, Volume 22, Issue 6, pp 3755–3771 | Cite as

Fabrication of cellulose nanocrystal supported stable Fe(0) nanoparticles: a sustainable catalyst for dye reduction, organic conversion and chemo-magnetic propulsion

  • Prodyut Dhar
  • Amit Kumar
  • Vimal KatiyarEmail author
Original Paper


This article reports a single-step “green protocol” for the environmentally friendly synthesis of zerovalent iron (ZVI) nanoparticles supported on cellulose nanocrystals (CNCs) fabricated from bamboo pulp. The high content of available hydroxyl groups on the CNC surfaces is utilized as an anchor point for the simultaneous reduction and stabilization of the CNC-supported ZVIs. In this approach, Na-CNCs act as corrosion inhibitors and enhance the catalytic activity of ZVI as it retains a zero state even after 5 days of exposure to air. Furthermore, CNC-supported ZVIs are found with narrow size distribution along with improved dispersion stability in water. The CNC-supported ZVIs successfully degraded the methylene blue, making it a potentially active and nontoxic biocatalyst for wastewater remediation. Moreover, it was also found to be active toward the hydrogenation of 4-nitrophenol into 4-aminophenol. Furthermore, we observed the autonomous motion of CNC-supported ZVIs in the presence of peroxide fuel whose trajectories were found to be externally controlled under both magnetic fields and pH gradients. Interestingly, we can remotely tune the speed and controlled trajectory of CNC-supported ZVIs, making these motors a potential candidate for the next-generation nanomachines for sensors, imaging and drug delivery applications.


Cellulose nanocrystals Reducing agent Zerovalent iron Catalyst 



Authors would like to thank the Department of Chemicals and Petrochemicals (DCPC), Government of India-funded Centre of Excellence for Sustainable Polymers (CoE-SusPol) and Central Instruments Facilities at IIT Guwahati for providing the research facilities. The authors are also thankful to the Department of Biotechnology, Ministry of Science and Technology, India, for the research grant (BT/345/NE/TBP/2012). Authors are also thankfull to Hindustan Paper Corp. Ltd. (HPCL, Assam, India) for providing cellulose pulp for current investigation.

Compliance with ethical standards

Author contribution

The authors declare that they have no conflict of interest. The manuscript was written with contributions of all authors. All authors have approved the final version of the manuscript.

Supplementary material

10570_2015_759_MOESM1_ESM.docx (692 kb)
Supplementary material 1 (DOCX 692 kb)

Supplementary material 2 (AVI 6349 kb)

Supplementary material 3 (AVI 24334 kb)

Supplementary material 4 (AVI 13460 kb)

Supplementary material 5 (AVI 12204 kb)


