientists and staff members of Ion Beam Laboratory, Institute of Physics, Bhubaneswar for their help during INAA and PIXE experiments, respectively. Authors thank Mr Vishal Sharma, JRF (CSIR) at RCD for his help in PIXE and NAA experiments.

Compliance with ethical standards

Conflict of interest

There is no conflict of interest.


  1. 1.
    Abbasi SA, Soni R (1984) Teratogenic effects of chromium (VI) in environment as evidenced by the impact on larvae of amphibian rana tigrina: implications in the environmental management of chromium. Int J Environ Stud 23:131–137CrossRefGoogle Scholar
  2. 2.
    Acharya R, Naik B, Parida KM (2018) Cr(VI) remediation from aqueous environment through modified-TiO2-mediated photocatalytic reduction. Beilstein J Nanotechnol 9:1448–1470CrossRefGoogle Scholar
  3. 3.
    Acharya R, Martha S, Parida KM (2017) Remediation of Cr(VI) using clay minerals, biomasses and industrial wastes as adsorbents. In: Shahid Ul-Islam (ed) Advanced Materials for Waste water Treatment (John Wiley Scrivener USA), Series: Advanced Materials Series, 2017, p 129–170, ISBN: 9781119407768Google Scholar
  4. 4.
    Dubey R, Bajpai J, Bajpai AK (2015) Green synthesis of graphene sand composite (GSC) as novel adsorbent for efficient removal of Cr(VI) ions from aqueous solution. J Water Process Eng 5:83–94CrossRefGoogle Scholar
  5. 5.
    Sun X, Yang L, Li Q, Zhao J, Li X, Wang X, Liu H (2014) Amino-functionalized magnetic cellulose nanocomposite as adsorbent for removal of Cr(VI): synthesis and adsorption studies. Chem Eng J 241:175–183CrossRefGoogle Scholar
  6. 6.
    Patnaik S, Das KK, Mohanty A, Parida KM (2018) Enhanced photo catalytic reduction of Cr(VI) over polymer-sensitized g-C3N4/ZnFe2O4 and its synergism with phenol oxidation under visible light irradiation. Catal Today 315:52–66CrossRefGoogle Scholar
  7. 7.
    Hamdan SS, Naas MH (2014) Characterization of the removal of chromium(VI) from groundwater by electrocoagulation. J Ind Eng Chem 20:2775–2781CrossRefGoogle Scholar
  8. 8.
    Das S, Patnaik S, Parida KM (2019) Fabrication of a Au-loaded CaFe2O4/CoAl LDH p–n junction based architecture with stoichiometric H2 & O2 generation and Cr(VI) reduction under visible light. Inorg Chem Front 6:94–109CrossRefGoogle Scholar
  9. 9.
    Rafatullah M, Sulaiman O, Hashim R, Ahmad A (2010) Adsorption of methylene blue on low-cost adsorbents: a review. J Hazard Mater 177:70–80CrossRefGoogle Scholar
  10. 10.
    Ahmaruzzaman M (2008) Adsorption of phenolic compounds on low-cost adsorbents: a review. Adv Colloid Interface Sci 143:48–67CrossRefGoogle Scholar
  11. 11.
    Acharya R, Naik B, Parida KM (2017) Adsorption of Cr(VI) and textile dyes on to mesoporous silica, titanate nanotubes, and layered double hydroxides. In: Shahid Ul-Islam, Butola BS (eds) Nanomaterials in the Wet Processing of Textiles (John Wiley Scrivener USA), pp 219–260, ISBN: 9781119459842Google Scholar
  12. 12.
    Wu S, Ge Y, Wang Y, Chen X, Li F, Xuan H, Li X (2018) Adsorption of Cr(VI) on nano Uio-66-NH2 MOFs in water. Environ Technol (UK) 39:1937–1948CrossRefGoogle Scholar
  13. 13.
    Parida KM, Mishra KG, Dash SK (2012) Adsorption of toxic metal ion Cr(VI) from aqueous state by TiO2-MCM-41: equilibrium and kinetic studies. J Hazard Mater 241–242:395–403CrossRefGoogle Scholar
  14. 14.
    Acharya R, Subbaiah T, Anand S, Das RP (2003) Effect of precipitating agents on the physicochemical and electrolytic characteristics of nickel hydroxide. Mater Lett 57:3089–3095CrossRefGoogle Scholar
  15. 15.
