Synthesis of Aqueous Suspensions of Zero-Valent Iron Nanoparticles (nZVI) from Plant Extracts: Experimental Study and Numerical Modeling

Michalis Karavasilis, Christos D. Tsakiroglou


Plant extracts were produced from Camellia sinesis (Green Tea) and Punica granatum (pomegranate), and the total concentration of polyphenols was measured in terms of equivalent concentration of Gallic acid by using the Folin-Ciocalteu method. Zero Valent Iron nanoparticles (nZVIs) were synthesized in a semi-batch reactor by mixing a pre-specified volume of plant extract or Gallic Acid solution with an aqueous solution of iron sulfate heptahydrate (FeSO4·7H2O). To monitor the kinetics of nZVI synthesis, the transient responses of solution pH and redox potential (Eh) were recorded with two probes adequately connected with a data acquisition card. The nanoparticles were characterized by a variety of techniques: Dynamic Light Scattering (DLS), ζ-potential, Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy, Transmission Electron Microscopy (TEM). A kinetic parametric model, based on two parallel single electron transfer (SET) and hydrogen atom transfer (HAT) reactions, was suggested to quantify the dynamics of ferrous ions reduction to zero valence, and its parameters were estimated for each experimental system by matching the transient response of pH. The temporal changes of redox potential during nZVI synthesis were indicative of the reaction progress and agreed with the numerical predictions in semi-quantitative basis.  The numerical model enabled us to track the temporal variation of the concentration of iron and polyphenol species, and calculate the yield of ZVI synthesis. The reactivity of nZVIs was assessed by measuring their capacity to reduce hexavalent chromium Cr (VI) in aqueous solutions prepared from potassium dichromate (K2Cr2O7).


Zero Valent Iron; Nanoparticles; Hexavalent Chromium; Plant Extract; Polyphenol; Reaction Kinetics.


Taghizadeh, Maryam, Daryoush Yousefi Kebria, Gholamreza Darvishi, and Farshad Kootenaei. “The Use of Nano Zero Valent Iron in Remediation of Contaminated Soil and Groundwater.” International Journal of Scientific Research in Environmental Sciences 1 (2013): 152–57.

Kharissova, Oxana V., H.V. Rasika Dias, Boris I. Kharisov, Betsabee Olvera Pérez, and Victor M. Jiménez Pérez. “The Greener Synthesis of Nanoparticles.” Trends in Biotechnology 31, no. 4 (April 2013): 240–248. doi:10.1016/j.tibtech.2013.01.003.

Karn, Barbara, Todd Kuiken, and Martha Otto. “Nanotechnology and in Situ Remediation: A Review of the Benefits and Potential Risks.” Ciencia & Saude Coletiva 16, no. 1 (January 2011): 165–78.

Matlochova, Adela, Daniela Placha, and Nada Rapantova. “The Application of Nanoscale Materials in Groundwater Remediation.” Polish Journal of Environmental Studies 22 (2013): 1401–10.

Tratnyek, Paul G., and Richard L. Johnson. “Nanotechnologies for Environmental Cleanup.” Nano Today 1, no. 2 (May 1, 2006): 44–48. doi:10.1016/S1748-0132(06)70048-2.

Rajan, C.S. Rajan. “Nanotechnology in Groundwater Remediation.” International Journal of Environmental Science and Development 2, no. 3 (2011): 182–87. doi:10.7763/IJESD.2011.V2.121.

T. Satyanarayana, and S.Sudhakar Reddy. “A Review on Chemical and Physical Synthesis Methods of Nanomaterials.” International Journal for Research in Applied Science & Engineering Technology 6, no. 1 (2018): 2885–89.

Rajput N. “Methods of Preparation of Nanoparticles.” International Journal of Advances in Engineering & Technology 7, no. 6 (2013): 1806–11. doi:10.1016/j.jare.2015.02.007.

Machado, S., S. L. Pinto, J. P. Grosso, H. P A Nouws, J. T. Albergaria, and C. Delerue-Matos. “Green Production of Zero-Valent Iron Nanoparticles Using Tree Leaf Extracts.” Science of the Total Environment 445–446 (February 15, 2013): 1–8. doi:10.1016/j.scitotenv.2012.12.033.

Li, Xiao-qin, Daniel W Elliott, and Wei-xian Zhang. “Zero-Valent Iron Nanoparticles for Abatement of Environmental Pollutants: Materials and Engineering Aspects.” Critical Reviews in Solid State and Materials Sciences 31, no. 4 (2006): 111–22. doi:10.1080/10408430601057611.