  1. Agarwal UP, Sabo R, Reiner RS, Clemons CM, Rudie AW (2012) Spatially resolved characterization of cellulose nanocrystal-polypropylene composite by confocal Raman microscopy. Appl Spectrosc 66:750–756CrossRefGoogle Scholar
  2. Benaissi K, Johnson L, Walsh DA, Thielemans W (2010) Synthesis of platinum nanoparticles using cellulosic reducing agents. Green Chem 12:220–222CrossRefGoogle Scholar
  3. Bhardwaj U, Dhar P, Kumar A, Katiyar V (2014) Polyhydroxyalkanoates (PHA)-cellulose based nanobiocomposites for food packaging applications. In: Food additives and packaging 275–314. ACS symposium series, 1162. American Chemical SocietyGoogle Scholar
  4. Cao X, Habibi Y, Lucia LA (2009) One-pot polymerization, surface grafting, and processing of waterborne polyurethane-cellulose nanocrystal nanocomposites. J Mater Chem 19:7137–7145CrossRefGoogle Scholar
  5. Castro CS, Guerreiro MC, Oliveira LCA, Gonçalves M, Anastacio AS, Nazzarro M (2009) Iron oxide dispersed over activated carbon: support influence on the oxidation of the model molecule methylene blue. Appl Catal A 367:53–58CrossRefGoogle Scholar
  6. Ceraulo L, Fanara S, Ruggirello A, Liveri VT (2007) FT-IR investigation of the state of iron (III) chloride clusters confined in AOT reverse micelles dispersed in carbon tetrachloride. J Cluster Sci 18:883–895CrossRefGoogle Scholar
  7. Cirtiu CM, Dunlop-Brière AF, Moores A (2011) Cellulose nanocrystallites as an efficient support for nanoparticles of palladium: application for catalytic hydrogenation and Heck coupling under mild conditions. Green Chem 13:288–291CrossRefGoogle Scholar
  8. Dhar P, Bhardwaj U, Katiyar V (2014a) Polymers for packaging applications. CRC Press, Boca RatonGoogle Scholar
  9. Dhar P, Bhardwaj U, Kumar A, and Katiyar V (2014) Cellulose nanocrystals: a potential nanofiller for food packaging applications. In: Food additives and packaging. 197–239. ACS symposium series, 1162. American Chemical SocietyGoogle Scholar
  10. Dhar P, Bhardwaj U, Kumar A, Katiyar V (2015a) Poly (3‐hydroxybutyrate)/cellulose nanocrystal films for food packaging applications: barrier and migration studies. Polym Eng Sci. doi: 10.1002/pen.24127
  11. Dhar P, Tarafder D, Kumar A, Katiyar V (2015b) Effect of cellulose nanocrystal polymorphs on mechanical, barrier and thermal properties of poly (lactic acid) based bionanocomposites. RSC Adv 5:60426–60440CrossRefGoogle Scholar
  12. Dong H, Snyder JF, Tran DT, Leadore JL (2013a) Hydrogel, aerogel and film of cellulose nanofibrils functionalized with silver nanoparticles. Carbohydr Polym 95:760–767CrossRefGoogle Scholar
  13. Dong H, Snyder JF, Williams KS, Andzelm JW (2013b) Cation-induced hydrogels of cellulose nanofibrils with tunable moduli. Biomacromolecules 14:3338–3345CrossRefGoogle Scholar
  14. Farrell D, Majetich SA, Wilcoxon JP (2003) Preparation and characterization of monodisperse Fe nanoparticles. J Phys Chem B 107:11022–11030CrossRefGoogle Scholar
  15. Frost RL, Xi Y, He H (2010) Synthesis, characterization of palygorskite supported zero-valent iron and its application for methylene blue adsorption. J Colloid Interface Sci 341(1):153–161CrossRefGoogle Scholar
  16. Garner A (2014) Use of cellulose nanocrystals as a corrosion inhibitor. U.S. Patent Application 13/935,477Google Scholar
  17. Horzum N, Demir MM, Nairat M, Shahwan T (2013) Chitosan fiber-supported zero-valent iron nanoparticles as a novel sorbent for sequestration of inorganic arsenic. RSC Adv 3:7828–7837CrossRefGoogle Scholar
  18. Houas A, Lachheb H, Ksibi M, Elaloui E, Guillard C, Herrmann JM (2001) Photocatalytic degradation pathway of methylene blue in water. Appl Catal B 31:145–157CrossRefGoogle Scholar
  19. Huang KC, Ehrman SH (2007) Synthesis of iron nanoparticles via chemical reduction with palladium ion seeds. Langmuir 23:1419–1426CrossRefGoogle Scholar
