Skip to main content
SpringerLink
Log in

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

  • Original Paper
  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  • 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 66:750–756

    Article  CAS  Google Scholar 

  • Benaissi K, Johnson L, Walsh DA, Thielemans W (2010) Synthesis of platinum nanoparticles using cellulosic reducing agents. Green Chem 12:220–222

    Article  CAS  Google Scholar 

  • 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 Society

  • Cao X, Habibi Y, Lucia LA (2009) One-pot polymerization, surface grafting, and processing of waterborne polyurethane-cellulose nanocrystal nanocomposites. J Mater Chem 19:7137–7145

    Article  CAS  Google Scholar 

  • 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 367:53–58

    Article  CAS  Google Scholar 

  • 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 18:883–895

    Article  CAS  Google Scholar 

  • 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 13:288–291

    Article  CAS  Google Scholar 

  • Dhar P, Bhardwaj U, Katiyar V (2014a) Polymers for packaging applications. CRC Press, Boca Raton

    Google Scholar 

  • 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 Society

  • 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

  • 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 5:60426–60440

    Article  CAS  Google Scholar 

  • Dong H, Snyder JF, Tran DT, Leadore JL (2013a) Hydrogel, aerogel and film of cellulose nanofibrils functionalized with silver nanoparticles. Carbohydr Polym 95:760–767

    Article  CAS  Google Scholar 

  • Dong H, Snyder JF, Williams KS, Andzelm JW (2013b) Cation-induced hydrogels of cellulose nanofibrils with tunable moduli. Biomacromolecules 14:3338–3345

    Article  CAS  Google Scholar 

  • Farrell D, Majetich SA, Wilcoxon JP (2003) Preparation and characterization of monodisperse Fe nanoparticles. J Phys Chem B 107:11022–11030

    Article  CAS  Google Scholar 

  • 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):153–161

    Article  CAS  Google Scholar 

  • Garner A (2014) Use of cellulose nanocrystals as a corrosion inhibitor. U.S. Patent Application 13/935,477

  • 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 3:7828–7837

    Article  CAS  Google Scholar 

  • Houas A, Lachheb H, Ksibi M, Elaloui E, Guillard C, Herrmann JM (2001) Photocatalytic degradation pathway of methylene blue in water. Appl Catal B 31:145–157

    Article  CAS  Google Scholar 

  • Huang KC, Ehrman SH (2007) Synthesis of iron nanoparticles via chemical reduction with palladium ion seeds. Langmuir 23:1419–1426

    Article  CAS  Google Scholar 

  • 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 6:321

    CAS  Google Scholar 

  • Jiang F, Hsieh YL (2014) Synthesis of cellulose nanofibril bound silver nanoprism for surface enhanced Raman Scattering. Biomacromolecules 15:3608–3616

    Article  CAS  Google Scholar 

  • Johnson L, Thielemans W, Walsh DA (2011) Synthesis of carbon-supported Pt nanoparticle electrocatalysts using nanocrystalline cellulose as reducing agent. Green Chem 13:1686–1693

    Article  CAS  Google Scholar 

  • 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 2013

  • 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 250:220–228

    Article  Google Scholar 

  • 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 144:816–830

    Article  CAS  Google Scholar 

  • Lam E, Male KB, Chong JH, Leung AC, Luong JH (2012) Applications of functionalized and nanoparticle-modified nanocrystalline cellulose. Trends Biotechnol 30:283–290

    Article  CAS  Google Scholar 

  • 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 39:514–522

    Article  Google Scholar 

  • Li J, Xiao Q, Jiang JZ, Chen GN, Sun JJ (2014) Au–Fe/Ni alloy hybrid nanowire motors with dramatic speed. RSC Adv 4:27522–27525

    Article  CAS  Google Scholar 

  • 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:e85686

    Article  Google Scholar 

  • 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 4:57377–57382

    Article  CAS  Google Scholar 

  • 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 12:114–122

    Article  CAS  Google Scholar 

  • 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 27:264–271

    Article  Google Scholar 

  • 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 340:2376–2391

    Article  CAS  Google Scholar 

  • 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 3:10

    Article  Google Scholar 

  • Park M, Chang H, Jeong DH, Hyun J (2013) Spatial deformation of nanocellulose hydrogel enhances SERS. BioChip J 7:234–241