Hoag, George E., John B. Collins, Jennifer L. Holcomb, Jessica R. Hoag, Mallikarjuna N. Nadagouda, and Rajender S. Varma. “Degradation of Bromothymol Blue by ‘greener’ Nano-Scale Zero-Valent Iron Synthesized Using Tea Polyphenols.” Journal of Materials Chemistry 19, no. 45 (November 10, 2009): 8671–77. doi:10.1039/b909148c.

Saif, Sadia, Arifa Tahir, and Yongsheng Chen. “Green Synthesis of Iron Nanoparticles and Their Environmental Applications and Implications.” Nanomaterials (Basel, Switzerland) 6, no. 11 (November 12, 2016). doi:10.3390/nano6110209.

Machado, S., S.L. Pinto, J.P. Grosso, H.P.A. Nouws, J.T. Albergaria, and C. Delerue-Matos. “Green Production of Zero-Valent Iron Nanoparticles Using Tree Leaf Extracts.” Science of The Total Environment 445–446 (February 15, 2013): 1–8. doi:10.1016/j.scitotenv.2012.12.033.

Mystrioti, C., D. Sparis, N. Papasiopi, A. Xenidis, D. Dermatas, and M. Chrysochoou. “Assessment of Polyphenol Coated Nano Zero Valent Iron for Hexavalent Chromium Removal from Contaminated Waters.” Bulletin of Environmental Contamination and Toxicology 94, no. 3 (March 16, 2015): 302–7. doi:10.1007/s00128-014-1442-z.

Wang, Ting, Jiajiang Lin, Zuliang Chen, Mallavarapu Megharaj, and Ravendra Naidu. “Green Synthesized Iron Nanoparticles by Green Tea and Eucalyptus Leaves Extracts Used for Removal of Nitrate in Aqueous Solution.” Journal of Cleaner Production 83 (November 15, 2014): 413–19. doi:10.1016/J.JCLEPRO.2014.07.006.

Lin, Jiewen, Xiulan Weng, Rajarathnam Dharmarajan, and Zuliang Chen. “Characterization and Reactivity of Iron Based Nanoparticles Synthesized by Tea Extracts under Various Atmospheres.” Chemosphere 169 (February 1, 2017): 413–17. doi:10.1016/J.CHEMOSPHERE.2016.11.092.

Xin, Haiyan, Xin Yang, Xiaoli Liu, Xueping Tang, Lianjin Weng, and Yuanyuan Han. “Biosynthesis of Iron Nanoparticles Using Tie Guanyin Tea Extract for Degradation of Bromothymol Blue.” Journal of Nanotechnology 2016 (December 27, 2016): 1–8. doi:10.1155/2016/4059591.

Manquián-Cerda, Karen, Edgardo Cruces, María Angélica Rubio, Camila Reyes, and Nicolás Arancibia-Miranda. “Preparation of Nanoscale Iron (Oxide, Oxyhydroxides and Zero-Valent) Particles Derived from Blueberries: Reactivity, Characterization and Removal Mechanism of Arsenate.” Ecotoxicology and Environmental Safety 145 (November 2017): 69–77. doi:10.1016/j.ecoenv.2017.07.004.

Rosales, Emilio, M. Ángeles Sanromán, and Celia Dias-Ferreira. “Green Zero-Valent Iron Nanoparticles Synthesized Using Herbal Extracts for Degradation of Dyes from Wastewater.” DESALINATION AND WATER TREATMENT 92 (2017): 159–67. doi:10.5004/dwt.2017.20713.

Poguberovi , S. S., D. M. Kr mar, B. D. Dalmacija, S. P. Maleti , D. D. Toma evi -Pilipovi , D. V. Kerkez, and S. D. Ron evi . “Removal of Ni(II) and Cu(II) from Aqueous Solutions Using ’green Zero-Valent Iron Nanoparticles Produced by Oak and Mulberry Leaf Extracts.” Water Science and Technology 74, no. 9 (November 14, 2016): 2115–23. doi:10.2166/wst.2016.387.

Machado, S, J G Pacheco, H P A Nouws, J T Albergaria, and C Delerue-Matos. “Characterization of Green Zero-Valent Iron Nanoparticles Produced with Tree Leaf Extracts.” Science of The Total Environment 533 (2015): 76–81. doi:

Rao, Ashit, Ketakee Mahajan, Ashok Bankar, Rapole Srikanth, Ameeta Ravi Kumar, Suresh Gosavi, and Smita Zinjarde. “Facile Synthesis of Size-Tunable Gold Nanoparticles by Pomegranate (Punica Granatum) Leaf Extract: Applications in Arsenate Sensing.” Materials Research Bulletin 48, no. 3 (March 1, 2013): 1166–73. doi:10.1016/J.MATERRESBULL.2012.12.025.