  20. Jackson JK, Letchford K, Wasserman BZ, Ye L, Hamad WY, Burt HM (2011) The use of nanocrystalline cellulose for the binding and controlled release of drugs. Int J Nanomed 6:321Google Scholar
  21. Jiang F, Hsieh YL (2014) Synthesis of cellulose nanofibril bound silver nanoprism for surface enhanced Raman Scattering. Biomacromolecules 15:3608–3616CrossRefGoogle Scholar
  22. Johnson L, Thielemans W, Walsh DA (2011) Synthesis of carbon-supported Pt nanoparticle electrocatalysts using nanocrystalline cellulose as reducing agent. Green Chem 13:1686–1693CrossRefGoogle Scholar
  23. Klačanová K, Fodran P, Šimon P, Rapta P, Boča R, Jorík V, Miglierini M, Kolek E, Čaplovič L (2012) Formation of Fe(0)-nanoparticles via reduction of Fe(II) compounds by amino acids and their subsequent oxidation to iron oxides. J Chem 2013Google Scholar
  24. Lai B, Chen Z, Zhou Y, Yang P, Wang J, Chen Z (2013) Removal of high concentration p-nitrophenol in aqueous solution by zero valent iron with ultrasonic irradiation (US–ZVI). J Hazard Mater 250:220–228CrossRefGoogle Scholar
  25. Lai B, Zhang Y, Chen Z, Yang P, Zhou Y, Wang J (2014) Removal of p-nitrophenol (PNP) in aqueous solution by the micron-scale iron–copper (Fe/Cu) bimetallic particles. Appl Catal B 144:816–830CrossRefGoogle Scholar
  26. Lam E, Male KB, Chong JH, Leung AC, Luong JH (2012) Applications of functionalized and nanoparticle-modified nanocrystalline cellulose. Trends Biotechnol 30:283–290CrossRefGoogle Scholar
  27. Le Troedec M, Sedan D, Peyratout C, Bonnet JP, Smith A, Guinebretiere R, Gloaguen V, Krausz P (2008) Influence of various chemical treatments on the composition and structure of hemp fibres. Compos A Appl Sci Manuf 39:514–522CrossRefGoogle Scholar
  28. Li J, Xiao Q, Jiang JZ, Chen GN, Sun JJ (2014) Au–Fe/Ni alloy hybrid nanowire motors with dramatic speed. RSC Adv 4:27522–27525CrossRefGoogle Scholar
  29. Liang W, Dai C, Zhou X, Zhang Y (2014) Application of zero-valent iron nanoparticles for the removal of aqueous zinc ions under various experimental conditions. PLoS ONE 9:e85686CrossRefGoogle Scholar
  30. Liu A, Liu J, Pan B, Zhang WX (2014) Formation of lepidocrocite (γ-FeOOH) from oxidation of nanoscale zero-valent iron (nZVI) in oxygenated water. RSC Adv 4:57377–57382CrossRefGoogle Scholar
  31. Nadagouda MN, Castle AB, Murdock RC, Hussain SM, Varma RS (2010) In vitro biocompatibility of nanoscale zerovalent iron particles (NZVI) synthesized using tea polyphenols. Green Chem 12:114–122CrossRefGoogle Scholar
  32. Njagi EC, Huang H, Stafford L, Genuino H, Galindo HM, Collins JB, Hoag GE, Suib SL (2010) Biosynthesis of iron and silver nanoparticles at room temperature using aqueous sorghum bran extracts. Langmuir 27:264–271CrossRefGoogle Scholar
  33. Oh SY, Yoo DI, Shin Y, Kim HC, Kim HY, Chung YS, Park WH, Youk JH (2005) Crystalline structure analysis of cellulose treated with sodium hydroxide and carbon dioxide by means of X-ray diffraction and FTIR spectroscopy. Carbohydr Res 340:2376–2391CrossRefGoogle Scholar
  34. Park S, Baker JO, Himmel ME, Parilla PA, Johnson DK (2010) Research cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol Biofuels 3:10CrossRefGoogle Scholar
  35. Park M, Chang H, Jeong DH, Hyun J (2013) Spatial deformation of nanocellulose hydrogel enhances SERS. BioChip J 7:234–241CrossRefGoogle Scholar
  36. Pulgarin C, Kiwi J (1995) Iron oxide-mediated degradation, photodegradation, and biodegradation of aminophenols. Langmuir 11:519–526CrossRefGoogle Scholar
  37. Rezayat M, Blundell RK, Camp JE, Walsh DA, Thielemans W (2014) Green one-step synthesis of catalytically active palladium nanoparticles supported on cellulose nanocrystals. ACS Sustain Chem Eng 2:1241–1250CrossRefGoogle Scholar
  38. Sadasivuni KK, Kafy A, Zhai L, Ko HU, Mun S, Kim J (2014) Transparent and flexible cellulose nanocrystal/reduced graphene oxide film for proximity sensing. Small 11:994–1002CrossRefGoogle Scholar