    Acharya R, Subbaiah T, Anand S, Das RP (2002) Preparation, characterization and electrolytic behavior of β-nickel hydroxide. J Power Sources 109:494–499CrossRefGoogle Scholar
  16. 16.
    Pattnaik SP, Behera A, Martha S, Acharya R, Parida KM (2018) Synthesis, photoelectrochemical properties and solar light-induced photocatalytic activity of bismuth ferrite nanoparticles. J Nanoparticle Res 20:10CrossRefGoogle Scholar
  17. 17.
    Pattnaik SP, Behera A, Martha S, Acharya R, Parida KM (2019) Facile synthesis of exfoliated graphitic carbon nitride for photocatalytic degradation of ciprofloxacin under solar irradiation. J Mater Sci 54:5726–5742CrossRefGoogle Scholar
  18. 18.
    Subudhi S, Rath D, Parida KM (2018) A mechanistic approach towards the photocatalytic organic transformations over functionalised metal organic frameworks: a review. Catal Sci Technol 8:679–696CrossRefGoogle Scholar
  19. 19.
    Chen Z, Hanna SL, Redfern LR, Alezi D, Islamoglu T, Farha OK (2019) Reticular chemistry in the rational synthesis of functional zirconium cluster-based MOFs. Coord Chem Rev 386:32–49CrossRefGoogle Scholar
  20. 20.
    Subudhi S, Mansingh S, Swain G, Behera A, Rath D, Parida KM (2019) HPW-anchored UiO-66 metal–organic framework: a promising photocatalyst effective toward tetracycline hydrochloride degradation and H2 evolution via Z-scheme charge dynamics. Inorg Chem 58:4921–4934CrossRefGoogle Scholar
  21. 21.
    Yaghi OM, O’Keeffe M, Ockwig NW, Chae HK, Eddaoudi M, Kim J (2003) Reticular synthesis and the design of new materials. Nature 423:705–714CrossRefGoogle Scholar
  22. 22.
    Diercks CS, Kalmutzki MJ, Diercks NJ, Yaghi OM (2018) Conceptual advances from werner complexes to metal–organic frameworks. ACS Cent Sci 4:1457–1464CrossRefGoogle Scholar
  23. 23.
    Chen C, Chai Z, Wang X, Chen C, Chai Z, Alsaedi A, Hayatf T, Wang X (2018) Metal–organic framework-based materials: superior adsorbents for the capture of toxic and radioactive metal ions. Chem Soc Rev 47:2322–2356CrossRefGoogle Scholar
  24. 24.
    Kobielska PA, Howarth AJ, Farha OK, Nayak S (2018) Metal–organic frameworks for heavy metal removal from water. Coord Chem Rev 358:92–107CrossRefGoogle Scholar
  25. 25.
    Shokouhfar N, Aboutorabi L, Morsali A (2018) Improving the capability of UiO-66 for Cr(VI) adsorption from aqueous solutions by introducing isonicotinate: N-oxide as the functional group. Dalton Trans 47:14549–14555CrossRefGoogle Scholar
  26. 26.
    Li X, Gao X, Ai L, Jiang J (2015) Mechanistic insight into the interaction and adsorption of Cr(VI) with zeolitic imidazolate framework-67 microcrystals from aqueous solution. Chem Eng J 274:238–246CrossRefGoogle Scholar
  27. 27.
    Yang Q, Zhao Q, Ren SS, Lu Q, Guo X, Chen X (2016) Fabrication of core-shell Fe3O4@MIL-100(Fe) magnetic microspheres for the removal of Cr(VI) in aqueous solution. J Solid State Chem 244:25–30CrossRefGoogle Scholar
  28. 28.
    Shen L, Liang S, Wu W, Lianga R, Wu L (2013) Multifunctional NH2-mediated zirconium metal–organic framework as an efficient visible-light-driven photocatalyst for selective oxidation of alcohols and reduction of aqueous Cr(VI). Dalton Trans 42:13649–13657CrossRefGoogle Scholar
  29. 29.
    Das S, Dash SK, Parida KM (2018) Kinetics, isotherm, and thermodynamic study for ultrafast adsorption of azo dye by an efficient sorbent: ternary Mg/(Al + Fe) layered double hydroxides. ACS Omega 3:2532–2545CrossRefGoogle Scholar
  30. 30.
    Actu AC (1988) Analytica Chimica Actu 209:315–319CrossRefGoogle Scholar
  31. 31.