Makarov, V V, A J Love, O V Sinitsyna, S S Makarova, I V Yaminsky, M E Taliansky, and N O Kalinina. “‘Green’ Nanotechnologies: Synthesis of Metal Nanoparticles Using Plants.” Acta Naturae, 2014.

EPA, United States Environmental Protection Agency. “Method 7196A.” Chromium, Hexavalente (Colorimetric), no. July (1992): 1–6.

Karamac, Magdalena, Agnieszka Kosinska, and Ronald Pegg. “Content of Gallic Acid in Selected Plant Extracts.” Polish Journal of Food and Nutrition Sciences 15, no. 1 (2006): 55–58.

Lith, Robert van, and Guillermo A. Ameer. “Antioxidant Polymers as Biomaterial.” Oxidative Stress and Biomaterials, January 1, 2016, 251–96. doi:10.1016/B978-0-12-803269-5.00010-3.

Layek, Arunasish, Gargi Mishra, Archana Sharma, Marina Spasova, Subhabrata Dhar, Arindam Chowdhury, and Rajdip Bandyopadhyaya. “A Generalized Three-Stage Mechanism of ZnO Nanoparticle Formation in Homogeneous Liquid Medium.” Journal of Physical Chemistry C 116, no. 46 (November 26, 2012): 24757–69. doi:10.1021/jp211613b.

Prior, Ronald L., Xianli Wu, and Karen Schaich. “Standardized Methods for the Determination of Antioxidant Capacity and Phenolics in Foods and Dietary Supplements.” Journal of Agricultural and Food Chemistry, May 18, 2005. doi:10.1021/jf0502698.

Stewart, Warren E., and Michael. Caracotsios. Computer-Aided Modeling of Reactive Systems. Hoboken,New Jersey: Wiley-Interscience, 2008.

Kumar, R., N. Singh, and S. N. Pandey. “Potential of Green Synthesized Zero-Valent Iron Nanoparticles for Remediation of Lead-Contaminated Water.” International Journal of Environmental Science and Technology 12, no. 12 (December 14, 2015): 3943–50. doi:10.1007/s13762-015-0751-z.

R SenthilkumarT, S, Sivakumar Thirumal, Ks Arulmozhi, and N.Mythili. “FT-IR Analysis and Correlation Studies on the Antioxidant Activity, Total Phenolics and Total Flavonoids of Indian Commercial Teas (.” International Research Journal of Biological Sciences 6 (2017): 1–7.

Park, Yong-Seo, Mi-Kyung Lee, Buk-Gu Heo, Kyung-Sik Ham, Seong-Gook Kang, Ja-Yong Cho, and Shela Gorinstein. “Comparison of the Nutrient and Chemical Contents of Traditional Korean Chungtaejeon and Green Teas.” Plant Foods for Human Nutrition 65, no. 2 (June 21, 2010): 186–91. doi:10.1007/s11130-010-0170-8.

Eddebbagh, Malak, Abdelmjid Abourriche, Mohamed Berrada, Mourad Ben Zina, and Ahmed Bennamara. “Adsorbent Material from Pomegranate (Punica Granatum) Leaves: Optimization on Removal of Methylene Blue Using Response Surface Methodology.” Journal of Materials and Environmental Science 7, no. 6 (2016): 2021–33.

Nisha, M Haniff, R Tamileswari, Sr S Jesurani, S Kanagesan, M Hashim, and S Catherine P Alexander. “Green Synthesis of Silver Nanoparticles From Pomegranate (Punicagranatum) Leaves and Analysis of Anti-Bacterial Activity.” International Journal of Advanced Technology in Engineering and Science 4, no. 03 (2015): 1–8.

Kannan, R R R, R Arumugam, and P Anantharaman. “Fourier Transform Infrared Spectroscopy Analysis of Seagrass Polyphenols.” Current Bioactive Compounds 7, no. 2 (2011): 118–25.

Hirun, Namon, Supaporn Dokmaisrijan, and Vimon Tantishaiyakul. “Experimental FTIR and Theoretical Studies of Gallic Acid–Acetonitrile Clusters.” Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 86 (February 1, 2012): 93–100. doi:10.1016/J.SAA.2011.10.009.

S Oakes, Jacqueline. “Investigation of Iron Reduction by Green Tea Polyphenols for Application in Soil Remediation.” University of Connecticut, 2013.

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DOI: 10.28991/esj-2019-01197


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Copyright (c) 2019 Michalis Karavasilis, Christos Tsakiroglou