  39. Schmidt J, Marcovitch O, Lubezky A, Kozirovski Y, Folman M (1980) IR and FIR spectra of ammonia adsorbed on calcium chloride and bromide: evidence for complex formation. J Colloid Interface Sci 75:85–94CrossRefGoogle Scholar
  40. Shin Y, Exarhos GJ (2007) Template synthesis of porous titania using cellulose nanocrystals. Mater Lett 61:2594–2597CrossRefGoogle Scholar
  41. Shin Y, Bae IT, Arey BW, Exarhos GJ (2007a) Simple preparation and stabilization of nickel nanocrystals on cellulose nanocrystal. Mater Lett 61:3215–3217CrossRefGoogle Scholar
  42. Shin Y, Blackwood JM, Bae IT, Arey BW, Exarhos GJ (2007b) Synthesis and stabilization of selenium nanoparticles on cellulose nanocrystal. Mater Lett 61:4297–4300CrossRefGoogle Scholar
  43. Shin Y, Bae IT, Arey BW, Exarhos GJ (2008) Facile stabilization of gold-silver alloy nanoparticles on cellulose nanocrystal. J Phys Chem C 112:4844–4848CrossRefGoogle Scholar
  44. Singh AK, Dey KK, Chattopadhyay A, Mandal TK, Bandyopadhyay D (2014) Multimodal chemo–magnetic control of self-propelling microbots. Nanoscale 6:1398–1405CrossRefGoogle Scholar
  45. Socrates G (2004) Infrared and Raman characteristic group frequencies: tables and charts. Wiley, New YorkGoogle Scholar
  46. Sun YP, Li XQ, Zhang WX, Wang HP (2007) A method for the preparation of stable dispersion of zero-valent iron nanoparticles. Colloids Surf A 308:60–66CrossRefGoogle Scholar
  47. Tian C, Fu S, Lucia LA (2015) Magnetic Cu0.5Co0.5Fe2O4 ferrite nanoparticles immobilized in situ on the surfaces of cellulose nanocrystals. Cellulose 22(4):2571–2587. doi: 10.1007/s10570-015-0658-3 CrossRefGoogle Scholar
  48. Tseng HH, Su JG, Liang C (2011) Synthesis of granular activated carbon/zero valent iron composites for simultaneous adsorption/dechlorination of trichloroethylene. J Hazard Mater 192:500–506CrossRefGoogle Scholar
  49. Turcheniuk K, Tarasevych AV, Kukhar VP, Boukherroub R, Szunerits S (2013) Recent advances in surface chemistry strategies for the fabrication of functional iron oxide based magnetic nanoparticles. Nanoscale 5:10729–10752CrossRefGoogle Scholar
  50. Valle-Orta M, Diaz D, Santiago-Jacinto P, Vázquez-Olmos A, Reguera E (2008) Instantaneous synthesis of stable zerovalent metal nanoparticles under standard reaction conditions. J Phys Chem B 112:14427–14434CrossRefGoogle Scholar
  51. Wei H, Rodriguez K, Renneckar S, Vikesland PJ (2014) Environmental science and engineering applications of nanocellulose-based nanocomposites. Environ Sci Nano 1:302–316CrossRefGoogle Scholar
  52. Williams KS, Andzelm JW, Dong H, Snyder JF (2014) DFT study of metal cation-induced hydrogelation of cellulose nanofibrils. Cellulose 21:1091–1101CrossRefGoogle Scholar
  53. Wu X, Lu C, Zhou Z, Yuan G, Xiong R, Zhang X (2014) Green synthesis and formation mechanism of cellulose nanocrystal-supported gold nanoparticles with enhanced catalytic performance. Environ Sci Nano 1:71–79CrossRefGoogle Scholar
  54. Yang G, Xie J, Deng Y, Bian Y, Hong F (2012) Hydrothermal synthesis of bacterial cellulose/AgNPs composite: a “green” route for antibacterial application. Carbohydr Polym 87:2482–2487CrossRefGoogle Scholar
  55. Zhang WX (2003) Nanoscale iron particles for environmental remediation: an overview. J Nanopart Res 5:323–332CrossRefGoogle Scholar
  56. Zhang S, Wang D, Quan X, Zhou L, Zhang X (2013) Multi-walled carbon nanotubes immobilized on zero-valent iron plates (Fe0-CNTs) for catalytic ozonation of methylene blue as model compound in a bubbling reactor. Sep Purif Technol 116:351–359CrossRefGoogle Scholar
  57. Zhou Y, Ding EY, Li WD (2007) Synthesis of TiO2 nanocubes induced by cellulose nanocrystal (CNC) at low temperature. Mater Lett 61:5050–5052CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2015

Authors and Affiliations

  1. 1.Department of Chemical EngineeringIndian Institute of Technology GuwahatiGuwahatiIndia

Personalised recommendations