    Wang J, Liang Y, Jin Q, Hou J, Liu B, Li X, Chen W, Hayat T, Alsaedi A, Wang X (2017) Simultaneous removal of graphene oxide and chromium(VI) on the rare earth doped titanium dioxide coated carbon sphere composites. ACS Sustain Chem Eng 5:5550–5561CrossRefGoogle Scholar
  32. 32.
    Ho WH, Srinivasu V, Das R, Srinivasu V, Maity A (2017) A novel method for removal of Cr(VI) using polypyrrole magnetic nanocomposite in the presence of unsteady magnetic fields. Sep Purif Technol 194:377–387Google Scholar
  33. 33.
    Zhang J, Xia T, Zhao D, Cui Y, Yang Y, Qian G (2018) In situ secondary growth of Eu(III)-organic framework film for fluorescence sensing of sulfur dioxide. Sens Actuators B Chem 260:63–69CrossRefGoogle Scholar
  34. 34.
    Usseglio S, Larabi C, Kandiah M, Jakobsen S, Olsbye U, Tilset M, Larabi C, Quadrelli EA, Bonino F, Lillerud KP (2010) Synthesis and stability of tagged UiO-66 Zr-MOFs. Chem Mater 22:6632–6640CrossRefGoogle Scholar
  35. 35.
    Molavi H, Hakimian A, Shojaei A, Raeiszadeh M (2018) Applied surface science selective dye adsorption by highly water stable metal-organic framework: long term stability analysis in aqueous media. Appl Surf Sci 445:424–436CrossRefGoogle Scholar
  36. 36.
    Kong Q, Wei J, Hu Y, Wei C (2019) Fabrication of terminal amino hyperbranched polymer modified graphene oxide and its prominent adsorption performance towards Cr(VI). J Hazard Mater 363:161–169CrossRefGoogle Scholar
  37. 37.
    Kapur M, Mondal MK (2013) Mass transfer and related phenomena for Cr(VI) adsorption from aqueous solutions onto Mangifera indica sawdust. Chem Eng J 218:138–146CrossRefGoogle Scholar
  38. 38.
    Oyetade OA, Nyamori VO, Martincigh BS, Jonnalagadda SB (2016) Nitrogen-functionalised carbon nanotubes as a novel adsorbent for the removal of Cu(II) from aqueous solution. RSC Adv 6:2731–2745CrossRefGoogle Scholar
  39. 39.
    Khan TA, Dahiya S, Ali I (2012) Use of kaolinite as adsorbent: equilibrium, dynamics and thermodynamic studies on the adsorption of Rhodamine B from aqueous solution. Appl Clay Sci 69:58–66CrossRefGoogle Scholar
  40. 40.
    Acharya R, Swain KK, Shinde AD, Bhamra NS, Chakrabarty K, Karhadkar CG, Singh T, Rana YS, Pujari PK, Shukla DK, Reddy AVR (2014) Utilization of pneumatic carrier facility of Dhruva reactor for trace element determination by neutron activation analysis. J Radioanal Nucl Chem 302:1525–1530CrossRefGoogle Scholar
  41. 41.
    Shinde AD, Acharya R, Reddy AVR (2017) Analysis of zirconium and nickel based alloys and zirconium oxides by relative and internal monostandard neutron activation analysis methods. Nucl Eng Technol 49:562–568CrossRefGoogle Scholar
  42. 42.
    Lagad RA, Dasari KB, Alamelu D, Acharya R, Aggarwal SK (2014) Evaluation of soil to tea plant elemental correlation using instrumental neutron activation a nalysis. J Radioanal Nucl Chem 302:1507–1512CrossRefGoogle Scholar
  43. 43.
    Kumar R, Alamelu D, Acharya R, Rai AK (2014) Determination of concentrations of chromium and other elements in soil and plant samples from leather tanning area by Instrumental Neutron Activation Analysis. J Radioanal Nucl Chem 300:213–218CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  1. 1.Centre for Nanoscience and NanotechnologyS‘O’A Deemed to be UniversityBhubaneswarIndia
  2. 2.Radiochemistry DivisionBhabha Atomic Research Centre (BARC)MumbaiIndia
  3. 3.Department of ChemistryS‘O’A Deemed to be UniversityBhubaneswarIndia
  4. 4.Department of Atomic EnergyHomi Bhabha National InstituteMumbaiIndia

Personalised recommendations