    Article  CAS  Google Scholar 

  • Pulgarin C, Kiwi J (1995) Iron oxide-mediated degradation, photodegradation, and biodegradation of aminophenols. Langmuir 11:519–526

    Article  CAS  Google Scholar 

  • 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 2:1241–1250

    Article  CAS  Google Scholar 

  • 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 11:994–1002

    Article  Google Scholar 

  • 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 75:85–94

    Article  CAS  Google Scholar 

  • Shin Y, Exarhos GJ (2007) Template synthesis of porous titania using cellulose nanocrystals. Mater Lett 61:2594–2597

    Article  CAS  Google Scholar 

  • Shin Y, Bae IT, Arey BW, Exarhos GJ (2007a) Simple preparation and stabilization of nickel nanocrystals on cellulose nanocrystal. Mater Lett 61:3215–3217

    Article  CAS  Google Scholar 

  • Shin Y, Blackwood JM, Bae IT, Arey BW, Exarhos GJ (2007b) Synthesis and stabilization of selenium nanoparticles on cellulose nanocrystal. Mater Lett 61:4297–4300

    Article  CAS  Google Scholar 

  • Shin Y, Bae IT, Arey BW, Exarhos GJ (2008) Facile stabilization of gold-silver alloy nanoparticles on cellulose nanocrystal. J Phys Chem C 112:4844–4848

    Article  CAS  Google Scholar 

  • Singh AK, Dey KK, Chattopadhyay A, Mandal TK, Bandyopadhyay D (2014) Multimodal chemo–magnetic control of self-propelling microbots. Nanoscale 6:1398–1405

    Article  CAS  Google Scholar 

  • Socrates G (2004) Infrared and Raman characteristic group frequencies: tables and charts. Wiley, New York

    Google Scholar 

  • 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 308:60–66

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • 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 192:500–506

    Article  CAS  Google Scholar 

  • 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 5:10729–10752

    Article  CAS  Google Scholar 

  • 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 112:14427–14434

    Article  CAS  Google Scholar 

  • Wei H, Rodriguez K, Renneckar S, Vikesland PJ (2014) Environmental science and engineering applications of nanocellulose-based nanocomposites. Environ Sci Nano 1:302–316

    Article  CAS  Google Scholar 

  • Williams KS, Andzelm JW, Dong H, Snyder JF (2014) DFT study of metal cation-induced hydrogelation of cellulose nanofibrils. Cellulose 21:1091–1101

    Article  CAS  Google Scholar 

  • 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 1:71–79

    Article  CAS  Google Scholar 

  • 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 87:2482–2487

    Article  CAS  Google Scholar 

  • Zhang WX (2003) Nanoscale iron particles for environmental remediation: an overview. J Nanopart Res 5:323–332

    Article  CAS  Google Scholar 

  • 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 116:351–359

    Article  CAS  Google Scholar 

  • Zhou Y, Ding EY, Li WD (2007) Synthesis of TiO2 nanocubes induced by cellulose nanocrystal (CNC) at low temperature. Mater Lett 61:5050–5052

    Article  CAS  Google Scholar 

Download references

Acknowledgments

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.

Author information

Authors and Affiliations

  1. Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati, Assam, India

    Prodyut Dhar, Amit Kumar & Vimal Katiyar

Authors
  1. Prodyut Dhar
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Amit Kumar
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Vimal Katiyar
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Vimal Katiyar.

Ethics declarations

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.

Electronic supplementary material

Below is the link to the electronic supplementary material.

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)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Dhar, P., Kumar, A. & Katiyar, V. Fabrication of cellulose nanocrystal supported stable Fe(0) nanoparticles: a sustainable catalyst for dye reduction, organic conversion and chemo-magnetic propulsion. Cellulose 22, 3755–3771 (2015). https://doi.org/10.1007/s10570-015-0759-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-015-0759-z

Keywords

Search

Navigation